Antibacterial mildew-proof coating as well as preparation method and application thereof

Abstract

The invention discloses an antibacterial and mildew-proof coating as well as a preparation method and application thereof, and belongs to the technical field of coatings, the antibacterial and mildew-proof coating comprises the following components in parts by mass: 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 fatty acid polyoxyethylene ether, 1-5 parts of a stabilizer and 0.5-2 parts of an auxiliary agent; the antibacterial composition is prepared from molybdenum sulfide coated with polydopamine, spherical copper powder and methacryloyloxyethyl trimethyl ammonium chloride according to the mass ratio of 1: (0.5 to 1): (1 to 1.5). The antibacterial and mildew-proof coating disclosed by the invention has excellent mildew-proof, damp-proof and antibacterial effects and antibacterial and mildew-proof stability, and can effectively solve the problem that the surfaces of furniture and household appliances are easy to mildew.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to an antibacterial and mildew-proof coating, a preparation method thereof, and an application thereof. Background Art

[0002] Traditional furniture finishes are often sprayed with paint, which not only contains harmful substances such as formaldehyde, which is harmful to the environment and human health, but also has emission pollution problems in terms of environmental protection. It is also easy to deform, mold, and get dirty. The paint coating is easily affected by moisture and deformed and breeds bacteria and viruses. It is easy to lose stability and leave marks after long-term use, affecting the appearance. The coating is relatively thin and has relatively low hardness, requiring regular maintenance. With the continuous development of technology and the continuous improvement of environmental protection concepts, solvent-based non-fouling paints will gradually be replaced by more environmentally friendly and healthy products.

[0003] Existing antibacterial coatings have the following defects: 1. Organic antibacterial agents (such as quaternary ammonium salts and isothiazolinones) are volatile and have poor heat resistance, and long-term use may lead to drug resistance; 2. Inorganic antibacterial agents (such as silver ions) have the risk of agglomeration and easy inactivation, resulting in a decrease in antibacterial effect; 3. Photocatalytic coatings (such as TiO2) require ultraviolet light excitation, which limits their antibacterial efficiency in practical applications.

[0004] In view of this, this application is filed. Summary of the Invention

[0005] The purpose of the present invention is to overcome the shortcomings of the existing technology and provide an antibacterial and mildew-proof coating and its preparation method and application. The antibacterial and mildew-proof coating of the present invention has excellent mildew-proof, moisture-proof and antibacterial effects as well as antibacterial and mildew-proof stability, and can effectively solve the problem of mold on the surfaces of furniture and household appliances.

[0006] To achieve the above object, the technical solution adopted by the present invention is:

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

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

[0009] The antibacterial and mildew-proof coating of the present invention is based on polyurethane resin and acrylic resin. By adding an antibacterial composition and a stabilizer, it has excellent mildew-proof, moisture-proof and antibacterial effects as well as antibacterial and mildew-proof stability. It can effectively solve the problem of mold on the surfaces of furniture and home appliances. The antibacterial and mildew-proof coating of the present invention is particularly suitable for the fields of furniture and home appliances.

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

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

[0012] Among them, methacryloyloxyethyltrimethylammonium chloride, as a cationic surfactant, has significant antibacterial properties. Its antibacterial mechanism mainly includes interacting with bacterial cell membranes to destroy membrane structures, interfere with metabolic processes within cells, and inhibit biofilm formation.

[0013] The present invention creatively combines polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyltrimethylammonium chloride according to the above-mentioned specific mass ratio. On the one hand, the polydopamine coating and the long-chain alkyl group of methacryloyloxyethyltrimethylammonium chloride can enhance the steric hindrance effect and the coating effect, improve the dispersion of the spherical copper powder and molybdenum sulfide in the system, avoid agglomeration, improve the stability of the antibacterial composition in the system, and improve the adhesion effect on bacteria and molds. On the other hand, the synergistic antibacterial effect of the polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyltrimethylammonium chloride enhances the antibacterial and mildew-proof 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 mildew-proof effect and antibacterial and mildew-proof stability.

[0014] As a preferred embodiment of the present invention, the stabilizer includes chitosan and acrylic acid-2-methyl-2-acrylamidopropanesulfonic acid copolymer in a mass ratio of 1: (0.5-2). The present invention uses chitosan and acrylic acid-2-methyl-2-acrylamidopropanesulfonic acid copolymer as a stabilizer. On the one hand, chitosan itself has an antibacterial effect and good compatibility. It can electrostatically attract the negatively charged part of the bacterial cell membrane, thereby enhancing the contact and interaction between the antibacterial composition and bacteria, and improving the killing effect on bacteria and molds. On the other hand, chitosan and acrylic acid-2-methyl-2 -Acrylamide-propanesulfonic acid copolymers maintain the stability of the antibacterial component in the coating through electrostatic repulsion or steric hindrance effects, prevent the antibacterial composition from settling and aggregating in a humid or hot and humid environment, promote the formation of an antibacterial network structure in the system, and enhance the binding force between the antibacterial agent and the bacterial surface, so that the antibacterial agent stays on the bacterial surface for a longer time. In addition, the cationic group of chitosan and the high hydrophilicity of acrylic acid-2-methyl-2-acrylamide-propanesulfonic acid copolymers can improve the binding and penetration of the antibacterial agent to the bacterial surface, so that the antibacterial agent can more effectively enter the interior of the bacteria and increase its killing effect on the bacteria.

[0015] As a preferred embodiment of the present invention, the average particle size of the spherical copper powder is 300 to 500 nm. In particular, when the average particle size of the spherical copper powder is within 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 invention, the mass ratio of the antibacterial composition to the stabilizer is 1: (0.5-1), especially when the mass ratio of the antibacterial composition to the stabilizer is within this range, the antibacterial and mildew-proof effect and antibacterial and mildew-proof stability can be further improved.

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

[0018] Add molybdenum sulfide, isopropyl tris(dioctyl pyrophosphate) titanate, and citric acid to a hydrochloric acid solution and stir evenly to obtain a precursor solution;

[0019] Dopamine hydrochloride and trihydroxyaminomethane solution are added to the precursor solution, reacted, filtered, and dried to obtain polydopamine-coated molybdenum sulfide.

[0020] The present invention pretreats molybdenum sulfide with isopropyl tri(dioctyl pyrophosphate) titanate, citric acid and hydrochloric acid solution, thereby effectively improving the activity of molybdenum sulfide, promoting the stable coating of polydopamine on the surface of molybdenum sulfide, improving the stability of the polydopamine coating layer, effectively improving the dispersibility of molybdenum sulfide in the system, avoiding agglomeration, improving stability and adhesion effect on bacteria, and further improving the antibacterial and mildew-proof effect and antibacterial and mildew-proof stability.

[0021] As a preferred embodiment of the present invention, the mass ratio of the molybdenum sulfide, isopropyl tris(dioctyl pyrophosphate) 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 present invention, the mass ratio of the precursor solution, dopamine hydrochloride, and trishydroxyaminomethane 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 to 2 mol / L; and / or

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

[0025] As a preferred embodiment of the present invention, the reaction temperature is 60-80° C. and the reaction time is 2-8 hours.

[0026] As a preferred embodiment of the present invention, the polyurethane resin has a viscosity of 55,000 to 75,000 cps at 25°C, an average molecular weight of 1,000 to 2,000, and a glass transition temperature of 100 to 110°C; and / or

[0027] The acrylic resin has an acid value of 7 to 8 mgKOH / g, a solid content of 43 to 47%, and a viscosity of 500 to 1000 cps at 25° C.; and / or

[0028] The photoinitiator includes at least one of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2-isopropylthioxanthone.

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

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

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

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

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

[0034] The beneficial effects of the present invention are as follows: the antibacterial and mildew-proof coating of the present invention is based on polyurethane resin and acrylic resin, and by adding an antibacterial composition and a stabilizer, it has excellent mildew-proof, moisture-proof and antibacterial effects and antibacterial and mildew-proof stability, and can effectively solve the problem of mold on the surfaces of furniture and home appliances. The antibacterial and mildew-proof coating of the present invention is particularly suitable for the fields of furniture and home appliances. DETAILED DESCRIPTION

[0035] To make the purpose, technical solutions, and advantages of the embodiments of this application more clear, the technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments of this application, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of this application.

[0036] In this application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0037] In this application, when referring to numerical ranges, unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values of the range is included. In addition, when multiple ranges are provided to describe a feature or characteristic, the ranges can be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges subsumed therein.

[0038] In the present application, there is no particular limitation on the specific dispersion and stirring treatment methods.

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

[0040] Wherein, the raw materials of embodiment and comparative example are as follows:

[0041] Polyurethane resin: ETERCURE 6145-100, Changxing Chemical, viscosity at 25°C is 55,000-75,000 cps, average molecular weight is 1,000-2,000, and glass transition temperature is 104.1°C.

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

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

[0044] Acrylic resin-3: SK6547 water-based acrylic resin, Shuai Ke Chemical, the acrylic resin has an acid value of 40-65 mgKOH / g, a solid content of 68-72%, and a viscosity of 18,000-26,000 cps at 25°C.

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

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

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

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

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

[0050] Chitosan: CB50348, MacLean reagent.

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

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

[0053] Additives: leveling agent TEGO2100.

[0054] The following examples are provided to facilitate understanding of the present invention. These examples are not provided to limit the scope of the claims.

[0055] Example 1

[0056] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

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

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

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

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

[0062] Dopamine hydrochloride and a 0.05 mol / L tris(hydroxyaminomethane) solution were added to a precursor solution, reacted at 70°C for 5 hours, filtered, and dried to obtain polydopamine-coated molybdenum sulfide. The mass ratio of the precursor solution, dopamine hydrochloride, and tris(hydroxyaminomethane) solution was 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] The difference between Example 2 and Example 1 is that the amount of raw materials used is different, and everything else is the same.

[0066] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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] The difference between Example 3 and Example 1 is that the amount of raw materials used is different, and everything else is the same.

[0069] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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] The difference between Example 4 and Example 1 is that the mass ratios of polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyltrimethylammonium chloride in the antibacterial composition are different, and the other contents are the same.

[0072] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0074] Example 5

[0075] The difference between Example 5 and Example 1 is that the amounts of the antibacterial composition and the stabilizer are adjusted, and then the mass ratio of the antibacterial composition and the stabilizer is adjusted; the other aspects are the same.

[0076] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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 comprises polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyltrimethylammonium chloride in a mass ratio of 1:1:1.

[0078] The stabilizer comprises chitosan and acrylic acid-2-methyl-2-acrylamidopropanesulfonic acid copolymer in a mass ratio of 1:0.5.

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

[0080] Example 6

[0081] The difference between Example 6 and Example 1 is that the amounts of the antibacterial composition and the stabilizer are adjusted, and then the mass ratio of the antibacterial composition and the stabilizer is adjusted; the other aspects are the same.

[0082] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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 part of auxiliary agent.

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

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

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

[0086] Example 7

[0087] The difference between Example 7 and Example 1 is that the amounts of the antibacterial composition and the stabilizer are adjusted, and then the mass ratio of the antibacterial composition and the stabilizer is adjusted; the other aspects are the same.

[0088] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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 part of auxiliary agent.

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

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

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

[0092] Example 8

[0093] The difference between Example 8 and Example 1 is that spherical copper powder-2 is used instead of spherical copper powder-1, and all other aspects are the same.

[0094] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0096] Example 9

[0097] The difference between Example 9 and Example 1 is that spherical copper powder-3 is used instead of spherical copper powder-1, and all other aspects are the same.

[0098] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0100] Example 10

[0101] The difference between Example 10 and Example 1 is that spherical copper powder-4 is used instead of spherical copper powder-1, and all other aspects are the same.

[0102] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0104] Example 11

[0105] The difference between Example 11 and Example 1 is that acrylic resin-2 is used instead of acrylic resin-1, and all other aspects are the same.

[0106] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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 part of auxiliary agent.

[0107] Example 12

[0108] The difference between Example 12 and Example 1 is that acrylic resin-3 is used instead of acrylic resin-1, and all other aspects are the same.

[0109] An antibacterial and mildew-proof coating comprises the following components in parts by mass: 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] The difference between Example 13 and Example 1 is that the preparation parameters of the polydopamine-coated molybdenum sulfide are different, and the other parameters are the same.

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

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

[0114] Dopamine hydrochloride and 0.05 mol / L tris(hydroxyaminomethane) solution were added to the precursor solution, reacted at 70°C for 5 hours, filtered, and dried to obtain polydopamine-coated molybdenum sulfide. The mass ratio of the precursor solution, dopamine hydrochloride, and tris(hydroxyaminomethane) solution was 1:0.02:0.05.

[0115] Comparative Example 1

[0116] The difference between Comparative Example 1 and Example 1 is that the antibacterial composition of Comparative Example 1 does not contain polydopamine-coated molybdenum sulfide, and all other aspects are the same.

[0117] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0119] Comparative Example 2

[0120] The difference between Comparative Example 2 and Example 1 is that the antibacterial composition of Comparative Example 2 does not contain spherical copper powder-1, and all other aspects are the same.

[0121] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

[0122] The antibacterial composition comprises polydopamine-coated molybdenum sulfide and methacryloyloxyethyltrimethylammonium chloride in a mass ratio of 1:1.

[0123] Comparative Example 3

[0124] The difference between Comparative Example 3 and Example 1 is that the antibacterial composition of Comparative Example 3 does not contain methacryloyloxyethyltrimethylammonium chloride, and all other aspects are the same.

[0125] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0127] Comparative Example 4

[0128] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 uses an equal amount of polydopamine-coated molybdenum sulfide to replace the antibacterial composition, and all other conditions are the same.

[0129] An antibacterial and mildew-proof coating comprises 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 polydopamine-coated molybdenum sulfide, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 part of auxiliary agent.

[0130] Comparative Example 5

[0131] The difference between Comparative Example 5 and Example 1 is that Comparative Example 5 uses an equal amount of spherical copper powder-1 to replace the antibacterial composition, and all other aspects are the same.

[0132] An antibacterial and mildew-proof coating comprises 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 spherical copper powder-1, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 part of auxiliary agent.

[0133] Comparative Example 6

[0134] The difference between Comparative Example 6 and Example 1 is that Comparative Example 6 uses an equal amount of methacryloyloxyethyltrimethylammonium chloride to replace the antibacterial composition, and all other aspects are the same.

[0135] An antibacterial and mildew-proof coating comprises 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 methacryloyloxyethyltrimethylammonium chloride, 2 parts of fatty acid polyoxyethylene ether, 3 parts of stabilizer and 0.8 parts of auxiliary agent.

[0136] Comparative Example 7

[0137] The difference between Comparative Example 7 and Example 1 is that the mass ratio of polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyltrimethylammonium chloride in Comparative Example 7 is not within the scope of the present invention, and the others are the same.

[0138] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0140] Comparative Example 8

[0141] The difference between Comparative Example 8 and Example 1 is that the mass ratio of polydopamine-coated molybdenum sulfide, spherical copper powder-1 and methacryloyloxyethyltrimethylammonium chloride in Comparative Example 8 is not within the scope of the present invention, and the others are the same.

[0142] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0144] Comparative Example 9

[0145] The difference between Comparative Example 9 and Example 1 is that Comparative Example 9 uses molybdenum sulfide to replace the polydopamine-coated molybdenum sulfide, and the other aspects are the same.

[0146] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0148] Comparative Example 10

[0149] The difference between Comparative Example 10 and Example 1 is that zinc oxide is used to replace the polydopamine-coated molybdenum sulfide in Comparative Example 10, and all other aspects are the same.

[0150] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0152] Comparative Example 11

[0153] The difference between Comparative Example 11 and Example 1 is that titanium dioxide is used to replace methacryloyloxyethyl trimethylammonium chloride in Comparative Example 11, and all other aspects are the same.

[0154] An antibacterial and mildew-proof coating comprises 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 part of auxiliary agent.

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

[0156] Test Case

[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] Antimicrobial persistence: Test panels were prepared according to the method in GB / T 21866-2008. The coating thickness was 20 μm. The panels were placed in 85% humidity and 70°C for 10 days. The antimicrobial persistence was then tested according to the method in GB / T 21866-2008. The test bacteria were Escherichia coli and Staphylococcus aureus.

[0159] Anti-mildew performance: Anti-mildew performance testing was carried out in accordance with GB21551.2-2010. The coating thickness was 20 μm, and the mold coverage area (growth coverage area) was recorded. The test strains were Aspergillus niger and Aspergillus terreus.

[0160] Anti-mildew durability: A test plate was prepared according to the method of GB / T 21866-2008, with a coating thickness of 20 μm. The test plate was placed at 85% humidity and 70°C for 10 days. The antimicrobial durability was then tested according to the method of GB21551.2-2010. The test strains were Aspergillus niger and Aspergillus terreus, and 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 of the present invention is based on polyurethane resin and acrylic resin. By adding an antibacterial composition and a stabilizer, it has excellent mildew-proof, moisture-proof and antibacterial effects as well as antibacterial and mildew-proof stability. It can effectively solve the problem of mold on the surfaces of furniture and household appliances. The antibacterial and mildew-proof coating of the present invention is particularly suitable for the fields of furniture and household appliances.

[0164] By comparing Example 1 with Comparative Examples 1 to 6 and 10 to 11, it can be seen that the polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyltrimethylammonium chloride in the antibacterial composition of the present invention have significant synergistic effects in terms of antibacterial and mildew proofing effect and antibacterial and mildew proofing stability. Under the joint action of the three, the antibacterial and mildew proofing effect is effectively improved. The lack of any one of them or the replacement with other components will lead to a significant decrease in the antibacterial and mildew proofing effect and antibacterial and mildew proofing stability.

[0165] By comparing Example 1 with Comparative Examples 7 to 8, it can be seen that the present invention can significantly improve the antibacterial and mildew proof effect and antibacterial and mildew proof stability by controlling the mass ratio of the polydopamine-coated molybdenum sulfide, spherical copper powder and methacryloyloxyethyltrimethylammonium chloride to 1: (0.5-1): (1-1.5). 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 methacryloyloxyethyltrimethylammonium chloride have a more significant synergistic effect. If the mass ratio of the three deviates from the range of the present invention, the antibacterial and mildew proof effect and antibacterial and mildew proof stability will be significantly reduced.

[0166] Comparison of Example 1 and Comparative Example 9 shows that the polydopamine-coated molybdenum sulfide used in the present invention can more significantly improve the antibacterial and mildew-proof effect and antibacterial and mildew-proof stability.

[0167] Comparing Examples 1 and 5 with Examples 6 to 7, it can be seen that by controlling the mass ratio of the antibacterial composition to the stabilizer to 1: (0.5 to 1), the antibacterial and mildew-proofing effect and the antibacterial and mildew-proofing stability can be further improved.

[0168] Comparing Examples 1 and 8 with Examples 9 to 10, it can be seen that by controlling the average particle size of the spherical copper powder to be 300 to 500 nm, the antibacterial and antifungal effect and the antibacterial and antifungal stability can be further improved.

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

[0170] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solutions of the present invention.

Claims

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

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

3. The antibacterial and mildew-proof coating according to claim 1, characterized in that: The average particle size of the spherical copper powder is 300-500 nm.

4. The antibacterial and mildew-proof coating according to claim 1, characterized in that: The mass ratio of the antibacterial composition to the stabilizer is 1:(0.5-1).

5. The antibacterial and mildew-proof coating according to claim 1, characterized in that: The preparation method of the polydopamine-coated molybdenum sulfide is: Add molybdenum sulfide, isopropyl tris(dioctyl pyrophosphate) titanate, and citric acid to a hydrochloric acid solution and stir evenly to obtain a precursor solution; Dopamine hydrochloride and trihydroxyaminomethane solution are added to the precursor solution, reacted, filtered, and dried to obtain polydopamine-coated molybdenum sulfide.

6. The antibacterial and mildew-proof coating according to claim 5, characterized in that: The mass ratio of the molybdenum sulfide, isopropyl tris(dioctyl pyrophosphate) 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 trishydroxyaminomethane solution is 1: (0.02-0.05): (0.02-0.05).

7. The antibacterial and mildew-proof coating according to claim 5, characterized in that: The molar concentration of the hydrochloric acid solution is 0.2 to 2 mol / L; and / or The molar concentration of the trishydroxyaminomethane solution is 0.04 to 0.1 mol / L; The reaction temperature is 60-80° C. and the reaction time is 2-8 hours.

8. The antibacterial and mildew-proof coating according to claim 1, characterized in that: The polyurethane resin has a viscosity of 55,000 to 75,000 cps at 25° C., an average molecular weight of 1,000 to 2,000, and a glass transition temperature of 100 to 110° C.; The acrylic resin has an acid value of 7 to 8 mgKOH / g, a solid content of 43 to 47%, and a viscosity of 500 to 1000 cps at 25° C.; The photoinitiator includes at least one of ethyl 2,4,6-trimethylbenzoylphenylphosphonate, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone, and 2-isopropylthioxanthone.

9. The method for preparing the antibacterial and mildew-proof coating according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing polyurethane resin, acrylic resin, photoinitiator, antibacterial composition, fatty acid polyoxyethylene ether, stabilizer and auxiliary agent to obtain antibacterial and mildew-proof coating.

10. Use of the antibacterial and anti-mildew coating according to any one of claims 1 to 8 in the preparation of furniture and household appliances.

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