Antibacterial and mildew-proof coating, and preparation method and application thereof

Abstract

The application discloses an antibacterial and mildew-proof paint as well as a preparation method and application thereof, and belongs to the technical field of paints. The antibacterial and mildew-proof paint comprises the following components in mass fraction: 10-30 parts of polyurethane resin, 40-60 parts of acrylic resin, 1-8 parts of a photoinitiator, 2-5 parts of an antibacterial composition, 1-3 parts of a fatty acid polyoxyethylene ether, 1-5 parts of a stabilizer and 0.5-2 parts of an auxiliary agent. The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:(0.5-1):(1-1.5). The antibacterial and mildew-proof paint has excellent mildew-proof, moisture-proof and antibacterial effects and antibacterial and mildew-proof stability, and can effectively solve the mildew problem on the surface of furniture and household appliances.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of coating technology, in particular to an antibacterial and mildew-proof coating, a preparation method and application thereof. BACKGROUND

[0002] Traditional furniture finishing often adopts the way of spraying paint, which not only exists harmful substances such as formaldehyde, causes harm to the environment and human health, and has emission pollution problems in environmental protection, but also is easy to deform, mildew and get dirty, and the paint coating is easy to be affected by deformation and breeding of bacteria and viruses, and long-term use is easy to lose stability and leave traces, affect the appearance, the coating is relatively thin, the hardness is relatively low, and regular maintenance is needed.

[0003] The existing antibacterial coating has the following defects: 1. Organic antibacterial agents (such as quaternary ammonium salt, isothiazolinone) are easy to volatilize, have poor heat resistance, and may produce drug resistance after long-term use; 2. Inorganic antibacterial agents (such as silver ions) have the risk of aggregation and are easy to lose activity, resulting in a decrease in antibacterial effect; 3. Photocatalytic coatings (such as TiO2) need to be excited by ultraviolet light, and the antibacterial efficiency is limited in actual application.

[0004] In view of this, the present application is proposed. SUMMARY

[0005] The present application aims to overcome the deficiencies in the prior art and provide an antibacterial and mildew-proof coating, a preparation method and application thereof. The antibacterial and mildew-proof coating has excellent mildew-proof, moisture-proof and antibacterial effects, and antibacterial and mildew-proof stability, and can effectively solve the problem of easy mildew on the surface of furniture and household appliances.

[0006] To achieve the above-mentioned purpose, the technical scheme adopted by the present application is as follows:

[0007] An antibacterial and mildew-proof coating comprises the following components by mass: 10-30 parts of polyurethane resin, 40-60 parts of acrylic resin, 1-8 parts of photoinitiator, 2-5 parts of antibacterial composition, 1-3 parts of fatty acid polyoxyethylene ether, 1-5 parts of stabilizer and 0.5-2 parts of auxiliary agent.

[0008] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:(0.5-1):(1-1.5).

[0009] The anti-mildew and antibacterial coating has polyurethane resin and acrylic resin as a matrix, and by adding an antibacterial composition and a stabilizer, excellent anti-mildew, moisture-proof and antibacterial effects and antibacterial and anti-mildew stability are obtained, and the problem of easy mildew on the surface of furniture and household appliances can be effectively solved.

[0010] The polydopamine-coated molybdenum sulfide can interact with the cell wall or cell membrane of mold, destroy the integrity of the cell membrane, and thus inhibit the metabolic activity of mold; the molybdenum sulfide can reduce bacterial reproduction and growth; the molybdenum sulfide can also interfere with the adhesion process of microorganisms through adsorption or charge effect, reduce the formation of biofilm, and thus block the colonization of mold; and the molybdenum sulfide also has certain photocatalytic activity. By coating the molybdenum sulfide with polydopamine, on the one hand, the polydopamine can improve the dispersibility of the molybdenum sulfide in the system and avoid agglomeration; on the other hand, the coating of polydopamine can improve the stability of the molybdenum sulfide and promote the adhesion of the antibacterial composition to bacteria, and further improve the antibacterial effect of the molybdenum sulfide.

[0011] The spherical copper powder has excellent antibacterial activity, can interact with phospholipids and proteins on the bacterial cell membrane, change the permeability of the cell membrane, and cause damage or rupture of the cell membrane; and the spherical copper powder has a high specific surface area, is positively charged on the surface, can adsorb negatively charged microbial cell membranes through electrostatic action, destroy the membrane potential stability, and cause cell membrane rupture.

[0012] The methacryloyloxyethyl trimethyl ammonium chloride has significant antibacterial performance as a cationic surfactant. The antibacterial mechanism mainly includes destroying the membrane structure by interacting with the bacterial cell membrane, interfering with the metabolic process inside the cell, and inhibiting the formation of biofilm.

[0013] The polydopamine-coated molybdenum sulfide, the spherical copper powder and the methacryloyloxyethyl trimethyl ammonium chloride are combined in the above specific mass ratio, on the one hand, the coating of polydopamine and the long-chain alkyl of the methacryloyloxyethyl trimethyl ammonium chloride can improve the steric hindrance effect and coating effect, improve the dispersion of the spherical copper powder and the molybdenum sulfide in the system, avoid agglomeration, improve the stability of the antibacterial composition in the system, improve the adhesion effect to bacteria and mold, and on the other hand, the synergistic antibacterial effect of the polydopamine-coated molybdenum sulfide, the spherical copper powder and the methacryloyloxyethyl trimethyl ammonium chloride enhances the antibacterial and anti-mildew effect through multiple mechanisms, can effectively inhibit different types of bacteria and fungi, avoid the development of antibacterial resistance, and significantly improve the antibacterial and anti-mildew effect and the antibacterial and anti-mildew stability.

[0014] As a preferred embodiment of the present application, the stabilizer comprises chitosan and acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer in a mass ratio of 1:(0.5-2). The present application uses chitosan and acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer as the stabilizer. On the one hand, chitosan itself has antibacterial effect and good compatibility, and can have electrostatic attraction with the negative charge part of the bacterial cell membrane, thereby enhancing the contact and interaction of the antibacterial composition with bacteria, improving the killing effect on bacteria and mold. On the other hand, the combination of chitosan and acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer can maintain the stability of the antibacterial ingredients in the coating through electrostatic repulsion or steric hindrance effect, avoid the settlement and aggregation of the antibacterial composition in humid or hot and humid environment, promote the formation of antibacterial network structure in the system, improve the binding force of the antibacterial agent to the bacterial surface, make the antibacterial agent stay on the bacterial surface for a longer time, and the cationic groups of chitosan and the high hydrophilicity of acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer can improve the binding and penetration of the antibacterial agent to the bacterial surface, so that the antibacterial agent can enter the bacterial interior more effectively and increase its killing effect on bacteria.

[0015] As a preferred embodiment of the present application, the average particle size of the spherical copper powder is 300-500 nm. Especially when the average particle size of the spherical copper powder is in this range, the antibacterial and mildew-proof effect and the antibacterial and mildew-proof stability can be further improved.

[0016] As a preferred embodiment of the present application, the mass ratio of the antibacterial composition and the stabilizer is 1:(0.5-1). Especially when the mass ratio of the antibacterial composition and the stabilizer is in this range, the antibacterial and mildew-proof effect and the antibacterial and mildew-proof stability can be further improved.

[0017] As a preferred embodiment of the present application, the preparation method of the polydopamine-coated molybdenum sulfide is as follows:

[0018] The molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoric acid acyloxy) titanate and citric acid are added to a hydrochloric acid solution, stirred uniformly to obtain a precursor solution;

[0019] The dopamine hydrochloride and trihydroxy aminomethane solution are added to the precursor solution, reacted, filtered and dried to obtain the polydopamine-coated molybdenum sulfide.

[0020] The application can effectively improve the activity of molybdenum sulfide, promote the stable coating of polydopamine on the surface of molybdenum sulfide, improve the stability of the polydopamine coating layer, effectively improve the dispersity of molybdenum sulfide in the system, avoid the agglomeration phenomenon, and improve the stability and adhesion effect on bacteria, further improve the antibacterial and mildew-proof effect and stability.

[0021] As a preferred embodiment of the application, the mass ratio of the molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoryl oxy) titanate, citric acid, and hydrochloric acid solution is 1:(0.01-0.02):(0.02-0.05):(5-12).

[0022] As a preferred embodiment of the application, the mass ratio of the precursor solution, dopamine hydrochloride, and trisaminomethane solution is 1:(0.02-0.05):(0.02-0.05); and / or

[0023] The molar concentration of the hydrochloric acid solution is 0.2-2 mol / L; and / or

[0024] The molar concentration of the trisaminomethane solution is 0.04-0.1 mol / L.

[0025] As a preferred embodiment of the application, the temperature of the reaction is 60-80℃, and the time is 2-8h.

[0026] As a preferred embodiment of the application, the viscosity of the polyurethane resin at 25℃ is 55000-75000 cps, the average molecular weight is 1000-2000, and the glass transition temperature is 100-110℃; and / or

[0027] The acid value of the acrylic resin is 7-8 mgKOH / g, the solid content is 43-47%, and the viscosity at 25℃ is 500-1000 cps; and / or

[0028] The photoinitiator includes at least one of 2,4,6-trimethylbenzoyl phenyl ethyl phosphonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone, and 2-isopropyl thioxanthone.

[0029] As a preferred embodiment of the application, the auxiliary agent includes at least one of a defoaming agent and a leveling agent.

[0030] As a preferred embodiment of the application, the defoaming agent includes at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate, and silicone resin.

[0031] As a preferred embodiment of the present application, the leveling agent comprises at least one of an acrylated polysiloxane, a polyether-modified polysiloxane, a polysiloxane polyether copolymer, and a polysiloxane.

[0032] The application further provides a preparation method of the antibacterial and mildew-proof coating, comprising the following steps: uniformly mixing polyurethane resin, acrylic resin, a photoinitiator, an antibacterial composition, a fatty acid polyoxyethylene ether, a stabilizer and an auxiliary agent to obtain the antibacterial and mildew-proof coating.

[0033] The application further provides application of the antibacterial and mildew-proof coating in preparation of furniture and household appliances.

[0034] The application has the advantages that the antibacterial and mildew-proof coating has polyurethane resin and acrylic resin as a matrix, and has excellent mildew-proof and moisture-proof effects and antibacterial effects and stability, and can effectively solve the mildew problem of furniture and household appliances, and is particularly suitable for furniture and household appliances. DETAILED DESCRIPTION

[0035] To make the objectives, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are some but not all of the embodiments of the present application. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work fall within the scope of protection of the present application.

[0036] In the present application, the technical features described in an open way include both a closed technical solution consisting of listed features and an open technical solution containing listed features.

[0037] In the present application, if no special description is provided, the numerical range is regarded as continuous and includes the minimum value and the maximum value of the range and each value between the minimum value and the maximum value. Further, when a range is referred to as an integer, each integer between the minimum value and the maximum value of the range is included. In addition, when multiple ranges are provided to describe a feature or a characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0038] In the present application, the specific dispersion and stirring treatment methods are not particularly limited.

[0039] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present application are commercially available raw materials and instruments, and the components and raw materials used in each parallel experiment are the same.

[0040] The raw materials of the examples and comparative examples are as follows:

[0041] Polyurethane resin: ETERCURE 6145-100, Changxing Chemical, viscosity at 25°C: 55000-75000 cps, average molecular weight: 1000-2000, glass transition temperature: 104.1°C.

[0042] Acrylic resin-1: SK6340 water-based acrylic resin, Shuikai Chemical, acid value of the acrylic resin: 7-8 mgKOH / g, solid content: 43-47%, viscosity at 25°C: 500-1000 cps.

[0043] Acrylic resin-2: SK6480 water-based acrylic resin, Shuikai Chemical, acid value of the acrylic resin: 0.5-1.5 mgKOH / g, solid content: 48-52%, viscosity at 25°C: 140-500 cps.

[0044] Acrylic resin-3: SK6547 water-based acrylic resin, Shuikai Chemical, acid value of the acrylic resin: 40-65 mgKOH / g, solid content: 68-72%, viscosity at 25°C: 18000-26000 cps.

[0045] Spherical copper powder-1: XT-Cu-04, Xiangtian Nanometer, average particle size: 300 nm.

[0046] Spherical copper powder-2: XT-Cu-05, Xiangtian Nanometer, average particle size: 500 nm.

[0047] Spherical copper powder-3: XT-Cu-01, Xiangtian Nanometer, average particle size: 50 nm.

[0048] Spherical copper powder-4: XT-Cu-07, Xiangtian Nanometer, average particle size: 5 μm.

[0049] Molybdenum sulfide: XT-MOS2-05, Xiangtian Nanometer.

[0050] Chitosan: CB50348, Macklin Reagent.

[0051] Acrylic-2-methyl-2-acrylamidopropyl sulfonic acid copolymer: AA-AMPS, Yuanrong Chemical.

[0052] Fatty acid polyoxyethylene ether: AEO-9, Shengcang Chemical.

[0053] Auxiliary agent: leveling agent TEGO 2100.

[0054] The following examples are provided to facilitate understanding of the present application. The provision of these examples is not intended to limit the scope of the claims.

[0055] Example 1

[0056] An antibacterial and mildew-proof coating, comprising the following components by mass fraction: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0057] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:1:1.

[0058] The stabilizer comprises chitosan and 2-methyl-2-acrylamidoglycolic acid copolymer at a mass ratio of 1:0.5.

[0059] The mass ratio of the antibacterial composition and the stabilizer is 1:1.

[0060] The preparation method of the polydopamine-coated molybdenum sulfide is as follows:

[0061] Molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoryl) titanate and citric acid are added into a 1 mol / L hydrochloric acid solution, uniformly stirred at a speed of 150 rpm for 30 min to obtain a precursor solution; the mass ratio of the molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoryl) titanate, citric acid and hydrochloric acid solution is 1:0.02:0.02:10.

[0062] Dopamine hydrochloride and 0.05 mol / L trishydroxy aminomethane solution are added into the precursor solution, and the mixture is reacted at 70°C for 5 h, filtered and dried to obtain the polydopamine-coated molybdenum sulfide; the mass ratio of the precursor solution, dopamine hydrochloride and trishydroxy aminomethane solution is 1:0.05:0.02.

[0063] The preparation method of the antibacterial and mildew-proof coating comprises the following steps: uniformly mixing polyurethane resin, acrylic resin-1, photoinitiator, antibacterial composition, fatty acid polyoxyethylene ether, stabilizer and auxiliary agent to obtain the antibacterial and mildew-proof coating.

[0064] Example 2

[0065] Example 2 is different from example 1 in that the amounts of raw materials are different, and other aspects are the same.

[0066] An antibacterial and mildew-proof coating, comprising the following components by mass fraction: 10 parts of polyurethane resin, 60 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0067] Example 3

[0068] Example 3 is different from example 1 in that the amount of raw materials is different, and others are the same.

[0069] An antibacterial and mildew-proof coating includes the following components in mass parts: 30 parts of polyurethane resin, 40 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0070] Example 4

[0071] Example 4 is different from example 1 in that the mass ratio of polydopamine coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride in the antibacterial composition is different, and others are the same.

[0072] An antibacterial and mildew-proof coating includes the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0073] The antibacterial composition includes polydopamine coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:0.5:1.5.

[0074] Example 5

[0075] Example 5 is different from example 1 in that the amount of antibacterial composition and stabilizer is adjusted, and the mass ratio of antibacterial composition and stabilizer is adjusted, and others are the same.

[0076] An antibacterial and mildew-proof coating includes the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 4 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 2 parts of stabilizer and 0.8 parts of auxiliary agent.

[0077] The antibacterial composition includes polydopamine coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:1:1.

[0078] The stabilizer includes chitosan and 2-methyl-2-acrylamidoglycolic acid propyl sulfonic acid copolymer in a mass ratio of 1:0.5.

[0079] The mass ratio of the antibacterial composition and the stabilizer is 1:0.5.

[0080] Example 6

[0081] Example 6 is different from example 1 in that the amount of antibacterial composition and stabilizer is adjusted, and the mass ratio of antibacterial composition and stabilizer is adjusted, and others are the same.

[0082] An antibacterial and mildew-proof paint comprises the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 5 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 1 part of stabilizer and 0.8 parts of auxiliary agent.

[0083] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:1:1.

[0084] The stabilizer comprises chitosan and acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer at a mass ratio of 1:0.5.

[0085] The mass ratio of the antibacterial composition and the stabilizer is 1:5.

[0086] Example 7

[0087] Example 7 differs from Example 1 in that the use amount of the antibacterial composition and the stabilizer is adjusted, thereby adjusting the mass ratio of the antibacterial composition and the stabilizer, and other aspects are the same.

[0088] An antibacterial and mildew-proof paint comprises the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 2 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 5 parts of stabilizer and 0.8 parts of auxiliary agent.

[0089] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:1:1.

[0090] The stabilizer comprises chitosan and acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer at a mass ratio of 1:0.5.

[0091] The mass ratio of the antibacterial composition and the stabilizer is 1:2.5.

[0092] Example 8

[0093] Example 8 differs from Example 1 in that spherical copper powder-2 is used to replace spherical copper powder-1, and other aspects are the same.

[0094] An antibacterial and mildew-proof paint comprises the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0095] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-2 and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:1:1.

[0096] Example 9

[0097] Example 9 differs from example 1 in that spherical copper powder-3 is used in place of spherical copper powder-1, and the others are the same.

[0098] An antibacterial and mildew-proof paint includes the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer, and 0.8 parts of auxiliary agent.

[0099] The antibacterial composition includes polydopamine-coated molybdenum sulfide, spherical copper powder-3, and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:1:1.

[0100] Example 10

[0101] Example 10 differs from example 1 in that spherical copper powder-4 is used in place of spherical copper powder-1, and the others are the same.

[0102] An antibacterial and mildew-proof paint includes the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer, and 0.8 parts of auxiliary agent.

[0103] The antibacterial composition includes polydopamine-coated molybdenum sulfide, spherical copper powder-4, and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:1:1.

[0104] Example 11

[0105] Example 11 differs from example 1 in that acrylic resin-2 is used in place of acrylic resin-1, and the others are the same.

[0106] An antibacterial and mildew-proof paint includes the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-2, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer, and 0.8 parts of auxiliary agent.

[0107] Example 12

[0108] Example 12 differs from example 1 in that acrylic resin-3 is used in place of acrylic resin-1, and the others are the same.

[0109] An antibacterial and mildew-proof paint includes the following components in mass parts: 18 parts of polyurethane resin, 52 parts of acrylic resin-3, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer, and 0.8 parts of auxiliary agent.

[0110] Example 13

[0111] Example 13 differs from example 1 in that the preparation parameters of the polydopamine-coated molybdenum sulfide are different, and others are the same.

[0112] The preparation method of the polydopamine-coated molybdenum sulfide is as follows:

[0113] Molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoryloxy) titanate, and citric acid are added into a 1 mol / L hydrochloric acid solution, uniformly stirred at a speed of 150 rpm for 30 min to obtain a precursor solution; the mass ratio of the molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoryloxy) titanate, citric acid, and hydrochloric acid solution is 1:0.01:0.05:10.

[0114] Dopamine hydrochloride and 0.05 mol / L of a trishydroxy aminomethane solution are added into the precursor solution, and the mixture is reacted at 70℃ for 5 h, filtered, and dried to obtain the polydopamine-coated molybdenum sulfide. The mass ratio of the precursor solution, dopamine hydrochloride, and trishydroxy aminomethane solution is 1:0.02:0.05.

[0115] Comparative example 1

[0116] Comparative example 1 differs from example 1 in that the antibacterial composition of comparative example 1 does not contain polydopamine-coated molybdenum sulfide, and others are the same.

[0117] An antibacterial and mildew-proof coating, comprising the following components in parts by mass: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer, and 0.8 parts of auxiliary agent.

[0118] The antibacterial composition comprises spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:1.

[0119] Comparative example 2

[0120] Comparative example 2 differs from example 1 in that the antibacterial composition of comparative example 2 does not contain spherical copper powder-1, and others are the same.

[0121] An antibacterial and mildew-proof coating, comprising the following components in parts by mass: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer, and 0.8 parts of auxiliary agent.

[0122] The antibacterial composition comprises polydopamine-coated molybdenum sulfide and methacryloyloxyethyl trimethyl ammonium chloride at a mass ratio of 1:1.

[0123] Comparative example 3

[0124] Comparative Example 3 differs from Example 1 in that the antibacterial composition of Comparative Example 3 does not contain methacryloyloxyethyl trimethyl ammonium chloride, and is otherwise identical.

[0125] An antibacterial and mildew-proof paint includes the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of acrylic resin-1, 5 parts of a photoinitiator, 3 parts of an antibacterial composition, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0126] The antibacterial composition includes polydopamine-coated molybdenum sulfide and spherical copper powder-1 in a mass ratio of 1:1.

[0127] Comparative Example 4

[0128] Comparative Example 4 differs from Example 1 in that Comparative Example 4 uses an equal amount of polydopamine-coated molybdenum sulfide to replace the antibacterial composition, and is otherwise identical.

[0129] An antibacterial and mildew-proof paint includes the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of acrylic resin-1, 5 parts of a photoinitiator, 3 parts of polydopamine-coated molybdenum sulfide, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0130] Comparative Example 5

[0131] Comparative Example 5 differs from Example 1 in that Comparative Example 5 uses an equal amount of spherical copper powder-1 to replace the antibacterial composition, and is otherwise identical.

[0132] An antibacterial and mildew-proof paint includes the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of acrylic resin-1, 5 parts of a photoinitiator, 3 parts of spherical copper powder-1, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0133] Comparative Example 6

[0134] Comparative Example 6 differs from Example 1 in that Comparative Example 6 uses an equal amount of methacryloyloxyethyl trimethyl ammonium chloride to replace the antibacterial composition, and is otherwise identical.

[0135] An antibacterial and mildew-proof paint includes the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of acrylic resin-1, 5 parts of a photoinitiator, 3 parts of methacryloyloxyethyl trimethyl ammonium chloride, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0136] Comparative Example 7

[0137] Comparative Example 7 differs from Example 1 in that the mass ratio of polydopamine-coated molybdenum sulfide, spherical copper powder-1, and methacryloyloxyethyl trimethyl ammonium chloride of Comparative Example 7 is not within the scope of the present application, and is otherwise identical.

[0138] An antibacterial and mildew-proof paint comprising the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of an acrylic resin-1, 5 parts of a photoinitiator, 3 parts of an antibacterial composition, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0139] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1, and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:0.25:2.75.

[0140] Comparative Example 8

[0141] Comparative Example 8 differs from Example 1 in that the mass ratio of polydopamine-coated molybdenum sulfide, spherical copper powder-1, and methacryloyloxyethyl trimethyl ammonium chloride of Comparative Example 8 is not within the scope of the present application, and the other aspects are the same.

[0142] An antibacterial and mildew-proof paint comprising the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of an acrylic resin-1, 5 parts of a photoinitiator, 3 parts of an antibacterial composition, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0143] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1, and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:2.75:0.25.

[0144] Comparative Example 9

[0145] Comparative Example 9 differs from Example 1 in that molybdenum sulfide is used instead of polydopamine-coated molybdenum sulfide in Comparative Example 9, and the other aspects are the same.

[0146] An antibacterial and mildew-proof paint comprising the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of an acrylic resin-1, 5 parts of a photoinitiator, 3 parts of an antibacterial composition, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0147] The antibacterial composition comprises molybdenum sulfide, spherical copper powder-1, and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:1:1.

[0148] Comparative Example 10

[0149] Comparative Example 10 differs from Example 1 in that zinc oxide is used instead of polydopamine-coated molybdenum sulfide in Comparative Example 10, and the other aspects are the same.

[0150] An antibacterial and mildew-proof paint comprising the following components in parts by mass: 18 parts of a polyurethane resin, 52 parts of an acrylic resin-1, 5 parts of a photoinitiator, 3 parts of an antibacterial composition, 2 parts of a fatty acid polyoxyethylene ether, 3 parts of a stabilizer, and 0.8 parts of an auxiliary agent.

[0151] The antibacterial composition comprises zinc oxide (average particle size 1 μm), spherical copper powder-1 and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:1:1.

[0152] Comparative Example 11

[0153] Comparative Example 11 is different from Example 1 in that Comparative Example 11 uses titanium dioxide instead of methacryloyloxyethyl trimethyl ammonium chloride, and is otherwise the same.

[0154] An antibacterial and mildew-proof coating, comprising the following components in parts by mass: 18 parts of polyurethane resin, 52 parts of acrylic resin-1, 5 parts of photoinitiator, 3 parts of antibacterial composition, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0155] The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1 and titanium dioxide (average particle size 1 μm) in a mass ratio of 1:1:1.

[0156] Test Example

[0157] Antibacterial performance: The antibacterial performance was tested according to the method of GB / T 21866-2008, the coating thickness was 20 μm, and the test bacteria were Escherichia coli and Staphylococcus aureus.

[0158] Antibacterial durability: The test plate was prepared according to the method of GB / T 21866-2008, the coating thickness was 20 μm, and the test plate was placed at 85% humidity and 70°C for 10 days. The antibacterial durability was then tested according to the method of GB / T 21866-2008, and the test bacteria were Escherichia coli and Staphylococcus aureus.

[0159] Mildew resistance: The mildew resistance was tested according to GB21551.2-2010, the coating thickness was 20 μm, and the mold coverage area (growth coverage area) was recorded. The test bacteria were Aspergillus niger and Aspergillus terreus.

[0160] Mildew resistance durability: The test plate was prepared according to the method of GB / T 21866-2008, the coating thickness was 20 μm, and the test plate was placed at 85% humidity and 70°C for 10 days. The antibacterial durability was then tested according to the method of GB21551.2-2010, and the test bacteria were Aspergillus niger and Aspergillus terreus. The mold coverage area (growth coverage area) was recorded.

[0161] Table 1

[0162]

[0163] As can be seen from Table 1, the antibacterial and mildew-proof coating described in the application has polyurethane resin and acrylic resin as a matrix, and has excellent antibacterial and mildew-proof effects and antibacterial and mildew-proof stability by adding the antibacterial composition and the stabilizer, and can effectively solve the problem of easy mildew on the surface of furniture and household appliances. The antibacterial and mildew-proof coating described in the application is particularly suitable for furniture and household appliances.

[0164] As can be seen from Comparative Example 1 and Comparative Examples 1-6, 10-11, the polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride in the antibacterial composition described in the application have a significant synergistic effect in terms of antibacterial and mildew-proof effects and antibacterial and mildew-proof stability. Under the combined action of the three, the antibacterial and mildew-proof effects are effectively improved. If any one of them is missing or other ingredients are used instead, the antibacterial and mildew-proof effects and the antibacterial and mildew-proof stability will be significantly reduced.

[0165] As can be seen from Comparative Example 1 and Comparative Examples 7-8, by controlling the mass ratio of the polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride to be 1:(0.5-1):(1-1.5), the antibacterial and mildew-proof effects and the antibacterial and mildew-proof stability can be more significantly improved. When the mass ratio of the three is controlled to be 1:(0.5-1):(1-1.5), the polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride have a more significant synergistic effect. If the mass ratio of the three deviates from the range of the application, the antibacterial and mildew-proof effects and the antibacterial and mildew-proof stability will be significantly reduced.

[0166] As can be seen from Comparative Example 1 and Comparative Example 9, the polydopamine-coated molybdenum sulfide used in the application can more significantly improve the antibacterial and mildew-proof effects and the antibacterial and mildew-proof stability.

[0167] As can be seen from Comparative Examples 1 and 5 and Examples 6-7, by controlling the mass ratio of the antibacterial composition and the stabilizer to be 1:(0.5-1), the antibacterial and mildew-proof effects and the antibacterial and mildew-proof stability can be further improved.

[0168] As can be seen from Comparative Examples 1 and 8 and Examples 9-10, by controlling the average particle size of the spherical copper powder to be 300-500 nm, the antibacterial and mildew-proof effects and the antibacterial and mildew-proof stability can be further improved.

[0169] As can be seen from Comparative Example 1 and Examples 11-12, by controlling the acid value of the acrylic resin to be 7-8 mgKOH / g, the solid content to be 43-47%, and the viscosity at 25℃ to be 500-1000 cps, the antibacterial and mildew-proof stability can be further improved.

[0170] It should be pointed out finally that the above embodiments are only used to illustrate the technical solutions of the present application but not to limit the protection scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be appreciated by those skilled in the art that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. An antimicrobial mildew-proof paint, characterized by comprising: The components include the following mass parts: 10-30 parts of polyurethane resin, 40-60 parts of acrylic resin, 1-8 parts of photoinitiator, 2-5 parts of antibacterial composition, 1-3 parts of fatty acid polyoxyethylene ether, 1-5 parts of stabilizer and 0.5-2 parts of auxiliary agent; The antibacterial composition comprises polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride in a mass ratio of 1:(0.5-1):(1-1.5).

2. The antimicrobial mildew-resistant coating according to claim 1, characterized in that, The stabilizer comprises chitosan and acrylic acid-2-methyl-2-acrylamidoglycolic acid copolymer in a mass ratio of 1:(0.5-2).

3. The antimicrobial mildew-resistant coating according to claim 1, wherein The average particle size of the spherical copper powder is 300-500 nm.

4. The antimicrobial mildew resistant coating of claim 1, wherein, The mass ratio of the antibacterial composition and the stabilizer is 1:(0.5-1).

5. The antimicrobial mildew-resistant coating of claim 1, wherein, The preparation method of the polydopamine-coated molybdenum sulfide is as follows: The molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoric acyloxy) titanate and citric acid are added into a hydrochloric acid solution, stirred uniformly to obtain a precursor solution; The dopamine hydrochloride and trihydroxy aminomethane solution are added into the precursor solution, reacted, filtered and dried to obtain the polydopamine-coated molybdenum sulfide.

6. The antimicrobial mildew-resistant coating of claim 5, wherein, The mass ratio of the molybdenum sulfide, isopropyl tri(dioctyl pyrophosphoric acyloxy) titanate, citric acid and hydrochloric acid solution is 1:(0.01-0.02):(0.02-0.05):(5-12). The mass ratio of the precursor solution, dopamine hydrochloride and trihydroxy aminomethane solution is 1:(0.02-0.05):(0.02-0.05).

7. The antimicrobial mildew-resistant coating of claim 5, wherein, The molar concentration of the hydrochloric acid solution is 0.2-2 mol / L; and / or The molar concentration of the trihydroxy aminomethane solution is 0.04-0.1 mol / L; The reaction temperature is 60-80℃, and the reaction time is 2-8 h.

8. The antimicrobial mildew resistant coating of claim 1, wherein, The viscosity of the polyurethane resin at 25℃ is 55,000-75,000 cps, the average molecular weight is 1,000-2,000, and the glass transition temperature is 100-110℃. The acid value of the acrylic resin is 7-8 mgKOH / g, the solid content is 43-47%, and the viscosity at 25℃ is 500-1,000 cps. The photoinitiator comprises at least one of 2,4,6-trimethylbenzoyl phenyl phosphonic acid ethyl ester, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholino-1-propanone and 2-isopropyl thioxanthone.

9. The method of producing the antibacterial and mildew-proof paint according to any one of claims 1 to 8, characterized by, The steps include mixing the polyurethane resin, acrylic resin, photoinitiator, antibacterial composition, fatty acid polyoxyethylene ether, stabilizer and auxiliary agent uniformly to obtain the antibacterial and mildew-proof coating.

10. The antibacterial and mildew-proof coating according to any one of claims 1-8 is applied to the preparation of furniture and household appliances.

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