Preparation method and application of an ultra-hard wear-resistant and anti-fouling composite coating

Abstract

This invention provides a method for preparing and applying an ultra-hard, wear-resistant, and anti-fouling composite coating, relating to the field of coating materials. The coating comprises 30-80 parts by weight of a coupling agent, 3-10 parts by weight of deionized water, 100-300 parts by weight of anhydrous ethanol, 5-50 parts by weight of amino silicone oil, 1-30 parts by weight of hydroxyl silicone oil, 1-20 parts by weight of glycerol, 200-500 parts by weight of pentaerythritol triacrylate, 50-200 parts by weight of propylene glycol methyl ether acetate, and 20-200 parts by weight of a nanoparticle dispersion. This invention, employing the above-mentioned method for preparing and applying an ultra-hard, wear-resistant, and anti-fouling composite coating, possesses advantages such as high hardness, wear resistance, scratch resistance, and low cost.

Description

Technical Field

[0001] This invention relates to the field of coating materials, and in particular to a method for preparing and applying an ultra-hard, wear-resistant, and anti-fouling composite coating. Background Technology

[0002] Existing superhard, scratch-resistant, and abrasion-resistant coating technologies are widely used in various fields, including industrial manufacturing, aerospace, automotive, and consumer electronics. However, current technologies mostly employ single organic or inorganic materials, generally suffering from insufficient abrasion resistance, poor adhesion, toxicity to humans, or complex application. For example, traditional organic coatings (such as polyurethane) are prone to aging, while inorganic coatings (such as silica) are brittle and easily peel off. Although some research has attempted to improve performance through organic-inorganic hybrid technologies, these generally suffer from high costs, poor weather resistance, or complex processes. Furthermore, materials such as rigid polyurethane foam are flammable and require the addition of flame retardants, but existing flame-retardant coatings often contain halogens or heavy metals, posing environmental risks. Therefore, developing a superhard, abrasion-resistant, and high-performance organic-inorganic hybrid coating is of great significance. Summary of the Invention

[0003] The purpose of this invention is to provide a method for preparing and applying an ultra-hard, wear-resistant, and anti-fouling composite coating, which has good wear resistance.

[0004] To achieve the above objectives, the present invention provides an ultra-hard, wear-resistant, and anti-fouling composite coating, comprising:

[0005] 30-80 parts by weight of coupling agent

[0006] 3-10 parts by weight of deionized water

[0007] 100-300 parts by weight of anhydrous ethanol

[0008] 5-50 parts by weight of amino silicone oil

[0009] 1-30 parts by weight of hydroxyl silicone oil

[0010] 1-20 parts by weight of glycerol

[0011] Pentaerythritol triacrylate 200-500 parts by weight

[0012] 50-200 parts by weight of propylene glycol methyl ether acetate

[0013] 20-200 parts by weight of nanoparticle dispersion.

[0014] Preferably, the mass ratio of hydroxyl silicone oil, amino silicone oil and glycerol is 3:5:2;

[0015] The mass ratio of pentaerythritol triacrylate, anhydrous ethanol, and propylene glycol methyl ether acetate is 3:1:1.

[0016] Preferably, the coupling agent is one or more of silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconate coupling agents.

[0017] Preferably, the coupling agent is one or more of γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, vinyltriethoxysilane, tetrabutyl titanate, bis(ethyl acetoacetate) di-n-butoxytitanate, aluminum triacetylacetonate, (ethyl acetoacetate) diisopropoxyaluminate, tetra(triethanolamine)zirconium, and alkoxytris(p-aminophenoxy)zirconium ester.

[0018] Preferably, the nanoparticle dispersion is one of zirconium oxide, aluminum oxide, titanium oxide, and silicon oxide.

[0019] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating includes the following steps:

[0020] Preparation of coupling agent hydrolysate: Mix coupling agent and anhydrous ethanol in a certain proportion, then add deionized water, and stir in a constant temperature water bath to obtain coupling agent hydrolysate;

[0021] Preparation of Solution A: Mix hydroxyl silicone oil, amino silicone oil and glycerol, stir to form a homogeneous mixture of Solution A;

[0022] Preparation of nanoparticle dispersion: Nanoparticles are dispersed in an aqueous solution to obtain nanoparticle dispersion;

[0023] Preparation of solution B: Pentaerythritol triacrylate, anhydrous ethanol and propylene glycol methyl ether acetate are mixed and stirred to form a homogeneous solution B.

[0024] Preparation of mixed emulsion: Slowly add liquid A to liquid B and mix evenly, stir, slowly add coupling agent hydrolysate and stir, and finally slowly add nanoparticle dispersion and continue stirring to obtain a uniform mixed emulsion;

[0025] Coating curing: The mixed emulsion is applied to the surface of the pretreated substrate and cured to obtain the coating.

[0026] Preferably, the substrate includes glass, metal, wood, or ceramic.

[0027] Preferably, in the preparation step of the coupling agent hydrolysate, the mixed solution of coupling agent and deionized water, wherein the deionized water accounts for 10% of the mass of the coupling agent, and the mass ratio of coupling agent: anhydrous ethanol: deionized water is 10:10:1.

[0028] In the preparation steps of the nanoparticle dispersion, the nanoparticles account for 20% of the mass of the dispersion.

[0029] Preferably, in the preparation step of the silane coupling agent hydrolysate, the heating temperature in the constant temperature water bath is 40℃-60℃, and the stirring time is 2-4 hours.

[0030] In the preparation steps of solution A, stir at room temperature for 5-10 minutes;

[0031] In the preparation of solution B, stir at room temperature for 10-30 minutes;

[0032] In the preparation steps of the mixed emulsion, the mixture of solution A and solution B is stirred at room temperature for 10-30 minutes; after adding the coupling agent hydrolysate, it is stirred at room temperature for 30-60 minutes; after adding the nanoparticle dispersion, it is stirred at room temperature for 24 hours.

[0033] In the coating curing process, the curing treatment includes placing it at room temperature for 10 minutes, then pre-curing it in a 100℃ oven for 30 minutes, and then curing it in a 150-180℃ oven for 2-3 hours.

[0034] In the preparation steps of the nanoparticle dispersion, the particle size is less than 10 nanometers.

[0035] Application of an ultra-hard, wear-resistant, and stain-resistant composite coating in building decoration, electronic equipment, machinery manufacturing, or optical devices.

[0036] Therefore, the present invention employs the above-mentioned method for preparing and applying an ultra-hard, wear-resistant, and anti-fouling composite coating, which has several significant advantages in terms of hardness, wear resistance, and scratch resistance, making it a low-cost option:

[0037] Abrasion resistance: The coating possesses excellent mechanical strength and abrasion resistance, maintaining its integrity during prolonged use. This makes it widely applicable in applications requiring abrasion resistance, such as mechanical parts and tool surfaces.

[0038] Low cost: Compared to other high-performance coating materials, such as fluorocarbon or ceramic coatings, organic-inorganic hybrid coatings have lower manufacturing costs and relatively simpler application processes. This makes silicone coatings economically advantageous in many applications requiring large-area coating or mass production.

[0039] This technical solution constructs a "rigid-flexible" organic-inorganic hybrid network through coupling agents, physical reinforcement of nanoparticles, curing and cross-linking of PETA, and flexible adjustment of silicone oil. This effectively resolves the contradictions between hardness, wear resistance, adhesion, and processability inherent in traditional coatings. Its design balances performance requirements with industrial feasibility, making it suitable for multiple high-value-added fields such as automotive, electronics, and machinery manufacturing. Attached Figure Description

[0040] Figure 1 This is a picture of the finished mixed emulsion product;

[0041] Figure 2 This is a picture of a sample of the coating.

[0042] Figure 3 The image shows the test results for the abrasion resistance of the coating.

[0043] Figure 4 This is a graph showing the test results of the water contact angle of the coating. Detailed Implementation

[0044] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0045] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.

[0046] Example 1

[0047] An ultra-hard, wear-resistant, and stain-resistant composite coating comprises γ-aminopropyltriethoxysilane, deionized water, anhydrous ethanol, amino silicone oil, hydroxy silicone oil, glycerol, pentaerythritol triacrylate, propylene glycol methyl ether acetate, and nano-zirconia dispersion.

[0048] In this process, the silane coupling agent is hydrolyzed by a mixture of anhydrous ethanol and deionized water, and reacts with water to generate silanol groups (Si-OH).

[0049] Hydroxy silicone oil, amino silicone oil, and glycerol are physically mixed. Glycerol is mainly used to enhance the dispersibility of subsequent nanoparticles and emulsions. Amino silicone oil reacts with the hydrolysate of silane coupling agents, and the hydroxyl groups in hydroxy silicone oil can enhance molecular polarity. Silicone oil also provides antifouling properties to the coating.

[0050] Pentaerythritol triacrylate (PETA), anhydrous ethanol, and propylene glycol methyl ether acetate (PMA) are physically mixed. PETA may not be completely soluble in anhydrous ethanol, but it is usually very soluble in PMA. When mixing the three, ensure that the solution does not become cloudy, separate into layers, or precipitate. The presence of PMA usually helps to dissolve PETA.

[0051] Add solution A slowly to solution B and mix thoroughly. Adding it too quickly will cause a violent reaction, resulting in a cloudy emulsion or even a gel.

[0052] After mixing solution A and solution B, add the hydrolysate of silane coupling agent and stir. If the addition is too rapid, the reaction will be violent and cause gelation.

[0053] Finally, the nano-zirconia dispersion was slowly added to obtain a white, uniformly mixed emulsion.

[0054] The mixed emulsion is applied to the surface of a pretreated substrate and cured to obtain a coating.

[0055] The clean glass surface has a large number of exposed silanol groups (Si-OH). The oxygen on the silanol groups undergoes nucleophilic substitution of the silicon on APTES, removing one methanol atom to form a Si-O-Si bond. This is the main way for silane coupling agents to form covalent bonds with the surface. The amino groups undergo Michael addition reactions with the double bonds in PETA. Through the coupling of APTES, the physical reinforcement of nano-zirconia particles, the curing and cross-linking of PETA, and the flexibility adjustment of silicone oil, a "rigid-flexible" organic-inorganic hybrid network is constructed, thereby improving wear resistance.

[0056] Preferably, the organic-inorganic hybrid coating provided in this embodiment comprises 30-80 parts by weight of γ-aminopropyltriethoxysilane, 3-10 parts by weight of deionized water, 100-300 parts by weight of anhydrous ethanol, 5-50 parts by weight of amino silicone oil, 1-30 parts by weight of hydroxyl silicone oil, 1-20 parts by weight of glycerol, 200-500 parts by weight of pentaerythritol triacrylate, 50-200 parts by weight of propylene glycol methyl ether acetate, and 20-200 parts by weight of nano-zirconia dispersion. Furthermore, this embodiment has experimentally determined a composition ratio with better coating performance as follows: (6g PETA, 2g PMA, 2g anhydrous ethanol, 0.5g amino silicone oil, 0.3g hydroxyl silicone oil, 0.2g glycerol, 2.4g KH550 hydrolysate, and 2g nano-zirconia dispersion). The specific amount of 1 part by weight is determined based on the total amount of coating required.

[0057] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating includes the following steps:

[0058] Preparation of silane coupling agent hydrolysate: Mix silane coupling agent and anhydrous ethanol, then add 10% of the amount of silane coupling agent in deionized water, and stir in a constant temperature water bath at 40℃-60℃ for 2-4 hours to obtain silane coupling agent hydrolysate.

[0059] Preparation of solution A: Mix hydroxy silicone oil, amino silicone oil and glycerol in a mass ratio of 3:5:2 and stir at room temperature for 5-10 minutes to form a homogeneous solution A;

[0060] Preparation of nano-zirconia dispersion: Zirconia particles with a particle size of less than 10 nanometers were dispersed in an aqueous solution with a solid content of 20% to obtain nano-zirconia dispersion.

[0061] Preparation of solution B: Mix pentaerythritol triacrylate, anhydrous ethanol and propylene glycol methyl ether acetate in a mass ratio of 3:1:1, and stir at room temperature for 10-30 minutes to form a homogeneous solution B.

[0062] Preparation of mixed emulsion: Slowly add liquid A to liquid B and mix evenly. Stir at room temperature for 10-30 minutes, then slowly add silane coupling agent hydrolysate and stir at room temperature for 30-60 minutes. Finally, slowly add nano-zirconia dispersion and continue stirring for 24 hours to obtain a white and uniform mixed emulsion.

[0063] Coating curing: Apply the mixed emulsion to the surface of a pretreated dry substrate (such as glass, metal, wood, ceramics, etc.) by spraying, scraping, spin coating or dipping. After leaving it at room temperature for 10 minutes, pre-cur it in a 100℃ oven for 30 minutes, and then cure it in a 150-180℃ oven for 2-3 hours.

[0064] Example 2

[0065] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0066] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0067] (2) Weigh 2.4g of hydrolysate, 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 1g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0068] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0069] Example 3

[0070] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0071] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0072] (2) Weigh 2.4g of hydrolysate, 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.3g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0073] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0074] Example 4

[0075] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0076] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0077] (2) Weigh 2.4g of hydrolysate, 4g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0078] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0079] Example 5

[0080] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0081] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0082] (2) Weigh 2.0g of hydrolysate, 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0083] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0084] Example 6

[0085] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0086] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0087] (2) Weigh 2.0g of hydrolysate, 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0088] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 150°C for 2 hours to obtain the coating.

[0089] Example 7

[0090] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0091] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0092] (2) Weigh 2.0g of hydrolysate, 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxy silicone oil and 0.2g of glycerol, mix them and stir for 24h to allow them to react fully and obtain a mixture.

[0093] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0094] Example 8

[0095] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0096] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0097] (2) Weigh 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0098] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0099] Example 9

[0100] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0101] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0102] (2) Weigh 2.0g of hydrolysate, 2g of anhydrous ethanol, 2g of PMA, 0.5g of amino silicone oil, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0103] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0104] Example 10

[0105] A method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating, the specific process of which is as follows:

[0106] (1) First, mix 5g KH-550 and 5g anhydrous ethanol evenly, then add 0.5g deionized water and mix evenly. Hydrolyze the mixture at a constant temperature of 60℃ for 4 hours to obtain the hydrolysate.

[0107] (2) Weigh 2.0g of hydrolysate, 6g of PETA, 2g of anhydrous ethanol, 2g of PMA, 0.3g of hydroxyl silicone oil, 0.2g of glycerol, and 2g of nano-zirconia dispersion, mix them, stir for 24h, and allow them to react fully to obtain a mixture;

[0108] (3) Finally, the above mixture is coated on the surface of the substrate, left at room temperature for 10 minutes, pre-cured at 100°C for 30 minutes, and cured at 180°C for 2 hours to obtain the coating.

[0109] The substrate used in Examples 1 to 10 is preferably a glass substrate.

[0110] Comparing Examples 1 with Examples 2, 5, 7, and 8, it is evident that the amount of added nanoparticles and hydrolysate significantly affects the hardness and wear resistance of the coating. The coupling effect after hydrolysis of the coupling agent and the physical strengthening by the nanoparticles further enhance the hardness of the hybrid coating.

[0111] Comparing Examples 1 with Examples 3, 4, 9 and 10, it can be seen that adding appropriate amounts of amino silicone oil and pentaerythritol triacrylate helps to improve the contact angle of the coating through the construction of the surface silicone oil. The Michael addition reaction between the amino group and the double bond in PETA will affect the construction of the antifouling performance of the coating to a certain extent.

[0112] As can be seen from the comparison between Example 1 and Example 6, the coating hardness is insufficient when the curing temperature is low, and the coating hardness will increase as the curing temperature increases.

[0113] Figure 1 The mixed emulsion was prepared using the method described in Example 1;

[0114] Figure 2A sample of a coating obtained by coating a mixed emulsion onto a substrate;

[0115] Figure 3 Under a 500-gram load, after 10,000 cycles of cyclic rubbing with #0000 steel wool, the coating showed no scratches and minimal weight loss. This coating exhibits excellent wear resistance.

[0116] Figure 4 The measured water contact angle of the coating is L: 103.362, R: 100.596, CA: 101.979, with an inclination angle of 0.00. Its water contact angle is greater than 100°, indicating hydrophobic properties. Drawing on the coating with an oil-based pen can be quickly erased, demonstrating anti-graffiti properties. The coating has high hardness, reaching 9H. Under a 500g load, after 10,000 cycles of cyclic scraping with #0000 steel wool, the coating showed no scratches and minimal weight loss, indicating good wear resistance.

[0117] Therefore, the present invention adopts the above-mentioned method for preparing and applying an ultra-hard wear-resistant and anti-fouling composite coating, which has the advantages of high hardness, wear resistance, scratch resistance and low cost.

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical solutions of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A super-hard, wear-resistant, and stain-resistant composite coating, characterized in that, include 30-80 parts by weight of coupling agent 3-10 parts by weight of deionized water 100-300 parts by weight of anhydrous ethanol 5-50 parts by weight of amino silicone oil 1-30 parts by weight of hydroxyl silicone oil 1-20 parts by weight of glycerol Pentaerythritol triacrylate 200-500 parts by weight 50-200 parts by weight of propylene glycol methyl ether acetate 20-200 parts by weight of nanoparticle dispersion; The coupling agent is γ-aminopropyltriethoxysilane, and the nanoparticles are zirconium oxide; The coating preparation method includes the following steps: Preparation of coupling agent hydrolysate: Mix coupling agent and anhydrous ethanol in a certain proportion, then add deionized water, and stir in a constant temperature water bath to obtain coupling agent hydrolysate; Preparation of Solution A: Hydroxy silicone oil, amino silicone oil and glycerol are mixed in a mass ratio of 3:5:2 and stirred to form a homogeneous mixture of Solution A; Preparation of nanoparticle dispersion: Nanoparticles are dispersed in an aqueous solution to obtain nanoparticle dispersion; Preparation of solution B: Pentaerythritol triacrylate, anhydrous ethanol and propylene glycol methyl ether acetate are mixed in a mass ratio of 3:1:1 and stirred to form a homogeneous solution B. Preparation of mixed emulsion: Slowly add liquid A to liquid B and mix evenly, stir, slowly add coupling agent hydrolysate and stir, and finally slowly add nanoparticle dispersion and continue stirring to obtain a uniform mixed emulsion; Coating curing: The mixed emulsion is applied to the surface of the pretreated substrate and cured to obtain the coating.

2. The method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating according to claim 1, characterized in that, Includes the following steps: Preparation of coupling agent hydrolysate: Mix coupling agent and anhydrous ethanol in a certain proportion, then add deionized water, and stir in a constant temperature water bath to obtain coupling agent hydrolysate; Preparation of Solution A: Mix hydroxyl silicone oil, amino silicone oil and glycerol, stir to form a homogeneous mixture of Solution A; Preparation of nanoparticle dispersion: Nanoparticles are dispersed in an aqueous solution to obtain nanoparticle dispersion; Preparation of solution B: Pentaerythritol triacrylate, anhydrous ethanol and propylene glycol methyl ether acetate are mixed and stirred to form a homogeneous solution B. Preparation of mixed emulsion: Slowly add liquid A to liquid B and mix evenly, stir, slowly add coupling agent hydrolysate and stir, and finally slowly add nanoparticle dispersion and continue stirring to obtain a uniform mixed emulsion; Coating curing: The mixed emulsion is applied to the surface of the pretreated substrate and cured to obtain the coating.

3. The method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating according to claim 2, characterized in that, The substrate can be glass, metal, wood or ceramic.

4. The method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating according to claim 2, characterized in that, In the preparation steps of the coupling agent hydrolysate, deionized water accounts for 10% of the mass of the coupling agent, and the mass ratio of coupling agent: anhydrous ethanol: deionized water is 10:10:

1. In the preparation steps of the nanoparticle dispersion, the nanoparticles account for 20% of the mass of the dispersion.

5. The method for preparing an ultra-hard, wear-resistant, and anti-fouling composite coating according to claim 2, characterized in that, In the preparation steps of the silane coupling agent hydrolysate, the heating temperature in the constant temperature water bath is 40℃-60℃, and the stirring time is 2-4 hours. In the preparation steps of liquid A, stir at room temperature for 5-10 minutes; In the preparation of solution B, stir at room temperature for 10-30 minutes; In the preparation steps of the mixed emulsion, the mixture of solution A and solution B is stirred at room temperature for 10-30 minutes; after adding the coupling agent hydrolysate, it is stirred at room temperature for 30-60 minutes; after adding the nanoparticle dispersion, it is stirred at room temperature for 24 hours. In the coating curing process, the curing treatment includes placing it at room temperature for 10 minutes, then pre-curing it in a 100℃ oven for 30 minutes, and then curing it in a 150-180℃ oven for 2-3 hours. In the preparation steps of the nanoparticle dispersion, the particle size is less than 10 nanometers.

6. The application of the ultra-hard wear-resistant and anti-fouling composite coating according to claim 1 in building decoration, electronic equipment, machinery manufacturing or optical devices.

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