Solvent-resistant folding-resistant EB curing ink and preparation method thereof

Abstract

The invention relates to solvent-resistant folding-resistant EB curing ink and a preparation method thereof. Comprising the following components in parts by mass: 50-60 parts of a prepolymer system, 25-35 parts of aliphatic polyurethane acrylate, 13-17 parts of epoxy acrylate, 4-6 parts of polyacrylate, 25-35 parts of a reactive diluent, 10-15 parts of pigment filler, 2-5 parts of an auxiliary agent, 0.5-1 part of a flatting agent, 0.5-1 part of a defoaming agent, 1-2 parts of an adhesion promoter, 0.5-1 part of a stabilizer, 1-2 parts of a dispersing agent and 15-25 parts of a polymerized emulsion system, the prepolymer system comprises organic silicon modified acrylate, fluorine modified acrylate and phosphate acrylate. The ink has the effect of improving the solvent resistance and the folding resistance of the ink.

Description

Technical Field

[0001] This application relates to the field of inks, and in particular to a solvent-resistant, fold-resistant EB-curable ink and its preparation method. Background Technology

[0002] EB ink is short for electron beam cured ink. It is a type of ink that uses electron beam radiation energy to induce polymerization and cross-linking reactions in the chemical substances in the ink system, thereby achieving rapid curing and drying.

[0003] However, friction during the transportation and storage of EB ink products can cause wear and tear on the ink film, making the text and patterns blurry. Small amounts of solvents in the environment can then penetrate the worn areas, further damaging the ink film and affecting product identification. In addition, the environment in which the product comes into contact with also contains solvent components, which can further corrode the ink film and reduce the quality of the product. Summary of the Invention

[0004] To further improve the solvent resistance and abrasion resistance of inks, this application provides a solvent-resistant and fold-resistant EB-cured ink and its preparation method.

[0005] Firstly, this application provides a solvent-resistant and fold-resistant EB curable ink, which adopts the following technical solution: A solvent-resistant and fold-resistant EB-curable ink comprises the following components in parts by weight: The composition includes 50-60 parts of prepolymer system, 25-35 parts of aliphatic polyurethane acrylate, 13-17 parts of epoxy acrylate, 4-6 parts of polyacrylate, 25-35 parts of reactive diluent, 10-15 parts of pigments and fillers, 2-5 parts of additives, 0.5-1 part of leveling agent, 0.5-1 part of defoamer, 1-2 parts of adhesion promoter, 0.5-1 part of stabilizer, 1-2 parts of dispersant, and 15-25 parts of polymer emulsion system; the prepolymer system includes silicone-modified acrylate, fluorinated acrylate, and phosphate acrylate.

[0006] By adopting the above technical solution, the prepolymer system participates in the curing of aliphatic polyurethane acrylate, epoxy acrylate, and polyurethane acrylate, and then uses modified monomers for further polymerization. The resulting system has a good cross-linking network. At the same time, through the soft and hard segment prepolymers, the prepolymer system works synergistically, and the functional monomers and pigments and fillers enhance the ink, thereby giving the prepared ink good adhesion, toughness and density, effectively improving the overall solvent resistance and folding resistance of the ink system.

[0007] Preferably, the raw materials of the polymer emulsion system include an emulsifier, mixed monomer B, and an initiator; the emulsifier includes diethylene glycol dimethyl ether, mixed monomer A, benzoyl peroxide, and tert-butyl peroxide.

[0008] Preferably, the emulsifier is prepared by the following method: The acrylic acid, butyl acrylate, methyl methacrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate are mixed to obtain a mixed monomer A, the mixed monomer A is mixed with diethylene glycol dimethyl ether, and after warming, benzoyl peroxide and tert-butyl benzoyl peroxide are added, and the reaction is incubated, and after cooling, water is added to obtain the emulsifier.

[0009] By using the above technical solution, the polymeric emulsion system is also added to the ink, and the polymeric emulsion system is prepared by polymerization of the emulsifier, monomer and initiator. The emulsifier is prepared by using diethylene glycol dimethyl ether, acrylic acid, hydroxyethyl methacrylate, butyl acrylate as monomers, and using benzoyl peroxide and tert-butyl benzoyl peroxide for initiation. The emulsion prepared has uniform particle size and good stability, which can further improve the stability and adhesion of the ink.

[0010] Preferably, the mass ratio of benzoyl peroxide to tert-butyl benzoyl peroxide is (8-9):1.

[0011] By using the above technical solution, the mass ratio of benzoyl peroxide to tert-butyl benzoyl peroxide is preferably within the above range, which can further improve the stability of the emulsifier prepared as a whole.

[0012] Preferably, the mass ratio of acrylic acid, butyl acrylate and methyl methacrylate in the mixed monomer A is (0.45-0.55):1:1.33.

[0013] By using the above technical solution, the mass ratio of acrylic acid, butyl acrylate and methyl methacrylate in the mixed monomer A is preferably within the above range, and the emulsifier prepared has uniform particle size and good dispersion performance.

[0014] Preferably, the polymeric emulsion system is prepared by the following method: The sodium bicarbonate, sodium persulfate and water are mixed to obtain an initiator; the emulsifier is mixed with the mixed monomer B, pre-emulsified by stirring, the initiator is added under water bath, and then the mixed monomer B and the remaining initiator are added, and the polymeric emulsion system is obtained after reaction and cooling.

[0015] By using the above technical solution, the emulsifier is mixed in the water phase to obtain an emulsion system, and under the action of aggregation, the micelles formed can act as the shell structure of the polymeric emulsion system. After adding the acrylic monomer, it is solubilized into the shell layer by emulsion polymerization, and the core is formed in the shell layer. The polymeric emulsion system is prepared by adding it to the ink, which can effectively improve the adhesion of the ink as a whole.

[0016] Preferably, the mass ratio between the sodium bicarbonate and the sodium persulfate is 1:(0.95-1.05).

[0017] By adopting the above technical solution, preferably, the mass ratio between the sodium bicarbonate and the sodium persulfate is within the above range, which can further improve the stability of the prepared polymer emulsion system.

[0018] Preferably, the color filler comprises pigments and a dispersed nanosystem, which is prepared by the following method: The water, the silane coupling agent and the polyvinyl alcohol are mixed and stirred, the nanosilica and the nanoalumina are added, the boric acid is added, and stirring and dispersion are performed, and then washing, freeze-drying are performed to obtain the dispersed nanosystem.

[0019] By adopting the above technical solution, the nanodispersion system has good stability in the system after the above dispersion treatment, the silica ink coating has the advantages of high porosity, strong ink absorption and strong scratch resistance, can quickly absorb ink, and after compounding with alumina, the surface performance of the whole inkjet can be further improved, thereby further improving the adhesion performance and solvent resistance of the whole system.

[0020] Preferably, the mass ratio between the polyvinyl alcohol, the nanosilica and the nanoalumina is 0.1:1:(1.1-1.3).

[0021] By adopting the above technical solution, preferably, the mass ratio between the polyvinyl alcohol, the nanosilica and the nanoalumina is within the above range, which can further improve the stability of the whole nanodispersion system prepared.

[0022] In a second aspect, the application provides a preparation method of a solvent-resistant and fold-resistant EB curing ink, which adopts the following technical solution: a preparation method of a solvent-resistant and fold-resistant EB curing ink, comprising the following steps: The prepolymer system, the aliphatic polyurethane acrylate, the epoxy acrylate, the polyester acrylate and the active diluent are mixed and stirred, the polymer emulsion system is added, stirring and standing are performed, the color filler is added, the leveling agent, the defoaming agent, the adhesion promoter, the stabilizer and the dispersant are added after stirring, and then stirring is performed to obtain the EB curing ink.

[0023] In summary, the application has at least one of the following beneficial technical effects: 1. The prepolymer system participates in the curing of aliphatic polyurethane acrylate, epoxy acrylate, and polyurethane acrylate, and is then polymerized again using modified monomers. The resulting system has a good cross-linking network. At the same time, through the soft and hard segment prepolymers, the prepolymer system works synergistically, and the functional monomers and pigments and fillers enhance the ink, resulting in good adhesion, toughness and density. This effectively improves the overall solvent resistance and folding resistance of the ink system. 2. The emulsifier is mixed in the aqueous phase to obtain an emulsion system. Under the aggregation effect, the micelles formed can serve as the shell structure of the polymer emulsion system. Then, acrylic monomers are added, and through emulsion polymerization, they are solubilized and enter the shell layer, and aggregate in the shell layer to form nuclei, thus preparing a polymer emulsion system. When added to ink, it can effectively improve the overall adhesion performance of the ink. 3. After the above dispersion treatment, the nano-dispersion system has good stability in the system. Silica can give the ink coating advantages such as high porosity, strong ink absorption and strong scratch resistance. It can quickly absorb ink. When compounded with alumina, it can further improve the overall surface performance of inkjet printing, thereby further improving the overall adhesion and solvent resistance of the system. Detailed Implementation

[0024] The present application will be further described in detail below with reference to the embodiments: Raw material description: All raw materials in the examples are commercially available; among them, the silane coupling agent is KH550 (CAS No.: 919-30-2); the reactive diluent is isobornyl acrylate (CAS No.: 5888-33-5); the leveling agent is polyethylene glycol (CAS No.: 25322-68-3); the defoamer is dimethyl silicone oil (CAS No.: 9006-65-9); the adhesion promoter is ethoxyethoxyethyl acrylate (CAS No.: 7328-17-8); the stabilizer is butylated hydroxytoluene (CAS No.: 128-37-0); the dispersant is sodium dodecyl sulfate (CAS No.: 151-21-3); the organosilicon-modified acrylate is methyl silicone acrylate; the pigments and fillers include any one of titanium dioxide and carbon black.

[0025] Example 1 Preparation of mixed monomer A: 26.71g of acrylic acid (CAS No.: 79-10-7), 59.35g of butyl acrylate (CAS No.: 141-32-2), 78.94g of methyl methacrylate (CAS No.: 80-62-6), 6.5g of hydroxypropyl acrylate (CAS No.: 2918-23-2) and 3g of hydroxyethyl methacrylate (CAS No.: 868-77-9) were mixed to obtain mixed monomer A.

[0026] Preparation of mixed monomer B: 3g of acrylic acid, 104g of butyl acrylate, 156g of methyl methacrylate, 13.5g of hydroxypropyl acrylate, 7g of hydroxyethyl methacrylate and 20g of tributyl acetyl citrate (CAS No.: 77-90-7) were mixed to obtain mixed monomer B.

[0027] Preparation of emulsifiers: The above-mentioned mixed monomer A was mixed with 25g of diethylene glycol dimethyl ether (CAS No.: 111-96-6), heated to 130℃, and then 1.78g of benzoyl peroxide (CAS No.: 94-36-0) and 0.22g of tert-butyl peroxide (CAS No.: 614-45-9) were added. The mixture was reacted for 2 hours and then kept at the temperature for 1 hour. The mixture was then cooled to 25℃ and neutralized with ammonia water to a pH of 8. Finally, 150g of water was added to obtain the emulsifier.

[0028] Preparation of polymer emulsion system: 1.54 g of sodium bicarbonate, 1.46 g of sodium persulfate, and 100 g of deionized water were mixed to obtain an initiator. 200 g of emulsifier and 25 g of mixed monomer B were mixed and stirred for pre-emulsification for 30 min. Then, 34 g of initiator was added to a water bath at 90 °C until the system turned blue. Then, 225 g of mixed monomer B and the remaining initiator were added. The reaction was carried out for 3 h and kept at the temperature for 1 h. After cooling to 25 °C, the pH of the system was adjusted to 8 using ammonia water to obtain a polymer emulsion system.

[0029] Preparation of dispersed nanosystems: 100g of deionized water, 1.6g of silane coupling agent and 0.91g of polyvinyl alcohol (CAS No.: 9002-89-5) were mixed and stirred at 300rpm for 15min. Then 9.09g of nano silica and 10g of nano alumina were added, followed by 0.11g of boric acid. The mixture was stirred at 2000rpm for 30min and then dispersed at 10000rpm for 15min. The mixture was then freeze-dried at -20℃ to obtain the dispersed nano system.

[0030] Preparation of EB-curable ink: 16.6g of silicone-modified acrylate, 16.6g of fluorine-modified acrylate, and 16.8g of phosphate acrylate were mixed to obtain a prepolymer system. The above prepolymer system, 25g of aliphatic polyurethane acrylate, 13g of epoxy acrylate, 4g of polyester acrylate, and 25g of reactive diluent were mixed and stirred for 2 hours. Then, 15g of polymer emulsion system was added, stirred for 15 minutes, and allowed to stand for 30 minutes. Then, 10g of titanium dioxide and 2g of dispersible nano system were added and stirred for 15 minutes. Finally, 0.5g of leveling agent, 0.5g of defoamer, 1g of adhesion promoter, 0.5g of stabilizer, and 1g of dispersant were added and stirred for 15 minutes to ensure that the system is fully mixed and homogeneous, thus obtaining EB-cured ink.

[0031] Example 2 Preparation of mixed monomer A: 28.51g of acrylic acid, 57.29g of butyl acrylate, 79.2g of methyl methacrylate, 6.5g of hydroxypropyl acrylate and 3g of hydroxyethyl methacrylate were mixed to obtain mixed monomer A.

[0032] Preparation of mixed monomer B: 3g of acrylic acid, 104g of butyl acrylate, 156g of methyl methacrylate, 13.5g of hydroxypropyl acrylate, 7g of hydroxyethyl methacrylate and 20g of tributyl acetyl citrate were mixed to obtain mixed monomer B.

[0033] Preparation of emulsifiers: Mix the above-mentioned monomer A with 25g of diethylene glycol dimethyl ether, heat to 130℃, then add 1.8g of benzoyl peroxide and 0.2g of tert-butyl peroxide, react for 2h and keep warm for 1h, cool to 25℃, neutralize with ammonia water to pH 8, and then add 150g of water to obtain the emulsifier.

[0034] Preparation of polymer emulsion system: 1.46 g of sodium bicarbonate, 1.54 g of sodium persulfate, and 100 g of deionized water were mixed to obtain an initiator. 200 g of emulsifier and 25 g of mixed monomer B were mixed and stirred for pre-emulsification for 30 min. Then, 34 g of initiator was added to a water bath at 90 °C until the system turned blue. Then, 225 g of mixed monomer B and the remaining initiator were added. After reacting for 3 h, the mixture was kept at this temperature for 1 h. After cooling to 25 °C, the pH of the system was adjusted to 8 using ammonia water to obtain a polymer emulsion system.

[0035] Preparation of dispersed nanosystems: Mix 100g of deionized water, 1.6g of silane coupling agent and 0.83g of polyvinyl alcohol, stir at 300rpm for 15min, then add 8.33g of nano-silica and 10.84g of nano-alumina, then add 0.11g of boric acid, stir at 2000rpm for 30min, then disperse at 10000rpm for 15min, and freeze-dry at -20℃ to obtain the dispersed nano system.

[0036] Preparation of EB-curable ink: 20g of silicone-modified acrylate, 20g of fluorine-modified acrylate, and 20g of phosphate acrylate were mixed to obtain a prepolymer system. The above prepolymer system, 35g of aliphatic polyurethane acrylate, 17g of epoxy acrylate, 6g of polyester acrylate, and 35g of reactive diluent were mixed and stirred for 2 hours. Then, 25g of polymer emulsion system was added, stirred for 15 minutes, and allowed to stand for 30 minutes. Then, 15g of carbon black and 5g of dispersed nano system were added and stirred for 15 minutes. Finally, 1g of leveling agent, 1g of defoamer, 2g of adhesion promoter, 1g of stabilizer, and 2g of dispersant were added and stirred for 15 minutes to ensure that the system is fully mixed and homogeneous, thus obtaining EB-cured ink.

[0037] Example 3 Preparation of mixed monomer A: 29.16g of acrylic acid, 58.3g of butyl acrylate, 77.54g of methyl methacrylate, 6.5g of hydroxypropyl acrylate and 3g of hydroxyethyl methacrylate were mixed to obtain mixed monomer A.

[0038] Preparation of mixed monomer B: 3g of acrylic acid, 104g of butyl acrylate, 156g of methyl methacrylate, 13.5g of hydroxypropyl acrylate, 7g of hydroxyethyl methacrylate and 20g of tributyl acetyl citrate were mixed to obtain mixed monomer B.

[0039] Preparation of emulsifiers: Mix the above-mentioned monomer A with 25g of diethylene glycol dimethyl ether, heat to 130℃, then add 1.79g of benzoyl peroxide and 0.21g of tert-butyl peroxide, react for 2h and keep warm for 1h, cool to 25℃, neutralize with ammonia water to pH 8, and then add 150g of water to obtain the emulsifier.

[0040] Preparation of polymer emulsion system: 1.5g of sodium bicarbonate, 1.5g of sodium persulfate, and 100g of deionized water were mixed to obtain an initiator. 200g of emulsifier and 25g of mixed monomer B were mixed and stirred for pre-emulsification for 30min. Then, 34g of initiator was added to a water bath at 90℃ until the system turned blue. 225g of mixed monomer B and the remaining initiator were added, and the reaction was carried out for 3h. After incubation for 1h, the system was cooled to 25℃, and the pH of the system was adjusted to 8 using ammonia water to obtain a polymer emulsion system.

[0041] Preparation of dispersed nanosystems: Mix 100g of deionized water, 1.6g of silane coupling agent and 0.87g of polyvinyl alcohol, stir at 300rpm for 15min, then add 8.7g of nano-silica and 10.43g of nano-alumina, then add 0.11g of boric acid, stir at 2000rpm for 30min, then disperse at 10000rpm for 15min, and freeze-dry at -20℃ to obtain the dispersed nano system.

[0042] Preparation of EB-curable ink: 18.33g of silicone-modified acrylate, 18.33g of fluorine-modified acrylate, and 18.34g of phosphate acrylate were mixed to obtain a prepolymer system. The above prepolymer system, 30g of aliphatic polyurethane acrylate, 15g of epoxy acrylate, 5g of polyester acrylate, and 30g of reactive diluent were mixed and stirred for 2 hours. Then, 20g of polymer emulsion system was added, stirred for 15 minutes, and allowed to stand for 30 minutes. Then, 13g of titanium dioxide and 4g of dispersible nano system were added and stirred for 15 minutes. Finally, 0.7g of leveling agent, 0.7g of defoamer, 1.5g of adhesion promoter, 0.7g of stabilizer, and 1.5g of dispersant were added and stirred for 15 minutes to ensure that the system is fully mixed and homogeneous, thus obtaining EB-cured ink.

[0043] Example 4 Example 4 is based on Example 3. In Example 4, when preparing mixed monomer A, 21.55g of acrylic acid, 61.57g of butyl acrylate, and 81.88g of methyl methacrylate were used.

[0044] Example 5 Example 5 is based on Example 3. In Example 5, when preparing mixed monomer A, 35.99g of acrylic acid, 55.37g of butyl acrylate, and 73.64g of methyl methacrylate were used.

[0045] Example 6 Example 6 is based on Example 3. In Example 6, when preparing the emulsifier, the amount of benzoyl peroxide used is 1.75g ​​and the amount of tert-butyl peroxide used is 0.25g.

[0046] Example 7 Example 7 is based on Example 3. In Example 7, when preparing the emulsifier, the amount of benzoyl peroxide used is 1.82g and the amount of tert-butyl peroxide used is 0.18g.

[0047] Example 8 Example 8 is based on Example 3. In Example 8, when preparing the polymer emulsion system, the amount of sodium bicarbonate used in the initiator is 1.67g and the amount of sodium persulfate used is 1.33g.

[0048] Example 9 Example 9 is based on Example 3. In Example 9, when preparing the polymer emulsion system, the amount of sodium bicarbonate used in the initiator is 1.36g and the amount of sodium persulfate used is 1.64g.

[0049] Example 10 Example 10 is based on Example 3. In Example 10, when preparing the dispersed nano system, 1g of polyvinyl alcohol, 10g of nano-silica, and 9g of nano-alumina were used.

[0050] Example 11 Example 11 is based on Example 3. In Example 11, when preparing the dispersed nano system, the amount of polyvinyl alcohol used was 0.77g, the amount of nano-silica was 7.69g, and the amount of nano-alumina was 11.54g.

[0051] Example 12 Example 12 is based on Example 3, but no polyvinyl alcohol was added when preparing the dispersed nanosystem in Example 12.

[0052] Example 13 Example 13 is based on Example 3, but no nano-silica was added when preparing the dispersed nano system in Example 13.

[0053] Example 14 Example 14 is based on Example 3, but no nano-alumina was added when preparing the dispersed nano system in Example 14.

[0054] Comparative Example 1 Comparative Example 1 is based on Example 3, except that the polymer emulsion system was replaced with an emulsifier when preparing the EB curable ink.

[0055] Comparative Example 2 Comparative Example 2 is based on Example 3. In Comparative Example 2, the prepolymer system was replaced with ordinary water-based acrylate when preparing EB curable ink.

[0056] Performance testing The following performance tests were performed on the samples of Examples 1-14 and Comparative Examples 1-2: (1) Solvent resistance Solvent resistance: The sample was cured on the surface of liquid crystal glass by electron beam scanning and immersed in a beaker containing 50 ml of solvent (EC:IPA = 1:1) at 25°C. The color density loss at 10s and 20s was measured by an X-rite 528 densitometer and the test results were recorded in Table 1.

[0057] (2) Flexural strength The sample was cured onto the surface of the liquid crystal glass by electron beam scanning and placed at room temperature until it dried naturally to form a film. After the film dried, the sample was folded back and forth nearly 180° 300 times, and the test results were recorded in Table 1.

[0058] (3) Abrasion resistance The sample was solidified onto the surface of the liquid crystal glass by electron beam scanning and rubbed with steel wool. Each sample was tested 3 times, and the average value was taken. The test results were recorded in Table 1.

[0059] Table 1 Performance test results of Examples 1-14 and Comparative Examples 1-2 As shown in Table 1, the losses in Examples 1-3 at 25℃ for 10 seconds were all 40.5% or less, and the losses at 25℃ for 20 seconds were all 41.8% or less, indicating that the EB-cured ink prepared in this application has good solvent resistance. The folding resistance results of Examples 1-3 were all without cracks or peeling, indicating that the EB-cured ink prepared in this application has good folding resistance. The steel wool abrasion resistance of Examples 1-3 was all more than 60 times without scratches, indicating that the EB-cured ink prepared in this application has good abrasion resistance.

[0060] In Examples 4 and 5, the mass ratios of acrylic acid, butyl acrylate, and methyl methacrylate during the preparation of mixed monomer A were not within the range specified in this application. When the acrylic acid content was too low, the emulsifier particle size was too small, making it difficult to prepare a more stable emulsifier, which affected the overall stability of the system. When the acrylic acid content was too high, the emulsifier particle size was too large, and the hydrophilicity of the polymer decreased, resulting in excessive viscosity of the emulsifier, which affected the overall stability of the system. Therefore, the performance of Examples 4 and 5 was reduced.

[0061] In Examples 6 and 7, the mass ratio between benzoyl peroxide and tert-butyl peroxide was not within the range specified in this application when preparing the emulsifier. When the content of benzoyl peroxide was too low, the conversion rate of the monomer was difficult to further improve, which affected the overall stability of the system. When the content of benzoyl peroxide was too high, the particle size of the emulsifier was too large, which affected the overall stability of the system. Therefore, the overall performance of the system decreased.

[0062] In Examples 8 and 9, the mass ratio of sodium bicarbonate to sodium persulfate in the initiator was not within the range specified in this application when preparing the polymer emulsion system. When the content of sodium persulfate was too low, the reaction rate was too slow, the conversion rate of the system decreased, and the stability of the prepared polymer emulsion system decreased. When the content of sodium persulfate was too high, the reaction rate was too fast, the viscosity of the emulsion was too high, and the overall stability of the system was affected. Therefore, the performance of Examples 8 and 9 was reduced.

[0063] In Examples 10 and 11, the mass ratios of polyvinyl alcohol, nano-silica, and nano-alumina in the preparation of the dispersed nanosystems were not within the range specified in this application. When the content of nano-alumina was too low or too high, it was difficult to form a stable system with nano-silica, and the bonding stability with polyvinyl alcohol also decreased. The dispersibility in the system decreased, and agglomeration occurred. Therefore, the performance of Examples 10 and 11 was reduced.

[0064] In Example 12, no polyvinyl alcohol was added. The nano-silica and nano-alumina were modified only by KH550. The rheological properties of the dispersed nano system in the ink were difficult to improve further, and the binding performance with the ink decreased, resulting in a decrease in adhesion performance and affecting the binding performance of the ink. Therefore, the performance of Example 12 was reduced.

[0065] In Example 13, no nano-silica was added when preparing the dispersed nano system; in Example 14, no nano-alumina was added when preparing the dispersed nano system. Single nanomaterials are difficult to further synergistically improve the overall performance of the system, and the mechanical strength in the ink is difficult to be further improved, and the adhesion performance of the system is affected. Therefore, the performance of both Example 14 and Example 15 has decreased.

[0066] In Comparative Example 1, when preparing EB-cured ink, the polymer emulsion system was replaced with an emulsifier. However, simply adding the emulsifier to the ink system did not significantly improve the viscosity and stability.

[0067] In Comparative Example 2, the prepolymer system was replaced with ordinary water-based acrylate. Ordinary water-based acrylate is difficult to polymerize further to form a stable cross-linked network, and its adhesion, solvent resistance and folding resistance are difficult to improve further.

[0068] This specific embodiment is merely an explanation of this application and is not intended to limit it. Based on the above description, those skilled in the art can make various changes and modifications without departing from the technical concept of this application. The technical scope of this application is not limited to the contents of the specification but must be determined according to the scope of the claims.

Claims

1. A solvent-resistant and fold-resistant EB curable ink, characterized in that: The components include the following parts by mass: The composition includes 50-60 parts of prepolymer system, 25-35 parts of aliphatic polyurethane acrylate, 13-17 parts of epoxy acrylate, 4-6 parts of polyacrylate, 25-35 parts of reactive diluent, 10-15 parts of pigments and fillers, 2-5 parts of additives, 0.5-1 part of leveling agent, 0.5-1 part of defoamer, 1-2 parts of adhesion promoter, 0.5-1 part of stabilizer, 1-2 parts of dispersant, and 15-25 parts of polymer emulsion system; the prepolymer system includes silicone-modified acrylate, fluorinated acrylate, and phosphate acrylate.

2. The solvent-resistant and fold-resistant EB curable ink according to claim 1, characterized in that: The raw materials of the polymer emulsion system include emulsifiers, mixed monomers B and initiators; the emulsifiers include diethylene glycol dimethyl ether, mixed monomers A, benzoyl peroxide and tert-butyl peroxide.

3. The solvent-resistant and fold-resistant EB curable ink according to claim 2, characterized in that: The emulsifier is prepared by the following method: Acrylic acid, butyl acrylate, methyl methacrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate are mixed to obtain mixed monomer A. Mixed monomer A is mixed with diethylene glycol dimethyl ether, heated and then benzoyl peroxide and tert-butyl peroxide are added. The reaction is kept at this temperature and then cooled and water is added to obtain an emulsifier.

4. The solvent-resistant and fold-resistant EB curable ink according to claim 3, characterized in that: The mass ratio of benzoyl peroxide to tert-butyl peroxide is (8-9):

1.

5. The solvent-resistant and fold-resistant EB curable ink according to claim 3, characterized in that: The mass ratio of acrylic acid, butyl acrylate and methyl methacrylate in the mixed monomer A is (0.45-0.55):1:1.

33.

6. The solvent-resistant and fold-resistant EB curable ink according to claim 1, characterized in that: The polymer emulsion system was prepared using the following method: Sodium bicarbonate, sodium persulfate, and water were mixed to obtain an initiator; an emulsifier was mixed with mixed monomer B, stirred and pre-emulsified, and the initiator was added under a water bath, followed by the addition of mixed monomer B and the remaining initiator. After the reaction was completed and cooled, a polymer emulsion system was obtained.

7. The solvent-resistant and fold-resistant EB curable ink according to claim 5, characterized in that: The mass ratio of sodium bicarbonate to sodium persulfate is 1:(0.95-1.05).

8. The solvent-resistant and fold-resistant EB curable ink according to claim 1, characterized in that: The pigments and fillers comprise pigments and a dispersed nanosystem, which is prepared using the following method: Water, silane coupling agent and polyvinyl alcohol were mixed and stirred, nano-silica and nano-alumina were added, and boric acid was added. The mixture was stirred and dispersed, washed and then freeze-dried to obtain a dispersed nano system.

9. The solvent-resistant and fold-resistant EB curable ink according to claim 8, characterized in that: The mass ratio of polyvinyl alcohol, nano-silica, and nano-alumina is 0.1:1:(1.1-1.3).

10. A method for preparing the solvent-resistant and fold-resistant EB curable ink according to any one of claims 1-9, characterized in that: Includes the following steps: The prepolymer system, aliphatic polyurethane acrylate, epoxy acrylate, polyester acrylate and reactive diluent are mixed and stirred. Then the polymer emulsion system is added, stirred and allowed to stand. Pigments and fillers are added, and after stirring, leveling agent, defoamer, adhesion promoter, stabilizer and dispersant are added and stirred to obtain EB cured ink.

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