An antibacterial composite coating for hospital wards and its preparation method

Abstract

This invention relates to the technical field, specifically disclosing an antibacterial composite coating for hospital wards and its preparation method. The antibacterial composite coating for hospital wards of this invention comprises: 50-70 parts of fluorine-modified silicone-acrylic emulsion, 10-20 parts of silica sol, 4-6 parts of anatase nano-titanium dioxide, 1-2 parts of nano-manganese dioxide, 2-4 parts of silver-loaded zinc zeolite antibacterial agent, 10-16 parts of modified nano-silica powder, 8-12 parts of ultrafine flake mica powder, 8-12 parts of rutile titanium dioxide, 0.8-1.6 parts of ammonium polyacrylate, 0.5-1.5 parts of polyether-modified silicone oil composite defoamer, 0.4-0.8 parts of HASE thickener, 0.1-0.3 parts of wetting agent, 0.5-1.5 parts of surfactant, 1.5-2.5 parts of tri-1-(2-methylaziridine)phosphine oxide, and 20-30 parts of deionized water. After forming a coating, this coating exhibits good antibacterial properties and a long service life.

Description

Technical Field

[0001] This invention relates to the field of pharmaceutical preparation technology, and more specifically, to an antibacterial composite coating for hospital wards and its preparation method. Background Technology

[0002] Hospital wards are places for patient treatment and recovery, but they are also environments with a high concentration of various pathogenic microorganisms (such as bacteria, viruses, and fungi). To control hospital-acquired infections, the ward environment requires frequent wiping and fumigation with strong oxidizing disinfectants (such as chlorine-based disinfectants and peroxides). This places extremely stringent requirements on the performance of interior wall coatings.

[0003] First, traditional antibacterial coatings are mostly single-function. They either rely solely on inorganic antibacterial agents (such as silver ions) for slow-release contact sterilization, which is slow to respond and prone to failure; or they rely solely on photocatalysts (such as nano-TiO2), whose effectiveness is greatly reduced in corners with insufficient light or at night, and cannot provide 24-hour uninterrupted protection. At the same time, they lack the ability to specifically inactivate viruses.

[0004] Secondly, existing coatings lack durability. Frequent chemical disinfection can erode the organic polymer components in the paint film, leading to chalking, discoloration, loss of gloss, and even damage. This not only causes premature coating failure but also makes the rough surface more prone to harboring bacteria, creating new sources of contamination. The coating passively undergoes disinfection, meaning its antibacterial function is independent of, or even weakens, the disinfection process.

[0005] Furthermore, achieving a balanced overall performance in coatings is challenging. There is a contradiction between the requirements for high filling volume and high hardness and good application leveling and anti-splashing properties; the introduction of multifunctional components can easily lead to unstable formulations, resulting in problems such as sedimentation and flocculation.

[0006] Currently, the market lacks a comprehensive solution that can proactively adapt to the extreme environment of hospitals, withstand high-intensity disinfection, work synergistically with disinfection, and achieve a perfect balance of multiple functions such as long-lasting antibacterial, antiviral, and self-cleaning.

[0007] Therefore, developing a new type of coating specifically for hospital wards, overcoming the shortcomings of the existing technologies, has significant practical application value and economic significance. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide an antibacterial composite coating for hospital wards and its preparation method.

[0009] To achieve the above objectives, the present invention provides the following technical solution:

[0010] An antibacterial composite coating for hospital wards comprises, by weight, the following raw materials: 50-70 parts of fluorine-modified silicone-acrylic emulsion, 10-20 parts of silica sol, 4-6 parts of anatase nano-titanium dioxide, 1-2 parts of nano-manganese dioxide, 2-4 parts of silver-loaded zinc zeolite antibacterial agent, 10-16 parts of modified nano-silica powder, 8-12 parts of ultrafine flake mica powder, 8-12 parts of rutile titanium dioxide, 0.8-1.6 parts of ammonium polyacrylate, 0.5-1.5 parts of polyether-modified silicone oil composite defoamer, 0.4-0.8 parts of HASE thickener, 0.1-0.3 parts of wetting agent, 0.5-1.5 parts of surfactant, 1.5-2.5 parts of tri-1-(2-methylaziridine)phosphine oxide, 0.1-0.3 parts of isobutanolamine, and 20-30 parts of deionized water.

[0011] Furthermore, the silica sol has a particle size of 10-20 nm, the anatase nano titanium dioxide has a particle size of 10-20 nm, the nano manganese dioxide has a particle size of 20-30 nm, the ultrafine flake mica powder has a particle size of 2-6 μm, and the rutile titanium dioxide has a particle size of 0.2-0.4 μm.

[0012] Furthermore, the HASE thickener is of at least one type selected from TT-115, TT-215, ML-818, ML-828, and ML-838.

[0013] Furthermore, the wetting agent includes at least one of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

[0014] Furthermore, the surfactant includes at least one of decyl glucoside, lauryl glucoside, and sucrose stearate.

[0015] Furthermore, the preparation method of the fluorine-modified silicone-acrylic emulsion includes the following steps:

[0016] a1. Weigh the following components separately according to their weight parts:

[0017] Core layer pre-emulsion components: 20-30 parts deionized water, 0.5-1.2 parts DNS-86 emulsifier, 15-25 parts methyl methacrylate, 10-20 parts styrene, and 5-15 parts butyl acrylate;

[0018] Shell pre-emulsion components: 15-25 parts deionized water, 0.3-0.8 parts DNS-86 emulsifier, 3-8 parts dodecafluoroheptyl methacrylate, 2-5 parts γ-methacryloyloxypropyltrimethoxysilane, 20-30 parts butyl acrylate, 5-10 parts methyl methacrylate, and 1-2 parts acrylic acid.

[0019] Initiator: 6-12 parts of ammonium persulfate solution with a mass fraction of 6%-10%;

[0020] Buffer: 2-6 parts of sodium bicarbonate solution with a mass fraction of 2%-4%;

[0021] Additives: 0.1-0.3 parts tert-butyl hydroperoxide, 0.1-0.3 parts sodium formaldehyde sulfoxylate;

[0022] Solvent: 15-25 parts deionized water;

[0023] a2. Add DNS-86 emulsifier to deionized water, and slowly add methyl methacrylate, styrene, and butyl acrylate while stirring at 300-500 rpm. Stir for 30-40 minutes to obtain the core layer pre-emulsion.

[0024] a3. Add DNS-86 emulsifier to deionized water, and slowly add dodecafluoroheptyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, butyl acrylate, methyl methacrylate, and acrylic acid while stirring at 300-500 rpm. Stir for 40-60 min to obtain a shell pre-emulsion.

[0025] a4. Add sodium bicarbonate solution to deionized water, along with 1 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution. Heat to 78-82℃ and stir at 200-250 rpm for 15-25 minutes to obtain the seed emulsion.

[0026] a5. Slowly add the remaining 9 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution dropwise to the seed emulsion over 2-3 hours. Stir the mixture at 200-250 rpm for 15-25 minutes at 78-82°C, and maintain the temperature for 15-30 minutes. Then slowly add the shell layer pre-emulsion and the remaining 1 / 3 of the ammonium persulfate solution dropwise over 1.5-2.5 hours. After the addition is complete, raise the temperature to 85-87°C and maintain the temperature for 1.0-1.5 hours. Then lower the temperature to 50-60°C, add tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate, and stir at 150-200 rpm for 30-45 minutes. Cool to room temperature, filter with a 180-200 mesh filter cloth, and add ammonia water to adjust the pH of the emulsion to 7.5-8.5 to obtain a fluorinated silicone-acrylic emulsion.

[0027] Furthermore, the preparation method of the modified nano-silicon powder includes the following steps:

[0028] b1. Weigh the following by weight: 100-120 parts of nano-silicon powder with a particle size of 10-20nm, 5-15 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 300-500 parts of anhydrous ethanol, 1-3 parts of deionized water, and 0.1-0.5 parts of glacial acetic acid.

[0029] b2. Mix deionized water, glacial acetic acid and 1 / 3 anhydrous ethanol and stir well. Slowly add γ-(2,3-epoxypropoxy)propyltrimethoxysilane at 400-600 rpm and continue stirring for 30-60 min to obtain the modified solution.

[0030] b3. Add the nano-silicon powder to the remaining 2 / 3 of the anhydrous ethanol, stir and mix at 500-800 rpm, then place it in an ultrasonic generator and ultrasonically disperse it at 300-500W for 30-45 minutes to obtain a suspension.

[0031] b4. Place the suspension in a water bath at 65-75℃ and slowly add the modified liquid dropwise over 1-2 hours. After the addition is complete, keep the mixture warm and reflux for 4-6 hours. Cool to room temperature, filter, wash the filter cake 3-5 times with anhydrous ethanol, dry in a vacuum drying oven at 100-110℃ for 6-8 hours, and grind to obtain modified nano-silicon powder.

[0032] Furthermore, the preparation method of the polyether-modified silicone oil composite defoamer includes the following steps:

[0033] c1. Weigh the following components by weight: 20-40 parts of hydrogen-containing silicone oil, 60-80 parts of allyl polyether, 0.01-0.05 parts of platinum-1,3-divinyltetramethyldisiloxane complex, 5-15 parts of isopropanol, 0.2-0.4 parts of 1-ethynyl-1-cyclohexanol, 40-60 parts of white oil, 3-8 parts of hydrophobic fumed silica, 1-3 parts of sorbitan oleate, 1-3 parts of dehydrated sorbitan monooleate polyoxyethylene ether, 0.2-0.8 parts of hydroxyethyl cellulose, 0.1-0.3 parts of 1,2-benzisothiazolin-3-one, and 15-25 parts of deionized water.

[0034] c2. Place hydrogen-containing silicone oil, allyl polyether, isopropanol and 1-ethynyl-1-cyclohexanol in a reaction vessel, stir evenly at 150-250 rpm, then introduce nitrogen protection, heat to 85-90℃, add platinum-1,3-divinyltetramethyldisiloxane complex using a microsyringe, keep the reaction at this temperature for 4-6 hours, cool to 50-60℃, remove isopropanol and low-boiling substances under vacuum for 1-2 hours, cool to room temperature, filter, and obtain polyether-modified silicone oil;

[0035] c3. Add white oil and sorbitan oleate to polyether modified silicone oil, heat to 60-70℃, stir at 300-500 rpm for 15-25 min, slowly add hydrophobic fumed silica, continue to disperse at 1000-1500 rpm for 35-45 min, keep warm, and obtain oil phase.

[0036] c4. Add sorbitan monooleate polyoxyethylene ether, hydroxyethyl cellulose and 1,2-benzisothiazolin-3-one to deionized water, heat to 60-70℃ and stir until completely dissolved and homogeneous to obtain the aqueous phase;

[0037] c5. Slowly add the aqueous phase to the oil phase, stir at 600-800 rpm for 15-20 minutes, then shear at 5000-10000 rpm for 5-10 minutes, cool to room temperature, filter with a 180-200 mesh filter, and discharge to obtain polyether modified silicone oil composite defoamer.

[0038] Furthermore, the preparation method of the antibacterial composite coating for hospital wards includes the following steps:

[0039] (1) Weigh each raw material component according to its weight percentage;

[0040] (2) Add ammonium polyacrylate, wetting agent, 1 / 2 polyether modified silicone oil composite defoamer, and isobutanolamine to deionized water and stir at a stirring speed of 300-500 rpm for 8-12 min to obtain a solution;

[0041] (3) Add silver-zinc zeolite antibacterial agent, anatase nano titanium dioxide, nano manganese dioxide, rutile titanium dioxide, modified nano silicon powder, and ultrafine flake mica powder to the solution in sequence and slowly. Stir at 800-1000 rpm until uniform, then increase to 1500-1800 rpm and disperse for 25-35 min to obtain a dispersion.

[0042] (4) Pump the dispersion into a sand mill and grind it for 2-4 hours with 0.6-0.8 mm zirconia beads. Discharge the material to obtain a slurry.

[0043] (5) Slowly add the fluorine-modified silicone-acrylic emulsion and silica sol to the slurry, stir at 300-500 rpm for 10-20 min, slowly add the remaining 1 / 2 of the polyether-modified silicone oil composite defoamer and surfactant, continue stirring for 8-10 min, then add HASE thickener, adjust the speed to 100-200 rpm, slowly add tri-1-(2-methylaziridine)phosphine oxide, stir for 10-20 min, continue adjusting the speed to 50-100 rpm, mature for 1-2 h, filter with a 180-200 mesh filter, package, and obtain the antibacterial composite coating for hospital wards.

[0044] In summary, this application includes at least the following beneficial effects:

[0045] (1) This invention uses fluorinated silicone acrylic emulsion as a base material and mixes it with silica sol to prepare a coating. The "core-shell structure" and "organofluorine-organosilicon-acrylate" ternary synergistic design of the fluorinated silicone acrylic emulsion make the shell layer rich in fluorine and silicon elements, providing the coating with extreme chemical corrosion resistance and low surface energy. It can chemically combine with silica sol (Si-OH condensation) to form a denser network. The fluorinated silicone acrylic emulsion provides excellent film-forming properties, adhesion and toughness. It and silica sol jointly construct a rigid inorganic siloxane network (Si-O-Si) through the crosslinking agent tri-1-(2-methylaziridine)phosphine oxide. The two form an organic-inorganic interpenetrating network (IPN) through chemical bonding. Its dense structure can effectively block the penetration and erosion of disinfectant molecules. Meanwhile, the ultrafine flake mica powder is arranged in parallel in the coating, which greatly extends the path of disinfectant penetration; while the crosslinking agent tri-1-(2-methylaziridine)phosphine oxide forms a strong covalent bond network between polymer molecular chains, which greatly reduces the swelling of the coating. The two work together to enable the coating to withstand repeated scrubbing with high concentrations of disinfectant, thereby extending the service life of the coating.

[0046] (2) By adding ammonium polyacrylate and wetting agent, this invention ensures the full dispersion and long-term stability of high surface energy nanomaterials and heavy fillers, preventing sedimentation and agglomeration. At the same time, HASE thickener is added. The anionic properties of HASE thickener have a good electrostatic stabilizing effect on inorganic pigments and fillers, preventing sedimentation. HASE thickener can also provide good low shear viscosity, ensuring storage stability. Meanwhile, its associative structure is destroyed under high shear, and the viscosity decreases. While providing good anti-settling properties, it also gives the coating excellent leveling and anti-splashing properties. Together with surfactant and polyether modified silicone oil composite defoamer, it ensures that the paint film is flat, smooth and defect-free after construction.

[0047] (3) This invention uses silver-loaded zinc zeolite antibacterial agent and nano-titanium dioxide as antibacterial agents, giving the coating excellent broad-spectrum and long-lasting antibacterial and antiviral capabilities. Photocatalytic nano-titanium dioxide generates strong oxidizing free radicals under light irradiation, which instantaneously and non-selectively oxidize and decompose pathogenic microorganisms. During ultraviolet disinfection, the nano-titanium dioxide in the coating is activated, and the free radicals it generates can catalyze the decomposition of the disinfectant on the surface, generating more active free radicals, instantly and significantly improving the disinfection efficiency, and achieving thorough disinfection in a shorter time. At the same time, the silver-loaded zinc zeolite antibacterial agent continuously... Slow-release silver and zinc ions provide continuous contact-based sterilization and mildew prevention. Their complementary properties enhance the antibacterial effect of the coating, addressing the issue of decreased antibacterial efficacy of nano-titanium dioxide under insufficient light. Furthermore, the addition of nano-manganese dioxide effectively catalyzes peroxide disinfectants such as hydrogen peroxide and peracetic acid, causing their rapid decomposition to generate active free radicals, instantly and significantly improving disinfection efficiency. The inorganic network structure formed by modified nano-silica powder and silica sol possesses natural physical antibacterial properties, which, combined with the aforementioned chemical sterilization mechanism, constitute a multi-layered protective barrier. Under light, nano-titanium dioxide not only sterilizes but also decomposes organic contaminants adhering to the coating surface. Its photoinduced superhydrophilic effect allows water to spread completely on the surface, forming a water film that washes away residual decomposed contaminants, maintaining long-term surface cleanliness and reducing cleaning burden. Detailed Implementation

[0048] It should be noted that, where there is no conflict, the embodiments and features described in this application can be combined with each other. The present invention will now be described in detail with reference to the embodiments.

[0049] It should be noted that, unless otherwise specified, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0050] This invention provides a method for preparing an antibacterial composite coating for hospital wards, comprising the following steps:

[0051] (1) Weigh the following components by weight:

[0052] Core layer pre-emulsion components: 20-30 parts deionized water, 0.5-1.2 parts DNS-86 emulsifier, 15-25 parts methyl methacrylate, 10-20 parts styrene, and 5-15 parts butyl acrylate;

[0053] Shell pre-emulsion components: 15-25 parts deionized water, 0.3-0.8 parts DNS-86 emulsifier, 3-8 parts dodecafluoroheptyl methacrylate, 2-5 parts γ-methacryloyloxypropyltrimethoxysilane, 20-30 parts butyl acrylate, 5-10 parts methyl methacrylate, and 1-2 parts acrylic acid.

[0054] Initiator: 6-12 parts of ammonium persulfate solution with a mass fraction of 6%-10%;

[0055] Buffer: 2-6 parts of sodium bicarbonate solution with a mass fraction of 2%-4%;

[0056] Additives: 0.1-0.3 parts tert-butyl hydroperoxide, 0.1-0.3 parts sodium formaldehyde sulfoxylate;

[0057] Solvent: 15-25 parts deionized water;

[0058] (2) Add DNS-86 emulsifier to deionized water, and slowly add methyl methacrylate, styrene and butyl acrylate at a stirring speed of 300-500 rpm. Stir for 30-40 min to obtain core layer pre-emulsion.

[0059] (3) Add DNS-86 emulsifier to deionized water, and slowly add dodecafluoroheptyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, butyl acrylate, methyl methacrylate and acrylic acid at a stirring speed of 300-500 rpm. Stir for 40-60 min to obtain shell pre-emulsion.

[0060] (4) Add sodium bicarbonate solution to deionized water, and add 1 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution. Heat to 78-82℃ and stir at 200-250 rpm for 15-25 min to obtain seed emulsion.

[0061] (5) Slowly add the remaining 9 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution to the seed emulsion for 2-3 hours. Stir the reaction at 200-250 rpm at 78-82℃ for 15-25 minutes and keep warm for 15-30 minutes. Then slowly add the shell layer pre-emulsion and the remaining 1 / 3 of the ammonium persulfate solution for 1.5-2.5 hours. After the addition is complete, raise the temperature to 85-87℃ and keep warm for 1.0-1.5 hours. Then lower the temperature to 50-60℃, add tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate and stir at 150-200 rpm for 30-45 minutes. Cool to room temperature and filter with 180-200 mesh filter cloth. Add ammonia water to adjust the pH of the emulsion to 7.5-8.5 to obtain fluorine-modified silicone-acrylic emulsion.

[0062] (6) Weigh the following by weight: 100-120 parts of nano-silicon powder with a particle size of 10-20 nm, 5-15 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 300-500 parts of anhydrous ethanol, 1-3 parts of deionized water, and 0.1-0.5 parts of glacial acetic acid.

[0063] (7) Mix deionized water, glacial acetic acid and 1 / 3 of anhydrous ethanol and stir until homogeneous. Slowly add γ-(2,3-epoxypropoxy)propyltrimethoxysilane at 400-600 rpm and continue stirring for 30-60 min to obtain the modified solution.

[0064] (8) Add the nano-silicon powder to the remaining 2 / 3 of the anhydrous ethanol, stir and mix at a speed of 500-800 rpm, and then place it in an ultrasonic generator and ultrasonically disperse it at a power of 300-500W for 30-45 minutes to obtain a suspension.

[0065] (9) Place the suspension in a water bath at 65-75℃ and slowly add the modified liquid dropwise for 1-2 hours. After the addition is complete, keep it warm and reflux for 4-6 hours. Cool to room temperature, filter, wash the filter cake with anhydrous ethanol 3-5 times, dry it in a vacuum drying oven at 100-110℃ for 6-8 hours, grind it, and obtain modified nano-silicon powder.

[0066] (10) Weigh the following by weight: 20-40 parts of hydrogen-containing silicone oil, 60-80 parts of allyl polyether, 0.01-0.05 parts of platinum-1,3-divinyltetramethyldisiloxane complex, 5-15 parts of isopropanol, 0.2-0.4 parts of 1-ethynyl-1-cyclohexanol, 40-60 parts of white oil, 3-8 parts of hydrophobic fumed silica, 1-3 parts of sorbitan anhydride oleate, 1-3 parts of dehydrated sorbitan monooleate polyoxyethylene ether, 0.2-0.8 parts of hydroxyethyl cellulose, 0.1-0.3 parts of 1,2-benzisothiazolin-3-one, and 15-25 parts of deionized water;

[0067] (11) Place hydrogen-containing silicone oil, allyl polyether, isopropanol and 1-ethynyl-1-cyclohexanol in a reaction vessel, stir evenly at a speed of 150-250 rpm, then introduce nitrogen for protection, heat to 85-90℃, add platinum-1,3-divinyltetramethyldisiloxane complex using a microsyringe, keep the reaction at the temperature for 4-6 h, cool to 50-60℃, remove isopropanol and low-boiling substances under vacuum for 1-2 h, cool to room temperature, filter, and obtain polyether modified silicone oil;

[0068] (12) Add white oil and sorbitan oleate to polyether modified silicone oil, heat to 60-70℃, stir at 300-500 rpm for 15-25 min, slowly add hydrophobic fumed silica, continue to disperse at 1000-1500 rpm for 35-45 min, keep warm, and obtain oil phase;

[0069] (13) Add sorbitan monooleate polyoxyethylene ether, hydroxyethyl cellulose and 1,2-benzisothiazolin-3-one to deionized water, heat to 60-70℃ and stir until completely dissolved and homogeneous to obtain an aqueous phase;

[0070] (14) Slowly add the aqueous phase to the oil phase, stir at 600-800 rpm for 15-20 min, then shear at 5000-10000 rpm for 5-10 min, cool to room temperature, filter with 180-200 mesh, and discharge to obtain polyether modified silicone oil composite defoamer.

[0071] (15) Weigh the following by weight: 50-70 parts of fluorine-modified silicone-acrylic emulsion, 10-20 parts of silica sol with a particle size of 10-20 nm, 4-6 parts of anatase nano-titanium dioxide with a particle size of 10-20 nm, 1-2 parts of nano-manganese dioxide with a particle size of 20-30 nm, 2-4 parts of silver-zinc zeolite antibacterial agent, 10-16 parts of modified nano-silica powder, 8-12 parts of ultrafine flake mica powder with a particle size of 2-6 μm, and other components. The following ingredients are used: 8-12 parts of rutile titanium dioxide with a diameter of 0.2-0.4 μm, 0.8-1.6 parts of ammonium polyacrylate, 0.5-1.5 parts of polyether-modified silicone oil composite defoamer, 0.4-0.8 parts of HASE thickener, 0.1-0.3 parts of wetting agent, 0.5-1.5 parts of surfactant, 1.5-2.5 parts of tri-1-(2-methylaziridine)phosphine oxide, 0.1-0.3 parts of isobutanolamine, and 20-30 parts of deionized water;

[0072] (16) Add ammonium polyacrylate, wetting agent, 1 / 2 of polyether modified silicone oil composite defoamer and isobutanolamine to deionized water, and stir at a stirring speed of 300-500 rpm for 8-12 min to obtain a solution;

[0073] (17) Add silver-zinc zeolite antibacterial agent, anatase nano titanium dioxide, nano manganese dioxide, rutile titanium dioxide, modified nano silicon powder, and ultrafine flake mica powder to the solution in sequence and slowly. Stir at 800-1000 rpm until uniform, then increase to 1500-1800 rpm and disperse for 25-35 min to obtain a dispersion.

[0074] (18) Pump the dispersion into a sand mill and grind it for 2-4 hours with 0.6-0.8 mm zirconia beads. Discharge the material to obtain a slurry.

[0075] (19) Slowly add fluorine-modified silicone-acrylic emulsion and silica sol to the slurry, stir at 300-500 rpm for 10-20 min, slowly add the remaining 1 / 2 of polyether-modified silicone oil composite defoamer and surfactant, continue stirring for 8-10 min, add HASE thickener, adjust the speed to 100-200 rpm, slowly add tri-1-(2-methylaziridine)phosphine oxide, stir for 10-20 min, continue adjusting the speed to 50-100 rpm, mature for 1-2 h, filter with 180-200 mesh filter, package, and obtain antibacterial composite coating for hospital wards.

[0076] The HASE thickener includes at least one of TT-115, TT-215, ML-818, ML-828, and ML-838; the wetting agent includes at least one of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether; and the surfactant includes at least one of decyl glucoside, lauryl glucoside, and sucrose stearate.

[0077] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention. Example 1

[0078] The preparation method of the antibacterial composite coating for hospital wards in this embodiment includes the following steps:

[0079] (1) Weigh the following components by weight:

[0080] Core layer pre-emulsion components: 20 parts deionized water, 0.5 parts DNS-86 emulsifier, 15 parts methyl methacrylate, 10 parts styrene, and 5 parts butyl acrylate;

[0081] Shell pre-emulsion components: 15 parts deionized water, 0.3 parts DNS-86 emulsifier, 3 parts dodecafluoroheptyl methacrylate, 2 parts γ-methacryloyloxypropyltrimethoxysilane, 20 parts butyl acrylate, 5 parts methyl methacrylate, and 1 part acrylic acid.

[0082] Initiator: 6 parts of 6% ammonium persulfate solution;

[0083] Buffer: 2 parts of 2% sodium bicarbonate solution;

[0084] Additives: 0.1 parts tert-butyl hydroperoxide, 0.1 parts sodium formaldehyde sulfoxylate;

[0085] Solvent: 15 parts deionized water;

[0086] (2) Add DNS-86 emulsifier to deionized water, and slowly add methyl methacrylate, styrene and butyl acrylate at a stirring speed of 300 rpm. Stir for 30 min to obtain core layer pre-emulsion.

[0087] (3) Add DNS-86 emulsifier to deionized water, and slowly add dodecafluoroheptyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, butyl acrylate, methyl methacrylate and acrylic acid at a stirring speed of 300 rpm. Stir for 40 min to obtain shell pre-emulsion.

[0088] (4) Add sodium bicarbonate solution to deionized water, and add 1 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution. Heat to 78°C and stir at 200 rpm for 15 min to obtain seed emulsion.

[0089] (5) The remaining 9 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution were slowly added dropwise to the seed emulsion for 2 hours. The mixture was stirred at 200 rpm for 15 minutes at 78°C and kept warm for 15 minutes. Then the shell layer pre-emulsion and the remaining 1 / 3 of the ammonium persulfate solution were slowly added dropwise for 1.5 hours. After the addition was completed, the temperature was raised to 85°C and kept warm for 1 hour. Then the temperature was lowered to 50°C. Tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate were added and stirred at 150 rpm for 30 minutes. The mixture was cooled to room temperature and filtered with 180 mesh filter cloth. Ammonia water was added to adjust the pH of the emulsion to 7.5 to obtain fluorine-modified silicone-acrylic emulsion.

[0090] (6) Weigh the following by weight: 100 parts of 10 nm nano-silicon powder, 5 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 300 parts of anhydrous ethanol, 1 part of deionized water, and 0.1 parts of glacial acetic acid.

[0091] (7) Mix deionized water, glacial acetic acid and 1 / 3 of anhydrous ethanol and stir until homogeneous. Slowly add γ-(2,3-epoxypropoxy)propyltrimethoxysilane at 400 rpm and continue stirring for 30 min to obtain the modified solution.

[0092] (8) Add the nano-silicon powder to the remaining 2 / 3 of the anhydrous ethanol, stir and mix at 500 rpm, then place it in an ultrasonic generator and ultrasonically disperse it for 30 min at 300 W to obtain a suspension.

[0093] (9) The suspension was placed in a water bath at 65°C and the modified liquid was slowly added dropwise for 1 hour. After the addition was completed, the mixture was kept warm and refluxed for 4 hours. The mixture was cooled to room temperature, filtered, and the filter cake was washed three times with anhydrous ethanol. The mixture was then placed in a vacuum drying oven at 100°C and dried for 6 hours. The mixture was then ground to obtain modified nano-silicon powder.

[0094] (10) Weigh the following by weight: 20 parts of hydrogen-terminated silicone oil, 60 parts of allyl polyether, 0.01 parts of platinum-1,3-divinyltetramethyldisiloxane complex, 5 parts of isopropanol, 0.2 parts of 1-ethynyl-1-cyclohexanol, 40 parts of white oil, 3 parts of hydrophobic fumed silica, 1 part of sorbitan anhydride oleate, 1 part of dehydrated sorbitan monooleate polyoxyethylene ether, 0.2 parts of hydroxyethyl cellulose, 0.1 parts of 1,2-benzisothiazolin-3-one, and 15 parts of deionized water.

[0095] (11) Hydrogen-terminated silicone oil, allyl polyether, isopropanol and 1-ethynyl-1-cyclohexanol were placed in a reaction vessel and stirred evenly at a speed of 150 rpm. Nitrogen gas was introduced for protection, and the temperature was raised to 85°C. Platinum-1,3-divinyltetramethyldisiloxane complex was added using a microsyringe. The reaction was kept at the temperature for 4 h, and then cooled to 50°C. Isopropanol and low-boiling substances were removed under vacuum for 1 h. The mixture was cooled to room temperature and filtered to obtain polyether-modified silicone oil.

[0096] (12) Add white oil and sorbitan oleate to polyether modified silicone oil, heat to 60°C, stir at 300 rpm for 15 min, slowly add hydrophobic fumed silica, continue to disperse at 1000 rpm for 35 min, keep warm, and obtain oil phase.

[0097] (13) Add sorbitan monooleate polyoxyethylene ether, hydroxyethyl cellulose and 1,2-benzisothiazolin-3-one to deionized water, heat to 60°C and stir until completely dissolved and homogeneous to obtain an aqueous phase;

[0098] (14) Slowly add the aqueous phase to the oil phase, stir at 600 rpm for 15 min, then shear at 5000 rpm for 5 min, cool to room temperature, filter with a 180 mesh filter, and discharge to obtain polyether modified silicone oil composite defoamer.

[0099] (15) Weigh the following by weight: 50 parts of fluorine-modified silicone-acrylic emulsion, 10 parts of silica sol with a particle size of 10 nm, 4 parts of anatase nano-titanium dioxide with a particle size of 10 nm, 1 part of nano-manganese dioxide with a particle size of 20 nm, 2 parts of silver-loaded zinc zeolite antibacterial agent, 10 parts of modified nano-silica powder, 8 parts of ultrafine flake mica powder with a particle size of 2 μm, 8 parts of rutile titanium dioxide with a particle size of 0.2 μm, 0.8 parts of ammonium polyacrylate, 0.5 parts of polyether-modified silicone oil composite defoamer, 0.4 parts of TT-115 type HASE thickener, 0.1 parts of nonylphenol polyoxyethylene ether, 0.5 parts of decyl glucoside, 1.5 parts of tri-1-(2-methylaziridine)phosphine oxide, 0.1 parts of isobutanolamine, and 20 parts of deionized water.

[0100] (16) Add ammonium polyacrylate, nonylphenol polyoxyethylene ether, 1 / 2 of the polyether modified silicone oil composite defoamer and isobutanolamine to deionized water and stir at 300 rpm for 8 min to obtain a solution.

[0101] (17) Add silver-zinc zeolite antibacterial agent, anatase nano titanium dioxide, nano manganese dioxide, rutile titanium dioxide, modified nano silicon powder, and ultrafine flake mica powder to the solution in sequence and stir evenly at 800 rpm, then increase to 1500 rpm and disperse for 25 min to obtain a dispersion.

[0102] (18) Pump the dispersion into a sand mill and grind it for 2 hours with 0.6 mm zirconia beads. Discharge the material to obtain a slurry.

[0103] (19) The fluorine-modified silicone-acrylic emulsion and silica sol were slowly added to the slurry and stirred at 300 rpm for 10 min. The remaining 1 / 2 of the polyether-modified silicone oil composite defoamer and decyl glucoside were added slowly in sequence and stirred for 8 min. Then TT-115 type HASE thickener was added and the speed was adjusted to 100 rpm. Tri-1-(2-methylaziridine)phosphine oxide was added slowly and stirred for 10 min. The speed was adjusted to 50 rpm and matured for 1 h. The mixture was filtered through a 180 mesh filter and packaged to obtain an antibacterial composite coating for hospital wards. Example 2

[0104] This embodiment describes a method for preparing an antibacterial composite coating for hospital wards, comprising the following steps:

[0105] (1) Weigh the following components by weight:

[0106] Core layer pre-emulsion components: 25 parts deionized water, 0.8 parts DNS-86 emulsifier, 20 parts methyl methacrylate, 15 parts styrene, and 10 parts butyl acrylate;

[0107] Shell pre-emulsion components: 20 parts deionized water, 0.5 parts DNS-86 emulsifier, 6 parts dodecafluoroheptyl methacrylate, 4 parts γ-methacryloyloxypropyltrimethoxysilane, 25 parts butyl acrylate, 7 parts methyl methacrylate, and 1.5 parts acrylic acid.

[0108] Initiator: 8 parts of 8% ammonium persulfate solution;

[0109] Buffer: 4 parts of 3% sodium bicarbonate solution;

[0110] Additives: 0.2 parts tert-butyl hydroperoxide, 0.2 parts sodium formaldehyde sulfoxylate;

[0111] Solvent: 20 parts deionized water;

[0112] (2) Add DNS-86 emulsifier to deionized water, and slowly add methyl methacrylate, styrene and butyl acrylate at a stirring speed of 400 rpm. Stir for 35 min to obtain core layer pre-emulsion.

[0113] (3) Add DNS-86 emulsifier to deionized water, and slowly add dodecafluoroheptyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, butyl acrylate, methyl methacrylate and acrylic acid at a stirring speed of 400 rpm. Stir for 50 min to obtain shell pre-emulsion.

[0114] (4) Add sodium bicarbonate solution to deionized water, and add 1 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution. Heat to 80°C and stir at 225 rpm for 20 min to obtain seed emulsion.

[0115] (5) The remaining 9 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution were slowly added dropwise to the seed emulsion for 2.5 hours. The mixture was stirred at 225 rpm at 80°C for 20 minutes and kept warm for 20 minutes. Then the shell layer pre-emulsion and the remaining 1 / 3 of the ammonium persulfate solution were slowly added dropwise for 2 hours. After the addition was completed, the temperature was raised to 86°C and kept warm for 1.3 hours. Then the temperature was lowered to 55°C. Tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate were added and stirred at 175 rpm for 38 minutes. The mixture was cooled to room temperature and filtered with a 190-mesh filter cloth. Ammonia was added dropwise to adjust the pH of the emulsion to 8 to obtain fluorine-modified silicone-acrylic emulsion.

[0116] (6) Weigh the following by weight: 110 parts of 15nm nano-silicon powder, 10 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 400 parts of anhydrous ethanol, 2 parts of deionized water, and 0.3 parts of glacial acetic acid.

[0117] (7) Mix deionized water, glacial acetic acid and 1 / 3 of anhydrous ethanol and stir until homogeneous. Slowly add γ-(2,3-epoxypropoxy)propyltrimethoxysilane at 500 rpm and continue stirring for 45 min to obtain the modified solution.

[0118] (8) Add the nano-silicon powder to the remaining 2 / 3 of the anhydrous ethanol, stir and mix at 650 rpm, then place it in an ultrasonic generator and ultrasonically disperse it for 38 min at 400 W to obtain a suspension.

[0119] (9) The suspension was placed in a water bath at 70°C and the modified liquid was slowly added dropwise over a period of 1.5 hours. After the addition was completed, the mixture was kept warm and refluxed for 5 hours. The mixture was then cooled to room temperature, filtered, and the filter cake was washed four times with anhydrous ethanol. The cake was then placed in a vacuum drying oven at 105°C and dried for 7 hours. The mixture was then ground to obtain modified nano-silicon powder.

[0120] (10) Weigh the following by weight: 30 parts of hydrogen-containing silicone oil, 70 parts of allyl polyether, 0.03 parts of platinum-1,3-divinyltetramethyldisiloxane complex, 10 parts of isopropanol, 0.3 parts of 1-ethynyl-1-cyclohexanol, 50 parts of white oil, 5 parts of hydrophobic fumed silica, 2 parts of sorbitan anhydride oleate, 2 parts of dehydrated sorbitan monooleate polyoxyethylene ether, 0.5 parts of hydroxyethyl cellulose, 0.2 parts of 1,2-benzisothiazolin-3-one, and 20 parts of deionized water.

[0121] (11) Hydrogen-terminated silicone oil, allyl polyether, isopropanol and 1-ethynyl-1-cyclohexanol were placed in a reaction vessel and stirred evenly at a speed of 200 rpm. Nitrogen gas was introduced for protection, and the temperature was raised to 88°C. Platinum-1,3-divinyltetramethyldisiloxane complex was added using a microsyringe. The reaction was kept at this temperature for 5 h, and then cooled to 55°C. Isopropanol and low-boiling substances were removed under vacuum for 1.5 h. The mixture was cooled to room temperature and filtered to obtain polyether-modified silicone oil.

[0122] (12) Add white oil and sorbitan oleate to polyether modified silicone oil, heat to 65°C, stir at 400 rpm for 20 min, slowly add hydrophobic fumed silica, continue to disperse at 1250 rpm for 40 min, keep warm, and obtain oil phase.

[0123] (13) Add sorbitan monooleate polyoxyethylene ether, hydroxyethyl cellulose and 1,2-benzisothiazolin-3-one to deionized water, heat to 65°C and stir until completely dissolved and homogeneous to obtain an aqueous phase;

[0124] (14) Slowly add the aqueous phase to the oil phase, stir at 700 rpm for 17 min, then shear at 7500 rpm for 8 min, cool to room temperature, filter with a 190 mesh filter, and discharge to obtain polyether modified silicone oil composite defoamer.

[0125] (15) Weigh the following by weight: 60 parts of fluorine-modified silicone-acrylic emulsion, 15 parts of silica sol with a particle size of 15 nm, 5 parts of anatase nano-titanium dioxide with a particle size of 15 nm, 1.5 parts of nano-manganese dioxide with a particle size of 25 nm, 3 parts of silver-loaded zinc zeolite antibacterial agent, 13 parts of modified nano-silica powder, 10 parts of ultrafine flake mica powder with a particle size of 4 μm, 10 parts of rutile titanium dioxide with a particle size of 0.3 μm, 1.2 parts of ammonium polyacrylate, 1 part of polyether-modified silicone oil composite defoamer, 0.6 parts of TT-215 type HASE thickener, 0.2 parts of octylphenol polyoxyethylene ether, 1 part of lauryl glucoside, 2 parts of tri-1-(2-methylaziridine)phosphine oxide, 0.2 parts of isobutanolamine, and 25 parts of deionized water.

[0126] (16) Add ammonium polyacrylate, octylphenol polyoxyethylene ether, 1 / 2 of the polyether modified silicone oil composite defoamer and isobutanolamine to deionized water and stir at 400 rpm for 10 min to obtain a solution;

[0127] (17) Add silver-zinc zeolite antibacterial agent, anatase nano titanium dioxide, nano manganese dioxide, rutile titanium dioxide, modified nano silicon powder, and ultrafine flake mica powder to the solution in sequence and slowly. Stir at 900 rpm until uniform, then increase to 1650 rpm and disperse for 30 min to obtain a dispersion.

[0128] (18) Pump the dispersion into a sand mill and grind it for 3 hours with 0.7 mm zirconia beads. Discharge the material to obtain a slurry.

[0129] (19) The fluorine-modified silicone-acrylic emulsion and silica sol were slowly added to the slurry and stirred at 400 rpm for 15 min. The remaining 1 / 2 of the polyether-modified silicone oil composite defoamer and lauryl glucoside were added slowly in sequence and stirred for 9 min. Then TT-215 type HASE thickener was added and the speed was adjusted to 150 rpm. Tri-1-(2-methylaziridine)phosphine oxide was added slowly and stirred for 15 min. The speed was adjusted to 75 rpm and matured for 1.5 h. The mixture was filtered through a 190 mesh filter and packaged to obtain an antibacterial composite coating for hospital wards. Example 3

[0130] This embodiment describes a method for preparing an antibacterial composite coating for hospital wards, comprising the following steps:

[0131] (1) Weigh the following components by weight:

[0132] Core layer pre-emulsion components: 30 parts deionized water, 1.2 parts DNS-86 emulsifier, 25 parts methyl methacrylate, 20 parts styrene, and 15 parts butyl acrylate;

[0133] Shell pre-emulsion components: 25 parts deionized water, 0.8 parts DNS-86 emulsifier, 8 parts dodecafluoroheptyl methacrylate, 5 parts γ-methacryloyloxypropyltrimethoxysilane, 30 parts butyl acrylate, 10 parts methyl methacrylate, and 2 parts acrylic acid.

[0134] Initiator: 12 parts of 10% ammonium persulfate solution;

[0135] Buffer: 6 parts of 4% sodium bicarbonate solution;

[0136] Additives: 0.3 parts tert-butyl hydroperoxide, 0.3 parts sodium formaldehyde sulfoxylate;

[0137] Solvent: 25 parts deionized water;

[0138] (2) Add DNS-86 emulsifier to deionized water, and slowly add methyl methacrylate, styrene and butyl acrylate at a stirring speed of 500 rpm. Stir for 40 min to obtain core layer pre-emulsion.

[0139] (3) Add DNS-86 emulsifier to deionized water, and slowly add dodecafluoroheptyl methacrylate, γ-methacryloyloxypropyltrimethoxysilane, butyl acrylate, methyl methacrylate and acrylic acid at a stirring speed of 500 rpm. Stir for 60 min to obtain shell pre-emulsion.

[0140] (4) Add sodium bicarbonate solution to deionized water, and add 1 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution. Heat to 82°C and stir at 250 rpm for 25 min to obtain seed emulsion.

[0141] (5) The remaining 9 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution were slowly added dropwise to the seed emulsion for 3 hours. The mixture was stirred at 250 rpm at 82°C for 25 minutes and kept warm for 30 minutes. Then the shell layer pre-emulsion and the remaining 1 / 3 of the ammonium persulfate solution were slowly added dropwise for 2.5 hours. After the addition was completed, the temperature was raised to 87°C and kept warm for 1.5 hours. Then the temperature was lowered to 60°C. Tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate were added and stirred at 200 rpm for 45 minutes. The mixture was cooled to room temperature and filtered with a 200-mesh filter cloth. Ammonia was added dropwise to adjust the pH of the emulsion to 8.5 to obtain fluorine-modified silicone-acrylic emulsion.

[0142] (6) Weigh the following by weight: 120 parts of 20nm nano-silicon powder, 15 parts of γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 500 parts of anhydrous ethanol, 3 parts of deionized water, and 0.5 parts of glacial acetic acid.

[0143] (7) Mix deionized water, glacial acetic acid and 1 / 3 of anhydrous ethanol and stir until homogeneous. Slowly add γ-(2,3-epoxypropoxy)propyltrimethoxysilane at 600 rpm and continue stirring for 60 min to obtain the modified solution.

[0144] (8) Add the nano-silicon powder to the remaining 2 / 3 of the anhydrous ethanol, stir and mix at 800 rpm, then place it in an ultrasonic generator and ultrasonically disperse it at 500 W for 45 min to obtain a suspension.

[0145] (9) The suspension was placed in a water bath at 75°C and the modified liquid was slowly added dropwise over a period of 2 hours. After the addition was completed, the mixture was kept warm and refluxed for 6 hours. The mixture was then cooled to room temperature, filtered, and the filter cake was washed 5 times with anhydrous ethanol. The mixture was then placed in a vacuum drying oven at 110°C and dried for 8 hours. The mixture was then ground to obtain modified nano-silicon powder.

[0146] (10) Weigh the following by weight: 40 parts of hydrogen-containing silicone oil, 80 parts of allyl polyether, 0.05 parts of platinum-1,3-divinyltetramethyldisiloxane complex, 15 parts of isopropanol, 0.4 parts of 1-ethynyl-1-cyclohexanol, 60 parts of white oil, 8 parts of hydrophobic fumed silica, 3 parts of sorbitan oleate, 3 parts of dehydrated sorbitan monooleate polyoxyethylene ether, 0.8 parts of hydroxyethyl cellulose, 0.3 parts of 1,2-benzisothiazolin-3-one, and 25 parts of deionized water.

[0147] (11) Hydrogen-terminated silicone oil, allyl polyether, isopropanol and 1-ethynyl-1-cyclohexanol were placed in a reaction vessel and stirred evenly at a speed of 250 rpm. Nitrogen gas was introduced for protection, and the temperature was raised to 90°C. Platinum-1,3-divinyltetramethyldisiloxane complex was added using a microsyringe. The reaction was kept at the temperature for 6 h, and then cooled to 60°C. Isopropanol and low-boiling substances were removed under vacuum for 2 h. The mixture was cooled to room temperature and filtered to obtain polyether-modified silicone oil.

[0148] (12) Add white oil and sorbitan oleate to polyether modified silicone oil, heat to 70°C, stir at 500 rpm for 25 min, slowly add hydrophobic fumed silica, continue to disperse at 1500 rpm for 45 min, keep warm, and obtain oil phase.

[0149] (13) Add sorbitan monooleate polyoxyethylene ether, hydroxyethyl cellulose and 1,2-benzisothiazolin-3-one to deionized water, heat to 70°C and stir until completely dissolved and homogeneous to obtain an aqueous phase;

[0150] (14) Slowly add the aqueous phase to the oil phase, stir at 800 rpm for 20 min, then shear at 10000 rpm for 10 min, cool to room temperature, filter with a 200 mesh filter, and discharge to obtain polyether modified silicone oil composite defoamer.

[0151] (15) Weigh the following by weight: 70 parts of fluorine-modified silicone-acrylic emulsion, 20 parts of silica sol with a particle size of 20 nm, 6 parts of anatase nano-titanium dioxide with a particle size of 20 nm, 2 parts of nano-manganese dioxide with a particle size of 30 nm, 4 parts of silver-loaded zinc zeolite antibacterial agent, 16 parts of modified nano-silica powder, 12 parts of ultrafine flake mica powder with a particle size of 6 μm, 12 parts of rutile titanium dioxide with a particle size of 0.4 μm, 1.6 parts of ammonium polyacrylate, 1.5 parts of polyether-modified silicone oil composite defoamer, 0.8 parts of ML-818 type HASE thickener, 0.3 parts of lauryl alcohol polyoxyethylene ether, 1.5 parts of sucrose stearate, 2.5 parts of tri-1-(2-methylaziridine)phosphine oxide, 0.3 parts of isobutanolamine, and 30 parts of deionized water.

[0152] (16) Add ammonium polyacrylate, lauryl alcohol polyoxyethylene ether, 1 / 2 of the polyether modified silicone oil composite defoamer and isobutanolamine to deionized water and stir at 500 rpm for 12 min to obtain a solution.

[0153] (17) Add silver-zinc zeolite antibacterial agent, anatase nano titanium dioxide, nano manganese dioxide, rutile titanium dioxide, modified nano silicon powder, and ultrafine flake mica powder to the solution in sequence and slowly. Stir at 1000 rpm until uniform, then increase to 1800 rpm and disperse for 35 min to obtain a dispersion.

[0154] (18) Pump the dispersion into a sand mill and grind it for 4 hours with 0.8 mm zirconia beads. Discharge the material to obtain a slurry.

[0155] (19) The fluorine-modified silicone-acrylic emulsion and silica sol were slowly added to the slurry and stirred at 500 rpm for 20 min. The remaining 1 / 2 of the polyether-modified silicone oil composite defoamer and sucrose stearate were added slowly in sequence and stirred for 10 min. Then, ML-818 HASE thickener was added and the speed was adjusted to 200 rpm. Tri-1-(2-methylaziridine)phosphine oxide was added slowly and stirred for 20 min. The speed was adjusted to 100 rpm and the mixture was allowed to mature for 2 h. The mixture was then filtered through a 200-mesh filter and packaged to obtain an antibacterial composite coating for hospital wards.

[0156] Comparative Example 1

[0157] The preparation method of the antibacterial composite coating for hospital wards in this comparative example is basically the same as that in Example 1. The difference is that silicone-acrylic emulsion is used instead of fluorine-modified silicone-acrylic emulsion in this comparative example.

[0158] Comparative Example 2

[0159] The preparation method of the antibacterial composite coating for hospital wards in this comparative example is basically the same as that in Example 1. The difference is that in this comparative example, the fluorine-modified silicone-acrylic emulsion and silica sol are directly mixed by shear dispersion, and the crosslinking agent tris-1-(2-methylaziridine)phosphine oxide in this invention is not added.

[0160] Comparative Example 3

[0161] The preparation method of the antibacterial composite coating for hospital wards in this comparative example is basically the same as that in Example 1. The difference is that white oil defoamer is used instead of polyether modified silicone oil composite defoamer in this comparative example.

[0162] Comparative Example 4

[0163] The preparation method of the antibacterial composite coating for hospital wards in this comparative example is basically the same as that in Example 1, except that nano-manganese dioxide was not added in this comparative example.

[0164] Comparative Example 5

[0165] The preparation method of the antibacterial composite coating for hospital wards in this comparative example is basically the same as that in Example 1, except that no manganese anatase nano titanium dioxide is added in this comparative example.

[0166] Experimental Example

[0167] The coating samples from Examples 1-3 and Comparative Examples 1-3 were applied to tinplate or cement slabs and cured under constant temperature and humidity for 7 days before testing, including:

[0168] Sodium hypochlorite scrubbing resistance: Tested according to ASTM D1308 Standard Test Method for the Effects of Household Chemicals on Transparent and Tinted Organic Topcoats;

[0169] Enhanced disinfection effect of hydrogen peroxide and antibacterial rate under visible light: The antibacterial rate of the coating against Escherichia coli was tested according to ISO 22196 Determination of antimicrobial properties of plastic products.

[0170] Contact angle: The contact angle between the coating and water is tested according to GB / T 30693-2014 Measurement of contact angle between plastic film and water.

[0171] Self-cleaning property: Photocatalytic activity was evaluated using the methylene blue degradation method according to ISO 10678:2010 standard. Specific results are shown in Table 1.

[0172] Table 1: Performance Test Results of Oral Film Samples from Examples and Comparative Examples

[0173] As can be seen from the comparison between Example 1 and Comparative Example 1 in Table 1, Comparative Example 1 uses ordinary silicone-acrylic emulsion compared to Example 1, which results in the coating's chemical resistance being lower than that of Example 1. This is because the "core-shell structure" and "organofluorine-organosilicon-acrylate" ternary synergistic design of the fluorinated silicone-acrylic emulsion make the shell layer rich in fluorine and silicon elements, providing the coating with extreme chemical corrosion resistance and low surface energy. It can chemically combine with silica sol (Si-OH condensation) to form a denser network, thereby effectively resisting the oxidative erosion of disinfectant.

[0174] A comparison of Example 1 and Comparative Example 2 in Table 1 shows that Comparative Example 2 lacks the crosslinking agent tris-1-(2-methylaziridine)phosphine oxide, which significantly reduces the coating's resistance to sodium hypochlorite scrubbing. This is because the absence of the crosslinking agent prevents the formation of strong chemical bonds (Si-O-Si+CN covalent bonds) between the silica sol and the emulsion. Relying solely on physical mixing, under prolonged immersion in disinfectant, water molecules easily penetrate the fragile physical interface, leading to blistering, peeling, and a severe decrease in adhesion. This demonstrates that the crosslinking agent directly contributes to improving the physical and mechanical strength of the coating film. The mixing of silica sol and fluorinated silicone-acrylic emulsion produces a chemical bond, forming a dense network. The fluorinated silicone-acrylic emulsion provides excellent film-forming properties, adhesion, and toughness. Together with silica sol, a rigid inorganic siloxane network is constructed through the crosslinking agent tris(2-methylaziridine)phosphine oxide. The two form an organic-inorganic interpenetrating network through chemical bonding. Its dense structure can effectively block the penetration and erosion of disinfectant molecules. Meanwhile, the crosslinking agent tris(2-methylaziridine)phosphine oxide forms a strong covalent bond network between polymer molecular chains, which greatly reduces the swelling of the coating. The synergistic effect of the two allows the coating to withstand repeated scrubbing with high-concentration disinfectants, thereby extending the service life of the coating.

[0175] As can be seen from the comparison between Example 1 and Comparative Example 3 in Table 1, Comparative Example 3 uses a common white oil defoamer compared to Example 1. Common defoamers have poor compatibility with the complex high-performance system of this invention and are prone to causing surface defects such as pinholes. These defects become stress concentration points and contamination collection points. Although they do not affect scrub resistance, they will seriously damage the density of the paint film, affect the aesthetics, and reduce the anti-fouling properties. In contrast, the Example 1 uses a polyether-modified silicone oil composite defoamer in synergy with surfactants, ensuring that the paint film is smooth, even, and free of defects after application.

[0176] As can be seen from the comparison between Example 1 and Comparative Example 4 in Table 1, Comparative Example 4 lacks nano-manganese dioxide compared to Example 1, which leads to a decrease in the coating's resistance to sodium hypochlorite scrubbing and a reduction in its synergistic effect on hydrogen peroxide disinfection. This is because the addition of nano-manganese dioxide can effectively catalyze peroxide disinfectants such as hydrogen peroxide and peracetic acid, causing them to decompose rapidly and generate active free radicals, thereby instantly and significantly improving disinfection efficiency. The lack of nano-manganese dioxide to catalyze the disinfectant will slightly reduce the scrubbing resistance and disinfection performance. However, due to the presence of silver-zinc zeolite antibacterial agent and nano-titanium dioxide, its antibacterial performance under visible light remains good.

[0177] As can be seen from the comparison between Example 1 and Comparative Example 5 in Table 1, Comparative Example 5 lacks manganese anatase nano-titanium dioxide compared to Example 1. This results in a significant decrease in antibacterial and self-cleaning properties under visible light. This is because photocatalytic nano-titanium dioxide generates strong oxidizing free radicals under light irradiation, which instantaneously and non-selectively oxidize and decompose pathogenic microorganisms. During ultraviolet disinfection, the nano-titanium dioxide in the coating is activated, and the free radicals it generates can catalyze the decomposition of the disinfectant on the surface, generating more active free radicals, which instantly and significantly improves the disinfection efficiency, enabling thorough disinfection in a shorter time. At the same time, the silver-zinc zeolite antibacterial agent continuously releases silver and zinc ions, providing uninterrupted contact sterilization and antifungal effects. The two complement each other, which can effectively improve the antibacterial effect of the coating. Furthermore, nano-titanium dioxide can also decompose organic contaminants attached to the coating surface under light irradiation. Its photoinduced superhydrophilic effect allows water to spread completely on the surface, forming a water film, which washes away the decomposed contaminant residue, keeping the surface clean for a long time and reducing the cleaning burden.

[0178] Therefore, the antibacterial composite coating for hospital wards provided by this invention forms a coating with good scrub resistance and antibacterial effect, which can effectively keep the surface clean for a long time, reduce the cleaning burden, and has good application prospects.

[0179] Based on the above-described preferred embodiments of the present invention, and through the foregoing description, those skilled in the art can make various changes and modifications without departing from the inventive concept. The technical scope of this invention is not limited to the contents of the specification, but must be determined according to the scope of the claims.

Claims

1. An antibacterial composite paint for a hospital room, characterized by comprising: a base paint; a silver ion-containing antibacterial agent; and a polyol compound. The raw materials include, in parts by weight: fluorine-modified silicone-acrylic emulsion 50-70 parts, silica sol 10-20 parts, anatase nano-titanium dioxide 4-6 parts, nano-manganese dioxide 1-2 parts, silver-loaded zinc zeolite antibacterial agent 2-4 parts, modified nano-silicon powder 10-16 parts, ultra-fine flaky mica powder 8-12 parts, rutile titanium dioxide 8-12 parts, ammonium polyacrylate 0.8-1.2 parts, polyether-modified silicone oil composite defoaming agent 0.5-1.5 parts, HASE thickening agent 0.4-0.8 parts, wetting agent 0.1-0.3 parts, surfactant 0.5-1.5 parts, tris-1-(2-methylaziridine) phosphine oxide 1.5-2.5 parts, isobutanol amine 0.1-0.3 parts, and deionized water 20-30 parts; The preparation method of the fluorine-modified silicone-acrylic emulsion comprises the following steps: a1, the following components are weighed, respectively, in parts by weight: The core layer pre-emulsion component: deionized water 20-30 parts, DNS-86 emulsifier 0.5-1.2 parts, methyl methacrylate 15-25 parts, styrene 10-20 parts, and butyl acrylate 5-15 parts; The shell layer pre-emulsion component: deionized water 15-25 parts, DNS-86 emulsifier 0.3-0.8 parts, dodecafluoroheptyl methacrylate 3-8 parts, γ-methacryloyloxypropyl trimethoxysilane 2-5 parts, butyl acrylate 20-30 parts, methyl methacrylate 5-10 parts, and acrylic acid 1-2 parts; The initiator: 6-12 parts of ammonium persulfate solution with a mass fraction of 6%-10%; The buffer: 2-6 parts of sodium bicarbonate solution with a mass fraction of 2%-4%; The auxiliary agent: 0.1-0.3 parts of tert-butyl hydroperoxide and 0.1-0.3 parts of sodium dodecylbenzenesulfonate; The solvent: 15-25 parts of deionized water; a2, the DNS-86 emulsifier is added to deionized water, and methyl methacrylate, styrene, and butyl acrylate are slowly added under stirring at a speed of 300-500 rpm, and stirring is performed for 30-40 min to obtain the core layer pre-emulsion; a3, the DNS-86 emulsifier is added to deionized water, and dodecafluoroheptyl methacrylate, γ-methacryloyloxypropyl trimethoxysilane, butyl acrylate, methyl methacrylate, and acrylic acid are slowly added under stirring at a speed of 300-500 rpm, and stirring is performed for 40-60 min to obtain the shell layer pre-emulsion; a4, the sodium bicarbonate solution is added to deionized water, and 1 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution are added, the temperature is raised to 78-82℃, and stirring is performed at a speed of 200-250 rpm for 15-25 min to obtain the seed emulsion; a5. Slowly add the remaining 9 / 10 of the core layer pre-emulsion and 1 / 3 of the ammonium persulfate solution dropwise to the seed emulsion over 2-3 hours. Stir the mixture at 200-250 rpm for 15-25 minutes at 78-82°C, and maintain the temperature for 15-30 minutes. Then slowly add the shell layer pre-emulsion and the remaining 1 / 3 of the ammonium persulfate solution dropwise over 1.5-2.5 hours. After the addition is complete, raise the temperature to 85-87°C and maintain the temperature for 1.0-1.5 hours. Then lower the temperature to 50-60°C, add tert-butyl hydroperoxide and sodium formaldehyde sulfoxylate, and stir at 150-200 rpm for 30-45 minutes. Cool to room temperature, filter with a 180-200 mesh filter cloth, and add ammonia water to adjust the pH of the emulsion to 7.5-8.5 to obtain a fluorinated silicone-acrylic emulsion. The preparation method of the polyether-modified silicone oil composite defoamer includes the following steps: c1. Weigh the following components by weight: 20-40 parts of hydrogen-containing silicone oil, 60-80 parts of allyl polyether, 0.01-0.05 parts of platinum-1,3-divinyltetramethyldisiloxane complex, 5-15 parts of isopropanol, 0.2-0.4 parts of 1-ethynyl-1-cyclohexanol, 40-60 parts of white oil, 3-8 parts of hydrophobic fumed silica, 1-3 parts of sorbitan oleate, 1-3 parts of dehydrated sorbitan monooleate polyoxyethylene ether, 0.2-0.8 parts of hydroxyethyl cellulose, 0.1-0.3 parts of 1,2-benzisothiazolin-3-one, and 15-25 parts of deionized water. c2. Place hydrogen-containing silicone oil, allyl polyether, isopropanol and 1-ethynyl-1-cyclohexanol in a reaction vessel, stir evenly at 150-250 rpm, then introduce nitrogen protection, heat to 85-90℃, add platinum-1,3-divinyltetramethyldisiloxane complex using a microsyringe, keep the reaction at this temperature for 4-6 hours, cool to 50-60℃, remove isopropanol and low-boiling substances under vacuum for 1-2 hours, cool to room temperature, filter, and obtain polyether-modified silicone oil; c3. Add white oil and sorbitan oleate to polyether modified silicone oil, heat to 60-70℃, stir at 300-500 rpm for 15-25 min, slowly add hydrophobic fumed silica, continue to disperse at 1000-1500 rpm for 35-45 min, keep warm, and obtain oil phase. c4. Add dehydrated sorbitan monooleate polyoxyethylene ether, hydroxyethyl cellulose and 1,2-benzisothiazolin-3-one to deionized water, heat to 60-70℃ and stir until completely dissolved and homogeneous to obtain the aqueous phase; c5. Slowly add the aqueous phase to the oil phase, stir at 600-800 rpm for 15-20 minutes, then shear at 5000-10000 rpm for 5-10 minutes, cool to room temperature, filter with a 180-200 mesh filter, and discharge to obtain polyether modified silicone oil composite defoamer.

2. The antimicrobial composite coating for hospital room according to claim 1, characterized in that, The particle size of the silicon dioxide in the silica sol is 10-20 nm, the particle size of the anatase nano-titanium dioxide is 10-20 nm, the particle size of the nano-manganese dioxide is 20-30 nm, the particle size of the ultra-fine flaky mica powder is 2-6 μm, and the particle size of the rutile titanium dioxide is 0.2-0.4 μm.

3. The antimicrobial composite coating for hospital room according to claim 1, characterized in that, The HASE thickening agent includes at least one of TT-115, TT-215, ML-818, ML-828, and ML-838.

4. The antimicrobial composite coating for hospital room according to claim 1, characterized in that, The wetting agent includes at least one of nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, and lauryl alcohol polyoxyethylene ether.

5. The antimicrobial composite coating for hospital room according to claim 1, characterized in that, The surfactant includes at least one of decyl glucoside, lauryl glucoside, and sucrose stearate.

6. The antimicrobial composite coating for hospital room according to claim 1, characterized in that, The preparation method of the modified nano-silicon powder includes the following steps: b1. According to the weight fraction, 100-120 parts of nano-silicon powder with a particle size of 10-20 nm, 5-15 parts of γ-(2,3-epoxypropoxy) propyl trimethoxysilane, 300-500 parts of anhydrous ethanol, 1-3 parts of deionized water, and 0.1-0.5 parts of glacial acetic acid are weighed; b2. After the deionized water, glacial acetic acid, and 1 / 3 of the anhydrous ethanol are mixed and uniformly stirred, the γ-(2,3-epoxypropoxy) propyl trimethoxysilane is slowly added at a speed of 400-600 rpm, and the stirring is continued for 30-60 min to obtain a modified liquid; b3. The nano-silicon powder is added to the remaining 2 / 3 of the anhydrous ethanol, and after stirring and mixing at a speed of 500-800 rpm, it is placed in an ultrasonic generator for ultrasonic dispersion treatment at a power of 300-500 W for 30-45 min to obtain a suspension; b4. The suspension is placed in a water bath at 65-75°C and the modified liquid is slowly added dropwise, the dropwise addition time is 1-2 h, after the dropwise addition is completed, the reflux reaction is carried out for 4-6 h, and then the temperature is cooled to room temperature, the filter cake is washed with anhydrous ethanol for 3-5 times, and then it is placed in a vacuum drying oven at 100-110°C for drying for 6-8 h, and then it is ground to obtain the modified nano-silicon powder.

7. A method for preparing the antimicrobial composite coating for hospital room according to any one of claims 1 to 6, characterized in that, The preparation method includes the following steps: (1) The raw material components are weighed according to the weight fraction; (2) The ammonium polyacrylate, wetting agent, 1 / 2 of the polyether modified silicone oil composite defoaming agent, and isobutanol amine are added to the deionized water, and stirred at a stirring speed of 300-500 rpm for 8-12 min to obtain a solution; (3) The silver-loaded zinc zeolite antibacterial agent, anatase nano-titanium dioxide, nano-manganese dioxide, rutile titanium dioxide, modified nano-silicon powder, and ultra-fine flaky mica powder are sequentially and slowly added to the solution, uniformly stirred at a speed of 800-1000 rpm, and then the speed is increased to 1500-1800 rpm for dispersion for 25-35 min to obtain a dispersion liquid; (4) The dispersion liquid is pumped into a sand mill, 0.6-0.8 mm zirconium oxide beads are used for grinding for 2-4 h, and then the material is discharged to obtain a slurry. (5) slowly add fluorine modified silicone-acrylate emulsion and silica sol into the slurry, stirring at 300-500 rpm for 10-20 min, slowly add the rest 1 / 2 polyether modified silicone oil composite defoamer, surfactant, continue stirring for 8-10 min, then add HASE thickener, adjust the stirring speed to 100-200 rpm, slowly add tri-1-(2-methylaziridine) phosphine oxide, stirring for 10-20 min, continue to adjust the stirring speed to 50-100 rpm, aging for 1-2 h, filter with 180-200 mesh filter screen, package, to obtain the hospital room use antibacterial composite coating.

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