Wear-resistant and weather-resistant printing ink and preparation method thereof

Abstract

The invention belongs to the technical field of printing ink manufacturing, and particularly relates to wear-resistant and weather-resistant printing ink and a preparation method thereof. The modified weather-resistant acrylic resin emulsion prepared from polyurethane modified acrylic acid takes water as a main dispersion medium, and a small amount of alcohol substances are used for assisting dissolution, so that the content of VOC (volatile organic compounds) is reduced, and the environment-friendly effect is achieved; by grafting the polyurethane prepolymer and the acrylic monomer, polyurethane is introduced into the acrylic resin, so that the weather resistance and the water resistance are improved; the wear-resistant filler can modify the weather-resistant acrylic resin emulsion through double-bond grafting, and can be uniformly dispersed in the ink, so that phase separation is avoided, the stress is uniform after film formation, and the situation that the local part is easy to wear does not occur. The wear-resistant and weather-resistant printing ink is suitable for outdoor open environments.

Description

Technical Field

[0001] This invention belongs to the field of printing ink manufacturing technology, specifically relating to wear-resistant and weather-resistant printing inks and their preparation methods. Background Technology

[0002] Ink is a complex colloidal system composed of pigments, binder resins, solvents, and additives. It is used to represent patterns or text on a substrate through printing, inkjet printing, and other methods, and is an important material for printing.

[0003] Chinese invention patent CN120554891B discloses a wear-resistant and scratch-resistant printing ink, its preparation method, and its application. The printing ink comprises: a modified waterborne polyurethane emulsion, modified mica flakes, pigments, additives, and deionized water. The modified waterborne polyurethane emulsion is prepared by introducing a double-terminated hydroxyl chain extender into the polymer. The double-terminated hydroxyl chain extender is prepared by reacting a Schiff base-containing intermediate obtained from the reaction of salicylaldehyde and p-aminobenzyl alcohol with isocyanoethyl methacrylate, and then reacting the resulting double-bonded Schiff base-containing intermediate with 1,1,3,3-tetramethyldisiloxane. The modified mica flakes are prepared by reacting triethylenetetramine, formaldehyde, and acetone, followed by formaldehyde condensation under alkaline conditions, and then preparing cationic mica flakes with the resulting cationic polymer and glutaraldehyde. Finally, polyaniline is grown on the surface of the mica flakes through interfacial polymerization. The ink prepared by this invention has good adhesion, high hardness, and excellent water resistance, wear resistance, heat resistance, antistatic properties, and antibacterial properties. However, existing technologies have a technical problem: they do not improve the stability and abrasion resistance of printing inks by further modifying the composition of the binder resin. Summary of the Invention

[0004] The purpose of this invention is to provide wear-resistant and weather-resistant printing ink and its preparation method, in order to solve the technical problem in the prior art that the stability and wear resistance of printing ink have not been improved by further modifying the composition of the binder resin.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: The wear-resistant and weather-resistant printing ink is prepared from the following raw materials in parts by weight: 30-60 parts modified weather-resistant acrylic resin emulsion, 10-20 parts pigment, 4-10 parts wear-resistant filler, 15-25 parts alcohol, 20-30 parts deionized water, 1-10 parts photoinitiator, 0.5-2 parts antioxidant, 0.5-2 parts leveling agent, 0.5-2 parts defoamer, and 0.5-2 parts dispersant.

[0006] The pigment is a phthalocyanine blue pigment; The alcohol is any one of ethanol, isopropanol, and n-butanol; The antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1 to 2.

[0007] Preferably, the preparation method of the modified weather-resistant acrylic resin emulsion includes the following steps: S11. Polycaprolactone diol and N,N-dimethylacetamide are added to a reaction vessel. Dicyclohexylmethane diisocyanate and dibutyltin dilaurate catalyst are added under a nitrogen atmosphere. The temperature is raised and the reaction is carried out. 1,3-Butanediol and dimethylolpropionic acid are added and the reaction is kept at a constant temperature. Trimethylolpropane is added for crosslinking. The temperature is lowered to obtain polyurethane prepolymer. S12. Add the polyurethane prepolymer to the reactor, add hydroxyethyl methacrylate in a nitrogen atmosphere and heat to react, add triethanolamine to neutralize to neutral, keep warm, add deionized water and stir at high speed to emulsify, then add acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, methyl styrene linear dimer chain transfer agent, styrene and azobisisobutyronitrile to polymerize and obtain modified weather-resistant acrylic resin emulsion.

[0008] Preferably, in step S11, the temperature is raised to 70-80°C for 1-2 hours, the temperature is maintained for 1-2 hours, crosslinking is performed for 1-2 hours, and then the temperature is lowered to 35-40°C.

[0009] Preferably, the ratio of polycaprolactone diol, N,N-dimethylacetamide, dicyclohexylmethane diisocyanate, dibutyltin dilaurate, 1,3-butanediol, dimethylolpropionic acid and trimethylolpropane in S11 is (25~35) g : (15~25) mL : (15~20) g : (0.03~0.05) g : (1.5~2.5) g : (2~4) g : (1~2) g.

[0010] Preferably, after adding hydroxyethyl methacrylate to S12, the temperature is raised to 70-80℃ and reacted for 1-2 hours, then kept at 70-80℃ for 1-2 hours, deionized water is added and emulsified by stirring at 1000-3000 rpm for 20-40 minutes, and then azobisisobutyronitrile is added and polymerized at 70-80℃ for 1-2 hours.

[0011] Preferably, the ratio of polyurethane prepolymer, hydroxyethyl methacrylate, deionized water, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, methyl styrene linear dimer chain transfer agent, styrene, and azobisisobutyronitrile in S12 is (35~50) g ​​: (3~5) g : (100~120) g : (5~8) g : (10~15) g : (15~20) g : (40~45) g : (0.5~0.8) g : (5~10) g : (0.5~1.5) g.

[0012] Preferably, the method for preparing the wear-resistant filler includes the following steps: S21. Add P123 template agent to ethanol, add aluminum isopropoxide and acetylacetone stabilizer, add acetic acid to adjust pH, react at room temperature, react at elevated temperature, filter to collect solid, wash and dry, calcine to remove template to obtain mesoporous material. S22. Add the mesoporous material to a 50% ethanol aqueous solution, add tetraethyl orthosilicate and silane coupling agent kH-570, add ammonia water dropwise and stir, heat to react, filter to collect the solid, wash and dry to obtain the wear-resistant filler.

[0013] Preferably, in step S21, acetic acid is added dropwise to adjust the pH to 3-4, the reaction is carried out at room temperature for 8-10 hours, the temperature is raised to 35-45℃ for 1-2 hours, the mixture is washed sequentially with ethanol and deionized water, dried at 60-80℃, calcined at 400-500℃ for 3-4 hours, and then calcined at 650-750℃ for 1-2 hours.

[0014] Preferably, the ratio of the amount of P123 template agent, ethanol, aluminum isopropoxide and acetylacetone stabilizer in S21 is (1~2) g: (15~25) mL: (3~6) g: (1~2) mL.

[0015] Preferably, the ratio of the S22 mesoporous material, 50% ethanol aqueous solution, tetraethyl orthosilicate and silane coupling agent kH-570 is (5~6) g : (50~70) mL : (6~8) g : (8~10) g. Ammonia water is added dropwise to adjust the pH to 6.5~7.5, the temperature is raised to 40~50℃ and reacted for 1~2 h, washed with ethanol and deionized water in sequence, and dried at 60~80℃.

[0016] The preparation method of abrasion-resistant and weather-resistant printing ink includes the following steps: S1. Add alcohols, deionized water, dispersants, defoamers and antioxidants to a mixing tank, stir at low speed until uniform, add pigments and wear-resistant fillers, stir at high speed, let stand, add zirconium beads, grind and sieve to obtain color paste. S2. Add the color paste and leveling agent to the mixing tank, add the modified weather-resistant acrylic resin and photoinitiator, and stir evenly to obtain the printing ink.

[0017] Preferably, in step S1, the mixture is stirred at a low speed of 300-500 rpm for 20-30 minutes, stirred at a high speed of 4000-5000 rpm for 20-30 minutes, allowed to stand for 8-12 hours, ground for 3-4 hours, and then passed through a 200-400 mesh sieve.

[0018] Preferably, the mixture in step S2 is stirred at a speed of 300-500 rpm for 1-2 hours.

[0019] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are: 1. This invention improves the hydrophilicity of polyurethane prepolymers by reacting polycaprolactone diol and dicyclohexylmethane diisocyanate, followed by chain extension with 1,3-butanediol and hydrophilic dimethylolpropionic acid. The addition of triethylamine for crosslinking enhances the stability of the resulting polyurethane prepolymer. The reaction of the hydroxyl groups of hydroxyethyl methacrylate with the isocyanate groups of the polyurethane prepolymer, followed by emulsion polymerization with acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, and styrene, yields a modified weather-resistant acrylic resin. The polycaprolactone diol and dicyclohexylmethane diisocyanate molecules lack conjugated benzene rings easily damaged by ultraviolet light, exhibiting excellent resistance to yellowing and weathering. Grafting the polyurethane prepolymer with acrylic monomers introduces polyurethane into the acrylic resin, improving its weather resistance and water resistance.

[0020] 2. In this invention, micelles are formed by the self-assembly of P123 template agent in ethanol. Subsequently, alumina is deposited by acid hydrolysis and calcined to form mesoporous alumina microspheres. Then, the surface is modified with tetraethyl orthosilicate and silane coupling agent kH-570 to obtain a wear-resistant filler. The double bond groups of kH-570 can be grafted into the resin through photoinitiator, which improves the binding force between the filler and the resin, increases the scratch force that the ink film can withstand after formation, and significantly improves the wear resistance of the ink film. In addition, the filler itself has good weather resistance and will not fail due to environmental changes.

[0021] 3. The modified weather-resistant acrylic resin emulsion obtained by modifying acrylic acid with polyurethane in this invention uses water as the main dispersion medium and a small amount of alcohol as a solubilizer, reducing VOC content and making it environmentally friendly. The wear-resistant filler can be modified by grafting double bonds into the weather-resistant acrylic resin emulsion, ensuring uniform dispersion in the ink and preventing phase separation. After film formation, the film experiences uniform stress, avoiding localized wear. The wear-resistant and weather-resistant printing ink of this invention is suitable for outdoor open environments. Detailed Implementation

[0022] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0023] The dispersant in the additives involved in this invention is Tego670; the defoamer is Tego450; the leveling agent is BYK-333; and the photoinitiator is photoinitiator 1173.

[0024] Example 1: The wear-resistant and weather-resistant printing ink of this example is prepared from the following raw materials: 40g of modified weather-resistant acrylic resin emulsion, 10g of pigment, 5g of wear-resistant filler, 20g of alcohol, 30g of deionized water, 5g of photoinitiator, 1g of antioxidant, 1.5g of leveling agent, 0.5g of defoamer and 0.5g of dispersant.

[0025] The pigment is a phthalocyanine blue pigment; the alcohol is ethanol; the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0026] The preparation method of the modified weather-resistant acrylic resin emulsion in this embodiment includes the following steps: S11. Add 25g of polycaprolactone diol and 15mL of N,N-dimethylacetamide to a reaction vessel. Add 15g of dicyclohexylmethane diisocyanate and 0.03g of dibutyltin dilaurate catalyst under a nitrogen atmosphere. Heat to 70℃ and react for 1h. Add 1.5g of 1,3-butanediol and 2.5g of dimethylolpropionic acid and keep at 70℃ for 1h. Add 1g of trimethylolpropane and crosslink at 70℃ for 2h. Cool to 35℃ to obtain polyurethane prepolymer. S12. Add 35g of polyurethane prepolymer to a reactor. Under a nitrogen atmosphere, first add 3g of hydroxyethyl methacrylate and heat to 70℃ for 2 hours. Add triethanolamine to neutralize to neutral and keep at 70℃ for 1 hour. Add 100g of deionized water and stir at 1000rpm for 30 minutes to emulsify. Then add 8g of acrylic acid, 10g of methacrylic acid, 15g of methyl methacrylate, 40g of butyl acrylate, 0.5g of methylstyrene linear dimer chain transfer agent, 5g of styrene and 0.5g of azobisisobutyronitrile. Polymerize at 70℃ for 1 hour to obtain a modified weather-resistant acrylic resin emulsion.

[0027] The method for preparing the wear-resistant filler in this embodiment includes the following steps: S21. Add 1g of P123 template agent to 15mL of ethanol, add 3g of aluminum isopropoxide and 1mL of acetylacetone stabilizer, add acetic acid to adjust the pH to 3.5, stir at room temperature for 8h, heat to 35℃ for 1h, filter to collect the solid, wash with ethanol and deionized water in sequence, dry at 60℃, calcine at 400℃ for 3h, and then heat to 650℃ for 1h to obtain the mesoporous material. S22. Add 5g of mesoporous material to 50mL of 50% ethanol aqueous solution, add 6g of tetraethyl orthosilicate and 8g of silane coupling agent kH-570, add ammonia water dropwise and stir to adjust the pH to 7, heat to 40℃ and react for 1.5h, filter to collect the solid, wash with ethanol and deionized water in sequence, and dry at 60℃ to obtain wear-resistant filler.

[0028] The method for preparing the wear-resistant and weather-resistant printing ink in this embodiment includes the following steps: S1. Add alcohols, deionized water, dispersant, defoamer and antioxidant to a mixing tank and stir at a low speed of 500 rpm for 20 min. Add pigment and wear-resistant filler and stir at a high speed of 4000 rpm for 20 min. Let stand for 8 h, add zircon beads and grind for 4 h. Pass through a 400 mesh sieve to obtain color paste. S2. Add the color paste and leveling agent to the mixing tank, add the modified weather-resistant acrylic resin and photoinitiator, and stir at 300 rpm for 1 hour to obtain the printing ink.

[0029] Example 2: The wear-resistant and weather-resistant printing ink of this example is prepared from the following raw materials: 30g of modified weather-resistant acrylic resin emulsion, 13g of pigment, 6.5g of wear-resistant filler, 15g of alcohol, 20g of deionized water, 3g of photoinitiator, 2g of antioxidant, 1g of leveling agent, 1g of defoamer and 1g of dispersant.

[0030] The pigment is a phthalocyanine blue pigment; the alcohol is isopropanol; and the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0031] The preparation method of the modified weather-resistant acrylic resin emulsion in this embodiment includes the following steps: S11. Add 30g of polycaprolactone diol and 20mL of N,N-dimethylacetamide to a reaction vessel. Add 17g of dicyclohexylmethane diisocyanate and 0.04g of dibutyltin dilaurate catalyst under a nitrogen atmosphere. Heat to 75℃ and react for 2h. Add 2g of 1,3-butanediol and 2.5g of dimethylolpropionic acid and keep at 75℃ for 2h. Add 1g of trimethylolpropane and crosslink at 75℃ for 2h. Cool to 35℃ to obtain polyurethane prepolymer. S12. Add 45g of polyurethane prepolymer to a reactor. Under a nitrogen atmosphere, first add 4g of hydroxyethyl methacrylate and heat to 75℃ for 2h. Add triethanolamine to neutralize to neutral and keep at 75℃ for 2h. Add 110g of deionized water and stir emulsify at 2000rpm for 20min. Then add 8g of acrylic acid, 10g of methacrylic acid, 17.5g of methyl methacrylate, 40g of butyl acrylate, 0.8g of methylstyrene linear dimer chain transfer agent, 7g of styrene and 1g of azobisisobutyronitrile. React at 75℃ for 2h to obtain modified weather-resistant acrylic resin emulsion.

[0032] The method for preparing the wear-resistant filler in this embodiment includes the following steps: S21. Add 1.5g of P123 template agent to 20mL of ethanol, add 5g of aluminum isopropoxide and 1.5mL of acetylacetone stabilizer, add acetic acid to adjust the pH to 4, stir at room temperature for 10h, heat to 35℃ for 2h, filter to collect solid, wash with ethanol and deionized water in sequence, dry at 80℃, calcine at 450℃ for 3h, and then heat to 650℃ for 2h to obtain mesoporous material; S22. Add 5.5g of mesoporous material to 70mL of 50% ethanol aqueous solution, add 8g of tetraethyl orthosilicate and 10g of silane coupling agent kH-570, add ammonia water dropwise and stir to adjust the pH to 7.5, heat to 45℃ and react for 1h, filter to collect the solid, wash with ethanol and deionized water in sequence, and dry at 80℃ to obtain wear-resistant filler.

[0033] The method for preparing the wear-resistant and weather-resistant printing ink in this embodiment includes the following steps: S1. Add alcohols, deionized water, dispersant, defoamer and antioxidant to a mixing tank and stir at a low speed of 300 rpm for 20 min. Add pigment and wear-resistant filler and stir at a high speed of 4500 rpm for 25 min. Let stand for 8 h, add zircon beads and grind for 4 h. Pass through a 200 mesh sieve to obtain color paste. S2. Add the color paste and leveling agent to the mixing tank, add the modified weather-resistant acrylic resin and photoinitiator, and stir at 400 rpm for 1 hour to obtain the printing ink.

[0034] Example 3: The wear-resistant and weather-resistant printing ink of this example is prepared from the following raw materials: 50g of modified weather-resistant acrylic resin emulsion, 15g of pigment, 8g of wear-resistant filler, 15g of alcohol, 30g of deionized water, 8g of photoinitiator, 1.5g of antioxidant, 0.5g of leveling agent, 0.5g of defoamer and 0.5g of dispersant.

[0035] The pigment is a phthalocyanine blue pigment; the alcohol is n-butanol; and the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.5.

[0036] The preparation method of the modified weather-resistant acrylic resin emulsion in this embodiment includes the following steps: S11. Add 25g of polycaprolactone diol and 20mL of N,N-dimethylacetamide to a reaction vessel. Add 17g of dicyclohexylmethane diisocyanate and 0.05g of dibutyltin dilaurate catalyst under a nitrogen atmosphere. Heat to 80℃ and react for 2h. Add 1.5g of 1,3-butanediol and 4g of dimethylolpropionic acid and keep the reaction at the same temperature for 1h. Add 2g of trimethylolpropane for crosslinking for 1h. Cool to 40℃ to obtain polyurethane prepolymer. S12. Add 45g of polyurethane prepolymer to a reactor. Under a nitrogen atmosphere, first add 5g of hydroxyethyl methacrylate and heat to 80℃ for 1 hour. Add triethanolamine to neutralize to neutral and keep at 80℃ for 2 hours. Add 120g of deionized water and stir and emulsify at 2500rpm for 30 minutes. Then add 7.5g of acrylic acid, 12.5g of methacrylic acid, 17.5g of methyl methacrylate, 42.5g of butyl acrylate, 0.75g of methylstyrene linear dimer chain transfer agent, 8g of styrene, and 0.8g of azobisisobutyronitrile. Polymerize at 80℃ for 2 hours to obtain a modified weather-resistant acrylic resin emulsion.

[0037] The method for preparing the wear-resistant filler in this embodiment includes the following steps: S21. Add 2g of P123 template agent to 25mL of ethanol, add 6g of aluminum isopropoxide and 2mL of acetylacetone stabilizer, add acetic acid to adjust the pH to 3, stir at room temperature for 8h, heat to 40℃ for 2h, filter to collect solid, wash with ethanol and deionized water in sequence, dry at 60℃, calcine at 500℃ for 3h, and then heat to 750℃ for 2h to obtain mesoporous material. S22. Add 6g of mesoporous material to 70mL of 50% ethanol aqueous solution, add 6g of tetraethyl orthosilicate and 9g of silane coupling agent kH-570, add ammonia water dropwise and stir to adjust the pH to 6.5, heat to 50℃ and react for 2h, filter to collect the solid, wash with ethanol and deionized water in sequence, and dry at 70℃ to obtain wear-resistant filler.

[0038] The method for preparing the wear-resistant and weather-resistant printing ink in this embodiment includes the following steps: S1. Add alcohols, deionized water, dispersant, defoamer and antioxidant to a mixing tank and stir at a low speed of 300 rpm for 20 min. Add pigments and wear-resistant fillers and stir at a high speed of 4200 rpm for 30 min. Let stand for 8~12 h, add zirconium beads and grind for 3 h. Pass through a 300 mesh sieve to obtain color paste. S2. Add the color paste and leveling agent to the mixing tank, add the modified weather-resistant acrylic resin and photoinitiator, and stir at 500 rpm for 2 hours to obtain the printing ink.

[0039] Example 4: The wear-resistant and weather-resistant printing ink of this example is prepared from the following raw materials: 60g of modified weather-resistant acrylic resin emulsion, 20g of pigment, 10g of wear-resistant filler, 25g of alcohol, 30g of deionized water, 10g of photoinitiator, 2g of antioxidant, 2g of leveling agent, 2g of defoamer and 2g of dispersant.

[0040] The pigment is a phthalocyanine blue pigment; the alcohol is ethanol; the antioxidant is prepared by mixing antioxidant 1010 and antioxidant 168 in a mass ratio of 1:2.

[0041] The preparation method of the modified weather-resistant acrylic resin emulsion in this embodiment includes the following steps: S11. Add 35g of polycaprolactone diol and 25mL of N,N-dimethylacetamide to a reaction vessel. Add 20g of dicyclohexylmethane diisocyanate and 0.05g of dibutyltin dilaurate catalyst under a nitrogen atmosphere. Heat to 80℃ and react for 1h. Add 2.5g of 1,3-butanediol and 4g of dimethylolpropionic acid and keep the reaction at the temperature for 2h. Add 2g of trimethylolpropane for crosslinking for 1h. Cool to 35℃ to obtain polyurethane prepolymer. S12. Add 50g of polyurethane prepolymer to a reactor. Under a nitrogen atmosphere, first add 5g of hydroxyethyl methacrylate and heat to 80℃ for 2h. Add triethanolamine to neutralize to neutral and keep at 80℃ for 2h. Add 120g of deionized water and stir at 1000rpm for 20min to emulsify. Then add 5g of acrylic acid, 10g of methacrylic acid, 20g of methyl methacrylate, 40g of butyl acrylate, 0.5g of methylstyrene linear dimer chain transfer agent, 10g of styrene and 1.5g of azobisisobutyronitrile. Polymerize at 80℃ for 2h to obtain modified weather-resistant acrylic resin emulsion.

[0042] The method for preparing the wear-resistant filler in this embodiment includes the following steps: S21. Add 1.5g of P123 template agent to 25mL of ethanol, add 4.5g of aluminum isopropoxide and 1.5mL of acetylacetone stabilizer, add acetic acid to adjust the pH to 4, stir at room temperature for 10h, heat to 40℃ and react for 2h, filter to collect solid, wash with ethanol and deionized water in sequence, dry at 80℃, calcine at 500℃ for 4h, and then heat to 720℃ and calcine for 2h to obtain mesoporous material; S22. Add 5g of mesoporous material to 50mL of 50% ethanol aqueous solution, add 6g of tetraethyl orthosilicate and 10g of silane coupling agent kH-570, add ammonia water dropwise and stir to adjust the pH to 7.5, heat to 50℃ and react for 2h, filter to collect the solid, wash with ethanol and deionized water in sequence, and dry at 80℃ to obtain wear-resistant filler.

[0043] The method for preparing the wear-resistant and weather-resistant printing ink in this embodiment includes the following steps: S1. Add alcohols, deionized water, dispersant, defoamer and antioxidant to a mixing tank and stir at a low speed of 500 rpm for 20 min. Add pigment and wear-resistant filler and stir at a high speed of 5000 rpm for 20 min. Let stand for 8 h, add zircon beads and grind for 4 h. Pass through a 400 mesh sieve to obtain color paste. S2. Add the color paste and leveling agent to the mixing tank, add the modified weather-resistant acrylic resin and photoinitiator, and stir at 500 rpm for 1 hour to obtain the printing ink.

[0044] Comparative Example 1 differs from Example 1 in that the modified weather-resistant acrylic resin emulsion is replaced with a water-based acrylic resin, model JONCRYL 678.

[0045] Comparative Example 2 differs from Example 1 in that the wear-resistant filler is replaced with fumed silica.

[0046] Comparative Example 3 differs from Example 1 in that it does not contain wear-resistant filler.

[0047] Performance testing The printing inks prepared in each embodiment and comparative example were sprayed onto the surface of a PE plastic plate and cured by ultraviolet light to obtain test samples.

[0048] The fineness of the printing inks prepared in each example and comparative example was tested according to GB / T 13217.3-2022 "Ink Fineness Test Method".

[0049] The adhesion of the printing inks prepared in each example and comparative example was tested according to GB / T 13217.7-2023 "Ink Adhesion Test Method".

[0050] According to GB / T 1733-2021 "Determination of water resistance of paints and varnishes", the test samples prepared in each example and comparative example were completely immersed in deionized water at 23°C for 24 hours, and the appearance changes of the ink layer of the test samples were observed.

[0051] The test results are shown in Table 1 below: Table 1 Test Results As shown in the table above, the fineness of the printing inks prepared in Examples 1-4 is 13.9-17.3 μm, and the adhesion is 5B. This indicates that the wear-resistant filler prepared in this invention has excellent dispersibility and adhesion in the ink. The ink layer did not change after the test samples were immersed in deionized water for 24 hours, indicating that the ink prepared in this invention has excellent water resistance. This further shows that the printing ink prepared in this invention has excellent wear resistance and weather resistance.

[0052] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

[0053] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A wear and weather resistant printing ink, characterized in that, Prepared from the following raw materials by mass: 30~60 parts of modified weather-resistant acrylic resin emulsion, 10~20 parts of pigment, 4~10 parts of wear-resistant filler, 15~25 parts of alcohol, 20~30 parts of deionized water, 1~10 parts of photoinitiator, 0.5~2 parts of antioxidant, 0.5~2 parts of leveling agent, 0.5~2 parts of defoaming agent and 0.5~2 parts of dispersant.

2. The weatherable and abrasion resistant printing ink according to claim 1, characterized in that, The pigment is phthalo blue pigment; the alcohol is any one of ethanol, isopropyl alcohol and n-butanol; the antioxidant is a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1~2.

3. The abrasion and weather resistant printing ink according to claim 1, wherein, The preparation method of the modified weather-resistant acrylic resin emulsion comprises the following steps: S11, poly (caprolactone) glycol and N, N-dimethylacetamide are added into a reaction kettle, dicyclohexylmethane diisocyanate and catalyst dibutyltin dilaurate are added in a nitrogen atmosphere, and the reaction is carried out by heating, 1, 3-butanediol and dimethylol propionic acid are added for reaction, and cross-linking is carried out by adding trimethylolpropane, and the reaction is carried out by cooling to obtain a polyurethane prepolymer; S12, the polyurethane prepolymer is added into a reaction kettle, hydroxyethyl methacrylate is added in a nitrogen atmosphere, the reaction is carried out by heating, triethanolamine is added for neutralization to neutral, the reaction is carried out by heating, deionized water is added for emulsification by high-speed stirring, and the polymerization reaction is carried out by adding acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, methyl styrene linear dimer chain transfer agent, styrene and azobisisobutyronitrile, to obtain a modified weather-resistant acrylic resin emulsion.

4. The abrasion and weather resistant printing ink according to claim 3, characterized in that, The amount ratio of poly (caprolactone) glycol, N, N-dimethylacetamide, dicyclohexylmethane diisocyanate, dibutyltin dilaurate, 1, 3-butanediol, dimethylol propionic acid and trimethylolpropane in S11 is (25~35) g: (15~25) mL: (15~20) g: (0.03~0.05) g: (1.5~2.5) g: (2~4) g: (1~2) g. The reaction is carried out by heating to 70~80℃ for 1~2h, the reaction is carried out by heating for 1~2h, cross-linking is carried out for 1~2h, and the reaction is carried out by cooling to 35~40℃.

5. The abrasion and weather resistant printing ink according to claim 3, wherein, The amount ratio of polyurethane prepolymer, hydroxyethyl methacrylate, deionized water, acrylic acid, methacrylic acid, methyl methacrylate, butyl acrylate, methyl styrene linear dimer chain transfer agent, styrene and azobisisobutyronitrile in S12 is (35~50) g: (3~5) g: (100~120) g: (5~8) g: (10~15) g: (15~20) g: (40~45) g: (0.5~0.8) g: (5~10) g: (0.5~1.5) g; the reaction is carried out by heating to 70~80℃ for 1~2h after adding hydroxyethyl methacrylate, the reaction is carried out by heating for 1~2h at 70~80℃, the emulsification is carried out by stirring at a speed of 1000~3000 rpm for 20~40 min after adding deionized water, and the polymerization reaction is carried out by heating to 70~80℃ for 1~2h after adding azobisisobutyronitrile.

6. The abrasion and weather resistant printing ink of claim 1, wherein, The preparation method of the wear-resistant filler comprises the following steps: S21, the P123 template agent is added into ethanol, aluminum isopropyl alcohol and acetylacetone stabilizer are added, acetic acid is added dropwise to adjust pH, reaction at room temperature, reaction at elevated temperature, the solid is collected by filtration, washed, dried and calcined to remove the template to prepare mesoporous materials; S22, the mesoporous material is added into 50% ethanol aqueous solution, tetraethyl orthosilicate and silane coupling agent kH-570 are added, ammonia water is added dropwise and stirred, reaction at elevated temperature, the solid is collected by filtration, washed and dried to prepare wear-resistant fillers.

7. The abrasion and weather resistant printing ink according to claim 6, wherein, In S21, the amount ratio of P123 template agent, ethanol, aluminum isopropyl alcohol and acetylacetone stabilizer is (1-2) g:(15-25) mL:(3-6) g:(1-2) mL; acetic acid is added dropwise to adjust pH to 3-4, reaction at room temperature for 8-10 h, reaction at elevated temperature to 35-45℃ for 1-2 h, washed with ethanol and deionized water in turn, dried at 60-80℃, calcined at 400-500℃ for 3-4 h, and then calcined at 650-750℃ for 1-2 h; in S22, the amount ratio of mesoporous material, 50% ethanol aqueous solution, tetraethyl orthosilicate and silane coupling agent kH-570 is (5-6) g:(50-70) mL:(6-8) g:(8-10) g, ammonia water is added dropwise to adjust pH to 6.5-7.5, reaction at elevated temperature to 40-50℃ for 1-2 h, washed with ethanol and deionized water in turn, and dried at 60-80℃.

8. The method of preparing a weatherable and abrasion resistant printing ink according to any one of claims 1 to 7, characterized in that, The method comprises the following steps: S1, alcohol, deionized water, dispersant, defoamer and antioxidant are added into a stirring kettle, uniformly stirred at low speed, pigments and wear-resistant fillers are added, stirred at high speed, left to stand, zirconium beads are added to grind and sieve to prepare color paste; S2, the color paste and leveling agent are added into a stirring kettle, modified weather-resistant acrylic resin and photoinitiator are added, uniformly stirred to prepare printing ink.

9. The method for preparing the wear-resistant and weather-resistant printing ink according to claim 8, characterized in that, In S1, stirring is carried out at a speed of 300-500 rpm for 20-30 min, stirring is carried out at a speed of 4000-5000 rpm for 20-30 min, left to stand for 8-12 h, ground for 3-4 h, and sieved through a 200-400 mesh sieve; in S2, stirring is carried out at a speed of 300-500 rpm for 1-2 h.

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