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

Abstract

The present application relates to the technical field of water-based paint preparation, in particular to a water-based acrylic antibacterial and antiviral paint and a production process thereof, the modified nanoparticles provided by the present application have the characteristic of adjustable pore size, can capture bacteria or viruses through the mode of physical adsorption, and the modified nanoparticles can further act as a photodynamic platform to produce reactive oxygen species to destroy the structural integrity of bacteria and viruses, thereby having excellent antibacterial and antiviral capacity; meanwhile, the present application uses hydroxyl acrylic resin as a matrix, forms a multilayer physical crosslinking network through the hydroxyl acrylic resin, bisphenol A epoxy resin, ethylenediamine and modified nanoparticles, and the modified nanoparticles are anchored in the paint system, so that the paint can long-term maintain high-efficiency antiviral and antibacterial performance, and the paint has greatly improved paint fullness, good film coating effect, excellent water resistance, air permeability, and excellent mildew resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of water-based paint preparation, in particular to a water-based acrylic antibacterial and antiviral paint and a production process thereof. BACKGROUND

[0002] There are various viruses and bacteria in the environment, especially in places with many people such as hospitals and shopping malls, and the content of viruses and bacteria is higher. People contacting contaminated surfaces can easily cause bacterial or viral infections, especially for some special groups with poor resistance, who are more likely to have bacterial or viral infections after contacting contaminated surfaces. In addition, with the improvement of people's health and protection awareness, the demand for antiviral and antibacterial products is increasing. Coatings have huge demand for home houses, hospitals, shopping malls, etc., and are products that people frequently contact.

[0003] There are many reports on antibacterial and antiviral coatings in the prior art, such as Chinese patent CN105968973A, which discloses adding traditional Chinese medicine extract in water-based emulsion to achieve surface antibacterial and antiviral effect through slow release of traditional Chinese medicine extract, and CN111849266A discloses adding cuprous compound in copolymer emulsion to achieve antiviral effect. However, these products generally have the following problems: first, the antibacterial and antiviral additive doping amount is large, but the actual resistance effect is not obvious, and with the increase of the proportion of antibacterial and antiviral additive, the antibacterial and antiviral effect is not obviously improved; second, the functional components of antibacterial and antiviral additives are prone to segregation and separation, especially for public medical and health areas, which generally need to be disinfected several times a day, such as sodium hypochlorite and medical alcohol, which can accelerate the loss of functional additives and cannot achieve long-acting antibacterial and antiviral effect.

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

[0005] In order to overcome the shortcomings of the prior art, the purpose of the present application is to provide a water-based acrylic antibacterial and antiviral coating and its production process, the modified nanoparticles provided by the present application have the characteristics of adjustable pore size, can capture bacteria or viruses through physical adsorption, and the modified nanoparticles can further act as a photodynamic platform under light to produce reactive oxygen species, destroy the structural integrity of bacteria and viruses, and have excellent antibacterial and antiviral ability; at the same time, the present application uses hydroxy acrylic resin as the matrix, forms a multi-layer physical crosslinking network through the combination of 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 performance for a long time, but also greatly improves the coating fullness, film effect, and has excellent water resistance, air permeability, and excellent mildew resistance.

[0006] In order to achieve the above-mentioned purpose, the present application provides the following technical scheme:

[0007] A water-based acrylic antibacterial and antiviral coating, which comprises the following components in parts by mass: hydroxy acrylic resin 50-80 parts, bisphenol A epoxy resin 30-40 parts, titanium white 8-12 parts, modified nanoparticles 8-15 parts, isocyanate crosslinking agent 1-5 parts, ethylenediamine 4-8 parts, defoaming agent 3-4 parts, dispersing agent 1-3 parts, leveling agent 2-4 parts, and water 20-40 parts.

[0008] The modified nanoparticles are prepared by the following steps:

[0009] S11. 0.1-0.5 parts of zirconium tetrachloride, 5-10 parts of benzoic acid, 0.05-0.1 parts of tetrakis (p-carboxyphenyl) porphyrin, and 15-20 parts of N,N-dimethylformamide are mixed in a reaction kettle in parts by mass and uniformly mixed, and then subjected to hydrothermal reaction at 120-160 DEG C for 8-10 hours; the obtained product is sequentially washed with DMF, methanol and acetone, and dried to obtain PCN-224.

[0010] S12. 8-10 parts of PCN-224 and 50-70 parts of toluene are mixed in parts by mass, and then subjected to magnetic stirring for 15-20 minutes.

[0011] S13. 3-4 parts of 3-aminopropyl triethoxysilane, 2-3 parts of silver nitrate, and 1-2 parts of acetic acid are added dropwise to the mixed solution of step S12 in a drop-by-drop manner, and then subjected to water bath reflux reaction at 80-100 DEG C for 15-20 hours under the protection of nitrogen.

[0012] S14. The product obtained in step S13 is cooled to room temperature, centrifuged, washed and dried to obtain modified nanoparticles.

[0013] Preferably, the isocyanate crosslinking agent is selected from one or more of 1,6-hexane diisocyanate, diphenylmethane diisocyanate.

[0014] Preferably, the defoaming agent is TEGO Airex 810.

[0015] Preferably, the dispersing agent is LBD-1.

[0016] Preferably, the leveling agent is a polydimethylsiloxane leveling agent.

[0017] A production process of a water-based acrylic antibacterial and antiviral coating, for preparing the water-based acrylic antibacterial and antiviral coating, comprising the following steps:

[0018] S1. Mix the hydroxyl acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent, and ethylenediamine uniformly by mass parts, and stir at 50-60°C for 5-8h;

[0019] S2. Add titanium dioxide, defoaming agent, dispersing agent, leveling agent, and water to the mixed solution prepared in step S1 in sequence, mix uniformly, and stir at 70-80°C for 3-4h to prepare the water-based acrylic antibacterial and antiviral coating.

[0020] Compared with the prior art, the water-based acrylic antibacterial and antiviral coating has the following beneficial effects:

[0021] 1. The modified nanoparticles have the characteristics of adjustable pore size, can capture bacteria or viruses through physical adsorption, and the modified nanoparticles can further act as a photodynamic platform to produce reactive oxygen species under light to destroy the structural integrity of bacteria and viruses, thereby having excellent antibacterial and antiviral ability.

[0022] 2. The water-based acrylic antibacterial and antiviral coating uses hydroxyl acrylic resin as the matrix, forms a multi-layer physical crosslinking network with bisphenol A epoxy resin, ethylenediamine, and modified nanoparticles, and the modified nanoparticles are anchored in the coating system, so that the coating can maintain high-efficiency antiviral and antibacterial performance for a long time, and the coating has good fullness, good film forming effect, excellent water resistance, air permeability, and excellent mildew resistance. BRIEF DESCRIPTION OF DRAWINGS

[0023] Fig. 1 The preparation process flow chart of the water-based acrylic antibacterial and antiviral coating is shown in the following figure.

[0024] Fig. 2 The preparation process flow chart of the modified nanoparticles is shown in the following figure. DETAILED DESCRIPTION

[0025] The present application will be described clearly and completely below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0026] Please refer to Figs. 1-2 The present application provides a technical solution:

[0027] Embodiment 1: A production process of an aqueous acrylic antibacterial and antiviral coating

[0028] S1. Mix hydroxy acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine uniformly, and stir at 50℃ for 5h;

[0029] S2. Add titanium dioxide, defoaming agent, dispersant, leveling agent and water to the mixed solution prepared in step S1 in sequence, mix uniformly, and stir at 70℃ for 3h to prepare the aqueous acrylic antibacterial and antiviral coating;

[0030] In the above preparation process, the amounts of the components are as follows:

[0031]

[0032] 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 number is BYK-306; the hydroxy acrylic resin is R916-60; the bisphenol A epoxy resin is E-42;

[0033] In the above process, the modified nanoparticles are prepared by the following steps:

[0034] S11. Put 1g of zirconium tetrachloride, 50g of benzoic acid, 0.5g of tetra (p-carboxyphenyl) porphyrin, and 15ml of N,N-dimethylformamide into a reaction kettle and mix uniformly, hydrothermal reaction at 150℃ for 8h, wash the obtained product with DMF, methanol and acetone in sequence, and dry to prepare PCN-224; repeat step S11 to prepare a large amount of PCN-224;

[0035] S12. Mix 8g of PCN-224 and 50g of toluene, and magnetically stir for 15min;

[0036] S13. After adding 3g 3-aminopropyltriethoxysilane, 2g silver nitrate, and 1g acetic acid drop by drop to the mixed solution of step S12 in a drop-by-drop manner, the reaction was carried out under the protection of nitrogen at 80°C for 15h in a water bath reflux reaction;

[0037] S14. The product obtained in step S13 was cooled to room temperature, centrifuged, washed, and dried to obtain modified nanoparticles. Steps S12-S14 were repeated to mass-produce the modified nanoparticles, which were used in the preparation process of the water-based acrylic antibacterial and antiviral coating.

[0038] Example 2: Production process of a water-based acrylic antibacterial and antiviral coating:

[0039] S1. The hydroxyl acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent, and ethylenediamine were mixed uniformly and stirred at 60°C for 6h;

[0040] S2. The titanium dioxide, defoaming agent, dispersant, leveling agent, and water were sequentially added to the mixed solution obtained in step S1 and mixed uniformly, and then stirred at 80°C for 4h to obtain the water-based acrylic antibacterial and antiviral coating;

[0041] In the above preparation process, the amounts of the components are as follows:

[0042]

[0043] 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 a polydimethylsiloxane leveling agent with model number BYK-306; the hydroxyl acrylic resin has model number R916-60; and the bisphenol A epoxy resin has model number E-42;

[0044] In the above process, the modified nanoparticles were prepared by the following steps:

[0045] S11. 4g of zirconium tetrachloride, 60g of benzoic acid, 0.8g of tetra (p-carboxyphenyl) porphyrin, and 20ml of N,N-dimethylformamide were placed in a reaction kettle and mixed uniformly, and then subjected to hydrothermal reaction at 140°C for 8h. The obtained product was sequentially washed with DMF, methanol, and acetone and dried to obtain PCN-224. Step S11 was repeated to mass-produce PCN-224;

[0046] S12. 9g of PCN-224 and 60g of toluene were mixed and magnetically stirred for 15min;

[0047] S13. 4g 3 -ammoni apropyltriethoxysilane, 3g silver nitrate, 2g acetic acid were added dropwise to the mixed solution of step S12 in a dropwise manner, and the reaction was carried out under the protection of nitrogen at 90°C for 16h by water bath refluxing;

[0048] S14. The product obtained in step S13 was cooled to room temperature, centrifuged, washed, and dried to obtain modified nanoparticles. Steps S12-S14 were repeated to mass-produce the modified nanoparticles, which were used in the preparation process of the water-based acrylic antibacterial and antiviral coating.

[0049] Example 3, a production process of a water-based acrylic antibacterial and antiviral coating:

[0050] S1. Hydroxyl acrylic resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent, and ethylenediamine were mixed uniformly and stirred at 60°C for 6h;

[0051] S2. Titanium dioxide, defoaming agent, dispersant, leveling agent, and water were sequentially added to the mixed solution obtained in step S1, and the mixture was stirred uniformly at 80°C for 4h to obtain the water-based acrylic antibacterial and antiviral coating;

[0052] In the above preparation process, the amounts of the components are as follows:

[0053]

[0054] 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 a polydimethylsiloxane leveling agent with model number BYK-306; the hydroxyl acrylic resin has model number R916-60; the bisphenol A epoxy resin has model number E-42;

[0055] In the above process, the modified nanoparticles were prepared by the following steps:

[0056] S11. 5g zirconium tetrachloride, 55g benzoic acid, 1g tetrakis (p-carboxyphenyl) porphyrin, and 20ml N,N-dimethylformamide were placed in a reaction kettle and mixed uniformly, and the mixture was subjected to hydrothermal reaction at 160°C for 10h. The obtained product was sequentially washed with DMF, methanol, and acetone and dried to obtain PCN-224. Step S11 was repeated to mass-produce PCN-224;

[0057] S12. 10g PCN-224 and 70g toluene were mixed and magnetically stirred for 15min;

[0058] S13. 4g 3 -ammoniopropyltriethoxysilane, 3g silver nitrate, 2g acetic acid were added dropwise to the mixed solution of step S12 in a dropwise manner, and the reaction was carried out under the protection of nitrogen at 100℃ for 20h in a water bath reflux reaction;

[0059] S14. The product obtained in step S13 was cooled to room temperature, centrifuged, washed, and dried to obtain modified nanoparticles. Steps S12-S14 were repeated to mass-produce the modified nanoparticles, which were used in the preparation process of the water-based acrylic antibacterial and antiviral coating.

[0060] Comparative Example 2: Comparative Example 2 and Example 1 have the following differences, the only difference is that in Comparative Example 2, steps S13 and S14 originally existing in Example 1 are omitted, and in Comparative Example 2, the modified nanoparticles are not added to the antibacterial and antiviral coating, and the added component is PCN-224, and the remaining steps in Comparative Example 2 and Example 1 are exactly the same.

[0061] Comparative Example 2: Comparative Example 2 and Example 1 have the following differences, the only difference is that in Comparative Example 2, steps S13 and S14 originally existing in Example 1 are omitted, and in Comparative Example 2, the modified nanoparticles are not added to the antibacterial and antiviral coating, and the added component is PCN-224, and the remaining steps in Comparative Example 2 and Example 1 are exactly the same.

[0062] Performance test: According to T / CNCIA 03002-2020 standard, influenza A virus (H3N2) was used as test virus to test the antiviral performance of Examples 1-3 and Comparative Examples 1-2, and the test results are shown in Table 1; according to HG / T 3950-2007 standard, Staphylococcus aureus and Escherichia coli were used for antibacterial test, and the test results are shown in Table 2; according to GB / T4893.9-2019 standard, the surface wear resistance of Examples 1-3 was evaluated, and the antibacterial and antiviral performance of the coating after wear (wear thickness was 0.15mm) was tested according to the aforementioned test method, and the results are shown in Table 3:

[0063] Table 1. Antiviral and antibacterial performance test results of Examples 1-3 and Comparative Examples 1-2

[0064]

[0065] Table 2. Antiviral and antibacterial performance test results of Examples 1-3 and Comparative Examples 1-2

[0066]

[0067] Table 3. Wear resistance test results of Examples 1-3

[0068]

[0069] From the test results of Tables 1 and 2, the anti-virus rate and the antibacterial rate of the water-based acrylic antibacterial and antiviral coating prepared in Examples 1-3 are obviously higher than those of Comparative Example 1, which powerfully proves that the provided modified nanoparticles have the characteristics of adjustable pore size, can capture bacteria or viruses by physical adsorption, and the modified nanoparticles can further act as a photodynamic platform to produce reactive oxygen species to destroy the structural integrity of bacteria and viruses, and have excellent and long-term antibacterial and antiviral ability; at the same time, the anti-virus rate and the antibacterial rate of Examples 1-3 are obviously higher than those of Comparative Example 2, which proves that the modification of the nanoparticles can increase the charge density on the surface of the nanoparticles by grafting amino groups and metal anions, improve the capture efficiency of photo-generated carriers, and thus improve the production efficiency of reactive oxygen species, thereby improving the antibacterial and antiviral ability of the coating;

[0070] From the test results of Table 3, the water-based acrylic antibacterial and antiviral coating prepared in the application has good surface wear resistance, and maintains excellent antibacterial and antiviral ability when the wear thickness is within 0.15 mm.

[0071] Although the embodiments of the application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the application, and the scope of the application is defined by the appended claims and their equivalents.

Claims

1. An aqueous acrylic antimicrobial antiviral coating, characterized in that, By mass parts include the following components: hydroxy acrylic acid resin 50-80 parts, bisphenol A epoxy resin 30-40 parts, titanium white 8-12 parts, modified nanoparticles 8-15 parts, isocyanate crosslinking agent 1-5 parts, ethylenediamine 4-8 parts, defoaming agent 3-4 parts, dispersing agent 1-3 parts, leveling agent 2-4 parts, water 20-40 parts; The modified nanoparticles are prepared by the following steps: S11. By mass parts, 0.1-0.5 parts of zirconium tetrachloride, 5-10 parts of benzoic acid, 0.05-0.1 parts of tetra(p-carboxyphenyl)porphyrin, 15-20 parts of N,N-dimethylformamide are placed in a reaction kettle and mixed uniformly, and then hydrothermal reaction is carried out at 120-160℃ for 8-10h, and the obtained product is washed with DMF, methanol and acetone in turn and dried to prepare PCN-224; S12. 8-10 parts of PCN-224 and 50-70 parts of toluene are mixed by mass parts, and magnetic stirring is carried out for 15-20min; S13. 3-4 parts of 3-aminopropyltriethoxysilane, 2-3 parts of silver nitrate and 1-2 parts of acetic acid are added dropwise to the mixed solution of step S12 in a dropwise manner, and then the reaction is carried out under the protection of nitrogen at 80-100℃ for 15-20h by water bath refluxing; S14. The product obtained in step S13 is cooled to room temperature, centrifuged, washed and dried to obtain modified nanoparticles; The isocyanate crosslinking agent is selected from one or more of 1,6-hexane diisocyanate and diphenylmethane diisocyanate; The defoaming agent is TEGO Airex 810; The dispersing agent is LBD-1; The leveling agent is polydimethylsiloxane leveling agent.

2. A process for the production of an aqueous acrylic antimicrobial antiviral coating for the preparation of the aqueous acrylic antimicrobial antiviral coating according to claim 1, characterized in that, The following steps are included: S1. By mass parts, hydroxy acrylic acid resin, bisphenol A epoxy resin, modified nanoparticles, isocyanate crosslinking agent and ethylenediamine are mixed uniformly, and then stirring is carried out at 50-60℃ for 5-8h; S2. The mixed solution prepared in step S1 is added with titanium white, defoaming agent, dispersing agent, leveling agent and water in turn and mixed uniformly, and then stirring is carried out at 70-80℃ for 3-4h to prepare the water-based acrylic acid antibacterial and antiviral coating.

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