Coating with high performance broad-spectrum antibacterial and antiviral properties and application thereof

Abstract

The application relates to a coating with high-performance broad-spectrum antibacterial and antiviral properties and application thereof, and relates to the technical field of functional coating preparation.The coating is obtained by compounding a copper-based coating additive and a base coating.The application prepares a stable high-performance broad-spectrum antibacterial and antiviral coating by adding the copper-based coating additive and taking widely used indoor and outdoor base coatings such as latex paint as a carrier.The coating has the characteristics of excellent antibacterial and antiviral performance, good stability, easy storage and convenient transportation, no influence on aesthetics, green environmental protection and the like, can be widely applied to household, shopping mall, manufacturing and building and the surfaces of many solid objects, and the prepared coating has strong practicability and commerciality.

Description

Technical Field

[0001] This application relates to the field of functional coating preparation technology, and in particular to a coating that combines high performance with broad-spectrum antibacterial and antiviral properties, and its application. Background Technology

[0002] Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) can cause serious infections in some tissues and organs. Pseudomonas aeruginosa (P. aeruginosa), a more difficult-to-kill Gram-negative bacterium, can cause a wide range of diseases, including respiratory, blood, lung, and skin infections. Enterovirus 71 (EV71) can cause hand-foot-and-mouth disease, which can be fatal in severe cases, and Candida albicans can cause oral and skin infections. In particular, an effective way to inhibit solid surface contamination is to make the surface possess microbial inactivation properties, enabling it to rapidly kill microorganisms during the time window between human contact with the surface, or to shorten the lifespan of microorganisms on solid surfaces, thereby reducing the risk of human infection. Therefore, this type of surface treatment method has broad prospects and application value in fields such as environment, medical equipment, construction, antibacterial fabrics, wound dressings and antibacterial coatings.

[0003] Currently, antibacterial and antiviral coatings are receiving increasing attention, and their market demand is gradually expanding. However, existing antibacterial and antiviral coatings suffer from problems such as poor antibacterial and antiviral effects and inadequate stability. Summary of the Invention

[0004] To address the aforementioned issues, this application provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties with its application.

[0005] In a first aspect, this application provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties, wherein the coating is obtained by compounding copper-based coating additives and base coatings;

[0006] The copper-based coating additives include:

[0007] i) Using diatomaceous earth as a carrier;

[0008] ii) At least partially loaded on the surface of the carrier, and / or within the pores of the carrier, the antibacterial component being composed of cuprous oxide and copper pyrithione.

[0009] Furthermore, the microstructure of the copper-based coating additive includes:

[0010] 1) Copper pyridinethione particles with a three-dimensional rod-like structure; and,

[0011] 2) Nano cuprous oxide fragments attached to the surface of the pyridinethione copper particles, wherein the nano cuprous oxide fragments are formed by the destruction of the spherical microstructure of cuprous oxide.

[0012] Furthermore, the ratio of the weight of the diatomaceous earth to the total weight of the cuprous oxide and the copper pyridinethione is 1:(2~8), preferably 1:6.

[0013] Furthermore, the molar ratio of cuprous oxide to copper pyridinethione is 1:(1~3), preferably 1:(1.5~2.5).

[0014] Further, by weight percentage, the amount of the copper-based coating additive added accounts for 0.2% to 1.0% of the weight of the coating; the base coating includes at least one of latex paint, water-based paint, exterior wall paint, and polyurethane coating.

[0015] Furthermore, the preparation method of the copper-based coating additive includes the following steps:

[0016] Diatomaceous earth / cuprous oxide composite particles were prepared by reacting diatomaceous earth as a carrier and water-soluble divalent copper salt as the first copper source and reducing agent.

[0017] The diatomaceous earth / cuprous oxide composite particles were used as a second copper source and reacted with pyridinethione metal salt to generate copper pyridinethione, thus preparing a copper-based coating additive.

[0018] Furthermore, the steps for preparing diatomaceous earth / cuprous oxide composite particles by reacting diatomaceous earth as a carrier and water-soluble divalent copper salt as the first copper source and reducing agent include the following processes:

[0019] The water-soluble divalent copper salt was dissolved in the first ultrapure water, and then diatomaceous earth was added and mixed to obtain the first solution.

[0020] The dispersant was dissolved in the second ultrapure water, and then ethanol was added and mixed to obtain the second solution.

[0021] The second solution is added to the first solution, followed by an aqueous solution of an alkaline regulator with a concentration of 1.6~1.63 mol / L. After forming a copper hydroxide precipitate, an aqueous solution of a reducing agent with a concentration of 0.6~0.9 mol / L is added to carry out a redox reaction to obtain the diatomaceous earth / cuprous oxide composite particles.

[0022] Further, the redox reaction process includes: first adding a reducing agent, then heating to 65 ℃~75 ℃ for 2~3 h to obtain diatomaceous earth / cuprous oxide composite particles; the water-soluble divalent copper salt includes at least one of copper sulfate, copper chloride, copper nitrate and copper acetate; the dispersant includes at least one of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone and polyethylene glycol; the alkaline regulator aqueous solution includes at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and ammonia water; the reducing agent aqueous solution includes at least one of glucose aqueous solution, ascorbic acid aqueous solution, glycine aqueous solution, sodium sulfite aqueous solution and formaldehyde aqueous solution.

[0023] Further, when preparing the first solution, the weight ratio of the diatomaceous earth to the first ultrapure water is 1:(12~96), and the molar concentration of the water-soluble divalent copper salt is 0.262~0.267 mol / L; when preparing the second solution, the weight ratio of the dispersant, the ethanol, and the water is 1:(19.2~24):(38.4~48); and the volume ratio of the alkaline regulator aqueous solution, the reducing agent aqueous solution, and the first ultrapure water is 1:(1.5~2):(1.5~2).

[0024] Further, the step of preparing copper-based coating additives by reacting the diatomaceous earth / cuprous oxide composite particles as a second copper source with pyridinethione metal salt to generate copper pyridinethione includes the following process:

[0025] After the system undergoes a redox reaction and turns brick red for 15-20 minutes, a 0.1-0.9 mol / L aqueous solution of pyridinethione metal salt is added, and the reaction is carried out for 0.5-1.5 h. The mixture is then cooled to room temperature and filtered, washed, and dried to obtain a copper-based coating additive.

[0026] Further, the volume ratio of the pyridinethione metal salt aqueous solution to the first ultrapure water is 1:(1.5~2); the filtration uses a 0.22 µm nylon membrane; the pyridinethione metal salt includes at least one of pyridinethione sodium salt, pyridinethione ammonium salt, and pyridinethione magnesium salt.

[0027] Secondly, this application provides the use of the coatings described in any of the first aspects in the preparation of antibacterial products and / or, antiviral products.

[0028] Thirdly, this application provides a broad-spectrum antimicrobial coating, said coating being prepared using the coating described in any of the first aspects.

[0029] The technical solutions provided in this application have at least the following advantages compared with the prior art:

[0030] This application provides a coating with both high-performance, broad-spectrum antibacterial and antiviral properties. The coating contains a copper-based coating additive (specifically, a copper-based coating additive consisting of diatomaceous earth (DE), cuprous oxide (Cu2O), and copper pyridinethione (CPT) – abbreviated as DE / Cu2O / CPT). This copper-based composite material can be widely compounded with base coatings such as latex paint to form surface coatings for application on many solid surfaces, thereby preparing a stable antibacterial and antiviral coating. It can rapidly and effectively kill bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans, as well as enterovirus 71, within 2 hours. The coating exhibits good stability; the copper-based composite material does not significantly alter the color of the coating at effective doses. It releases no odorous gases, posing minimal environmental harm and meeting environmental protection requirements. This coating possesses broad-spectrum microbial inactivation properties, effectively inhibiting solid surface contamination. It rapidly kills microorganisms during the time window between human contact with the solid surface or shortens their lifespan, reducing the potential risk of pathogen transmission and minimizing the likelihood of infection in daily life. It can be widely applied to various solid object surfaces in homes, shopping malls, manufacturing, and construction, and the prepared coating exhibits strong practicality and commercial viability. Specifically, this invention achieves the following four objectives:

[0031] 1) It can quickly and effectively inactivate bacteria and viruses within 2 hours, with excellent antibacterial and antiviral properties; 2) It can be directly applied to the surfaces of many solid objects in homes, shopping malls, manufacturing, and construction, with a wide range of applications; 3) It has good stability and does not change the color of the paint at an effective addition level of no more than 1%, making it easy to store and transport without affecting the aesthetics; 4) Compared with organic antibacterial agents, it does not release odorous gases, has less environmental harm, and meets environmental protection requirements. Attached Figure Description

[0032] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.

[0033] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0034] Figure 1 This is a schematic flowchart illustrating the preparation method of the copper-based coating additive provided in the embodiments of this application.

[0035] Figure 2 This is a schematic diagram of the operation process for preparing copper-based coating additives in the embodiments of this application.

[0036] Figure 3 The images show SEM images of copper-based coating additives, pure CPT, and pure Cu2O obtained with different amounts of sodium pyridinethione in the test examples of this application.

[0037] Figure 4 This is a SEM image of the copper-based coating additive obtained when the ratio of Cu2O to CPT is 1:1.8 in the test example of this application.

[0038] Figure 5 The image shows the EDS and mapping results of the copper-based coating additive obtained in Example 4 of the test examples of this application.

[0039] Figure 6 The images show the XRD results of copper-based coating additives, pure CPT, and pure Cu2O prepared under different embodiments in the test examples of this application.

[0040] Figure 7 This is a diagram showing the color change process of copper-based coating additives, pure CPT, and pure Cu2O prepared under different embodiments in the test examples of this application.

[0041] Figure 8 This is a color difference comparison chart for Cu2O and CPT ratios of 1:1.5 and 1:1.8 in the test examples of this application.

[0042] Figure 9 This represents the macroscopic color of Cu2O in the test examples of this application.

[0043] Figure 10 The macroscopic color when the ratio of Cu2O to CPT in the test examples of this application is 1:1.0. Figure 1 .

[0044] Figure 11 The macroscopic color when the ratio of Cu2O to CPT in the test examples of this application is 1:1.0. Figure 2 .

[0045] Figure 12 The macroscopic color is the ratio of Cu2O to CPT of 1:1.5 in Example 1 of the test examples of this application.

[0046] Figure 13 The macroscopic color is the ratio of Cu2O to CPT of 1:1.8 in the test examples of this application.

[0047] Figure 14 This is the macroscopic color of CPT in the test examples of this application.

[0048] Figure 15 The image shows a comparison of the antibacterial effects of copper-based coating additives, monovalent cuprous oxide, divalent copper pyridinethione prepared by conventional methods, and copper pyridinethione prepared by physical mixing, as well as the antibacterial effects of these substances, as tested in the examples of this application.

[0049] Figure 16 This is a schematic diagram of the operation process for testing the antibacterial effect of the coating in the test examples of this application.

[0050] Figure 17 This is a simplified schematic diagram of the antibacterial treatment of the coating in the test examples of this application.

[0051] Figure 18 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 1 of this application at different addition amounts against Escherichia coli.

[0052] Figure 19 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 1 of this application at different addition amounts against Staphylococcus aureus.

[0053] Figure 20 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 1 of this application at different addition amounts against Pseudomonas aeruginosa.

[0054] Figure 21 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 1 of this application at different addition amounts against Candida albicans.

[0055] Figure 22 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 2 of this application at different addition amounts against Escherichia coli.

[0056] Figure 23 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 2 of this application at different addition amounts against Staphylococcus aureus.

[0057] Figure 24 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 2 of this application at different addition amounts against Pseudomonas aeruginosa.

[0058] Figure 25 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 2 of this application at different addition amounts against Candida albicans.

[0059] Figure 26 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 3 of this application at different addition amounts against Escherichia coli.

[0060] Figure 27 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 3 of this application at different addition amounts against Staphylococcus aureus.

[0061] Figure 28 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 3 of this application at different addition amounts against Pseudomonas aeruginosa.

[0062] Figure 29 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 3 of this application at different addition amounts against Candida albicans.

[0063] Figure 30 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 4 of this application at different addition amounts against Escherichia coli.

[0064] Figure 31 The image shows the antibacterial results of coatings prepared with the copper-based coating additive obtained in Example 4 of this application at different addition amounts against Staphylococcus aureus.

[0065] Figure 32 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 4 of this application at different addition amounts against Pseudomonas aeruginosa.

[0066] Figure 33 The image shows the antibacterial results of the coatings prepared with the copper-based coating additive obtained in Example 4 of this application at different addition amounts against Candida albicans.

[0067] Figure 34 The antiviral evaluation results of the coatings obtained in Examples 5-8 are presented in the test examples of this application. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0069] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0070] In a first aspect, this application provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties, wherein the coating is obtained by compounding copper-based coating additives and base coatings;

[0071] The copper-based coating additives include:

[0072] i) Using diatomaceous earth as a carrier;

[0073] ii) At least partially loaded on the surface of the carrier, and / or within the pores of the carrier, the antibacterial component being composed of cuprous oxide and copper pyrithione.

[0074] This application provides a coating with both high-performance, broad-spectrum antibacterial and antiviral properties. The coating contains a copper-based coating additive (specifically, a copper-based coating additive consisting of diatomaceous earth (DE), cuprous oxide (Cu2O), and copper pyridinethione (CPT) – abbreviated as DE / Cu2O / CPT). This copper-based composite material can be widely compounded with base coatings such as latex paint to form surface coatings for application on many solid surfaces, thereby preparing a stable antibacterial and antiviral coating. It can rapidly and effectively kill bacteria such as Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans, as well as enterovirus 71, within 2 hours. The coating exhibits good stability; the copper-based composite material does not significantly alter the color of the coating at effective doses. It releases no odorous gases, posing minimal environmental harm and meeting environmental protection requirements. This coating possesses broad-spectrum microbial inactivation properties, effectively inhibiting solid surface contamination. It rapidly kills microorganisms during the time window between human contact with the solid surface or shortens their lifespan, reducing the potential risk of pathogen transmission and minimizing the likelihood of infection in daily life. It can be widely applied to various solid object surfaces in homes, shopping malls, manufacturing, and construction, and the prepared coating exhibits strong practicality and commercial viability. Specifically, this invention achieves the following four objectives:

[0075] 1) It can quickly and effectively inactivate bacteria and viruses within 2 hours, with excellent antibacterial and antiviral properties; 2) It can be directly applied to the surfaces of many solid objects in homes, shopping malls, manufacturing, and construction, with a wide range of applications; 3) It has good stability and does not change the color of the paint at an effective addition level of no more than 1%, making it easy to store and transport without affecting the aesthetics; 4) Compared with organic antibacterial agents, it does not release odorous gases, has less environmental harm, and meets environmental protection requirements.

[0076] In some specific embodiments, the microstructure of the copper-based coating additive includes:

[0077] 1) Copper pyridinethione particles with a three-dimensional rod-like structure; and,

[0078] 2) Nano cuprous oxide fragments attached to the surface of the pyridinethione copper particles, wherein the nano cuprous oxide fragments are formed by the destruction of the spherical microstructure of cuprous oxide.

[0079] In some specific embodiments, the ratio of the weight of the diatomaceous earth to the total weight of the cuprous oxide and the copper pyridinethione is 1:(2~8), preferably 1:6.

[0080] In some specific embodiments, the molar ratio of cuprous oxide to copper pyridinethione is 1:(1~3), preferably 1:(1.5~2.5).

[0081] In some specific embodiments, the amount of the copper-based coating additive added accounts for 0.2% to 1.0% of the weight of the coating by weight; the base coating includes at least one of latex paint, water-based paint, exterior wall paint, and polyurethane coating.

[0082] In some specific embodiments, such as Figure 1 As shown, the preparation method of the copper-based coating additive includes the following steps:

[0083] Diatomaceous earth / cuprous oxide composite particles were prepared by reacting diatomaceous earth as a carrier and water-soluble divalent copper salt as the first copper source and reducing agent.

[0084] The diatomaceous earth / cuprous oxide composite particles were used as a second copper source and reacted with pyridinethione metal salt to generate copper pyridinethione, thus preparing a copper-based coating additive.

[0085] This invention uses insoluble monovalent copper oxide as a copper source and reacts it with pyridinethione metal salt to prepare copper pyridinethione. Based on this, the ratio of Cu2O to CPT in the composite material is controlled by adjusting the amount of pyridinethione metal salt, ultimately achieving control over different microstructures and macroscopic color depths of the composite material, providing a new approach for the preparation of copper-based coating additives.

[0086] In some specific embodiments, the steps for preparing diatomaceous earth / cuprous oxide composite particles by using diatomaceous earth as a carrier, water-soluble divalent copper salt as a first copper source and reducing agent include the following processes:

[0087] The water-soluble divalent copper salt was dissolved in the first ultrapure water, and then diatomaceous earth was added and mixed to obtain the first solution.

[0088] The dispersant was dissolved in the second ultrapure water, and then ethanol was added and mixed to obtain the second solution.

[0089] The second solution is added to the first solution, followed by an aqueous solution of an alkaline regulator with a concentration of 1.6~1.63 mol / L. After forming a copper hydroxide precipitate, an aqueous solution of a reducing agent with a concentration of 0.6~0.9 mol / L is added to carry out a redox reaction to obtain the diatomaceous earth / cuprous oxide composite particles.

[0090] In some specific embodiments, the redox reaction process includes: first adding a reducing agent, then heating to 65 ℃~75 ℃ for 2~3 h to obtain diatomaceous earth / cuprous oxide composite particles; the water-soluble divalent copper salt includes at least one of copper sulfate, copper chloride, copper nitrate and copper acetate; the dispersant includes at least one of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone and polyethylene glycol; the alkaline regulator aqueous solution includes at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and ammonia water; the reducing agent aqueous solution includes at least one of glucose aqueous solution, ascorbic acid aqueous solution, glycine aqueous solution, sodium sulfite aqueous solution and formaldehyde aqueous solution.

[0091] In some specific embodiments, when preparing the first solution, the weight ratio of the diatomaceous earth to the first ultrapure water is 1:(12~96), and the molar concentration of the water-soluble divalent copper salt is 0.262~0.267 mol / L; when preparing the second solution, the weight ratio of the dispersant, the ethanol, and the water is 1:(19.2~24):(38.4~48); and the volume ratio of the alkaline regulator aqueous solution, the reducing agent aqueous solution, and the first ultrapure water is 1:(1.5~2):(1.5~2).

[0092] In some specific embodiments, the steps for preparing copper-based coating additives by reacting the diatomaceous earth / cuprous oxide composite particles as a second copper source with pyridinethione metal salt to generate copper pyridinethione include the following processes:

[0093] After the system undergoes a redox reaction and turns brick red for 15-20 minutes, a 0.1-0.9 mol / L aqueous solution of pyridinethione metal salt is added, and the reaction is carried out for 0.5-1.5 h. The mixture is then cooled to room temperature and filtered, washed, and dried to obtain a copper-based coating additive.

[0094] In some specific embodiments, the volume ratio of the pyridinethione metal salt aqueous solution to the first ultrapure water is 1:(1.5~2); the filtration uses a 0.22 µm nylon membrane; the pyridinethione metal salt includes at least one of pyridinethione sodium salt, pyridinethione ammonium salt, and pyridinethione magnesium salt.

[0095] In some specific embodiments, as the amount of the pyridinethione metal salt gradually increases, the color change process of the copper-based coating additive includes: from brick red, milky yellow, yellowish green, green to dark green.

[0096] It should be noted that, unless otherwise specified or indicated, the raw materials used in the preparation method of the high-performance broad-spectrum antibacterial and antiviral coating provided in this application embodiment can be commercially available products. Furthermore, unless otherwise specified or indicated, the operational steps and parameters involved in the preparation process of the high-performance broad-spectrum antibacterial and antiviral coating provided in this application embodiment can be carried out according to existing preparation processes or using existing equipment.

[0097] Secondly, based on the same inventive concept, this application provides the use of the coatings described in any of the first aspects in the preparation of antibacterial products and / or, antiviral products.

[0098] The coatings provided in this application can be widely used on the surfaces of many solid objects in homes, shopping malls, manufacturing, and construction. The prepared coatings have strong practicality and commercial applicability, and can be used to produce equipment, devices, and other antibacterial products, and / or antiviral products containing this broad-spectrum antimicrobial coating.

[0099] Thirdly, based on the same inventive concept, this application provides a broad-spectrum antimicrobial coating, said coating being made using the coating described in any of the first aspects.

[0100] The broad-spectrum antimicrobial coating provided in the embodiments of this application is made based on the coating described in any one of the first aspects, and therefore has at least the beneficial effects described in the first aspect, which will not be elaborated here.

[0101] The present application is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the application. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If there is no corresponding national standard, then general international standards, conventional conditions, or conditions recommended by the manufacturer are followed.

[0102] Example 1

[0103] This example provides a copper-based coating additive and its preparation method, such as... Figure 2 As shown, it includes the following steps:

[0104] Dissolve 15.72 g of copper sulfate pentahydrate in 240 mL of ultrapure water, add 2.5 g of diatomaceous earth, and stir at 200 rpm for 10 min at room temperature until thoroughly mixed. Add 25 g of sodium dodecyl sulfate to 960 mL of ultrapure water, then add 480 mL of anhydrous ethanol. Stir at 200 rpm for 5 min at room temperature until thoroughly mixed. Mix the two solutions together at room temperature and continue stirring at 200 rpm for 1 min. Then add 120 mL of a 1.6 mol / L sodium hydroxide aqueous solution. After the addition is complete, add 240 mL of a 0.4 mol / L glucose aqueous solution. After the addition is complete, raise the temperature to 70 °C. After the reaction color turns brick red for 15 min, add 120 mL of a 0.15 mol / L sodium pyrithione aqueous solution and react for 0.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered under reduced pressure through a 0.22 µm nylon membrane, washed twice each with ultrapure water and anhydrous ethanol, dried under vacuum at 60 °C, and the sample was collected to obtain a copper-based coating additive. Specifically, in the copper-based coating additive prepared in this example, the mass ratio of diatomaceous earth to (Cu₂O + CPT) was 1:6; wherein the molar ratio of Cu₂O to CPT was 1:1.

[0105] Example 2

[0106] This example provides a copper-based coating additive and its preparation method, including the following steps:

[0107] Dissolve 7.68 g of copper sulfate pentahydrate in 120 mL of ultrapure water, add 3.2 g of diatomaceous earth, and stir at 200 rpm for 10 min at room temperature until thoroughly mixed. Add 12 g of sodium dodecyl sulfate to 480 mL of ultrapure water, followed by 240 mL of anhydrous ethanol. Stir at 200 rpm for 5 min at room temperature until thoroughly mixed. Mix the two solutions together at room temperature and continue stirring at 200 rpm for 1 min. Then add 60 mL of a 1.61 mol / L sodium hydroxide aqueous solution. After the addition is complete, add 120 mL of a 0.3 mol / L glucose aqueous solution. After the addition is complete, raise the temperature to 65 °C. After the reaction color turns brick red for 15 min, add 60 mL of a 0.5 mol / L sodium pyrithione aqueous solution and react for 1 h. After the reaction was completed, the mixture was cooled to room temperature, filtered under reduced pressure through a 0.22 µm nylon membrane, washed twice each with ultrapure water and anhydrous ethanol, dried under vacuum at 60 °C, and the sample was collected to obtain a copper-based coating additive. Specifically, in the copper-based coating additive prepared in this example, the mass ratio of diatomaceous earth to (Cu₂O + CPT) was 1:6; wherein the molar ratio of Cu₂O to CPT was 1:2.

[0108] Example 3

[0109] This example provides a copper-based coating additive and its preparation method, including the following steps:

[0110] Dissolve 23.58 g of copper sulfate pentahydrate in 360 mL of ultrapure water, add 5.1 g of diatomaceous earth, and stir at 200 rpm for 10 min at room temperature until thoroughly mixed. Add 37 g of sodium dodecyl sulfate to 1400 mL of ultrapure water, then add 720 mL of anhydrous ethanol. Stir at 200 rpm for 5 min at room temperature until thoroughly mixed. Mix the two solutions together at room temperature and continue stirring at 200 rpm for 1 min. Then add 180 mL of a 1.61 mol / L sodium hydroxide aqueous solution. After the addition is complete, add 360 mL of a 0.5 mol / L glucose aqueous solution. After the addition is complete, raise the temperature to 70 °C. After the reaction color turns brick red for 15 min, add 180 mL of a 0.6 mol / L sodium pyrithione aqueous solution and react for 1.5 h. After the reaction was completed, the mixture was cooled to room temperature, filtered under reduced pressure through a 0.22 µm nylon membrane, washed twice each with ultrapure water and anhydrous ethanol, dried under vacuum at 60 °C, and the sample was collected to obtain a copper-based coating additive. Specifically, in the copper-based coating additive prepared in this example, the mass ratio of diatomaceous earth to (Cu₂O + CPT) was 1:6; wherein the molar ratio of Cu₂O to CPT was 1:2.5.

[0111] Example 4

[0112] This example provides a copper-based coating additive and its preparation method, including the following steps:

[0113] Dissolve 10.48 g of copper sulfate pentahydrate in 160 mL of ultrapure water, add 3.1 g of diatomaceous earth, and stir at 200 rpm for 10 min at room temperature until thoroughly mixed. Add 20 g of sodium dodecyl sulfate to 640 mL of ultrapure water, followed by 320 mL of anhydrous ethanol. Stir at 200 rpm for 5 min at room temperature until thoroughly mixed. Mix the two solutions together at room temperature and continue stirring at 200 rpm for 1 min. Then add 80 mL of a 1.60 mol / L sodium hydroxide aqueous solution. After the addition is complete, add 160 mL of a 0.4 mol / L glucose aqueous solution. When half of the glucose aqueous solution has been added, raise the temperature to 75 °C. After the reaction color turns brick red for 15 min, add 80 mL of a 0.5 mol / L sodium pyrithione aqueous solution and react for 1 h. After the reaction was completed, the mixture was cooled to room temperature, filtered under reduced pressure through a 0.22 µm nylon membrane, washed twice each with ultrapure water and anhydrous ethanol, dried under vacuum at 60 °C, and the sample was collected to obtain a copper-based coating additive. Specifically, in the copper-based coating additive prepared in this example, the mass ratio of diatomaceous earth to (Cu₂O + CPT) was 1:4; wherein the molar ratio of Cu₂O to CPT was 1:2.0.

[0114] Example 5

[0115] This example provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties. The copper-based coating additive is added at 1% by weight of the base coating. The preparation method includes the following steps:

[0116] 0.1 g of the copper-based coating additive obtained in Example 1 and 10 g of latex paint (purchased from Guangdong Carpoly Chemical Group Co., Ltd.) were placed in a ball mill jar for physical mixing at a speed of 400 rpm / min for 30 min to obtain the coating.

[0117] This example also provides a coating with broad-spectrum antimicrobial activity, the coating being prepared using the coating material described above.

[0118] Example 6

[0119] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 5 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 2; the remaining steps and parameters are the same.

[0120] Example 7

[0121] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 5 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 3; the remaining steps and parameters are the same.

[0122] Example 8

[0123] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 5 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 4; the remaining steps and parameters are the same.

[0124] Example 9

[0125] This example provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties. The amount of copper-based coating additive added, by weight percentage, is 0.75% of the base coating. The preparation method includes the following steps:

[0126] 0.075 g of the copper-based coating additive obtained in Example 1 and 10 g of latex paint (purchased from Guangdong Carpoly Chemical Group Co., Ltd.) were placed in a ball mill jar for physical mixing at a speed of 400 rpm / min for 30 min to obtain the coating.

[0127] This example also provides a coating with broad-spectrum antimicrobial activity, the coating being prepared using the coating material described above.

[0128] Example 10

[0129] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 9 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 2; the remaining steps and parameters are the same.

[0130] Example 11

[0131] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 9 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 3; the remaining steps and parameters are the same.

[0132] Example 12

[0133] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 9 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 4; the remaining steps and parameters are the same.

[0134] Example 13

[0135] This example provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties. The copper-based coating additive is added at 0.5% by weight of the base coating. The preparation method includes the following steps:

[0136] 0.05 g of the copper-based coating additive obtained in Example 1 and 10 g of latex paint (purchased from Guangdong Carpoly Chemical Group Co., Ltd.) were placed in a ball mill jar for physical mixing at a speed of 400 rpm / min for 30 min to obtain the coating.

[0137] This example also provides a coating with broad-spectrum antimicrobial activity, the coating being prepared using the coating material described above.

[0138] Example 14

[0139] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 13 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 2; the remaining steps and parameters are the same.

[0140] Example 15

[0141] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 13 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 3; the remaining steps and parameters are the same.

[0142] Example 16

[0143] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 13 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 4; the remaining steps and parameters are the same.

[0144] Example 17

[0145] This example provides a coating that combines high-performance broad-spectrum antibacterial and antiviral properties. The amount of copper-based coating additive added, by weight percentage, is 0.25% of the base coating. The preparation method includes the following steps:

[0146] 0.025 g of the copper-based coating additive obtained in Example 1 and 10 g of latex paint (purchased from Guangdong Carpoly Chemical Group Co., Ltd.) were placed in a ball mill jar for physical mixing at a speed of 400 rpm / min for 30 min to obtain the coating.

[0147] This example also provides a coating with broad-spectrum antimicrobial activity, the coating being prepared using the coating material described above.

[0148] Example 18

[0149] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 17 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 2; the remaining steps and parameters are the same.

[0150] Example 19

[0151] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 17 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 3; the remaining steps and parameters are the same.

[0152] Example 20

[0153] This example provides a coating with both high performance and broad-spectrum antibacterial and antiviral properties, as well as its preparation method and coating. The only difference from Example 17 is that the copper-based coating additive obtained in Example 1 is adjusted to the copper-based coating additive obtained in Example 4; the remaining steps and parameters are the same.

[0154] Test Example 1

[0155] In this example, the copper-based coating additives obtained in Examples 1-4 were characterized and analyzed for their microstructure. The scanning electron microscopy results are as follows: Figure 3 As shown, Figure 3 SEM images of copper-based coating additives, pure CPT, and pure Cu2O obtained with different amounts of sodium pyridinethione are shown below. Among them: (a) is the SEM image of the copper-based coating additive obtained in Example 1; (b) is the SEM image of the copper-based coating additive obtained in Example 2; (c) is the SEM image of the copper-based coating additive obtained in Example 3; (d) is the SEM image of the copper-based coating additive obtained in Example 4; (e) is the SEM image of pure CPT particles; and (f) is the SEM image of pure Cu2O particles.

[0156] Depend on Figure 3 It can be seen that: 1) As Figure 3 As shown in (f), pure Cu₂O particles exhibit a regular spherical structure with a particle size of approximately 1 µm, are uniformly distributed, and show no agglomeration. Figure 3 As shown in (e), pure CPT particles exhibit a long, rod-like structure with a particle size of approximately 5 µm and a smooth surface. Figure 3 (a) Figure 3 (b) and Figure 3As shown in (c), both long, rod-shaped CPT particles and Cu2O particles exist in the copper-based coating additive. Specifically, the spherical structure of the Cu2O particles is no longer intact but disrupted, resulting in smaller, irregularly shaped fragments. Furthermore, some Cu2O fragments adhere to the surface of the CPT particles, making the CPT particle surface no longer smooth. These results demonstrate that nano-Cu2O particles can be successfully reacted with sodium pyridinethione to prepare CPT particles. 2) With the increase of sodium pyridinethione dosage, from Example 1 to Example 3, the number of Cu2O particles in the copper-based coating additive gradually decreases, the regular spherical structure of Cu2O gradually decreases, while the number of long, rod-shaped CPT particles gradually increases. Figure 3 (b) and Figure 3 As shown in (d), when the ratio of Cu2O to CPT particles is the same, there is no significant difference in the structure of the copper-based coating additives in Examples 2 and 4. This result proves that the structure and morphology of the copper-based coating additive can be controlled by adjusting the amount of sodium pyridinethione added, thereby controlling the ratio of Cu2O to CPT in the copper-based coating additive. 3) When the ratio of Cu2O to CPT is 1:1, there is relatively more cuprous oxide in the composite material, and its spherical structure is relatively more complete, with only some cuprous oxide structure being damaged; while the rod-shaped copper pyridinethione is less. In addition, based on Example 1, when the ratio of Cu2O to CPT is adjusted to 1:1.8, as shown in Example 4, the structure of the copper-based coating additive is significantly different. Figure 4 As shown, the composite material contains relatively less cuprous oxide, and its spherical structure is almost undetectable. The cuprous oxide structure is essentially destroyed, becoming smaller fragments attached to the surface of copper pyrithione, while rod-shaped copper pyrithione particles are relatively more abundant. This is because the increased amount of sodium pyrithione leads to a greater amount of cuprous oxide reacting. Furthermore, from... Figure 3 (b) Comparison revealed that its morphology was basically similar to that of Cu₂O and CPT in a 1:2 ratio, but the content differed. When the Cu₂O and CPT ratio was 1:2.5, the cuprous oxide in the composite material was relatively less, its spherical structure was almost impossible to detect, and the structure of cuprous oxide was basically destroyed, becoming smaller fragments attached to the surface of copper pyrithione, while rod-shaped copper pyrithione was relatively more abundant and its structure was more obvious. When sodium pyrithione was in excess, the cuprous oxide was almost completely consumed, resulting in sodium pyrithione with a regular morphology and high purity.

[0157] In summary, the microstructure of the composite material provided by this invention falls between cuprous oxide and copper pyrithione as the amount of sodium pyrithione increases. With the increase of sodium pyrithione, cuprous oxide is gradually consumed and distributed on the surface of copper pyrithione as smaller fragment particles, while when sodium pyrithione is in excess, copper pyrithione is completely formed. Overall, when the amount of sodium pyrithione added is controlled to be higher than 0.1 mol / L and lower than 0.4 mol / L, the microstructure of the composite material tends to show the presence of complete spherical cuprous oxide, with a morphology between cuprous oxide and copper pyrithione. When the amount of sodium pyrithione added is controlled to be higher than 0.4 mol / L and lower than 0.82 mol / L, the microstructure of the composite material tends to show the presence of a large number of cuprous oxide fragments distributed on the surface of pyrithione. When the amount of sodium pyrithione added is controlled to be higher than 0.82 mol / L, its micromorphology is close to or equivalent to the structure of pure copper pyrithione.

[0158] Test Example 2

[0159] This example analyzes the EDS and mapping results of the copper-based coating additive prepared in Example 4, such as... Figure 5 As shown, where: Figure 5 (a) Figure 5 (c) Figure 5 (b) Figure 5 (d) Figure 5 (e) Figure 5 (f) Figure 5 (g) Figure 5 (h) shows the mapping results for the DE / Cu2O / CPT composite particles. Figure 5 (b) represents the percentage content of each atom.

[0160] Depend on Figure 5 It can be seen that, taking the copper-based coating additive prepared in Example 4 as an example, the elemental composition of the copper-based coating additive was analyzed by EDS. The chemical formula of CPT is known to be Cu(C5H4NOS)2. Based on the molecular formula of CPT, the theoretical percentage content of S atoms and Cu atoms in CPT should be the same, but... Figure 3The compositional analysis results in (b) show that in the selected region, the content of S atoms is approximately 7.18%, while the content of Cu atoms is approximately 16.37%, which is more than half higher, further proving the presence of both Cu2O particles and CPT particles in the copper-based coating additive. Furthermore, as shown in Figures (a) and (d), the purple area represents the presence of Si atoms, originating from diatomaceous earth (whose main component is SiO2). As shown in Figures (c), (g), (h), and (e), Cu, S, N, and O atoms were detected, all distributed on elongated rods. The O atoms may originate from DE and Cu2O, the Cu atoms from CPT and Cu2O, while the S and N atoms can only originate from CPT. These results further demonstrate the successful preparation of the DE / Cu2O / CPT composite particles and reveal their morphology and distribution.

[0161] Test Example 3

[0162] XRD results of copper-based coating additives prepared under different examples were analyzed with varying amounts of the organic ligand sodium pyridinethione. The XRD results for Examples 1, 2, and 3, as well as pure CPT and pure Cu2O, are shown below. Figure 6 As shown.

[0163] Depend on Figure 6 It can be seen that the XRD diffraction peak positions of the three different ratios of diatomaceous earth / Cu2O / CPT composite particles are completely consistent, and characteristic diffraction peaks of CPT and Cu2O appear. Furthermore, from Example 1 to Example 3, as the ratio of Cu2O to CPT in the diatomaceous earth / Cu2O / CPT composite particles gradually decreases, the intensity of some XRD diffraction peaks of the CPT particles gradually increases. When Cu2O:CPT=1:1, the diffraction peak at 2θ=9° is almost undetectable. Conversely, the diffraction peak intensities of Cu2O at the 36.50°-(111) crystal plane, 42.40°-(200) crystal plane, and 61.52°-(220) crystal plane gradually decrease. These results indicate that the successful preparation of the diatomaceous earth / Cu2O / CPT composite particles and the compositional changes with different ratios are consistent with the SEM results. This result further demonstrates that the structure and morphology of copper-based coating additives can be controlled by adjusting the amount of sodium pyridinethione, thereby controlling the ratio of Cu2O to CPT.

[0164] Test Example 4

[0165] This example examines the macroscopic color changes of copper-based coating additives prepared in different embodiments as the amount of the organic ligand—sodium pyrithione—decies. Overall, the color change trend basically matches the structural changes. With the increase of sodium pyrithione, the color of the composite material falls between cuprous oxide and copper pyrithione. The color changes of the copper-based coating additives, pure CPT, and pure Cu2O prepared in different embodiments are shown below. Figure 7 As shown, two other ratios with large color differences are, for example... Figure 8 As shown.

[0166] Furthermore, this invention has discovered through research that: 1) when the amount of sodium pyridinethione added is controlled to be higher than 0.1 mol / L and lower than 0.4 mol / L, the color of the composite material is as follows: Figure 9 and Figure 10 The color of the composite material varies between these values. 2) Controlling the addition of sodium pyrithione to be above 0.4 mol / L and below 0.82 mol / L will result in a color range similar to... Figure 11 , Figure 12 , Figure 13 , Figure 14 The changes between them.

[0167] Test Example 5

[0168] This example examines the antibacterial properties of the DE / Cu2O / CPT composite material prepared in Example 2. The antibacterial effects of monovalent cuprous oxide, divalent copper pyridinethione, and copper pyridinethione prepared by conventional methods, as well as physically mixed formulations, are compared using the inhibition zone method. The size of the inhibition zone demonstrates the superior antibacterial properties of the composite material. The test results are as follows: Figure 15 As shown, Figure 15In the figures: 1 shows the antibacterial results of pure cuprous oxide; 2 shows the antibacterial results of pure pyridine copper sulfate; 3 shows the antibacterial results of pyridine copper sulfate prepared by conventional methods; 4 shows the antibacterial results of a mixture obtained by physically mixing pure cuprous oxide and pure pyridine copper sulfate; 5 shows the antibacterial results of the DE / Cu2O / CPT composite material prepared in Example 2; and 6 shows the antibacterial results of PBS. The preparation of pyridine copper sulfate by conventional methods includes the following steps: a certain amount of soluble copper salt, such as copper chloride or copper sulfate, is directly dissolved in deionized water containing a surfactant. Then, sodium pyridinethione is dissolved in deionized water, and sodium hydroxide is added to adjust the pH to 10-12. Finally, the sodium pyridinethione aqueous solution is added to the aqueous solution containing copper salt, the temperature is raised to 75°C, and the reaction is carried out for 1-2 hours. After cooling to room temperature, the mixture is filtered, washed, and dried at 60°C. The difference between the conventional method and the method provided in this invention is that the conventional method involves sodium pyridinethione directly coordinating with divalent copper ions. This method does not involve changes in valence state; adjusting the amount of sodium pyrithione only controls the content of copper pyrithione produced, without the presence of cuprous oxide, making it a single material. This method involves coordination between pyrithione salt and cuprous oxide, which involves changes in valence state (because copper in copper pyrithione is divalent). Adjusting the amount of pyrithione salt added can yield composite materials with different proportions of cuprous oxide and copper pyrithione.

[0169] Depend on Figure 15 It can be concluded that: 1) The comparison between 2, 3, and 6 shows that the copper pyridinethione prepared using cuprous oxide compounds has a relatively higher antibacterial effect than conventional copper pyridinethione; 2) The comparison between 1, 2, 5, and 6 effectively demonstrates the superior antibacterial properties of copper-based coating additives, namely the synergistic enhancing effect of monovalent and divalent copper; 3) The comparison between 4, 5, and 6 illustrates that copper-based coating additives differ from simple physical mixtures of cuprous oxide and copper pyridinethione. Their structural characteristics, through smaller nanoparticle structures, further enhance the antibacterial effect of copper-based coating additives.

[0170] Test Example 6

[0171] In this example, the coatings obtained in Examples 5 to 20 were prepared into dried coatings. The broad-spectrum antibacterial properties of the coatings were evaluated using a simulated drying method. In addition, the inactivation effect against enterovirus 71 was also tested. The operation process is illustrated in the diagram below. Figure 16As shown. Specifically, the process includes the following steps: 1) Pretreatment of the glass slide: Cut the glass slide into 2 cm × 2 cm × 1 mm pieces, soak in anhydrous ethanol for 1 h, then irradiate under ultraviolet light for 1 h, and allow it to air dry naturally for later use; 2) Preparation of the coating: Apply an appropriate amount of coating (specifically 0.15 g) to the glass slide (2 cm × 2 cm × 1 mm), coat evenly, and air dry naturally in a sterile laminar flow hood for 12 h, then place it in a CO2 incubator for later use; the control group is the coating without copper-based additives, treated in the same way as above. 3) Antibacterial treatment of the coating: Taking the copper-based additive prepared in Example 1 with an addition amount of 1% as an example (i.e., the coating obtained in Example 5), its simplified schematic diagram is shown below. Figure 17 As shown. 30 µL of bacterial suspension was coated onto the prepared coating and placed in a sterilized biochemical incubator, maintaining a humidity of 43% and a temperature of 23 °C. After 2 h, 300 µL of sterile PBS was transferred to the coating for neutralization and soaking for 30 min. Then, 100 µL of the neutralization solution was spread onto a plate, inverted, and incubated in a CO2 incubator for 24 h. Three parallel samples were prepared. Finally, the bacterial growth on the plates was recorded; specifically, the bacterial strains used included *Escherichia coli*, *Staphylococcus aureus*, *Pseudomonas aeruginosa*, and *Candida albicans*. The corresponding antibacterial experiments of the coating were performed following the same procedure as described above. Similarly, Examples 6 to 20 were performed using the same experiments as in Example 5.

[0172] Analysis of the broad-spectrum antibacterial results of the coating:

[0173] like Figures 18-33 As shown, the coatings prepared in Examples 5-20, after being exposed to the tested bacterial strains for 2 hours, exhibited antibacterial effects against *Escherichia coli*, *Pseudomonas aeruginosa*, *Staphylococcus aureus*, and *Candida albicans*. This indicates that the coatings prepared according to the present invention have good bactericidal effects against these four pathogenic microorganisms. When the amount of copper-based coating additive is higher than 0.75%, they also show good inhibitory effects against all four microorganisms. Therefore, the coatings prepared with the coating provided by the present invention (addition amount ≈ 1%), after being exposed to the test strains for 2 hours, achieve an inactivation rate of up to 99% against pathogenic microorganisms such as *Escherichia coli*, *Staphylococcus aureus*, *Pseudomonas aeruginosa*, or *Candida albicans*. This meets or exceeds Level I of the national standard GB / T 21866-2008 "Determination of Antibacterial Properties and Antibacterial Effects of Antibacterial Coatings (Films)" and the group standard T / GDTL 011-2020 "Antibacterial and Antiviral Coatings". The broad-spectrum antibacterial effect of the coatings prepared using the copper-based coating additive obtained in Example 1 at different addition amounts is as follows: Figure 18 , Figure 19 , Figure 20 and Figure 21 As shown; the broad-spectrum antibacterial effect of coatings prepared using the copper-based coating additive obtained in Example 2 at different addition amounts is as follows: Figure 22 , Figure 22 , Figure 23 and Figure 24 As shown; the broad-spectrum antibacterial effect of coatings prepared using the copper-based coating additive obtained in Example 3 at different addition amounts is as follows: Figure 25 , Figure 26 , Figure 27 and Figure 28 As shown; the broad-spectrum antibacterial effect of coatings prepared using the copper-based coating additive obtained in Example 4 at different addition amounts is as follows: Figure 29 , Figure 30 , Figure 31 and Figure 32 As shown.

[0174] Test Example 7

[0175] This example examines the antiviral evaluation results of the coatings obtained in Examples 5-8. The Guangdong Provincial Center for Microbiology Analysis and Testing was commissioned to conduct the tests, using Enterovirus 71 as the experimental virus and T / GDTL 011-2020 as the detection basis and method. The inactivation rate of the virus was calculated according to the following formulas (1) and (2):

[0176] Formula (1): Virus inactivation rate % = [1-10] -log（平均灭活病毒减少值） ]×100;

[0177] Formula (2): log (average reduction in inactivated virus value) = log 10 (The average viral titer of the control sample without antiviral treatment) - log 10 (The average viral titer of the test sample after antiviral treatment);

[0178] The test results are shown in Table 1 and Figure 34 As shown, the coatings obtained in Examples 5-8 all have good antiviral properties. After 2 hours of contact with the test virus, when the amount of the material added is 1%, the inactivation rates of the EV71 virus are 93%, 93%, 94% and 92%, respectively.

[0179] Table 1

[0180]

[0181] In summary, this application provides a coating with both high-performance broad-spectrum antibacterial and antiviral properties, and its application. The coating is obtained by compounding a copper-based coating additive and a base coating. On one hand, by adding a copper-based coating additive, and controlling the amount of sodium pyrithione added to the copper-based coating additive to be between 0.40 and 0.65 mol / L, the composite material exhibits superior overall performance in terms of color, structure, and antimicrobial properties. On the other hand, using widely used indoor and outdoor base coatings such as latex paint as a carrier, a stable, high-performance broad-spectrum antibacterial and antiviral coating is prepared. This coating possesses excellent antibacterial and antiviral properties, good stability, easy storage and transportation, does not affect aesthetics, and is environmentally friendly. It can be widely applied to the surfaces of many solid objects in homes, shopping malls, manufacturing, and construction, and the prepared coating has strong practicality and commercial applicability.

[0182] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.

Claims

1. A coating that combines high-performance broad-spectrum antibacterial and antiviral properties, characterized in that, The coating is obtained by compounding copper-based coating additives and base coatings; The copper-based coating additives include: i) Using diatomaceous earth as a carrier; ii) An antibacterial component at least partially loaded on the surface of the carrier and / or within the pores of the carrier; the antibacterial component is composed of cuprous oxide and copper pyrithione. The microstructure of the copper-based coating additive includes: 1) Copper pyridinethione particles with a three-dimensional rod-like structure; and, 2) Nano-cuprous oxide fragments attached to the surface of the pyridinethione copper particles, wherein the nano-cuprous oxide fragments are formed by the destruction of the spherical microstructure of cuprous oxide; The preparation method of the copper-based coating additive includes the following steps: Diatomaceous earth / cuprous oxide composite particles were prepared by reacting diatomaceous earth as a carrier and water-soluble divalent copper salt as the first copper source and reducing agent. The diatomaceous earth / cuprous oxide composite particles were used as a second copper source and reacted with pyridinethione metal salt to generate copper pyridinethione, thus preparing a copper-based coating additive.

2. The coating with both high-performance broad-spectrum antibacterial and antiviral properties according to claim 1, characterized in that, The ratio of the weight of the diatomaceous earth to the total weight of the cuprous oxide and the copper pyridinethione is 1:(2~8), and the molar ratio of the cuprous oxide and the copper pyridinethione is 1:(1~3).

3. The coating with both high-performance broad-spectrum antibacterial and antiviral properties according to claim 1, characterized in that, The amount of the copper-based coating additive added accounts for 0.2% to 1.0% of the weight of the coating, by weight percentage.

4. The coating with both high-performance broad-spectrum antibacterial and antiviral properties according to claim 1, characterized in that, The steps for preparing diatomaceous earth / cuprous oxide composite particles by reacting diatomaceous earth as a carrier and water-soluble divalent copper salt as the first copper source and reducing agent include the following processes: The water-soluble divalent copper salt was dissolved in the first ultrapure water, and then diatomaceous earth was added and mixed to obtain the first solution. The dispersant was dissolved in the second ultrapure water, and then ethanol was added and mixed to obtain the second solution. The second solution is added to the first solution, followed by the addition of an alkaline regulator aqueous solution with a concentration of 1.6~1.63 mol / L to form copper hydroxide precipitate. Then, a reducing agent aqueous solution with a concentration of 0.6~0.9 mol / L is added to carry out a redox reaction to obtain the diatomaceous earth / cuprous oxide composite particles. In the preparation of the first solution, the weight ratio of diatomaceous earth to the first ultrapure water is 1:(12~96), and the molar concentration of the water-soluble divalent copper salt is 0.262~0.267 mol / L; in the preparation of the second solution, the weight ratio of the dispersant, the ethanol and the water is 1:(19.2~24):(38.4~48); and the volume ratio of the alkaline regulator aqueous solution, the reducing agent aqueous solution and the first ultrapure water is 1:(1.5~2):(1.5~2).

5. The coating with both high-performance broad-spectrum antibacterial and antiviral properties according to claim 4, characterized in that, The redox reaction process includes: first adding a reducing agent, then heating to 65 ℃~75 ℃ for 2~3 h to obtain diatomaceous earth / cuprous oxide composite particles; the water-soluble divalent copper salt includes at least one of copper sulfate, copper chloride, copper nitrate and copper acetate; the dispersant includes at least one of sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, hexadecyltrimethylammonium bromide, hexadecyltrimethylammonium chloride, polyvinylpyrrolidone and polyethylene glycol; the alkaline regulator aqueous solution includes at least one of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution and ammonia water; the reducing agent aqueous solution includes at least one of glucose aqueous solution, ascorbic acid aqueous solution, glycine aqueous solution, sodium sulfite aqueous solution and formaldehyde aqueous solution.

6. The coating with both high-performance broad-spectrum antibacterial and antiviral properties according to claim 4, characterized in that, The steps for preparing copper-based coating additives by reacting the diatomaceous earth / cuprous oxide composite particles as a second copper source with pyridinethione metal salt to generate copper pyridinethione include the following processes: After the system undergoes a redox reaction and turns brick red for 15-20 min, a 0.1-0.9 mol / L aqueous solution of pyridinethione metal salt is added, and the reaction is carried out for 0.5-1.5 h. The mixture is then cooled to room temperature and filtered, washed, and dried to obtain a copper-based coating additive. The volume ratio of the pyridinethione metal salt aqueous solution to the first ultrapure water is 1:(1.5~2); the filtration uses a 0.22 µm nylon membrane; the pyridinethione metal salt includes at least one of pyridinethione sodium salt, pyridinethione ammonium salt, and pyridinethione magnesium salt.

7. The application of the coating with both high performance and broad-spectrum antibacterial and antiviral properties as described in any one of claims 1 to 6 in the preparation of antibacterial products and / or antiviral products.

8. A coating with broad-spectrum antimicrobial activity, characterized in that, The coating is prepared using the coating described in any one of claims 1 to 6, which has both high performance and broad-spectrum antibacterial and antiviral properties.

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