Ultraviolet light-curable modified acrylic resin coating and use thereof

Abstract

The present application belongs to the technical field of acrylic resin coating, and particularly relates to a kind of ultraviolet curing modified acrylic resin coating and its application. The present application mixes and stirs uniformly modified acrylic resin, diluent, adhesion promoter, antibacterial toughening filler, photoinitiator and levelling agent to prepare a kind of ultraviolet curing modified acrylic resin coating; the weather resistance and impact resistance of the coating can be improved by the rosin group and lactone monomer of the modified acrylic resin; the toughness and antibacterial performance of the coating can be improved by the uniform dispersion of the antibacterial toughening filler in the modified acrylic resin coating; the ultraviolet curing modified acrylic resin coating of the present application is applied to metal protective coating, and has excellent adhesion and long-acting antibacterial performance.

Description

Technical Field

[0001] This invention belongs to the field of acrylic resin coating technology, specifically relating to a UV-curable modified acrylic resin coating and its application. Background Technology

[0002] UV-curable coatings offer advantages such as rapid curing, low-temperature curing, and zero volatile organic compound emissions. They primarily consist of oligomers, photoinitiators, and reactive monomer diluents. Oligomers directly determine the coating's performance, hence their higher addition amount. Photoinitiators initiate the polymerization reaction, providing active polymerization centers and directly influencing the coating's formation and properties. Reactive monomer diluents are multifunctional components, serving both to dilute the coating, ensuring suitable application properties, and to regulate the polymerization rate.

[0003] Chinese invention patent CN114806388B discloses a UV-curable matte coating, its preparation method, and the product thereof. The UV-curable matte coating, by weight (100%), comprises 30-50 wt% easy-to-matte acrylic resin, 10-30 wt% multifunctional aliphatic polyurethane acrylate, 4-6 wt% photoinitiator, 10-20 wt% active monomer, and 6-10 wt% matting agent. The easy-to-matte acrylic resin is prepared by reacting HDI trimer with diethoxylated hydroxyethyl acrylate. The resulting coating film combines high matte finish with excellent abrasion resistance, as well as high adhesion, good water resistance, and alcohol resistance. However, the existing technology lacks the technical problem of further improving the antibacterial properties and adhesion of the acrylic resin coating by modifying the components of the functional filler and the monomers of the acrylic resin. Summary of the Invention

[0004] The purpose of this invention is to provide a UV-curable modified acrylic resin coating and its application, which solves the technical problem in the prior art that the antibacterial properties and adhesion of acrylic resin coatings are not further improved by combining and modifying the components of functional fillers and monomers of acrylic resin.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A UV-curable modified acrylic resin coating is prepared from the following components in parts by weight:

[0007] 60-70 parts modified acrylic resin, 2-5 parts photoinitiator, 30-40 parts diluent, 0.5-1.5 parts antibacterial toughening filler, 1-3 parts adhesion promoter and 0.5-2 parts leveling agent.

[0008] As preferred, the photoinitiator is any one of Darocur 1173, Irgacure 819.

[0009] As preferred, the diluent is any one of sec-butyl acetate, ethyl acetate, propylene glycol methyl ether acetate.

[0010] As preferred, the adhesion promoter is any one of acrylic phosphate ester type promoter, FM20, KM2106.

[0011] As preferred, the leveling agent is any one of BYK-333, BYK-331.

[0012] As preferred, the preparation method of the modified acrylic resin comprises the following steps:

[0013] S11, according to mass fraction, 50-60 parts of xylene is added into the reaction kettle, 5-10 parts of methyl acrylate, 15-20 parts of methyl methacrylate, 15-20 parts of hydroxy acrylate, 10-15 parts of isobornyl acrylate, 3-5 parts of lactone monomer, 5-8 parts of glycidyl methacrylate and 0.05-1 parts of di-t-butyl peroxide initiator are added, and the reaction is carried out at elevated temperature to prepare an acrylic prepolymer;

[0014] S12, according to mass fraction, 90-100 parts of rosin pentaerythritol ester is added into the reaction kettle, 10-15 parts of glycidyl methacrylate, 1-2 parts of p-methoxyphenol and 1-1.5 parts of triphenylphosphine are added, and the reaction is carried out to prepare a rosin modified acrylic ester;

[0015] S13, according to mass fraction, 50-60 parts of acrylic prepolymer, 12-14 parts of rosin modified acrylic ester and 0.05-1 parts of di-t-butyl peroxide initiator are added into the reaction kettle, and the reaction is carried out to prepare a modified acrylic resin.

[0016] As preferred, in S11, the reaction is carried out at 130-180℃ for 2-4h, and the lactone monomer is any one of acrylic hexalactone, 2-methylene butyrolactone, 3-methyl acrylate-4-butyrolactone.

[0017] As preferred, the reaction mechanism in S11 is free radical polymerization, and the methyl acrylate, methyl methacrylate, hydroxy acrylate, isobornyl acrylate, lactone monomer and glycidyl methacrylate all contain double bonds, the di-t-butyl peroxide initiator is cracked to form free radicals when heated, the free radicals attack the double bonds, the double bonds participate in the free radical polymerization, and the polymerization forms a chain type macromolecule containing hydroxyl, ester, lactone and epoxy groups, i.e. the acrylic prepolymer.

[0018] As preferred, in S12, the reaction is carried out at 110-130℃ for 2-4h.

[0019] As preferred, the reaction in S13 is heated to 130-180℃ for 2-4h.

[0020] As preferred, the reaction mechanism in S13 is free radical polymerization, and the double bonds of rosin modified acrylate and acrylate prepolymer are polymerized to introduce into rosin groups.

[0021] As preferred, the preparation method of the antibacterial toughening filler comprises the following steps:

[0022] S21, according to mass fraction, 2-2.5 parts of zinc nitrate, 0.05-0.15 parts of magnesium nitrate and 0.3-0.6 parts of ferrous nitrate are added into 40-50 parts of N, N-dimethylformamide, stirred uniformly, then 100-110 parts of 2-methyl imidazole and 30-40 parts of 2-amino benzimidazole mixed solution are added, stirred and reacted, and the zeolite framework is prepared by cooling.

[0023] S22, according to mass fraction, 0.4-0.6 parts of zeolite framework is added into 40-60 parts of dopamine hydrochloride solution, reacted at 20-30℃ for 12-18h, the solid is collected by dialysis, and the antibacterial aid is prepared; 1-2 parts of the antibacterial aid is added into 40-50 parts of deionized water, 0.3-0.5 parts of Tween-80 is added, stirred uniformly to prepare the water phase.

[0024] S23, according to mass fraction, 4-5 parts of isophorone diisocyanate trimer and 10-15 parts of dioctyl terephthalate are dissolved in 30-50 parts of ethyl acetate, 0.01-0.03 parts of dibutyltin dilaurate and 2-4 parts of polyethylene glycol are added, pre-polymerization is carried out, the oil phase is prepared; the oil phase and the water phase are mixed, high-speed homogenization stirring is carried out, the reaction is carried out by heating, then 0.5-2 parts of ethylene glycol is added to carry out the reaction, and the antibacterial toughening filler is prepared.

[0025] As preferred, the molar ratio of zinc nitrate, magnesium nitrate and ferrous nitrate in S21 is 8:0.5-1:0.5-1.5, the zinc nitrate, magnesium nitrate and ferrous nitrate are stirred uniformly after being added into N, N-dimethylformamide, then quickly added into the mixed solution, stirred at room temperature for 4-6h, heated to 40-50℃ for 1-2h, and the solid is collected by filtration after cooling and washed with anhydrous ethanol.

[0026] As preferred, the dopamine hydrochloride solution in S22 is prepared by adding 1.2-2g of tris-hydroxymethyl aminomethane into 40-50mL of deionized water, adjusting the pH to 8.5 with hydrochloric acid and sodium hydroxide solution, and then adding 0.4-0.5g of dopamine hydrochloride.

[0027] Preferably, in S23, the prepolymerization reaction is carried out at 40-50 DEG C for 5-10 minutes, high-speed homogenizing stirring is carried out at 2500-3500 rpm for 5-10 minutes, the temperature is raised to 50-60 DEG C, and the reaction is carried out for 1-2 hours, and then ethylene glycol is added and the reaction is carried out for 1-2 hours.

[0028] Preferably, the reaction mechanism in S23 is as follows: isophorone diisocyanate trimer as a crosslinking agent reacts with polyethylene glycol and ethylene glycol to form polyurethane, and the oil phase and the water phase form an emulsion during high-speed homogenizing stirring, and the polyurethane forms particle capsules at the emulsion interface, and the capsules encapsulate the antibacterial toughening filler to obtain the antibacterial toughening filler.

[0029] An application of an ultraviolet light-cured modified acrylic resin coating, used for preparing a metal protective coating, comprising the following steps:

[0030] S1, adding a modified acrylic resin, a diluent, an adhesion promoter and an antibacterial toughening filler into a stirring kettle, adding a photoinitiator and a leveling agent, stirring uniformly to obtain an ultraviolet light-cured modified acrylic resin coating;

[0031] S2, coating the resin coating on an aluminum plate, and curing by ultraviolet light irradiation to obtain a coating.

[0032] Preferably, in S2, the coating thickness is 100-200 microns, and the ultraviolet light irradiation curing is carried out for 30-50 minutes.

[0033] As described above, due to the adoption of the above technical solutions, the present application has the following beneficial effects:

[0034] 1. The present application selects a plurality of reaction monomers of methyl acrylate, methyl methacrylate, hydroxy acrylate, isobornyl acrylate, lactone monomer and glycidyl methacrylate, and then reacts to obtain an acrylic prepolymer, and then reacts with a rosin modified acrylate to obtain a modified acrylic resin; the lactone monomer has flexibility and steric hindrance, thereby improving the flexibility and impact resistance of the modified acrylic resin; the rosin modification improves the aging resistance and hydrophobicity of the acrylic resin; the hydroxy acrylate and the glycidyl methacrylate provide polar groups with hydroxyl and ester groups, which can synergistically act with the adhesion promoter to enhance the chemical bonding with the aluminum plate, thereby improving the adhesion and impact resistance; and the step-by-step polymerization can avoid the problem that the rosin modified acrylate cannot effectively participate in crosslinking due to the difference in reactivity ratio when directly copolymerized.

[0035] 2、The application uses zinc nitrate, magnesium nitrate and ferrous nitrate as raw materials, 2-amino benzimidazole and 2-methyl imidazole as ligands to prepare zeolite framework, then uses dopamine to coat the zeolite framework to obtain antibacterial additives, and finally uses polyurethane capsules to encapsulate to obtain antibacterial toughening fillers; the doping of ferrous ions in the zeolite framework improves the antibacterial performance, the use of 2-amino benzimidazole to partially replace 2-methyl imidazole as ligands introduces amino active sites which can react with hydroxyl groups, thereby improving the bonding strength of the zeolite framework and dopamine, and the use of polyurethane capsule encapsulation can make the antibacterial additives uniformly dispersed in the acrylic resin coating, the polyurethane capsule can release metal ions slowly, prolong the antibacterial time, and improve the service life of the acrylic resin coating.

[0036] 3、The modified acrylic resin, the diluent, the adhesion promoter, the antibacterial toughening filler, the photoinitiator and the leveling agent are uniformly mixed and stirred to obtain a kind of ultraviolet curing type modified acrylic resin coating; the rosin group and lactone monomer of the modified acrylic resin can improve the weather resistance and impact resistance of the coating; the antibacterial toughening filler can be uniformly dispersed in the coating in the modified acrylic resin coating, thereby improving the toughness and antibacterial performance of the coating; the ultraviolet curing type modified acrylic resin coating of the application is applied to metal protective coating and has excellent adhesion and long-acting antibacterial performance. DETAILED DESCRIPTION

[0037] The technical solutions in the embodiments of the application will be described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the application, rather than all the embodiments. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the application.

[0038] In example 1, a kind of ultraviolet curing type modified acrylic resin coating is prepared from the following components by mass:

[0039] 65g modified acrylic resin, 2g photoinitiator, 30g diluent, 0.8g antibacterial toughening filler, 1g adhesion promoter and 0.5g leveling agent.

[0040] The photoinitiator is photoinitiator 1173; the diluent is sec-butyl acetate; the adhesion promoter is acrylic phosphate ester type promoter, model FM20; and the leveling agent is model BYK-333.

[0041] The preparation method of the modified acrylic resin of the embodiment includes the following steps:

[0042] S11, 50g of xylene is added to the reaction kettle, 8g of methyl acrylate, 16g of methyl methacrylate, 20g of hydroxy acrylate, 13g of isobornyl acrylate, 4g of caprolactone, 8g of glycidyl methacrylate and 0.8g of di-t-butyl peroxide initiator are added, and the temperature is raised to 140℃ for 2h to prepare an acrylic pre-polymer;

[0043] S12, 90g of rosin pentaerythritol ester is added to the reaction kettle, 10g of glycidyl methacrylate, 1g of p-methoxyphenol and 1g of triphenylphosphine are added, and the temperature is raised to 130℃ for 2h to prepare a rosin modified acrylic ester;

[0044] S13, according to the mass fraction, 50g of acrylic pre-polymer, 12g of rosin modified acrylic ester and 0.5g of di-t-butyl peroxide initiator are added to the reaction kettle, and the temperature is raised to 150℃ for 2h to prepare a modified acrylic resin.

[0045] The preparation method of the antibacterial toughening filler of the embodiment comprises the following steps:

[0046] S21, 2g of zinc nitrate, 0.1g of magnesium nitrate and 0.36g of ferrous nitrate are added to 40g of N, N-dimethylformamide, stirred uniformly, then quickly added to a mixed solution composed of 100g of 2-methyl imidazole and 30g of 2-amino benzimidazole, stirred at room temperature for 4h, and stirred at 50℃ for 1h, then cooled, filtered to collect the solid, washed with anhydrous ethanol, dried and cooled to prepare a zeolite framework;

[0047] S22, 1.2g of tris-hydroxymethyl aminomethane is added to 40mL of deionized water, the pH is adjusted to 8.5 with hydrochloric acid and sodium hydroxide solution, then 0.4g of dopamine hydrochloride is added to prepare a dopamine hydrochloride solution, 0.4g of the zeolite framework is added to 40g of the dopamine hydrochloride solution, and reacted at 20℃ for 18h, then the solid is collected by dialysis to prepare an antibacterial aid, 1g of the antibacterial aid is added to 40g of deionized water, 0.3g of Tween-80 is added, and stirred uniformly to prepare an aqueous phase;

[0048] S23, 4g of isophorone diisocyanate trimer and 10g of dioctyl terephthalate are dissolved in 30g of ethyl acetate, 0.01g of dibutyl tin dilaurate and 2.5g of polyethylene glycol are added, the temperature is raised to 50℃ for 10min of prepolymerization to prepare an oil phase, the oil phase and the aqueous phase are mixed, high-speed homogenization stirring is carried out at 2500rpm for 5min, the temperature is raised to 60℃ for 2h, 1g of ethylene glycol is added, and the reaction is carried out for 2h to prepare an antibacterial toughening filler.

[0049] The ultraviolet light curing type modified acrylic resin coating of the embodiment is used for preparing a metal protective coating, comprising the following steps:

[0050] S1, adding the modified acrylic resin, diluent, adhesion promoter and antibacterial toughening filler into a stirring kettle, adding the photoinitiator and leveling agent, stirring uniformly to prepare the ultraviolet light curing type modified acrylic resin coating;

[0051] S2, coating the resin coating on an aluminum plate, the coating thickness is 100 microns, curing for 30 minutes under ultraviolet light to prepare the coating.

[0052] The ultraviolet light curing type modified acrylic resin coating of the embodiment is prepared from the following components by mass:

[0053] 60g modified acrylic resin, 3g photoinitiator, 35g diluent, 0.5g antibacterial toughening filler, 2g adhesion promoter and 1g leveling agent.

[0054] The photoinitiator is photoinitiator 1173; the diluent is propylene glycol methyl ether acetate; the adhesion promoter is acrylic acid phosphate ester type promoter, model number KM2106; the leveling agent is model number BYK-333.

[0055] The preparation method of the modified acrylic resin of the embodiment comprises the following steps:

[0056] S11, adding 55g of xylene into a reaction kettle, adding 5g of methyl acrylate, 20g of methyl methacrylate, 16g of hydroxy acrylate, 11g of isobornyl acrylate, 5g of 3-methyl methacrylate-4-butylolactone, 5g of glycidyl methacrylate and 0.1g of di-t-butyl peroxide initiator, heating to 160℃ for 2h to prepare an acrylic pre-polymer;

[0057] S12, adding 92g of rosin pentaerythritol ester into a reaction kettle, adding 13g of glycidyl methacrylate, 1.5g of p-methoxyphenol and 1.3g of triphenylphosphine, heating to 130℃ for 3h to prepare rosin modified acrylic ester;

[0058] S13, adding 55g of the acrylic pre-polymer, 13g of the rosin modified acrylic ester and 0.9g of di-t-butyl peroxide initiator into a reaction kettle, heating to 180℃ for 2h to prepare the modified acrylic resin.

[0059] The preparation method of the antibacterial toughening filler of the embodiment comprises the following steps:

[0060] S21, 2.5 g of zinc nitrate, 0.12 g of magnesium nitrate and 0.45 g of ferrous nitrate were added to 40-50 g of N, N-dimethylformamide, stirred uniformly, then quickly added to a mixed solution of 105 g of 2-methylimidazole and 35 g of 2-aminobenzimidazole, stirred at room temperature for 4 h, heated to 45°C and stirred for 1.5 h, cooled and filtered to collect the solid, washed with anhydrous ethanol and dried to obtain a zeolite framework;

[0061] S22, 1.5 g of trishydroxymethyl aminomethane was added to 50 mL of deionized water, the pH was adjusted to 8.5 with hydrochloric acid and sodium hydroxide solution, then 0.5 g of dopamine hydrochloride was added to prepare a dopamine hydrochloride solution, 0.4 g of zeolite framework was added to 50 g of dopamine hydrochloride solution and reacted at 30°C for 12 h, the solid was collected by dialysis to obtain an antibacterial aid, 1.5 g of the antibacterial aid was added to 45 g of deionized water, 0.4 g of Tween-80 was added and stirred uniformly to obtain an aqueous phase;

[0062] S23, 4.5 g of isophorone diisocyanate trimer and 12 g of terephthalic acid dioctyl ester were dissolved in 50 g of ethyl acetate, 0.02 g of dibutyltin dilaurate and 3 g of polyethylene glycol were added, the temperature was raised to 45°C for pre-polymerization for 10 min to obtain an oil phase, the oil phase and the aqueous phase were mixed and stirred at a high speed of 3000 rpm for 7 min, the temperature was raised to 55°C for reaction for 1.5 h, 0.5 g of ethylene glycol was added and reacted for 1.5 h to obtain an antibacterial toughening filler.

[0063] The ultraviolet light-curable modified acrylic resin coating of the present embodiment is used to prepare a metal protective coating, comprising the following steps:

[0064] S1, the modified acrylic resin, diluent, adhesion promoter and antibacterial toughening filler were added to a stirred tank, a photoinitiator and a leveling agent were added, and the mixture was stirred uniformly to obtain an ultraviolet light-curable modified acrylic resin coating;

[0065] S2, the resin coating was applied to an aluminum plate with a coating thickness of 130 μm, and cured with ultraviolet light for 35 min to obtain a coating.

[0066] Example 3, an ultraviolet light-curable modified acrylic resin coating of the present embodiment was prepared from the following components:

[0067] 70 g of modified acrylic resin, 5 g of photoinitiator, 40 g of diluent, 1.3 g of antibacterial toughening filler, 3 g of adhesion promoter and 2 g of leveling agent.

[0068] The photoinitiator is Darocur 819; the diluent is ethyl acetate; the adhesion promoter is an acrylic phosphonate type promoter, model number KM2106; and the leveling agent is BYK-331.

[0069] The preparation method of the modified acrylic resin of the present embodiment comprises the following steps:

[0070] S11, 60g of xylene is added to the reaction kettle, 10g of methyl acrylate, 18g of methyl methacrylate, 19g of hydroxy acrylate, 15g of isobornyl acrylate, 5g of 2-methylenyl butyrolactone, 8g of glycidyl methacrylate and 1g of di-t-butyl peroxide initiator are added, and the temperature is raised to 150℃ for 4h to prepare an acrylic prepolymer;

[0071] S12, 100g of rosin pentaerythritol ester is added to the reaction kettle, 15g of glycidyl methacrylate, 2g of p-methoxyphenol and 1.5g of triphenylphosphine are added, and the temperature is raised to 110℃ for 4h to prepare a rosin modified acrylic ester;

[0072] S13, 60g of the acrylic prepolymer, 14g of the rosin modified acrylic ester and 1g of di-t-butyl peroxide initiator are added to the reaction kettle, and the temperature is raised to 160℃ for 2h to prepare a modified acrylic resin.

[0073] The preparation method of the antibacterial toughening filler of the present embodiment comprises the following steps:

[0074] S21, 2g of zinc nitrate, 0.15g of magnesium nitrate and 0.3g of ferrous nitrate are added to 50g of N,N-dimethylformamide, stirred uniformly, then a mixed solution of 110g of 2-methylimidazole and 40g of 2-aminobenzimidazole is quickly added, stirred at room temperature for 6h, and then stirred at 50℃ for 2h, cooled, filtered to collect the solid, washed with anhydrous ethanol, dried and cooled to prepare a zeolite framework;

[0075] S22, 2g of trishydroxymethyl aminomethane is added to 50mL of deionized water, the pH is adjusted to 8.5 with hydrochloric acid and sodium hydroxide solution, then 0.5g of dopamine hydrochloride is added to prepare a dopamine hydrochloride solution, 0.6g of the zeolite framework is added to 60g of the dopamine hydrochloride solution, and the reaction is carried out at 30℃ for 12h, the solid is collected by dialysis to prepare an antibacterial aid, 2g of the antibacterial aid is added to 50g of deionized water, 0.5 parts of Tween-80 is added, and the mixture is stirred uniformly to prepare an aqueous phase;

[0076] S23, 5g of isophorone diisocyanate trimer and 15g of dioctyl terephthalate were dissolved in 50g of ethyl acetate, 0.03g of dibutyl tin dilaurate and 4g of polyethylene glycol were added, and pre-polymerization was carried out at 50℃ for 5min to prepare an oil phase, the oil phase and the water phase were mixed, high-speed homogenizing stirring was carried out at 3500rpm for 5min, and reaction was carried out at 60℃ for 2h, 2g of ethylene glycol was added, and reaction was carried out at 60℃ for 2h to prepare an antibacterial toughening filler.

[0077] The ultraviolet light curing type modified acrylic resin coating of the embodiment is used for preparing a metal protective coating, including the following steps:

[0078] S1, the modified acrylic resin, diluent, adhesion promoter and antibacterial toughening filler were added into a stirring kettle, a photoinitiator and a leveling agent were added, and stirring was carried out uniformly to prepare an ultraviolet light curing type modified acrylic resin coating;

[0079] S2, the resin coating was coated on an aluminum plate, the coating thickness was 200μm, and ultraviolet light was used for curing for 50min to prepare a coating.

[0080] Comparative Example 1, the difference between the comparative example and Example 1 is that the modified acrylic resin is not added with rosin modified acrylic ester.

[0081] Comparative Example 2, the difference between the comparative example and Example 1 is that the modified acrylic resin of the comparative example is prepared by polymerization of 5~10g of methyl acrylate, 15~20g of methyl methacrylate, 15~20g of hydroxy acrylate and 5~8g of glycidyl methacrylate.

[0082] Comparative Example 3, the difference between the comparative example and Example 1 is that the antibacterial auxiliary agent in the antibacterial toughening filler is replaced by zinc oxide.

[0083] Comparative Example 4, the difference between the comparative example and Example 1 is that the antibacterial toughening filler is replaced by an antibacterial auxiliary agent.

[0084] Performance test

[0085] The viscosity of the modified acrylic resin coating prepared in each example and comparative example was tested according to GB / T 1723-1993 “Determination of viscosity of paints”.

[0086] The solid content of the modified acrylic resin coating prepared in each example and comparative example was tested according to GB / T 1725-2007 “Determination of non-volatile matter content of color paints, varnishes and plastics”.

[0087] The modified acrylic resin coating prepared in each example and comparative example was stirred at 3000rpm for 15min, and the stability was measured by visual stratification.

[0088] The adhesion grade of the coating prepared from each example and the comparative example was tested according to GB / T 9286-2021 “Paints and varnishes Cross-hatch test”.

[0089] The pencil hardness of the coating prepared from each example and the comparative example was tested according to GB / T 6739-2006 “Paints and varnishes Determination of film hardness by the pencil test”, and the pencil used for testing was a Chinese pencil.

[0090] The impact resistance of the coating prepared from each example and the comparative example was tested according to GB / T 1732-2020 “Determination of impact resistance of paint films”.

[0091] The test results are shown in Table 1 below:

[0092]

[0093] Antibacterial test

[0094] According to GB / T 21866-2008 “Determination of antibacterial property of antibacterial coatings (paint films) and antibacterial effect”, Escherichia coli was inoculated into a plate count agar medium and cultured at 37°C for 24 h, diluted with a phosphate buffer solution to a concentration of 5.0 CFU / mL to prepare a bacterial solution.

[0095] An aluminum plate without acrylic coating was used as a control group, and the aluminum plate coatings prepared from each example and the comparative example and the control group were wiped with ethanol and then irradiated under a UV lamp for sterilization for 30 min. After being placed flat, the bacterial solution was uniformly applied, and the aluminum plate coatings with the applied bacterial solution and the control group were placed in a sterile incubator with a humidity of 90% and cultured at 37°C for 24 h. The number of colonies was recorded, and the antibacterial rate was calculated according to the following formula:

[0096]

[0097] R is the antibacterial rate;

[0098] R C is the number of colonies of the control group, with units of CFU / g;

[0099] R B is the number of colonies of the aluminum plate coating, with units of CFU / g.

[0100] The test results are shown in Table 2 below:

[0101]

[0102] From the experimental data, the viscosity of the resin coating prepared in Examples 1-3 is between 281-286 mPa·s, the solid content is between 64.39-68.14%, and the dispersion is stable at a rotation speed of 3000 rpm for 15 min, indicating that the ultraviolet curing modified acrylic resin coating prepared in the application meets the basic requirements of the coating, and the adhesion grade is 0 level, and the impact resistance is 50 kg·cm, indicating that the ultraviolet curing modified acrylic resin coating prepared in the application has excellent adhesion and impact resistance. The modified acrylic resin of Comparative Example 2 is prepared by polymerizing 5-10 g of methyl acrylate, 15-20 g of methyl methacrylate, 15-20 g of hydroxy acrylate, and 5-8 g of glycidyl methacrylate, without adding lactone monomer and modified acrylic resin modification, resulting in decreased hardness and impact resistance, so its pencil hardness is only 2H, and the impact resistance is only 30 kg·cm; the antibacterial rate of the resin coating prepared in Examples 1-3 is between 97.0-98.1%, indicating that the ultraviolet curing modified acrylic resin coating prepared in the application has excellent antibacterial performance.

[0103] The above description is only a preferred embodiment of the present application, but the protection scope of the present application is not limited thereto, and any skilled person in the art can make equivalent replacements or changes according to the technical solution and the inventive concept of the present application within the technical range disclosed in the present application, which should be covered within the protection scope of the present application.

[0104] The preferred embodiments of the application disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details, nor limit the application to the specific embodiments. Obviously, many modifications and changes can be made according to the content of the present application. The present application selects and describes these embodiments in order to better explain the principles and practical applications of the present application, so that those skilled in the art can well understand and utilize the present application. The present application is limited by the claims and their entire scope and equivalents.

Claims

1. An ultraviolet light-curable modified acrylic resin paint, characterized by, Is prepared from the following components by mass parts: 60~70 parts of modified acrylic resin, 2~5 parts of photoinitiator, 30~40 parts of diluent, 0.5~1.5 parts of antibacterial toughening filler, 1~3 parts of adhesion promoter and 0.5~2 parts of leveling agent; The modified acrylic resin is prepared from methyl acrylate, methyl methacrylate, hydroxy acrylate, isobornyl acrylate, lactone monomer and glycidyl methacrylate as raw materials, to obtain an acrylic prepolymer, and then the acrylic prepolymer is reacted with rosin modified acrylate prepared from rosin pentaerythritol ester and glycidyl methacrylate to obtain the modified acrylic resin; The antibacterial toughening filler is prepared by the following method: S21, according to mass parts, 2~2.5 parts of zinc nitrate, 0.05~0.15 parts of magnesium nitrate and 0.3~0.6 parts of ferrous nitrate are added to 40~50 parts of N, N-dimethylformamide, stirred uniformly, then 100~110 parts of 2-methyl imidazole and 30~40 parts of 2-amino benzimidazole mixed solution are added, stirred and reacted, and cooled to prepare a zeolite framework; S22, according to mass parts, 0.4~0.6 parts of zeolite framework is added to 40~60 parts of dopamine hydrochloride solution, reacted at 20~30℃ for 12~18h, the solid is collected by dialysis to prepare an antibacterial aid, 1~2 parts of the antibacterial aid is added to 40~50 parts of deionized water, 0.3~0.5 parts of Tween-80 is added, stirred uniformly to prepare an aqueous phase; S23, according to mass parts, 4~5 parts of isophorone diisocyanate trimer and 10~15 parts of terephthalic acid dioctyl ester are dissolved in 30~50 parts of ethyl acetate, 0.01~0.03 parts of dibutyltin dilaurate and 2~4 parts of polyethylene glycol are added, pre-polymerization is carried out, to prepare an oil phase, the oil phase and the aqueous phase are mixed, high-speed homogenization stirring is carried out, the temperature is raised, and then 0.5~2 parts of ethylene glycol is added to react, to prepare the antibacterial toughening filler.

2. The ultraviolet-curable modified acrylic resin paint according to claim 1, characterized by, The preparation method of the modified acrylic resin comprises the following steps: S11, according to mass parts, 50~60 parts of dimethylbenzene is added to a reaction kettle, then 5~10 parts of methyl acrylate, 15~20 parts of methyl methacrylate, 15~20 parts of hydroxy acrylate, 10~15 parts of isobornyl acrylate, 3~5 parts of lactone monomer, 5~8 parts of glycidyl methacrylate and 0.05~1 parts of di-t-butyl peroxide initiator are added, the temperature is raised to react, to prepare an acrylic prepolymer; S12, according to mass parts, 90~100 parts of rosin pentaerythritol ester is added to a reaction kettle, then 10~15 parts of glycidyl methacrylate, 1~2 parts of p-methoxyphenol and 1~1.5 parts of triphenylphosphine are added, to react to prepare rosin modified acrylate; S13, according to mass parts, 50~60 parts of acrylic prepolymer, 12~14 parts of rosin modified acrylate and 0.05~1 parts of di-t-butyl peroxide initiator are added to a reaction kettle, to react to prepare the modified acrylic resin.

3. The ultraviolet-curable modified acrylic resin paint according to claim 1, characterized by, The photoinitiator is any one of photoinitiator 1173, photoinitiator 819; the diluent is any one of sec-butyl acetate, ethyl acetate, propylene glycol methyl ether acetate; the adhesion promoter is an acrylic phosphate ester type promoter; the leveling agent is any one of model BYK-333, BYK-331.

4. The ultraviolet-curable modified acrylic resin paint according to claim 2, characterized by, In the S11, the temperature is raised to 130-180 DEG C and reacted for 2-4 h, the lactone monomer is any one of hexalactone, 2-methylenyl butyrolactone, 3-methyl acrylate-4-butyrolactone; in the S12, the temperature is raised to 110-130 DEG C and reacted for 2-4 h; in the S13, the temperature is raised to 130-180 DEG C and reacted for 2-4 h.

5. The ultraviolet light-curable modified acrylic resin paint according to claim 1, characterized by, In the S21, the molar ratio of zinc nitrate, magnesium nitrate and ferrous nitrate is 8: (0.5-1): (0.5-1.5), the zinc nitrate, magnesium nitrate and ferrous nitrate are stirred uniformly in N, N-dimethylformamide, then quickly added into the mixed solution, stirred at room temperature for 4-6 h, the temperature is raised to 40-50 DEG C and stirred for 1-2 h, then cooled and collected the solid by filtration, washed with anhydrous ethanol; in the S22, the dopamine hydrochloride solution is prepared by adding 1.2-2 g of tris-hydroxymethyl aminomethane into 40-50 mL of deionized water, adjusting the pH to 8.5 with hydrochloric acid and sodium hydroxide solution, and then adding 0.4-0.5 g of dopamine hydrochloride.

6. The ultraviolet-curable modified acrylic resin paint according to claim 1, characterized by, In the S23, the temperature is raised to 40-50 DEG C for prepolymerization for 5-10 min, high-speed homogenization stirring is carried out at 2500-3500 rpm for 5-10 min, the temperature is raised to 50-60 DEG C and reacted for 1-2 h, and then ethylene glycol is added and reacted for 1-2 h.

7. Use of an ultraviolet light-curable modified acrylic resin coating, characterized in that For preparing a metal protective coating, comprising the following steps: S1, adding modified acrylic resin, diluent, adhesion promoter and antibacterial toughening filler into a stirred tank, adding photoinitiator and leveling agent, stirring uniformly to prepare a UV-curable modified acrylic resin coating; S2, coating the resin coating on an aluminum plate, curing with UV light to prepare a coating.

8. The use of an ultraviolet light-cured modified acrylic resin paint according to claim 7, characterized by, In the S2, the coating thickness is 100-200 μm, and the UV light curing time is 30-50 min.

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