Water-based acrylic acid antibacterial and antiviral coating and production process thereof

Abstract

The invention relates to the technical field of water-based paint preparation, in particular to water-based acrylic acid antibacterial and antiviral paint and a production process thereof.The modified nano-particles have the characteristic of being adjustable in pore size, bacteria or viruses can be captured through the physical adsorption effect, and the antibacterial and antiviral performance of the paint is improved. Under illumination, the modified nanoparticles can further serve as a photodynamic platform to generate reactive oxygen species, structural integrity of bacteria and viruses is destroyed, and the modified nanoparticles have excellent antibacterial and antiviral capacity; meanwhile, hydroxy acrylic resin is used as a matrix, the hydroxy acrylic resin, bisphenol A epoxy resin, ethylenediamine and modified nanoparticles form a multi-layer physical cross-linked network, and the modified nanoparticles are anchored in a coating system, so that the coating can keep efficient antiviral and antibacterial properties for a long time, the coating fullness is greatly improved, the coating effect is good, and the coating is suitable for large-scale popularization and application. Meanwhile, excellent water resistance, air permeability, water impermeability and excellent mildew-proof effect are achieved.

Description

Technical Field

[0001] The invention relates to the technical field of water-based coating preparation, and in particular to a water-based acrylic antibacterial and antiviral coating and a production process thereof. Background Art

[0002] There are various viruses and bacteria in the environment, especially in crowded places such as hospitals and shopping malls, where the virus and bacteria content is higher. People are prone to bacterial or viral infection when they come into contact with contaminated surfaces, especially for some special groups with poor resistance. They are more likely to get bacterial or viral infection after coming into contact with contaminated surfaces. In addition, with the improvement of people's health and protection awareness, the demand for antiviral and antibacterial products is increasing. There is a huge demand for coatings in homes, hospitals, shopping malls, etc., and they are products that people frequently come into contact with.

[0003] There are many reports on antibacterial and antiviral coatings in the prior art. For example, Chinese patent CN105968973A discloses adding Chinese herbal medicine extracts to aqueous emulsions to achieve surface antibacterial and antiviral effects through the slow release of Chinese herbal medicine extracts. CN111849266A discloses adding cuprous compounds to copolymer emulsions to achieve antiviral effects. However, these products generally have the following problems: First, the amount of antibacterial and antiviral additives doped is large, but the actual resistance effect is not obvious, and as the proportion of the amount of antibacterial and antiviral additives increases, the improvement of the antibacterial and antiviral effect is not obvious; second, the functional components of the antibacterial and antiviral additives are easy to segregate and detach, especially for public medical and health areas, which are generally disinfected several times a day. For example, the use of sodium hypochlorite, medical alcohol, etc. will accelerate the loss of functional additives and fail to achieve long-term antibacterial and antiviral effects.

[0004] Therefore, it is an urgent problem to seek a new water-based acrylic antibacterial and antiviral coating and provide a new process for preparing the water-based acrylic antibacterial and antiviral coating to solve the defects in the prior art. Summary of the invention

[0005] In order to overcome the shortcomings of the prior art, the purpose of the present invention is to provide a water-based acrylic antibacterial and antiviral coating and a production process thereof. The modified nanoparticles provided by the present invention have the characteristic of adjustable pore size, can capture bacteria or viruses by physical adsorption, and under light, the modified nanoparticles can further serve as a photodynamic platform to generate active oxygen substances, destroy the structural integrity of bacteria and viruses, and have excellent antibacterial and antiviral capabilities; at the same time, the present invention uses hydroxyl acrylic resin as a matrix, and forms a multi-layer physical cross-linked network with bisphenol A epoxy resin, ethylenediamine, and modified nanoparticles, and the modified nanoparticles are anchored in the coating system, which not only enables the coating to maintain high-efficiency antiviral and antibacterial properties for a long time, but also greatly improves the fullness of the coating and the good coating effect. At the same time, it has excellent water resistance, is breathable and impermeable, and has excellent mildew resistance.

[0006] To achieve the above object, the present invention provides the following technical solutions: A water-based acrylic antibacterial and antiviral coating comprises the following components by mass: 50-80 parts of hydroxy acrylic resin, 30-40 parts of bisphenol A epoxy resin, 8-12 parts of titanium dioxide, 8-15 parts of modified nanoparticles, 1-5 parts of isocyanate crosslinking agent, 4-8 parts of ethylenediamine, 3-4 parts of defoaming agent, 1-3 parts of dispersant, 2-4 parts of leveling agent, and 20-40 parts of water; Wherein, the modified nanoparticles are prepared by the following steps: S11. 0.1-0.5 parts of zirconium tetrachloride, 5-10 parts of benzoic acid, 0.05-0.1 parts of tetrakis (p-carboxylic acid phenyl) porphyrin, and 15-20 parts of N, N-dimethylformamide were placed in a reaction kettle and mixed evenly, and hydrothermally reacted at 120-160 ° C for 8-10 hours, and the resulting product was washed with DMF, methanol and acetone, and dried to obtain PCN-224; S12. Mix 8-10 parts of PCN-224 and 50-70 parts of toluene by mass and stir magnetically for 15-20 min; S13. Add 3-4 parts of 3-aminopropyltriethoxysilane, 2-3 parts of silver nitrate and 1-2 parts of acetic acid to the mixed solution of step S12 dropwise, and react under reflux in a water bath at 80-100° C. for 15-20h under the protection of nitrogen; S14. Cool the product obtained in step S13 to room temperature, centrifuge, wash, and dry to obtain modified nanoparticles.

[0007] Preferably, the isocyanate cross-linking agent is selected from one or more of hexamethylene diisocyanate and diphenylmethane diisocyanate.

[0008] Preferably, the defoaming agent is TEGO Airex 810.

[0009] Preferably, the dispersant is LBD-1.

[0010] Preferably, the leveling agent is a polydimethylsiloxane leveling agent.

[0011] A production process of a water-based acrylic acid antibacterial and antiviral coating, for preparing the water-based acrylic acid antibacterial and antiviral coating, comprising the following steps: S1. Mix the hydroxy acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine in parts by mass and stir at 50-60° C. for 5-8 hours; S2. Add titanium dioxide, defoamer, dispersant, leveling agent and water to the mixed solution obtained in step S1 in sequence, mix well, and stir at 70-80° C. for 3-4 hours to obtain the water-based acrylic antibacterial and antiviral coating.

[0012] Compared with the prior art, the present invention has the following beneficial effects: 1. The modified nanoparticles provided by the present invention have the characteristic of adjustable pore size, and can capture bacteria or viruses by physical adsorption. Under light, the modified nanoparticles can further serve as a photodynamic platform to generate reactive oxygen species, destroy the structural integrity of bacteria and viruses, and have excellent antibacterial and antiviral capabilities; 2. The present invention uses hydroxy acrylic resin as a matrix, and forms a multi-layer physical cross-linked network with bisphenol A epoxy resin, ethylenediamine, and modified nanoparticles. The modified nanoparticles are anchored in the coating system, which not only enables the coating to maintain high-efficiency antiviral and antibacterial properties for a long time, but also greatly improves the fullness of the coating and the coating effect. At the same time, it has excellent water resistance, is breathable and impermeable, and has excellent mildew resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1 The present invention is a process flow chart for preparing the water-based acrylic acid antibacterial and antiviral coating; Figure 2 The present invention is a flow chart of the preparation process of the modified nanoparticles. DETAILED DESCRIPTION

[0014] The present invention will be described clearly and completely below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0015] See also Figure 1-2 , the present invention provides a technical solution: Example 1, a production process of a water-based acrylic acid antibacterial and antiviral coating: S1. Mix hydroxy acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine, and stir at 50° C. for 5 h; S2. Add titanium dioxide, defoamer, dispersant, leveling agent and water to the mixed solution obtained in step S1, mix well, and stir at 70° C. for 3 hours to obtain the water-based acrylic antibacterial and antiviral coating; In the above preparation process, the dosage of each component is as follows:

[0016] In the above process, the isocyanate crosslinking agent is diphenylmethane diisocyanate; the defoaming agent is TEGOAirex 810; the dispersant is LBD-1; the leveling agent is polydimethylsiloxane leveling agent, model BYK-306; the brand of the hydroxylated acrylic resin is R916-60; the brand of the bisphenol A epoxy resin is E-42; In the above process, the modified nanoparticles are prepared by the following steps: S11. 1 g zirconium tetrachloride, 50 g benzoic acid, 0.5 g tetrakis (p-carboxylic acid phenyl) porphyrin, and 15 ml N, N-dimethylformamide were placed in a reaction vessel and mixed evenly, and hydrothermally reacted at 150 ° C for 8 h. The resulting product was washed with DMF, methanol and acetone in turn, and dried to obtain PCN-224; step S11 was repeated to prepare PCN-224 in large quantities; S12. Mix 8 g PCN-224 and 50 g toluene and stir magnetically for 15 min; S13. After adding 3 g of 3-aminopropyltriethoxysilane, 2 g of silver nitrate and 1 g of acetic acid dropwise to the mixed solution of step S12, the mixture was refluxed in a water bath at 80° C. for 15 h under the protection of nitrogen; S14. The product obtained in step S13 is cooled to room temperature, centrifuged, washed, and dried to obtain modified nanoparticles, and steps S12-S14 are repeated to prepare a large amount of modified nanoparticles, which are then used in the preparation process of water-based acrylic antibacterial and antiviral coatings.

[0017] Embodiment 2, a production process of a water-based acrylic acid antibacterial and antiviral coating: S1. Mix hydroxy acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine, and stir at 60° C. for 6 h; S2. Add titanium dioxide, defoamer, dispersant, leveling agent and water to the mixed solution obtained in step S1, mix well, and stir at 80° C. for 4 hours to obtain the water-based acrylic antibacterial and antiviral coating; In the above preparation process, the dosage of each component is as follows:

[0018] In the above process, the isocyanate crosslinking agent is diphenylmethane diisocyanate; the defoaming agent is TEGOAirex 810; the dispersant is LBD-1; the leveling agent is polydimethylsiloxane leveling agent, model BYK-306; the brand of the hydroxylated acrylic resin is R916-60; the brand of the bisphenol A epoxy resin is E-42; In the above process, the modified nanoparticles are prepared by the following steps: S11. 4 g zirconium tetrachloride, 60 g benzoic acid, 0.8 g tetrakis (p-carboxylic acid phenyl) porphyrin, and 20 ml N, N-dimethylformamide were placed in a reaction kettle and mixed evenly, and hydrothermally reacted at 140 ° C for 8 h. The resulting product was washed with DMF, methanol and acetone in turn, and dried to obtain PCN-224; step S11 was repeated to prepare PCN-224 in large quantities; S12. Mix 9 g PCN-224 and 60 g toluene and stir magnetically for 15 min; S13. After 4 g of 3-aminopropyltriethoxysilane, 3 g of silver nitrate and 2 g of acetic acid were added dropwise to the mixed solution of step S12, the mixture was refluxed in a water bath at 90° C. for 16 h under the protection of nitrogen; S14. The product obtained in step S13 is cooled to room temperature, centrifuged, washed, and dried to obtain modified nanoparticles, and steps S12-S14 are repeated to prepare a large amount of modified nanoparticles, which are then used in the preparation process of water-based acrylic antibacterial and antiviral coatings.

[0019] Embodiment 3, a production process of a water-based acrylic acid antibacterial and antiviral coating: S1. Mix hydroxy acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine, and stir at 60° C. for 6 h; S2. Add titanium dioxide, defoamer, dispersant, leveling agent and water to the mixed solution obtained in step S1, mix well, and stir at 80° C. for 4 hours to obtain the water-based acrylic antibacterial and antiviral coating; In the above preparation process, the dosage of each component is as follows:

[0020] In the above process, the isocyanate crosslinking agent is diphenylmethane diisocyanate; the defoaming agent is TEGOAirex 810; the dispersant is LBD-1; the leveling agent is polydimethylsiloxane leveling agent, model BYK-306; the brand of the hydroxylated acrylic resin is R916-60; the brand of the bisphenol A epoxy resin is E-42; In the above process, the modified nanoparticles are prepared by the following steps: S11. 5 g zirconium tetrachloride, 55 g benzoic acid, 1 g tetra(p-carboxylic acid phenyl)porphyrin, and 20 ml N,N-dimethylformamide were placed in a reaction vessel and mixed evenly, and hydrothermally reacted at 160° C. for 10 h. The resulting product was washed with DMF, methanol, and acetone in turn, and dried to obtain PCN-224; step S11 was repeated to prepare PCN-224 in large quantities; S12. Mix 10 g PCN-224 and 70 g toluene and stir magnetically for 15 min; S13. After 4 g of 3-aminopropyltriethoxysilane, 3 g of silver nitrate and 2 g of acetic acid were added dropwise to the mixed solution of step S12, the mixture was refluxed in a water bath at 100 ° C for 20 h under the protection of nitrogen; S14. The product obtained in step S13 is cooled to room temperature, centrifuged, washed, and dried to obtain modified nanoparticles, and steps S12-S14 are repeated to prepare a large amount of modified nanoparticles, which are then used in the preparation process of water-based acrylic antibacterial and antiviral coatings.

[0021] Comparative example, Comparative example 1: Comparative example 1 is different from Example 1 in the following way. The only difference is that in Comparative example 1, step S1 originally existing in Example 1 is omitted, thereby eliminating the use of modified nanoparticles. The remaining steps are exactly the same in Comparative example 1 and Example 1.

[0022] Comparative Example 2: Comparative Example 2 differs from Example 1 in that steps S13 and S14 originally present in Example 1 are omitted in Comparative Example 2, modified nanoparticles are not added to the antibacterial and antiviral coating in Comparative Example 2, and the added component is PCN-224. The remaining steps are exactly the same in Comparative Example 2 and Example 1.

[0023] Performance test: Referring to the T / CNCIA 03002-2020 standard, influenza A virus (H3N2) was used as the test virus to test the antiviral properties of Examples 1-3 and Comparative Examples 1-2, and the test results are shown in Table 1; referring to the HG / T 3950-2007 standard, Staphylococcus aureus and Escherichia coli were used for antibacterial tests, and the test results are shown in Table 2; referring to the GB / T4893.9-2019 standard, the surface wear resistance of Examples 1-3 was evaluated, and the antibacterial and antiviral properties of the coating after wear were tested according to the aforementioned test method (wear thickness was 0.15 mm), and the results are shown in Table 3: Table 1. Test results of antiviral and antibacterial properties of Examples 1-3 and Comparative Examples 1-2

[0024] Table 2. Antibacterial performance test results of Examples 1-3 and Comparative Examples 1-2

[0025] Table 3. Wear resistance test results of Examples 1-3

[0026] It can be seen from the test results in Tables 1 and 2 that the antiviral rate and antibacterial rate of the water-based acrylic antibacterial and antiviral coatings prepared in Examples 1-3 of the present invention are significantly higher than those in Comparative Example 1, which strongly proves that the present invention uses the modified nanoparticles provided to have the characteristic of adjustable pore size, can capture bacteria or viruses by physical adsorption, and the modified nanoparticles can be further used as a photodynamic platform under light to generate active oxygen species, destroy the structural integrity of bacteria and viruses, and have excellent and long-term antibacterial and antiviral capabilities; at the same time, the antiviral rate and antibacterial rate of Examples 1-3 are significantly higher than those in Comparative Example 2, proving that the present invention can increase the charge density on the surface of the nanoparticles by grafting amino groups and metal anions through the modification of the nanoparticles, improve the capture efficiency of photogenerated carriers, thereby improving the generation efficiency of active oxygen species, thereby improving the antibacterial and antiviral capabilities of the coating; It can be seen from the test results in Table 3 that the water-based acrylic antibacterial and antiviral coating prepared in the present invention has good surface wear resistance, and maintains excellent antibacterial and antiviral capabilities within the wear thickness of 0.15 mm.

[0027] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A water-based acrylic antibacterial and antiviral coating, characterized in that: The composition comprises the following components by mass: 50-80 parts of hydroxy acrylic resin, 30-40 parts of bisphenol A epoxy resin, 8-12 parts of titanium dioxide, 8-15 parts of modified nanoparticles, 1-5 parts of isocyanate crosslinking agent, 4-8 parts of ethylenediamine, 3-4 parts of defoaming agent, 1-3 parts of dispersant, 2-4 parts of leveling agent, and 20-40 parts of water; Wherein, the modified nanoparticles are prepared by the following steps: S11. 0.1-0.5 parts of zirconium tetrachloride, 5-10 parts of benzoic acid, 0.05-0.1 parts of tetrakis(p-carboxylic acid phenyl)porphyrin, and 15-20 parts of N,N-dimethylformamide were placed in a reaction kettle and mixed evenly, and hydrothermally reacted at 120-160° C. for 8-10 hours. The obtained product was washed with DMF, methanol and acetone in turn, and dried to obtain PCN-224; S12. Mix 8-10 parts of PCN-224 and 50-70 parts of toluene by mass and stir magnetically for 15-20 min; S13. Add 3-4 parts of 3-aminopropyltriethoxysilane, 2-3 parts of silver nitrate and 1-2 parts of acetic acid to the mixed solution of step S12 dropwise, and react under reflux in a water bath at 80-100° C. for 15-20h under the protection of nitrogen; S14. Cool the product obtained in step S13 to room temperature, centrifuge, wash, and dry to obtain modified nanoparticles.

2. A water-based acrylic antibacterial and antiviral coating according to claim 1, characterized in that: The isocyanate crosslinking agent is selected from one or more of hexamethylene diisocyanate and diphenylmethane diisocyanate.

3. A water-based acrylic antibacterial and antiviral coating according to claim 1, characterized in that: The defoamer is TEGO Airex 810.

4. A water-based acrylic antibacterial and antiviral coating according to claim 1, characterized in that: The dispersant is LBD-1.

5. A water-based acrylic antibacterial and antiviral coating according to claim 1, characterized in that: The leveling agent is a polydimethylsiloxane leveling agent.

6. A production process of a water-based acrylic antibacterial and antiviral coating, used for preparing the water-based acrylic antibacterial and antiviral coating according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Mix the hydroxy acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine in parts by mass and stir at 50-60° C. for 5-8 hours; S2. Add titanium dioxide, defoamer, dispersant, leveling agent and water to the mixed solution obtained in step S1 in sequence, mix well, and stir at 70-80° C. for 3-4 hours to obtain the water-based acrylic antibacterial and antiviral coating.

Images