Preparation method of high-transparency super-wear-resistant self-cleaning antibacterial coating

Abstract

The application discloses a kind of high transparent super wear-resistant self-cleaning antibacterial coating and preparation method thereof.The steps of the application are as follows:(1) adding alcohol solvent, cosolvent, catalyst and inorganic nanoparticles into a container, mixing them evenly, then adding silane modifier, after reaction, filtering, washing and drying to obtain modified inorganic nanoparticles.(2) adding alcohol solvent, cosolvent, modified inorganic nanoparticles, silane coupling agent and antibacterial organosilicon monomer into a container, mixing them evenly, then adding catalyst, filtering, washing and drying to obtain polysiloxane grafted with inorganic nanoparticles.(3) dissolving the polysiloxane doped with inorganic nanoparticles and leveling agent in organic solvent respectively or mixedly, until the polysiloxane doped with inorganic nanoparticles and leveling agent are completely dissolved, to obtain high transparent wear-resistant self-cleaning antibacterial coating.(4) applying the high transparent wear-resistant self-cleaning antibacterial coating on a substrate by step or one-step method.The transparent wear-resistant coating prepared by the application has good self-cleaning and antibacterial effect.

Description

Technical Field

[0001] This invention belongs to the field of antibacterial coatings. Specifically, it relates to a method for preparing and applying a highly transparent, ultra-wear-resistant, self-cleaning antibacterial coating, particularly the use of this highly transparent, wear-resistant, self-cleaning coating for the protection of silicon-based optical panel surfaces. Background Technology

[0002] With the escalating global energy and environmental crisis, photovoltaic cells have emerged, and solar power plants have been built in many places. Since most photovoltaic panels operate outdoors, their surfaces inevitably become covered by pollutants over time, significantly impacting the power plant's efficiency and causing substantial losses. Manual cleaning of these pollutants is not only wasteful of manpower and resources but also ineffective. Therefore, developing new, highly efficient, and multifunctional self-cleaning coatings for photovoltaic panels is of great significance.

[0003] Inspired by the self-cleaning effect of lotus leaves, biomimetic principles are used to construct micro- and nano-rough structures to improve the hydrophobicity of coatings while reducing their surface energy. However, this method is not suitable for highly transparent self-cleaning coatings. Rayleigh and Mie scattering theories indicate that to achieve good light transmittance, in addition to ensuring the optical transmittance of the surface material, the surface roughness must be smaller than the wavelength of light. When the roughness is greater than 100 nm, light scattering is significantly enhanced; therefore, micron-level roughness cannot achieve light transmittance. This means that transparent self-cleaning coatings cannot improve hydrophobicity by increasing surface roughness; a balance must be struck between excellent optical transparency and hydrophobicity. Fluorinated substances are often chosen to modify material surfaces due to their low surface tension. Although the hydrophobicity of the resulting samples is improved, the presence of fluorinated substances poses a potential threat to the environment, contributing to ozone layer depletion. Therefore, replacing -FH3 with -CH3 is of great environmental significance. Furthermore, fluorinated materials are expensive and unsuitable for large-scale industrial production. Therefore, the relatively inexpensive and environmentally friendly -CH3 material is used as a modifier to reduce surface energy. However, although hydrophobic materials are very common in daily life, there are many difficulties in their preparation and application. The prepared hydrophobic materials have disadvantages such as complex processes, poor mechanical properties, high preparation costs, and poor weather resistance.

[0004] Polymer / inorganic nanocomposites have attracted much attention in many fields such as optics, chemical engineering, and biology. Composites formed by particles and polymers can leverage the individual effects of both particles and polymers, as well as their synergistic effects within the overall material. When inorganic nanoparticles are incorporated into polymers for composite modification, not only can the strength of the polymer be enhanced, but the toughness of the material can also be improved. Furthermore, by controlling the amount and size of the added particles to find a better balance between roughness and optical properties, the coating can exhibit both high hydrophobicity and good light transmittance. The addition of inorganic nanoparticles also contributes to the wear resistance of the composite coating.

[0005] This invention modifies inorganic nanoparticles, grafting active reactive groups onto their surfaces. This creates strong chemical bonds between the inorganic nanoparticles, polysiloxane, and leveling agent, tightly binding the three components. The microscopic aggregation and bonding of particles maintains a low surface roughness in the coating. The polysiloxane and leveling agent primarily provide the coating with low surface energy and surface bonding with the inorganic nanoparticles. The inorganic nanoparticles reduce light reflection, resulting in high light transmittance. The organosilicon monomers in the coating form Si-O-Si bonds through addition reactions, providing excellent wear resistance. Their unique microstructure and surface chemical composition endow the coating with good transparency and antibacterial self-cleaning capabilities. The coating prepared by this invention shows broad application prospects in outdoor photovoltaic module surfaces, curtain walls, electronic screens, and laser amplifiers. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. This method combines surface chemical grafting modification of inorganic nanoparticles to improve the compatibility between the nanoparticles and the substrate, and uses in-situ polymerization to chemically bond inorganic nanoparticles and organosilicon monomers to the surface of silicon-based materials. This allows for controllable adjustment of the wettability and roughness of the inorganic nanoparticles on the substrate surface, avoiding a decrease in coating transparency and improving the coating's wear resistance and antibacterial properties.

[0007] To achieve the above-mentioned objective, a method for preparing a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating is provided, the method comprising the following steps:

[0008] (1) A certain amount of alcohol solvent, co-solvent, catalyst and inorganic nanoparticles are added to a container at 25-40℃, wherein the concentration of inorganic nanoparticles is controlled at 1-1000 mg / mL and the volume ratio of alcohol solvent to co-solvent is 0.1-10; after the above reactants are mixed evenly at a speed of 50-1000 rpm, a silane modifier is added to the reaction system, the mass amount of the silane modifier is 0.5%-40% of the total mass of inorganic nanoparticles; after reacting for 0.5-30 h, the mixture is filtered and washed, and dried at 40-50℃ for 10-30 h to obtain modified inorganic nanoparticles.

[0009] (2) Add a certain amount of alcohol solvent, co-solvent, modified inorganic nanoparticles, silane coupling agent and antibacterial organosilicon monomer to a container at one time. The mass of modified inorganic nanoparticles is controlled at 0.25% to 10% of the total mass of the system, and the volume ratio of alcohol solvent to co-solvent is 0.1 to 10. After mixing the above reactants evenly at a speed of 100 rpm to 1000 rpm, add a catalyst and react at 60°C for 10 to 30 hours. After filtration and washing, dry at 40°C to 50°C for 10 to 30 hours to obtain polysiloxane grafted with inorganic nanoparticles.

[0010] (3) At 25℃~40℃ and a rotation speed of 100~1000rpm, the polysiloxane doped with inorganic nanoparticles and the leveling agent are dissolved separately or mixed in an organic solvent. The concentration of polysiloxane is controlled at 5wt%~30wt%, and the mass concentration of the leveling agent is 10wt%~20wt%. After the polysiloxane doped with inorganic nanoparticles and the leveling agent are completely dissolved, a highly transparent, wear-resistant, self-cleaning, and antibacterial coating is obtained.

[0011] (4) Apply the high-transparency wear-resistant self-cleaning antibacterial coating to the substrate in steps or one step. After curing in a fume hood at 20℃~80℃ for 10 minutes, cure at 100℃~200℃ for 1h~2h. The high-transparency wear-resistant self-cleaning antibacterial coating can be successfully adhered to the substrate to form a high-transparency wear-resistant self-cleaning antibacterial coating.

[0012] In this invention, the inorganic nanoparticles can be obtained by existing methods, (1) by synthesizing inorganic nanoparticles such as SiO2, ZnO, Ag, and Fe3O4 with sizes in the range of 10nm to 50nm by hydrothermal method; (2) by directly purchasing commercially available aqueous dispersions of SiO2, ZnO, Ag, and Fe3O4 nanoparticles in the same size range.

[0013] Considering the surface modification effect, dispersion stability, permeability, and antibacterial effect of nanoparticles, the average size of inorganic nanoparticles is preferably controlled between 10 nm and 30 nm.

[0014] The alcohol solvent is one or more of methanol, ethanol, isopropanol, propylene glycol, butanol, 1,4-butanediol, 1,3-butanediol, and glycerol.

[0015] The co-solvent is water, dimethyl sulfoxide, and N,N-dimethylformamide.

[0016] The catalyst is an ammonia-based catalyst, including but not limited to ammonia monohydrate and hydrazine hydrate. When using an ammonia-based catalyst, it should be added dropwise. During the dropwise addition of the catalyst, the pH value should be continuously monitored using a pH meter. When the pH value reaches 10-11, the addition of the catalyst can be stopped.

[0017] The method for achieving uniform mixing is magnetic stirring, which takes 1 to 2 hours.

[0018] The filtration and washing method is as follows: the reaction system is centrifuged in a high-speed centrifuge at a speed of 5000-8000 rpm for 5-10 min; after centrifugation, the mixture and supernatant are filtered and separated, and the mixture is ultrasonically dispersed with water and then centrifuged again in a high-speed centrifuge at a speed of 5000-8000 rpm for 5-10 min; this process is repeated three times to obtain a completely washed product.

[0019] In step (1) of this invention, the silane modifier is one of the following: γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, hexadecyltrimethoxysilane, and hexadecyltriethoxysilane.

[0020] In step (2) of this invention, the silane coupling agent is several of the following: phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltriisopropoxysilane, phenyltri-n-butoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane, ethylphenyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and methylethyldimethoxysilane.

[0021] In step (2) of this invention, the antibacterial organosilicon monomer is selected from at least one of the following: methyltriethoxysilane quaternary ammonium salt, methyldimethoxysilane quaternary ammonium salt, N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride, N-allyldimethylamine and 3-chloropropyltrimethoxysilane, acrylate ethoxysilane. Considering the actual antibacterial effect, N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride, N-allyldimethylamine and 3-chloropropyltrimethoxysilane are preferred; the amount used is 0.2wt% to 10wt% of the mass of the silane coupling agent.

[0022] In step (2) of this invention, the polysiloxane refers to a polymer whose main chain is composed of repeating silicon-oxygen (Si-O) bonds, wherein organic groups are attached to silicon atoms.

[0023] In step (3) of the present invention, the leveling agent is amino-modified polydimethylsiloxane, carboxyl-modified polydimethylsiloxane, epoxy-modified polydimethylsiloxane, isocyanate-modified polydimethylsiloxane, or mercapto-modified polydimethylsiloxane.

[0024] In step (3) of this invention, the separate or mixed dissolution in organic solvents refers to two methods for preparing highly transparent, wear-resistant, and self-cleaning coatings: Method 1: Take a certain amount of polysiloxane doped with inorganic nanoparticles and leveling agent at 25-40°C, and dissolve them separately in the same volume of organic solvent; Method 2: Take a certain amount of polysiloxane doped with inorganic nanoparticles and leveling agent at 25-40°C, and mix and dissolve them in a certain mass of organic solvent.

[0025] In step (3) of this invention, the organic solvent is one or more of methanol, ethanol, ethyl acetate, acetone, n-hexadecane, cyclohexane, tetrahydrofuran, dichloromethane, carbon tetrachloride, toluene, and xylene.

[0026] In step (4) of this invention, the stepwise or one-step wiping coating refers to two methods of applying a highly transparent, wear-resistant, and self-cleaning coating. Method 1: Take a certain amount of organic solvent containing polysiloxane doped with inorganic nanoparticles and wipe it onto the substrate, then take a certain amount of organic solvent containing leveling agent and wipe it onto the substrate. Method 2: Take a certain amount of organic solvent containing polysiloxane doped with inorganic nanoparticles and leveling agent and wipe it onto the substrate.

[0027] In step (4) of this invention, the wiping method is to use a non-woven fabric to apply about 1 to 1000 μL of highly transparent wear-resistant self-cleaning coating evenly to the substrate at a speed of 1 to 5 m / s.

[0028] In step (4) of this invention, the substrate is a silicon-based material such as glass or silicon wafer. It needs to be rinsed with water in advance to remove the impurities attached to it, and then dried at 40-80°C before it can be used as a substrate.

[0029] In this invention, inorganic nanoparticles of suitable size possess excellent anti-reflective properties. However, due to their surface only having hydrophilic hydroxyl groups, the limited surface characteristics of these nanoparticles severely restrict their applications. By modifying the surface of inorganic nanoparticles, reactive amphiphilic groups are grafted onto their surface through chemical reactions, greatly expanding their application range. Specifically, this invention employs in-situ polymerization, resulting in a highly stable chemical bond between the inorganic nanoparticles and polysiloxanes and leveling agents. This achieves excellent compatibility between the organosilicon and the inorganic nanoparticles, preventing agglomeration in the coating and realizing high dispersion of the inorganic nanoparticles within the coating. The inorganic nanoparticles, possessing a certain mechanical strength, provide a degree of wear resistance to the coating.

[0030] Through in-depth research, the inventors discovered that the formation of a strong cross-linked network between the organosilicon and inorganic nanoparticles gives the coating extremely high hardness. At the same time, the inorganic nanoparticles are uniformly and firmly bonded with polysiloxane and leveling agent, resulting in a uniform and smooth surface of the coating. Furthermore, the high dispersion of inorganic nanoparticles in the coating eliminates diffuse reflection at the source, enhancing the light transmittance of the coating. Therefore, the coating has excellent transparency.

[0031] Compared with existing technologies, the technical solution of this invention has the following advantages: 1) Simple process, readily available raw materials, and low cost; 2) High transparency of the coating, with the coated glass achieving a maximum transmittance of 91.5% in the visible light range and an average transmittance of 90.2%, which is superior to that of the glass substrate and has excellent commercial applications. (The highest known transmittance of glass in the visible light range is 91.4%, and the average transmittance is 90.1%); 3) Ultra-wear-resistant coating, maintaining self-cleaning properties after withstanding 1400 scissor scratches; 4) The coating has extremely high adhesion to the substrate, exhibits certain resistance to acids, alkalis, and salts, and has a long service life; 5) This invention connects inorganic nanoparticles, polysiloxane, and leveling agents together through chemical bonds, simultaneously achieving high transparency, ultra-wear resistance, and self-cleaning properties, while also possessing antibacterial properties. Attached Figure Description

[0032] Figure 1 Comparison of SEM images of the coating before and after 1500 scratches. Detailed Implementation

[0033] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and examples. The specific examples described herein are merely for explaining the invention and are not intended to limit the invention. The scope of protection of this invention is by no means limited thereto.

[0034] This invention utilizes in-situ polycondensation to form extremely stable covalent bonds between inorganic nanoparticles and polysiloxanes and leveling agents through chemical bonds. Due to the excellent compatibility between organosilicon and silica particles, agglomeration of inorganic nanoparticles in the coating is avoided, achieving high dispersion of inorganic nanoparticles within the coating. This significantly reduces diffuse reflection and enhances the light transmittance of the coating, resulting in excellent transparency. Furthermore, the robust cross-linked network formed between organosilicon monomers and inorganic nanoparticles in this invention endows the coating with extremely high hardness, and the inorganic nanoparticles, possessing a certain mechanical strength, provide excellent wear resistance. In addition, the prepared transparent wear-resistant coating exhibits good self-cleaning and antibacterial effects.

[0035] Example 1:

[0036] 1 g of silica nanoparticles (20 nm) was dissolved in 30 mL of an aqueous ethanol solution (ethanol to water volume ratio of 3:1) at 25 °C. The pH of the reaction system was adjusted to 10–11 using ammonia monohydrate. After stirring for 1 h at 600 rpm with a magnetic stirrer, 0.1 g of γ-glycidoxypropyltrimethoxysilane and 0.05 g of hexadecyltrimethylsilane were added to the reaction system. The mixture was stirred at 600 rpm for 8 h. The product was then centrifuged, washed, and dried at 45 °C for 10 h to obtain modified silica nanoparticles.

[0037] 0.0655 g of modified silica nanoparticles were dissolved in 30 mL of an aqueous ethanol solution (ethanol to water volume ratio 3:1). Then, 3.966 g of phenyltrimethoxysilane, 2.404 g of dimethyldimethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.437 g of N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride were added. The mixture was stirred at 600 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. After reacting at 60 °C for 10 h, the product was centrifuged, washed, and dried at 45 °C for 10 h to obtain polysiloxane doped with modified silica nanoparticles.

[0038] At 25℃, 0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene respectively. After mixing at 800rpm for 1h, 50μL of xylene containing the polysiloxane doped with modified silica nanoparticles was applied uniformly to a glass slide at a speed of 3m / s using a non-woven fabric. Then, another 50μL of xylene containing amino-modified polydimethylsiloxane was applied uniformly to the glass slide at the same speed using a non-woven fabric. After curing at 25℃ for 10min, the temperature was increased to 120℃ and cured for 1h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured using dynamic video contact angle measurement, and the transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800nm. The wear resistance of the coating was determined according to ASTM D 4213-2008. The prepared coating had a water contact angle of 125° and a light transmittance of 90.2% after coating the glass. According to GB / T21866-2008, the coating's bactericidal rates against Escherichia coli and Staphylococcus aureus were 97% and 95%, respectively.

[0039] Comparative Example 1:

[0040] 1 g of silica nanoparticles (10 nm) was dissolved in 30 mL of an aqueous ethanol solution (ethanol to water volume ratio of 3:1) at 25 °C. The pH of the reaction system was adjusted to 10–11 using ammonia monohydrate. After stirring for 1 h at 600 rpm with a magnetic stirrer, 0.1 g of γ-glycidoxypropyltrimethoxysilane and 0.05 g of hexadecyltrimethylsilane were added to the reaction system. The mixture was stirred at 600 rpm for 8 h. The product was then centrifuged, washed, and dried at 45 °C for 10 h to obtain modified silica nanoparticles.

[0041] 0.0655 g of modified silica nanoparticles were dissolved in 30 mL of an aqueous ethanol solution (ethanol to water volume ratio 3:1). Then, 3.966 g of phenyltrimethoxysilane, 2.404 g of dimethyldimethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.218 g of N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride were added. The mixture was stirred at 600 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. After reacting at 60 °C for 10 h, the product was centrifuged and washed, and then dried at 45 °C for 10 h to obtain polysiloxane doped with modified silica nanoparticles.

[0042] At 25℃, 0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene respectively. After mixing at 800rpm for 1h, 50μL of xylene containing the polysiloxane doped with modified silica nanoparticles was applied uniformly to a glass slide at a speed of 3m / s using a non-woven fabric. Then, another 50μL of xylene containing amino-modified polydimethylsiloxane was applied uniformly to the glass slide at the same speed using a non-woven fabric. After curing at 25℃ for 10min, the temperature was increased to 120℃ and cured for 1h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured using dynamic video contact angle measurement, and the transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800nm. The wear resistance of the coating was determined according to ASTM D 4213-2008. The prepared coating had a water contact angle of 120° and a light transmittance of 93.5% after coating the glass. According to GB / T21866-2008, the coating's bactericidal rates against Escherichia coli and Staphylococcus aureus were 93% and 92%, respectively.

[0043] Comparative Example 2:

[0044] 1 g of silica nanoparticles (30 nm) was dissolved in 30 mL of an aqueous ethanol solution (ethanol to water volume ratio of 3:1) at 25 °C. The pH of the reaction system was adjusted to 10–11 using ammonia monohydrate. After stirring for 1 h at 600 rpm with a magnetic stirrer, 0.1 g of γ-glycidoxypropyltrimethoxysilane and 0.05 g of hexadecyltrimethylsilane were added to the reaction system. The mixture was stirred at 600 rpm for 8 h. The product was then centrifuged, washed, and dried at 45 °C for 10 h to obtain modified silica nanoparticles.

[0045] 0.0655 g of modified silica nanoparticles were dissolved in 30 mL of an aqueous ethanol solution (ethanol to water volume ratio 3:1). Then, 3.966 g of phenyltrimethoxysilane, 2.404 g of dimethyldimethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.873 g of N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride were added. The mixture was stirred at 600 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. After reacting at 60 °C for 10 h, the product was centrifuged, washed, and dried at 45 °C for 10 h to obtain polysiloxane doped with modified silica nanoparticles.

[0046] At 25℃, 0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene respectively. After mixing at 800rpm for 1h, 50μL of xylene containing the polysiloxane doped with modified silica nanoparticles was applied uniformly to a glass slide at a speed of 3m / s using a non-woven fabric. Then, another 50μL of xylene containing amino-modified polydimethylsiloxane was applied uniformly to the glass slide at the same speed using a non-woven fabric. After curing at 25℃ for 10min, the temperature was increased to 120℃ and cured for 1h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured using dynamic video contact angle measurement, and the transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800nm. The wear resistance of the coating was determined according to ASTM D 4213-2008. The prepared coating had a water contact angle of 127° and a light transmittance of 87.1% after coating the glass. According to GB / T21866-2008, the coating's bactericidal rates against Escherichia coli and Staphylococcus aureus were 97% and 95%, respectively.

[0047] Example 2:

[0048] 2 g of silica nanoparticles (20 nm) were dissolved in 60 mL of dimethyl sulfoxide solution of isopropanol (volume ratio of isopropanol to dimethyl sulfoxide was 3:1) at 30 °C. The pH of the reaction system was adjusted to 10-11 using ammonia monohydrate. After stirring for 1 h at 800 rpm with a magnetic stirrer, 0.1 g of γ-glycidoxypropyltriethoxysilane and 0.05 g of hexadecyltriethylsilane were added to the reaction system. The mixture was stirred at 800 rpm for 12 h. The product was then centrifuged, washed, and dried at 50 °C for 10 h to obtain modified silica nanoparticles.

[0049] 0.1310 g of modified silica nanoparticles were dissolved in 60 mL of isopropanol in a dimethyl sulfoxide solution (isopropanol to dimethyl sulfoxide volume ratio 3:1). Then, 3.966 g of phenyltriethoxysilane, 2.404 g of dimethyldiethoxysilane, 2.363 g of γ-glycidyl etheroxypropylmethyldiethoxysilane, and 0.873 g of N-allyl dimethylamine were added. The mixture was stirred at 800 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. After reacting at 60 °C for 15 h, the product was centrifuged and washed, and then dried at 50 °C for 10 h to obtain polysiloxane doped with modified silica nanoparticles.

[0050] 1.0 g of polysiloxane doped with modified silica nanoparticles and 2.0 g of epoxy-modified polydimethylsiloxane were mixed and dissolved in 10 g of tetrahydrofuran at 30 °C. After mixing at 1000 rpm for 1 h, 100 μL of the tetrahydrofuran mixture containing the doped silica nanoparticles and epoxy-modified polydimethylsiloxane was applied uniformly to a glass slide at a speed of 3 m / s using a non-woven fabric. The mixture was cured at 45 °C for 10 min, and then the temperature was increased to 150 °C for 1.5 h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured using dynamic video contact angle analysis. The transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800 nm. The wear resistance of the coating was determined according to ASTM D 4213-2008. The prepared coating had a water contact angle of 140° and a transmittance of 83.4% after coating the glass. According to GB / T21866-2008, the bactericidal rates of the coating against Escherichia coli and Staphylococcus aureus were 97% and 95%, respectively.

[0051] Example 3:

[0052] 0.5 g of silica nanoparticles (20 nm) were dissolved in 30 mL of methanol in a dimethyl sulfoxide solution (methanol to dimethyl sulfoxide volume ratio of 3:1) at 30 °C. The pH of the reaction system was adjusted to 10–11 using hydrazine hydrate. After stirring for 1 h at 400 rpm with a magnetic stirrer, 0.05 g of γ-glycidoxypropyltriethoxysilane and 0.025 g of hexadecyltriethylsilane were added to the reaction system. The mixture was stirred at 400 rpm for 6 h. The product was then centrifuged, washed, and dried at 45 °C for 12 h to obtain modified silica nanoparticles.

[0053] 0.0655 g of modified silica nanoparticles were dissolved in 30 mL of methanol in a dimethyl sulfoxide solution (methanol to dimethyl sulfoxide volume ratio of 3:1). Then, 3.966 g of phenyltriethoxysilane, 2.404 g of dimethyldiethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.218 g of 3-chloropropyltrioxysilane were added. The mixture was stirred at 600 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using hydrazine hydrate. After reacting at 60 °C for 10 h, the product was centrifuged, washed, and dried at 45 °C for 12 h to obtain polysiloxane doped with modified silica nanoparticles.

[0054] At 25℃, 0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of isocyanate-modified polydimethylsiloxane were mixed and dissolved in 10g of dichloromethane. After mixing at 800rpm for 1h, 100μL of the dichloromethane mixture containing the doped silica nanoparticles and isocyanate-modified polydimethylsiloxane was applied uniformly to a glass slide at a speed of 3m / s using a non-woven fabric. After curing at 25℃ for 10min, the temperature was increased to 120℃ and cured for 1.5h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured by dynamic video contact angle measurement, and the transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800nm. The wear resistance of the coating was measured according to ASTM D 4213-2008. The prepared coating had a water contact angle of 115° and a transmittance of 92.1% after coating the glass. According to GB / T21866-2008, the bactericidal rates of the coating against Escherichia coli and Staphylococcus aureus were 93% and 91%, respectively.

[0055] Example 4:

[0056] 1 g of silver nanoparticles (20 nm) was dissolved in 30 mL of methanol aqueous solution (methanol to water volume ratio of 3:1) at 25 °C. The pH of the reaction system was adjusted to 10-11 using hydrazine hydrate. After stirring for 1 h at 800 rpm with a magnetic stirrer, 0.1 g of γ-glycidoxypropyltrimethoxysilane and 0.05 g of hexadecyltrimethylsilane were added to the reaction system. The mixture was stirred at 800 rpm for 15 h. The product was then centrifuged, washed, and dried at 50 °C for 14 h to obtain modified silver nanoparticles.

[0057] 0.0655 g of modified silver nanoparticles were dissolved in 30 mL of methanol aqueous solution (methanol to water volume ratio 3:1). Then, 3.966 g of phenyltrimethoxysilane, 2.404 g of dimethyldimethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.437 g of N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride were added. The mixture was stirred at 800 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using hydrazine hydrate. After reacting at 60 °C for 15 h, the product was centrifuged and washed, and then dried at 50 °C for 14 h to obtain polysiloxane doped with modified silver nanoparticles.

[0058] At 30℃, 0.5g of polysiloxane doped with modified silver nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of tetrahydrofuran, respectively. After mixing at 800rpm for 1h, 50μL of tetrahydrofuran containing the doped silver nanoparticle-modified polysiloxane was applied uniformly to a glass slide using a nonwoven fabric at a speed of 3m / s. Then, another 50μL of tetrahydrofuran containing the amino-modified polydimethylsiloxane was applied uniformly to the glass slide using the same speed. After curing at 45℃ for 10min, the temperature was increased to 150℃ and cured for 1.5h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured using dynamic video contact angle measurement, and the transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800nm. The wear resistance of the coating was determined according to ASTM D 4213-2008. The prepared coating had a water contact angle of 123° and a light transmittance of 89.2% after coating the glass. According to GB / T21866-2008, the coating's bactericidal rates against Escherichia coli and Staphylococcus aureus were 97% and 94%, respectively.

[0059] Example 5:

[0060] 1 g of ferric oxide nanoparticles (20 nm) was dissolved in 30 mL of butanediol aqueous solution (butanediol to water volume ratio 3:1) at 30 °C. The pH of the reaction system was adjusted to 10-11 using ammonia monohydrate. After stirring for 1 h at 800 rpm with a magnetic stirrer, 0.1 g of γ-glycidoxypropyltrimethoxysilane and 0.05 g of hexadecyltrimethylsilane were added to the reaction system. The mixture was stirred at 800 rpm for 12 h. The product was then centrifuged, washed, and dried at 50 °C for 14 h to obtain modified ferric oxide nanoparticles.

[0061] 0.0655 g of modified iron oxide nanoparticles were dissolved in 30 mL of butanediol aqueous solution (butanediol to water volume ratio 3:1). Then, 3.966 g of phenyltrimethoxysilane, 2.404 g of dimethyldimethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.437 g of N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride were added. The mixture was stirred at 800 rpm for 1 h, and the pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. After reacting at 60 °C for 15 h, the product was centrifuged and washed, and then dried at 50 °C for 14 h to obtain polysiloxane doped with modified iron oxide nanoparticles.

[0062] At 30℃, 0.5g of polysiloxane doped with modified iron oxide nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of tetrahydrofuran, respectively. After mixing at 800rpm for 1h, 50μL of tetrahydrofuran containing the doped iron oxide nanoparticles and polysiloxane was applied uniformly to a glass slide using a nonwoven fabric at a speed of 3m / s. Then, 50μL of xylene containing amino-modified polydimethylsiloxane was applied uniformly to the glass slide using the same speed using a nonwoven fabric. After curing at 45℃ for 10min, the temperature was increased to 150℃ and cured for 1.5h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating. The water contact angle of the coating was measured using dynamic video contact angle measurement, and the transmittance of the coating was measured using a UV-Vis spectrophotometer in the wavelength range of 300-800nm. The wear resistance of the coating was determined according to ASTM D 4213-2008. The prepared coating had a water contact angle of 122° and a light transmittance of 88.1% after coating the glass. According to GB / T21866-2008, the coating's bactericidal rates against Escherichia coli and Staphylococcus aureus were 96% and 94%, respectively.

[0063] Table 1

[0064]

[0065] As shown in Table 1 and the examples and comparative examples, the particle size, amount, and type of inorganic nanoparticles directly affect the contact angle and transmittance of the coating. In Comparative Example 1, the inorganic nanoparticles had a particle size of only 10 nm, which greatly improved the light transmittance, thus increasing it to 93.5%. However, the excessively small particle size reduced the surface roughness of the coating, affecting its self-cleaning performance and causing the contact angle to decrease to only 120°. In Comparative Example 2, the inorganic nanoparticles had a particle size of 30 nm. Although the contact angle of the coating increased to 127°, the transmittance remained relatively low. However, the transmittance dropped to 87.1%. In Example 2, the amount of inorganic nanoparticles was doubled, which greatly increased the contact angle to 140° and greatly reduced the transmittance to 83.4%, which was not worth the effort. Considering both self-cleaning and high transparency, the particle size and amount in Example 1 were optimal. Therefore, in Examples 4 and 5, the particle size and amount in Example 1 were used, but the type of inorganic nanoparticles was changed. However, it is obvious that the contact angle and transmittance were lower than in Example 1, indicating that the inorganic nanoparticles in Example 1, namely silicon dioxide, were optimal.

[0066] like Figure 1 As shown, a friction cycle test was conducted on the coating in Example 1: sharp scissors were held at a 45° angle to the coating and slid back and forth rapidly with force. The appearance of the coating was recorded by taking pictures every 100 times, and the water contact angle was tested. Figure 1Comparison of SEM images of the coating before and after 1500 scratches (left image is the original coating, right image is the coating after 1500 scratches);

[0067]

Claims

1. A method for preparing a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating, characterized in that, Includes the following steps: 1 g of silica nanoparticles with a particle size of 20 nm were dissolved in 30 mL of ethanol aqueous solution at 25 °C. The pH of the reaction system was adjusted to 10-11 using ammonia monohydrate. After stirring for 1 h with a magnetic stirrer at 600 rpm, 0.1 g of γ-glycidoxypropyltrimethoxysilane and 0.05 g of hexadecyltrimethylsilane were added to the reaction system. The mixture was stirred at 600 rpm for 8 h. The product was then centrifuged, washed, and dried at 45 °C for 10 h to obtain modified silica nanoparticles. 0.0655 g of modified silica nanoparticles were dissolved in 30 mL of ethanol aqueous solution. 3.966 g of phenyltrimethoxysilane, 2.404 g of dimethyldimethoxysilane, 2.363 g of γ-glycidyl etheroxypropyltrimethoxysilane, and 0.437 g of N,N-dimethyldodecylaminopropyltrimethoxysilane ammonium chloride were added to the solution. The mixture was stirred at 600 rpm for 1 h. The pH of the reaction system was adjusted to 10.5 using ammonia monohydrate. After reacting at 60 °C for 10 h, the product was centrifuged and washed, and then dried at 45 °C for 10 h to obtain polysiloxane doped with modified silica nanoparticles. At 25℃, 0.5g of polysiloxane doped with modified silica nanoparticles and 1.5g of amino-modified polydimethylsiloxane were dissolved in 5g of xylene respectively. After mixing at 800rpm for 1h, 50μL of xylene containing polysiloxane doped with modified silica nanoparticles was applied evenly to a glass slide at a speed of 3m / s using a non-woven fabric. Then, 50μL of xylene containing amino-modified polydimethylsiloxane was applied evenly to the glass slide at the same speed using a non-woven fabric. After curing at 25℃ for 10min, the temperature was increased to 120℃ and cured for 1h to obtain a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating.

2. The method for preparing a highly transparent, ultra-wear-resistant, self-cleaning, and antibacterial coating according to claim 1, characterized in that, In an aqueous solution of ethanol, the volume ratio of ethanol to water is 3:1.

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