Formula and in-situ modification preparation process of quantum dot-containing LED-UV (Light Emitting Diode-Ultraviolet) anti-forgery ink

Abstract

The invention relates to the technical field of ink preparation, in particular to a quantum dot-containing LED-UV anti-forgery ink formula and an in-situ modification preparation process thereof, and the quantum dot-containing LED-UV anti-forgery ink formula comprises the following components in parts by mass: 2-8 parts of core-shell structure quantum dots, 20-40 parts of LED-UV curing resin, 15-30 parts of a reactive diluent, 3-8 parts of a photoinitiator, 1-5 parts of a composite anti-forgery functional aid and 5-15 parts of a high-purity solvent. The quantum dots are uniformly dispersed in an ink system after being subjected to in-situ modification treatment, in-situ modification is realized through chemical bonding of a surface modifier and hydroxyl and amino groups on the surfaces of the quantum dots, and LED-UV cured resin, an active diluent and a photoinitiator cooperate with an LED-UV light source of 365-405 nm to perform in-situ surface modification on the quantum dots, so that the quantum dots are uniformly dispersed in the ink system. The fluorescent powder is tightly combined with a resin system through chemical bonding, so that agglomeration and migration are fundamentally prevented, and the uniformity and stability of the fluorescent property are ensured.

Description

Technical Field

[0001] This invention relates to the field of ink preparation technology, and in particular to an LED-UV anti-counterfeiting ink formulation with a content of sub-dots and its in-situ modification preparation process. Background Technology

[0002] Traditional anti-counterfeiting inks mostly rely on single optical color-changing, thermochromic, or chemical reagent color-developing principles. Their anti-counterfeiting features are easily counterfeited, and their durability is often insufficient. Quantum dots, due to their unique and precisely tunable fluorescence properties, are considered an ideal choice for next-generation anti-counterfeiting materials. However, applying quantum dots to ink systems faces several challenges: First, quantum dots have high surface energy, making them prone to aggregation in organic resins, leading to fluorescence quenching and uneven distribution; second, the interfacial bonding between quantum dots and the ink matrix is ​​weak, making them prone to migration and detachment during curing or use, affecting the durability of the anti-counterfeiting effect. Furthermore, traditional UV-cured inks use mercury lamps, which suffer from high energy consumption, significant thermal effects, and potential damage to the fluorescence properties of quantum dots. In addition, existing technologies mostly employ physical blending methods to add quantum dots, failing to fundamentally address the issues of compatibility and stability. Therefore, developing an environmentally friendly ink system that achieves stable dispersion and efficient curing of quantum dots, while possessing multiple anti-counterfeiting properties, has become a pressing technical challenge in this field. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the existing technology and to propose an LED-UV anti-counterfeiting ink formulation with a content of sub-dots and its in-situ modification preparation process.

[0004] To achieve the above objectives, the present invention adopts the following technical solution: a quantum dot-based LED-UV anti-counterfeiting ink formulation and its in-situ modification preparation process, comprising, by mass parts, 2-8 parts of core-shell structured quantum dots, 20-40 parts of LED-UV curing resin, 15-30 parts of reactive diluent, 3-8 parts of photoinitiator, 1-5 parts of composite anti-counterfeiting functional additive, and 5-15 parts of high-purity solvent; the quantum dots are uniformly dispersed in the ink system after in-situ modification treatment, and the in-situ modification is achieved by chemical bonding between the surface modifier and the hydroxyl and amino groups on the surface of the quantum dots; the LED-UV curing resin, reactive diluent, and photoinitiator are synergistically adapted to 365 to 405 nm LED-UV light source.

[0005] Preferably, the core material of the core-shell quantum dots is selected from one or more of CdSe, InP, ZnCdS, and PbS, and the shell material is selected from one or more of ZnS, CdS, SiO2, and Al2O3. The core-shell interface adopts a lattice-matched design. The quantum dot particle size is 2-10 nm, the particle size distribution variation coefficient is less than 15, the quantum yield is greater than 60 under excitation light of 365 to 405 nm, and the fluorescence half-width is less than 50 nm.

[0006] Preferably, the LED-UV curing resin is a composite resin system comprising a main resin and a modified resin. The main resin is selected from one or more of epoxy acrylic resin, polyurethane acrylic resin, and polyester acrylic resin. The modified resin is silane-modified acrylic resin or fluorine-modified acrylic resin, with a mass ratio of 3 to 5:1. The overall functionality of the resin is 2-6, the viscosity at 25°C is 500-5000 mPa·s, the acid value is below 10 mg KOH / g, and the curing shrinkage rate is below 5%.

[0007] Preferably, the reactive diluent is a compound of a multifunctional diluent and a monofunctional diluent in a mass ratio of 1 to 2:1; the multifunctional diluent is selected from one or more of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipropylene glycol diacrylate, and the monofunctional diluent is selected from one or more of isoborneol acrylate, 2-phenoxyethyl acrylate, and ethyl lactate acrylate; the overall double bond content of the reactive diluent is above 5 mmol / g, and the volatility is below 3% after 24 hours at 25°C.

[0008] Preferably, the AI ​​intelligent decision control module also has a built-in model update program that periodically retrieves historical inspection data, including collected data, fault records, processing results, and inspection effect evaluation data, to iteratively update the machine learning model, defect database, and normal operation acoustic model, thereby optimizing the algorithm's recognition accuracy and fault diagnosis accuracy.

[0009] Preferably, the composite anti-counterfeiting functional additive is composed of fluorescent whitening agent, infrared absorber, and magnetic powder in a mass ratio of 1:0.5 to 1.5:0.3 to 1; the fluorescent whitening agent is selected from stilbene biphenyl compounds and coumarin compounds, the infrared absorber is selected from phthalocyanine compounds and anthocyanin compounds, the magnetic powder is Fe3O4 nanoparticles with a particle size of 50-200 nm and a coercivity of 100-300 Oe; the high-purity solvent is selected from one or more of propylene glycol methyl ether acetate, ethyl acetate, ethanol, and isopropanol.

[0010] Preferably, an in-situ modification preparation process for LED-UV anti-counterfeiting ink with sub-dot content is also proposed, including the following steps: S1 Quantum Dot In-situ Modification: Disperse quantum dots in a high-purity solvent and ultrasonically disperse for 10-30 min until the system is uniformly transparent. Add a surface modifier and stir the reaction at 40-80℃ and 500-1500 r / min for 2-6 h under inert gas protection to obtain an in-situ modified quantum dot dispersion. The amount of surface modifier is 10 to 30 parts of the mass of the quantum dots. Preparation of S2 pre-dispersion system: LED-UV curing resin and reactive diluent are added to a high-speed disperser and stirred at 1000-3000 r / min for 30-60 min. Then, in-situ modified quantum dot dispersion is slowly added dropwise, the temperature is raised to 50-60℃, and dispersion is maintained at 2000-5000 r / min for 1-4 h. The particle size distribution D90 of the system is below 500 nm. S3 In-situ Crosslinking Integration: Add composite photoinitiator and composite anti-counterfeiting functional additive to the pre-dispersion system, heat to 50-90℃, adjust the stirring speed to 500-2000r / min, keep warm and stir for 1-3h, and realize the in-situ crosslinking of quantum dots and ink system through the free radical polymerization reaction between the terminal double bond of the surface modifier and the double bond of the resin and reactive diluent; S4 Ink Formulation and Post-processing: Cool the above system to 25-30℃, transfer it to a sand mill, and grind it for 0.5-2 hours using 0.1-0.5mm zirconia beads. Filter it through a 1-5μm filter membrane to remove impurities and agglomerated particles, and obtain a uniform and stable LED-UV anti-counterfeiting ink with a high content of sub-dots.

[0011] Preferably, the surface modifier in S1 is selected from one or more of the following: silane coupling agent KH550, silane coupling agent KH570, silane coupling agent KH560, hydroxyethyl methacrylate, isobornyl acrylate, and titanate coupling agent; the inert gas is nitrogen or argon, and the oxygen content of the system during the reaction is below 0.5%.

[0012] Preferably, the ink obtained in S4 is cured by irradiation with a 365-405nm LED-UV light source, with a curing energy of 80-300mJ / cm. 2 The curing rate is 5-30 m / min; the thickness of the ink film after curing is 1-10 μm, the film is free of pinholes and cracks, and the quantum dots are uniformly dispersed in the film.

[0013] Preferably, after the ink is cured, it emits fluorescence of a specific wavelength under 365nm ultraviolet light excitation, with a fluorescence peak wavelength of 450-650nm. After continuous ultraviolet irradiation for 100h, the fluorescence decay rate is less than 10, and after soaking in an acidic or alkaline environment with pH 3 to 10 for 24h, the fluorescence performance shows no significant change.

[0014] Compared with the prior art, the advantages and positive effects of the present invention are as follows: By modifying the surface of quantum dots in situ, they can be tightly bonded to the resin system through chemical bonding, which fundamentally prevents aggregation and migration, and ensures the uniformity and stability of fluorescence performance. Secondly, by selecting a suitable LED-UV curing resin and initiator system, low-temperature, rapid, and energy-saving curing at wavelengths of 365-405nm was achieved, avoiding thermal damage to quantum dots. By introducing composite anti-counterfeiting functional additives, the anti-counterfeiting level and the complexity of identification were improved. The final ink has the characteristics of fast curing speed, good film quality, high fluorescence intensity, and excellent weather resistance. Attached Figure Description

[0015] Figure 1 This is a system flowchart of the present invention. Detailed Implementation

[0016] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0017] In the description of this invention, it should be understood that the terms length, width, up, down, front, back, left, right, vertical, horizontal, top, bottom, inside, outside, etc., indicating orientation or positional relationships, are based on the orientation or positional relationships shown in the accompanying drawings and are only for the convenience of describing the invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of the invention. Furthermore, in the description of this invention, "multiple" means two or more, unless otherwise explicitly specified.

[0018] according to Figure 1 The present invention proposes an LED-UV anti-counterfeiting ink formulation containing quantum dots and its in-situ modification preparation process. By mass, it consists of 2-8 parts of core-shell structured quantum dots, 20-40 parts of LED-UV curing resin, 15-30 parts of reactive diluent, 3-8 parts of photoinitiator, 1-5 parts of composite anti-counterfeiting functional additive, and 5-15 parts of high-purity solvent. After in-situ modification, the quantum dots are uniformly dispersed in the ink system. The in-situ modification is achieved by chemical bonding between the surface modifier and the hydroxyl and amino groups on the surface of the quantum dots. The LED-UV curing resin, reactive diluent, and photoinitiator are synergistically adapted to 365 to 405 nm LED-UV light sources.

[0019] As an optional embodiment, the core material of the core-shell quantum dots is selected from one or more of CdSe, InP, ZnCdS, and PbS, and the shell material is selected from one or more of ZnS, CdS, SiO2, and Al2O3. The core-shell interface adopts a lattice-matched design. The quantum dot particle size is 2-10 nm, the particle size distribution variation coefficient is less than 15, the quantum yield is greater than 60 under excitation light of 365 to 405 nm, and the fluorescence half-width is less than 50 nm.

[0020] As an optional embodiment, the LED-UV curing resin is a composite resin system comprising a main resin and a modified resin. The main resin is selected from one or more of epoxy acrylic resin, polyurethane acrylic resin, and polyester acrylic resin. The modified resin is silane-modified acrylic resin or fluorine-modified acrylic resin, with a mass ratio of 3 to 5:1. The overall functionality of the resin is 2-6, the viscosity at 25°C is 500-5000 mPa·s, the acid value is below 10 mg KOH / g, and the curing shrinkage rate is below 5%.

[0021] As an optional embodiment, the reactive diluent is compounded from a multifunctional diluent and a monofunctional diluent at a mass ratio of 1 to 2:1; the multifunctional diluent is selected from one or more of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipropylene glycol diacrylate, and the monofunctional diluent is selected from one or more of isobornyl acrylate, 2-phenoxyethyl acrylate, and ethyl lactate acrylate; the overall double bond content of the reactive diluent is above 5 mmol / g, and the volatility is below 3% after 24 hours at 25°C.

[0022] As an optional embodiment, the AI ​​intelligent decision control module also has a built-in model update program that periodically retrieves historical inspection data, including collected data, fault records, processing results, and inspection effect evaluation data, to iteratively update the machine learning model, defect database, and normal operation acoustic model, thereby optimizing the algorithm's recognition accuracy and fault diagnosis accuracy.

[0023] As an optional embodiment, the composite anti-counterfeiting functional additive is composed of fluorescent whitening agent, infrared absorber, and magnetic powder in a mass ratio of 1:0.5 to 1.5:0.3 to 1; the fluorescent whitening agent is selected from stilbene biphenyl compounds and coumarin compounds, the infrared absorber is selected from phthalocyanine compounds and anthocyanin compounds, the magnetic powder is Fe3O4 nanoparticles with a particle size of 50-200nm and a coercivity of 100-300Oe; the high-purity solvent is selected from one or more of propylene glycol methyl ether acetate, ethyl acetate, ethanol, and isopropanol.

[0024] As an optional embodiment, an in-situ modification preparation process for LED-UV anti-counterfeiting ink containing sub-dots is also proposed, including the following steps: S1 Quantum Dot In-situ Modification: Disperse quantum dots in a high-purity solvent and ultrasonically disperse for 10-30 min until the system is uniformly transparent. Add a surface modifier and stir the reaction at 40-80℃ and 500-1500 r / min for 2-6 h under inert gas protection to obtain an in-situ modified quantum dot dispersion. The amount of surface modifier is 10 to 30 parts of the mass of the quantum dots. Preparation of S2 pre-dispersion system: LED-UV curing resin and reactive diluent are added to a high-speed disperser and stirred at 1000-3000 r / min for 30-60 min. Then, in-situ modified quantum dot dispersion is slowly added dropwise, the temperature is raised to 50-60℃, and dispersion is maintained at 2000-5000 r / min for 1-4 h. The particle size distribution D90 of the system is below 500 nm. S3 In-situ Crosslinking Integration: Add composite photoinitiator and composite anti-counterfeiting functional additive to the pre-dispersion system, heat to 50-90℃, adjust the stirring speed to 500-2000r / min, keep warm and stir for 1-3h, and realize the in-situ crosslinking of quantum dots and ink system through the free radical polymerization reaction between the terminal double bond of the surface modifier and the double bond of the resin and reactive diluent; S4 Ink Formulation and Post-processing: Cool the above system to 25-30℃, transfer it to a sand mill, and grind it for 0.5-2 hours using 0.1-0.5mm zirconia beads. Filter it through a 1-5μm filter membrane to remove impurities and agglomerated particles, and obtain a uniform and stable LED-UV anti-counterfeiting ink with a high content of sub-dots.

[0025] As an optional embodiment, the surface modifier in S1 is selected from one or more of the following: silane coupling agent KH550, silane coupling agent KH570, silane coupling agent KH560, hydroxyethyl methacrylate, isobornyl acrylate, and titanate coupling agent; the inert gas is nitrogen or argon, and the oxygen content of the system during the reaction is below 0.5%.

[0026] As an optional embodiment, the ink obtained in S4 is cured by irradiation with a 365 to 405 nm LED-UV light source, with a curing energy of 80-300 mJ / cm². 2 The curing rate is 5-30 m / min; the thickness of the ink film after curing is 1-10 μm, the film is free of pinholes and cracks, and the quantum dots are uniformly dispersed in the film.

[0027] As an optional embodiment, after the ink is cured, it emits fluorescence of a specific wavelength under 365nm ultraviolet light excitation, with a fluorescence peak wavelength of 450-650nm. After continuous ultraviolet irradiation for 100h, the fluorescence decay rate is less than 10, and after soaking in an acidic or alkaline environment with pH 3 to 10 for 24h, the fluorescence performance does not change significantly.

[0028] Example 1; 1. Raw materials and formula (by mass parts)

[0029] 2. Preparation steps; S1 quantum dot in-situ modification; Five parts of core-shell structured quantum dots were dispersed in 10 parts of propylene glycol methyl ether acetate; the dispersion was ultrasonically dispersed for 20 min until the system was uniformly transparent; 1.25 parts of silane coupling agent KH570 were added; nitrogen gas was introduced for protection (oxygen content of the system was 0.3); the reaction was stirred at 60℃ and 1000 r / min for 4 h to obtain an in-situ modified quantum dot dispersion; Preparation of S2 pre-dispersion system; Add 30 parts of LED-UV curing resin and 22 parts of reactive diluent to a high-speed disperser; stir and mix at 2000 r / min for 45 min; slowly add the above in-situ modified quantum dot dispersion; heat to 55℃; maintain dispersion at 3500 r / min for 2.5 h; the particle size distribution D90 of the system is 380 nm. S3 in-situ crosslinking and integration; Add 5 parts of composite photoinitiator and 3 parts of composite anti-counterfeiting functional additive to the pre-dispersion system; heat to 70℃; adjust the stirring speed to 1200r / min; keep warm and stir for 2h; free radical polymerization occurs between the terminal double bonds of KH570 and the double bonds of resin and reactive diluent; in-situ crosslinking of quantum dots and ink system is achieved. S4 ink formulation and post-treatment; The system was cooled to 28℃ and transferred to a sand mill. It was then ground for 1.2 hours using 0.3mm zirconia beads and filtered through a 3μm filter membrane to remove impurities and agglomerated particles, resulting in a uniform and stable LED-UV anti-counterfeiting ink with high content. 3. Performance test results;

[0030] Test results show that the curing performance, fluorescence performance, and stability of the ink in this embodiment all meet the requirements of the claims; the film layer is defect-free and the quantum dots are uniformly dispersed; it can achieve efficient anti-counterfeiting identification. II. Example 2; III. 1. Raw materials and formula (by mass parts)

[0031] S1 quantum dot in-situ modification; Two parts of core-shell structured quantum dots were dispersed in five parts of ethyl acetate; the mixture was ultrasonically dispersed for 10 min until the system was uniformly transparent; 0.2 parts of hydroxyethyl methacrylate were added; argon gas was introduced for protection (oxygen content of the system was 0.2); the mixture was stirred at 40℃ and 500 r / min for 2 h to obtain an in-situ modified quantum dot dispersion; Preparation of S2 pre-dispersion system; Add 20 parts of LED-UV curing resin and 15 parts of reactive diluent to a high-speed disperser; stir and mix at 1000 r / min for 30 min; slowly add the above in-situ modified quantum dot dispersion; heat to 50℃; maintain dispersion at 2000 r / min for 1 h; the particle size distribution D90 of the system is found to be 450 nm; S3 in-situ crosslinking and integration; Add 3 parts of composite photoinitiator and 1 part of composite anti-counterfeiting functional additive to the pre-dispersion system; heat to 50℃; adjust the stirring speed to 500 r / min; keep warm and stir for 1 h; achieve in-situ crosslinking through free radical polymerization of the terminal double bonds of the surface modifier with the double bonds of the resin and reactive diluent; S4 ink formulation and post-treatment; The system was cooled to 25℃ and transferred to a sand mill. It was then ground with 0.1mm zirconia beads for 0.5 hours and filtered through a 1μm filter membrane to obtain a uniform and stable LED-UV anti-counterfeiting ink. 3. Performance test results;

[0032] Test results show that the ink in this embodiment still meets the core performance indicators of the claims under the low limit parameters; although the curing rate and fluorescence intensity are lower than those of Example 1, they meet the basic requirements for anti-counterfeiting applications; and the preparation cost is lower, making it suitable for scenarios with moderate performance requirements. III. Example 3 1. Raw materials and formula (by mass parts)

[0033] S1 quantum dot in-situ modification; Eight parts of core-shell structured quantum dots were dispersed in 15 parts of isopropanol; the dispersion was ultrasonically dispersed for 30 min until the system was uniformly transparent; 2.4 parts of titanate coupling agent were added; nitrogen gas was introduced for protection (oxygen content of the system was 0.4); the reaction was stirred at 80℃ and 1500 r / min for 6 h to obtain an in-situ modified quantum dot dispersion; Preparation of S2 pre-dispersion system; Add 40 parts of LED-UV curing resin and 30 parts of reactive diluent to a high-speed disperser; stir and mix at 3000 r / min for 60 min; slowly add the above in-situ modified quantum dot dispersion; heat to 60℃; maintain dispersion at 5000 r / min for 4 h; the particle size distribution D90 of the system is found to be 420 nm; S3 in-situ crosslinking and integration; Add 8 parts of composite photoinitiator and 5 parts of composite anti-counterfeiting functional additive to the pre-dispersion system; heat to 90℃; adjust the stirring speed to 2000 r / min; keep warm and stir for 3 h; achieve in-situ crosslinking through free radical polymerization of the terminal double bonds of the surface modifier with the double bonds of the resin and reactive diluent; S4 ink formulation and post-treatment; The system was cooled to 30℃; transferred to a sand mill; ground with 0.5mm zirconia beads for 2 hours; filtered through a 5μm filter membrane; a uniform and stable LED-UV anti-counterfeiting ink was obtained.

[0034] Test results show that the ink in this embodiment exhibits the best fluorescence intensity and curing rate under high-limit parameters; it has the lowest fluorescence decay rate and better environmental stability; it is suitable for high-end application scenarios with high requirements for anti-counterfeiting effect and low sensitivity to cost. IV. Comparison of Implementation Examples and Analysis of Technical Effects

[0035] Through parameter gradient verification in Examples 1-3, the parameter range of the formulation and process of this invention is scientifically reasonable; the ink can meet the core performance requirements of the claims under different parameter combinations; and through in-situ modification and cross-linking technology of quantum dots, the technical pain points of uneven quantum dot dispersion and rapid fluorescence decay in traditional quantum dot inks are solved; the synergistic effect of composite anti-counterfeiting functional additives enables the ink to simultaneously possess fluorescent, infrared, and magnetic triple anti-counterfeiting properties; compared with single anti-counterfeiting inks, the anti-counterfeiting security is higher; the LED-UV curing system is compatible with 365~405nm light sources; it has high curing efficiency and no VOC emissions; and it conforms to the development trend of environmentally friendly anti-counterfeiting materials.

[0036] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention in any other way. Any person skilled in the art may make changes or modifications to the above-disclosed technical content to create equivalent embodiments that can be applied to other fields. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A formula for an LED-UV anti-counterfeiting ink containing sub-dots, characterized in that, By mass fraction, it consists of 2-8 parts core-shell structured quantum dots, 20-40 parts LED-UV curing resin, 15-30 parts reactive diluent, 3-8 parts photoinitiator, 1-5 parts composite anti-counterfeiting functional additive, and 5-15 parts high-purity solvent. The quantum dots are uniformly dispersed in the ink system after in-situ modification treatment. The in-situ modification is achieved by chemical bonding between the surface modifier and the hydroxyl and amino groups on the surface of the quantum dots. The LED-UV curing resin, reactive diluent, and photoinitiator are synergistically adapted to 365 to 405 nm LED-UV light sources.

2. The LED-UV anti-counterfeiting ink formulation with a content of sub-dots according to claim 1, characterized in that, The core material of the core-shell quantum dots is selected from one or more of CdSe, InP, ZnCdS, and PbS, and the shell material is selected from one or more of ZnS, CdS, SiO2, and Al2O3. The core-shell interface adopts a lattice-matched design. The quantum dot particle size is 2-10 nm, the particle size distribution variation coefficient is less than 15, the quantum yield is greater than 60 under excitation light of 365 to 405 nm, and the fluorescence half-width is less than 50 nm.

3. The LED-UV anti-counterfeiting ink formulation with a content of sub-dots according to claim 1, characterized in that, LED-UV curing resin is a composite resin system, comprising a main resin and a modified resin. The main resin is selected from one or more of epoxy acrylic resin, polyurethane acrylic resin, and polyester acrylic resin. The modified resin is silane-modified acrylic resin or fluorine-modified acrylic resin, with a mass ratio of 3 to 5:

1. The overall functionality of the resin is 2-6, the viscosity at 25℃ is 500-5000 mPa・s, the acid value is below 10 mg KOH / g, and the curing shrinkage rate is below 5%.

4. The LED-UV anti-counterfeiting ink formulation with a content of sub-dots according to claim 1, characterized in that, The reactive diluent is a compound of a multifunctional diluent and a monofunctional diluent in a mass ratio of 1 to 2:

1. The multifunctional diluent is selected from one or more of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, and dipropylene glycol diacrylate, and the monofunctional diluent is selected from one or more of isobornyl acrylate, 2-phenoxyethyl acrylate, and ethyl lactate acrylate. The overall double bond content of the reactive diluent is above 5 mmol / g, and the volatility is below 3% after 24 hours at 25°C.

5. The LED-UV anti-counterfeiting ink formulation with a content of sub-dots according to claim 4, characterized in that, The AI ​​intelligent decision control module also has a built-in model update program that periodically retrieves historical inspection data, including collected data, fault records, processing results, and inspection effect evaluation data, to iteratively update the machine learning model, defect database, and normal operation acoustic model, thereby optimizing the algorithm's recognition accuracy and fault diagnosis accuracy.

6. The LED-UV anti-counterfeiting ink formulation with a content of sub-dots according to claim 1, characterized in that, The composite anti-counterfeiting functional additive is composed of fluorescent whitening agent, infrared absorber, and magnetic powder in a mass ratio of 1:0.5 to 1.5:0.3 to 1. The fluorescent whitening agent is selected from stilbene biphenyl compounds and coumarin compounds, the infrared absorber is selected from phthalocyanine compounds and anthocyanin compounds, the magnetic powder is Fe3O4 nanoparticles with a particle size of 50-200nm and a coercivity of 100-300Oe, and the high-purity solvent is selected from one or more of propylene glycol methyl ether acetate, ethyl acetate, ethanol, and isopropanol.

7. An in-situ modification preparation process for LED-UV anti-counterfeiting ink with a content of sub-dots, used in the formulation of LED-UV anti-counterfeiting ink with a content of sub-dots as described in any one of claims 1 to 6, characterized in that, Includes the following steps: S1 Quantum Dot In-situ Modification: Disperse quantum dots in a high-purity solvent and ultrasonically disperse for 10-30 min until the system is uniformly transparent. Add a surface modifier and stir the reaction at 40-80℃ and 500-1500 r / min for 2-6 h under inert gas protection to obtain an in-situ modified quantum dot dispersion. The amount of surface modifier is 10 to 30 parts of the mass of the quantum dots. Preparation of S2 pre-dispersion system: LED-UV curing resin and reactive diluent are added to a high-speed disperser and stirred at 1000-3000 r / min for 30-60 min. Then, in-situ modified quantum dot dispersion is slowly added dropwise, the temperature is raised to 50-60℃, and dispersion is maintained at 2000-5000 r / min for 1-4 h. The particle size distribution D90 of the system is below 500 nm. S3 In-situ Crosslinking Integration: Add composite photoinitiator and composite anti-counterfeiting functional additive to the pre-dispersion system, heat to 50-90℃, adjust the stirring speed to 500-2000r / min, keep warm and stir for 1-3h, and realize the in-situ crosslinking of quantum dots and ink system through the free radical polymerization reaction between the terminal double bond of the surface modifier and the double bond of the resin and reactive diluent; S4 Ink Formulation and Post-processing: Cool the above system to 25-30℃, transfer it to a sand mill, and grind it for 0.5-2 hours using 0.1-0.5mm zirconia beads. Filter it through a 1-5μm filter membrane to remove impurities and agglomerated particles, and obtain a uniform and stable LED-UV anti-counterfeiting ink with a high content of sub-dots.

8. The in-situ modification preparation process of LED-UV anti-counterfeiting ink with sub-dot content according to claim 7, characterized in that, The surface modifier in S1 is selected from one or more of the following: silane coupling agent KH550, silane coupling agent KH570, silane coupling agent KH560, hydroxyethyl methacrylate, isobornyl acrylate, and titanate coupling agent; the inert gas is nitrogen or argon, and the oxygen content of the system during the reaction is below 0.5%.

9. The in-situ modification preparation process of LED-UV anti-counterfeiting ink with a content of sub-dots according to claim 7, characterized in that, The ink obtained in S4 is cured by irradiation with a 365-405nm LED-UV light source, with a curing energy of 80-300mJ / cm². 2 The curing rate is 5-30 m / min; the thickness of the ink film after curing is 1-10 μm, the film is free of pinholes and cracks, and the quantum dots are uniformly dispersed in the film.

10. The in-situ modification preparation process of LED-UV anti-counterfeiting ink with sub-dot content according to claim 1, characterized in that, After curing, the ink emits fluorescence at a specific wavelength under 365nm ultraviolet light excitation, with a fluorescence peak wavelength of 450-650nm. After 100 hours of continuous ultraviolet irradiation, the fluorescence decay rate is less than 10. After soaking in an acidic or alkaline environment with pH 3 to 10 for 24 hours, the fluorescence performance shows no significant change.

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