Super wear-resistant antifouling coating and preparation method thereof

Abstract

The application discloses an ultra-wear-resistant antifouling paint and a preparation method thereof, characterized by comprising the following main components and their weight parts: 40-60 parts of epoxy resin, 4-6 parts of fluorocarbon resin, 12-18 parts of organosilane modified nano hard wear-resistant filler, 4-8 parts of two-dimensional sheet-shaped barrier filler, 2-6 parts of environment-friendly antifouling agent, 10-15 parts of polyamide curing agent, 1-3 parts of dispersing agent and 10-20 parts of environment-friendly solvent, and the preparation method comprises the following steps: (1) batching; (2) pre-mixing; (3) filler modification; (4) adding the filler; (5) adding the antifouling agent; (6) filtering and packaging. The ultra-wear-resistant antifouling paint has excellent antifouling performance, wear resistance and adhesion, and is suitable for the protection of marine ships, underwater buildings and structures.

Description

Technical Field

[0001] This invention belongs to the field of novel functional materials and surface coating technology. Specifically, it is a coating for the protection of marine vessels, underwater buildings and structures, especially a washable, wear-resistant, antifouling and environmentally friendly coating for ships. Background Technology

[0002] Marine coatings, due to their need to withstand strong ultraviolet radiation, salt spray and high-salinity seawater erosion, water flow impact, and the abrasion caused by the attachment and secretions of marine organisms, require high levels of corrosion resistance, weather resistance, and adhesion resistance. While current marine coatings have achieved ideal results in corrosion and weather resistance, they still fall short of satisfactory results in preventing the attachment of marine organisms such as algae, shellfish, and especially barnacles.

[0003] The antifouling principle of antifouling coatings relies on two main methods: one is to use toxic chemicals (such as organotin and copper compounds) to poison marine organisms, or to release irritants that repel marine organisms, thereby preventing biofouling. However, due to the serious pollution caused by organotin and other toxic substances to the marine ecosystem, their use has been restricted or banned by international conventions. The development of environmentally friendly antifouling coatings, especially Wuxi self-polishing antifouling coatings, has been a research focus in recent years, as exemplified by CN116731574A's "Wuxi Self-Polishing Antifouling Coating" (application date: 2023-07-05, publication date: 2023-09-12). Self-polishing coatings are further divided into hydrolyzable and ion-exchange types. Hydrolyzable coatings involve covalently grafting the antifouling agent onto the main chain of a hydrolyzable polymer material, while ion-exchange coatings involve the antifouling agent being covalently linked to the main chain of a methacrylate copolymer via ester bonds or other bonds. The former releases the antifouling agent slowly through the hydrolysis of the covalent bonds between the antifouling agent and the resin or the resin main chain, while the latter releases it slowly through the exchange of high-valence metal ions in the antifouling agent with sodium ions in seawater. Simultaneously, the hydrolyzed resin on the coating surface is detached under the scouring action of seawater, thus continuously maintaining the effective concentration of the antifouling agent on the coating surface and keeping the coating surface clean and smooth, exhibiting a self-polishing effect to reduce biofouling. Furthermore, since self-polishing requires a certain water flow velocity, and ships are not always at high speeds, barnacles and other organisms attach to them when the ship is stationary or at low speeds. Therefore, even ships using self-polishing antifouling coatings need to periodically or irregularly clean the attached marine organisms, especially barnacles, using high-pressure water, underwater robots, or manual cleaning. This places high demands on the abrasion resistance of the antifouling coating. However, because the surface layer of this self-polishing material needs to detach under the action of water flow, the material has poor abrasion resistance. During underwater robot cleaning, the coating is easily damaged by mechanical forces, making it difficult to achieve a long-term, effective antifouling effect.

[0004] Lowering the surface free energy of the coating increases its hydrophobicity and also provides some antifouling effect. However, since the ship's hull is a metal with high surface free energy, the large difference in surface energy between the two leads to poor wettability of the low surface free energy coating on the coated surface, resulting in reduced adhesion. Under the mechanical force of high-pressure water or cleaning robots, there is a risk of coating peeling and falling off.

[0005] Another type of coating that combines wear resistance and antifouling properties involves adding fillers such as nano-silica, titanium dioxide, zinc oxide, and alumina to the coating. This increases hardness and thus wear resistance. Low surface energy materials are often added or synthesized, as seen in CN119060632A "An antifouling, super-slippery, hydrophobic coating and its preparation method and application" (application date: 2024-08-30, publication date: 2024-12-03) and CN110527390A "A low surface energy antifouling coating" (application date: 2019-09-11, publication date: 2019-12-03). However, existing wear-resistant and antifouling coatings of this type suffer from issues with the compatibility of filler polarity with resin polarity and surface free energy. The dispersion and stability of nanomaterials are also poor, leading to a weakening of the antifouling effect after long-term use. Furthermore, the wear resistance of the coating still fails to meet the requirements of mechanical cleaning.

[0006] The challenge in coating development lies in the fact that the physical and chemical properties of the coating formed after curing depend on the properties of the film-forming resin and functional additives, as well as the interactions between the film-forming substance and the functional additives and solvents, such as compatibility and dispersibility, and the curing effect of the coating. Often, adjusting the composition can improve one performance aspect while potentially decreasing others. For example, there's the contradiction between the self-polishing effect required by self-polishing coatings and the coating's abrasion resistance and mechanical strength; or the contradiction between the high abrasion resistance resulting from high abrasion-resistant filler content in abrasion-resistant coatings and the decreased mechanical properties due to poor dispersibility. Therefore, coating component design often suffers from trade-offs. While improving a single performance aspect is relatively easy, simultaneously improving comprehensive performance, especially multiple contradictory properties, is significantly more difficult. Summary of the Invention

[0007] In view of the above-mentioned problems of existing antifouling coatings for underwater substrates such as ships, the purpose of this invention is to provide an ultra-wear-resistant antifouling coating and a preparation method. Through the design of a new coating system, this coating has the characteristics of being environmentally friendly, having good wear resistance and strong antifouling ability, and is particularly suitable for waterproofing, corrosion prevention and antimicrobial adhesion of ships or underwater buildings and structures.

[0008] The ultra-wear-resistant and anti-fouling coating provided by this invention comprises the following main components and their weight parts:

[0009] 40-60 parts epoxy resin

[0010] 4-6 parts of fluorocarbon resin

[0011] 12-18 parts of organosilane modified nano-hard wear-resistant filler

[0012] 4-8 parts of barrier packing

[0013] 2-6 parts of environmentally friendly antifouling agent

[0014] 10-15 parts of polyamide curing agent

[0015] 1-3 parts of polymeric dispersant

[0016] 10-20 parts of environmentally friendly solvent.

[0017] To further explain, the ultra-wear-resistant and anti-fouling coating of the present invention may, as needed, include one or more of leveling agents, defoamers, and pigments.

[0018] Preferably, the fluorocarbon resin is polytetrafluoroethylene-vinyl ether resin (FEVE) and / or polyacrylate-fluorinated polysiloxane copolymer.

[0019] Preferably, the nano-hard wear-resistant filler is one or more of nano-alumina, nano-titanium carbide, and nano-silicon carbide with a Mohs hardness of not less than 9, so as to make the coating have high hardness and good wear resistance. After modification with organosilane, the epoxy groups in the organosilane modify the surface of fillers such as alumina, changing them from hydrophilic to hydrophobic, improving compatibility with the organic matrix, reducing particle agglomeration, and improving dispersibility; the silanol groups (-SiOH) in the organosilane react with the hydroxyl groups (-OH) on the surface of alumina to form covalent bonds (Al-O-Si) or combine with the lone pair electrons on the surface of titanium carbide and silicon carbide to form covalent bonds, while the organic end combines with the polymer matrix, significantly improving the interfacial adhesion strength; the modified nano-wear-resistant filler has better chemical stability in high temperature or humid environments and reduces interfacial defects.

[0020] The preferred barrier fillers are boron carbide and / or graphene. The two-dimensional sheet structure of graphene forms a physical barrier layer in the coating, while boron carbide can fill the pores in the coating to make it denser and enhance its impermeability, delaying the penetration of corrosive media into the coating. Both can also improve the mechanical strength of the coating. Together with high-hardness hard fillers, they further improve the wear resistance of the coating. In particular, graphene can reduce the coefficient of friction of the paint and give the coating self-healing ability, improving its wear resistance against high-pressure water cleaning and underwater cleaning by robots, as well as the coating layer's resistance to cracking.

[0021] The antifouling agent is preferably environmentally friendly copper pyridine thione and bromopyrrolidinone, which interfere with the physiological activities of marine organisms by releasing active groups, inhibiting their adhesion and growth on the coating surface, and meeting environmental protection requirements.

[0022] The epoxy resin is preferably bisphenol A type, with epoxy groups providing reactive crosslinking properties, benzene rings providing abrasion resistance and chemical stability, and hydroxyl groups providing adhesion. The curing agent is preferably polyamide, with amino groups providing reactive crosslinking properties, such as G640 and BS-8140.

[0023] The environmentally friendly solvent is preferably a mixture of one or more of xylene, n-butanol, dimethyl carbonate, or butyl acetate.

[0024] The preferred polymeric dispersants are BYK-161 and SOLSPERSE 32500.

[0025] The present invention further provides a method for producing an ultra-wear-resistant and anti-fouling coating, comprising the following steps:

[0026] (1) Ingredients: Weigh each ingredient according to the proportions;

[0027] (2) Premixing: Add epoxy resin, fluorocarbon resin, solvent and polymeric dispersant together into a mixing tank and stir until homogeneous;

[0028] (3) Filler modification: Add nano-hard wear-resistant filler and barrier filler to organic solvent, add organosilane coupling agent, stir and react at 60-80℃ for 2-3 hours, then filter and dry to obtain modified filler;

[0029] (4) Adding filler: The modified filler from step (3) is gradually added to the premixed mixing vessel from step (2) and stirred at high speed at about 1200 rpm to ensure that the filler is evenly dispersed;

[0030] (5) Add antifouling agent: Add copper pyridinethione and bromopyrrolidinone to the mixture, and then grind it in a sand mill until the fineness is qualified;

[0031] (6) Filtration: Pass the ground coating through a filter to remove impurities and then package it;

[0032] (7) Curing agent: The curing agent is prepared separately and filtered and packaged.

[0033] The paint and hardener are packaged separately and mixed before application to ensure that the paint does not deteriorate during long-term storage.

[0034] This invention relates to an ultra-wear-resistant and antifouling coating, which, through the complementary and synergistic functions of its components, forms a comprehensive protective system with high impermeability, corrosion resistance, fouling resistance, and wear resistance. The film-forming material, primarily epoxy resin, is cross-linked with a polyamide curing agent. Combined with the modification of nano-high-hardness fillers by organosilane coupling agents, the coating is firmly bonded to the substrate and does not detach under cleaning forces. The modified nano-high-hardness wear-resistant fillers, along with boron carbide and graphene two-dimensional sheet fillers, work together to give the coating extremely high wear resistance. The presence of graphene imparts a certain degree of self-healing ability to the coating, improving its durability. Modified fluorocarbon resin endows the coating with low surface energy and superhydrophobic properties, synergistically enhancing the antifouling function of the coating with the antifouling agent. Environmentally friendly solvents and antifouling agents are used, reducing environmental pollution. This coating is particularly suitable for the surface protection of marine vessel hulls and can also be used for the protection of underwater structures and buildings such as drilling platforms. Attached Figure Description

[0035] Figure 1 The images shown are photographs of the antifouling performance tests of the test samples from Examples 1-4.

[0036] Figure 2 Photographs of the antifouling performance tests of the test samples in Comparative Examples 1-3 are shown in image ac.

[0037] Figure 3 ad are photographs of the coating surfaces of the anti-fouling test samples from Examples 1-4 after robot cleaning and scribing.

[0038] Figure 4 Photographs of the coating surfaces of the anti-fouling test samples (Comparative Examples 1-3) after robot cleaning and grid marking are shown in ac. Detailed Implementation

[0039] The present invention will be further described below with reference to specific embodiments and accompanying drawings to help understand the content of the present invention.

[0040] In the following examples, unless otherwise specified, the epoxy resin used is bisphenol A type epoxy resin, the mixed solvent used is a blend of xylene and n-butanol, the environmentally friendly solvent used is one of dimethyl carbonate and butyl acetate, the polymeric dispersant used is either BYK-161 or SOLSPERSE 32500, and the polyamide curing agent used is either G640 or BS-8140. Example 1

[0041] 1. Coating Formulation

[0042] The components of the coating and their parts by weight:

[0043] Epoxy resin: 50 parts

[0044] Polytetrafluoroethylene-vinyl ether resin: 5 parts

[0045] Nano-alumina: 16 parts

[0046] Boron carbide: 6 parts

[0047] Environmentally friendly copper pyrithione antifouling agent: 6 parts

[0048] Polymer dispersant: 2 parts

[0049] Polyamide curing agent: 12 parts

[0050] Mixed solvent: 15 parts.

[0051] 2. Preparation method:

[0052] (1) Ingredients: Weigh each ingredient according to the proportions;

[0053] (2) Premixing: Add epoxy resin, polytetrafluoroethylene-vinyl ether resin, polymeric dispersant and mixed solvent together into a stirred tank and stir until uniform;

[0054] (3) Filler modification: Add nano-hard wear-resistant filler and barrier filler to organic solvent, add organosilane coupling agent, stir and react at 60-80℃ for 2-3 hours, then filter and dry to obtain modified filler;

[0055] (4) Adding filler: The modified filler from step (3) is gradually added to the premixed mixing vessel from step (2) and stirred at high speed at 1200 rpm to ensure that the filler is evenly dispersed;

[0056] (5) Add antifouling agent: Add environmentally friendly antifouling agent to the mixture and grind until the fineness is qualified;

[0057] (6) Filtration: Pass the mixed coating through a filter to remove impurities and then package it;

[0058] (7) Curing agent: The curing agent is prepared separately and filtered and packaged.

[0059] 3. Coating performance test

[0060] Performance tests were conducted on the cured coating, and the test data are as follows:

[0061] (1) Resistance to robotic cleaning: In natural seawater, using robotic cleaning equipment, the weight loss after 1 hour of rotation test is ≤1mg. Figure 3 The photo shows that the coating surface has no obvious peeling, cracks or wear marks, and has excellent scratch resistance.

[0062] (2) Abrasion resistance: Tested with a Taber abrasion tester, the weight loss after 1000 revolutions with a 500g load is ≤10mg, which shows excellent abrasion resistance.

[0063] (3) Antifouling performance: From October 2024 to April 2025, samples coated with the coating of this invention were immersed in natural seawater in Xiamen for 6 months. No marine organisms attached, demonstrating good and long-lasting antifouling performance. See attached photos of the sample surface. Figure 1 a.

[0064] (4) Adhesion: Cross-cut test, adhesion reached level 0, see sample photo. Figure 3 a. Example 2

[0065] 1. Coating formulation:

[0066] The components of the coating and their parts by weight:

[0067] Epoxy resin: 50 parts

[0068] Polytetrafluoroethylene-vinyl ether resin: 5 parts

[0069] Nano-titanium carbide: 12 parts

[0070] Graphene: 5 parts

[0071] Bromopyrrolidone: 5 parts

[0072] Polymer dispersant: 3 parts

[0073] Polyamide curing agent: 12 parts

[0074] Environmentally friendly solvent: 15 parts.

[0075] 2. Preparation method

[0076] (1) Ingredients: Weigh each ingredient according to the proportions;

[0077] (2) Premixing: Add epoxy resin, polytetrafluoroethylene-vinyl ether resin, polymeric dispersant and solvent together into a stirred tank and stir until uniform;

[0078] (3) Filler modification: Add nano-hard wear-resistant filler and barrier filler to organic solvent, add organosilane coupling agent, stir and react at 60-80℃ for 2-3 hours, then filter and dry to obtain modified filler;

[0079] (4) Adding filler: The modified filler and dispersant from step (3) are gradually added to the premixed mixing vessel from step (2) and stirred at high speed to ensure that the filler is evenly dispersed;

[0080] (5) Add antifouling agent: Add bromopyrrolidone to the mixture, continue stirring until uniform, and then grind in a sand mill until the fineness is qualified;

[0081] (6) Filtration: Pass the mixed coating through a filter to remove impurities and then package it;

[0082] (7) Curing agent: The curing agent is prepared separately and filtered and packaged.

[0083] 3. Experimental data:

[0084] (1) Resistance to robotic cleaning: In natural seawater, using robotic cleaning equipment, the weight loss after 1 hour of rotation test is ≤1mg. Figure 3 As shown in photo b, the coating surface shows no obvious peeling, cracks, or wear marks, indicating excellent scratch resistance.

[0085] (2) Abrasion resistance: Tested with a Taber abrasion tester, the weight loss after 1000 revolutions with a 500g load is ≤10mg, which shows excellent abrasion resistance.

[0086] (3) Antifouling properties: Immersed in natural seawater for 6 months, see sample photos. Figure 1 b. No marine organisms adhere to it, and it has good and long-lasting antifouling properties.

[0087] (4) Adhesion: Cross-cut adhesion test, adhesion reached level 0, see sample photo. Figure 3 b. Example 3

[0088] 1. Coating formulation:

[0089] The components of the coating and their parts by weight:

[0090] Epoxy resin: 40 parts

[0091] Polyacrylate-fluorinated polysiloxane copolymer resin: 6 parts

[0092] Nano-titanium carbide: 18 parts

[0093] Graphene: 4 parts

[0094] Bromopyrrolidone: 6 parts

[0095] Polymer dispersant: 1 part

[0096] Polyamide curing agent: 10 parts

[0097] Environmentally friendly solvent: 15 parts.

[0098] 2. Production method: Refer to Example 1, except that the different components of this example are used instead of the corresponding components of Example 1.

[0099] 3. Experimental data:

[0100] (1) Resistance to robotic cleaning: In natural seawater, using robotic cleaning equipment, the weight loss after 1 hour of rotation test is ≤1mg. Figure 3Photo c shows that the coating surface has no obvious peeling, cracks or wear marks, and has excellent scratch resistance.

[0101] (2) Abrasion resistance: Tested with a Taber abrasion tester, the weight loss after 1000 revolutions with a 500g load is ≤10mg, which shows excellent abrasion resistance.

[0102] (3) Antifouling properties: After being immersed in natural seawater for 6 months, no marine organisms adhered, demonstrating good and long-lasting antifouling performance. See photos. Figure 1 c.

[0103] (4) Adhesion: Cross-cut adhesion test, adhesion reached level 0, see sample photo. Figure 3 c. Example 4

[0104] 1. Coating Formulation

[0105] The components of the coating and their parts by weight:

[0106] Epoxy resin: 60 parts

[0107] Polyacrylate-fluorinated polysiloxane copolymer resin: 4 parts

[0108] Nano-silicon carbide: 12 parts

[0109] Boron carbide: 8 parts

[0110] Environmentally friendly copper pyrithione: 2 parts

[0111] Polymer dispersant: 2 parts

[0112] Polyamide curing agent: 15 parts

[0113] Mixed solvent: 15 parts.

[0114] 2. Production method: Refer to Example 1, except that the different components in this example are used instead of the corresponding components in Example 1.

[0115] 3. Performance Testing:

[0116] (1) Resistance to robotic cleaning: In natural seawater, using robotic cleaning equipment, the weight loss after 1 hour of rotation test is ≤1mg. Figure 3 The photos show that the coating surface has no obvious peeling, cracks or wear marks, and has excellent scratch resistance.

[0117] (2) Abrasion resistance: Tested with a Taber abrasion tester, the weight loss after 1000 revolutions with a 500g load is ≤10mg, which shows excellent abrasion resistance.

[0118] (3) Antifouling properties: After being immersed in natural seawater for 6 months, there is basically no marine organism attachment, demonstrating good and long-lasting antifouling performance. See photos. Figure 1 d.

[0119] (4) Adhesion: Cross-cut test, adhesion reached level 0, see sample photo. Figure 3 d.

[0120] Comparative Example 1 (Compared to Example 1, fluorocarbon resin and boron carbide were removed, and the amount of epoxy resin and titanium carbide was increased to maintain the total amount of resin and filler unchanged)

[0121] 1. Coating formulation:

[0122] The components of the coating and their parts by weight:

[0123] Epoxy resin: 60 parts

[0124] Nano-titanium carbide: 22 parts

[0125] Bromopyrrolidone: 6 parts

[0126] Polymer dispersant: 1 part

[0127] Polyamide curing agent: 10 parts

[0128] Environmentally friendly solvent: 15 parts.

[0129] 2. Performance Testing:

[0130] (1) Resistance to robotic cleaning: In natural seawater, using a robotic cleaning device, after a 1-hour rotation test, the weight loss was 10 mg. Figure 4 Photo a shows that there are no obvious peeling or cracks on the coating surface, but the scratch resistance is slightly reduced compared with Examples 1-4.

[0131] (2) Abrasion resistance: The Taber abrasion tester was used to test the abrasion resistance. With a load of 500g, the weight loss was 30mg after 1000 revolutions. The abrasion resistance decreased compared with Examples 1-4.

[0132] (3) Antifouling performance: After immersion in natural seawater for 6 months, a small amount of marine organisms attached, and the antifouling performance was slightly reduced compared with Examples 1-4. See photos. Figure 2 a.

[0133] (4) Adhesion: Cross-cut test, adhesion reached level 0, see sample photo. Figure 4 a.

[0134] Comparative Example 2 (Compared to Example 1, fluorocarbon resin and titanium carbide were omitted, but the total amount of resin and filler remained unchanged).

[0135] 1. Coating formulation:

[0136] The components of the coating and their parts by weight:

[0137] Epoxy resin: 60 parts

[0138] Boron carbide: 22 parts

[0139] Bromopyrrolidone: 6 parts

[0140] Polymer dispersant: 1 part

[0141] Polyamide curing agent: 10 parts

[0142] Environmentally friendly solvent: 25 parts.

[0143] 2. Performance Testing:

[0144] (1) Resistance to robotic cleaning: In natural seawater, using robotic cleaning equipment, after a 1-hour rotation test, the weight loss was 15mg. Figure 4 Photo b shows that there are no obvious peeling, cracks or wear marks on the coating surface, and the scratch resistance is slightly reduced and the rate of decrease is greater compared with Examples 1-4.

[0145] (2) Abrasion resistance: The Taber abrasion tester was used to test the abrasion resistance. With a load of 500g, the weight loss was 50mg after 1000 revolutions. The abrasion resistance decreased significantly compared with Examples 1-4.

[0146] (3) Antifouling performance: After being immersed in natural seawater for 6 months, a small amount of marine organisms attached, and the antifouling performance decreased slightly. See the photo. Figure 2 b.

[0147] (4) Adhesion: Cross-cut test, adhesion reached level 0, see photo. Figure 4 b.

[0148] Comparative Example 3 (Antifouling agent removed)

[0149] 1. Components of the coating and their weight parts:

[0150] Epoxy resin: 52 parts

[0151] Fluorocarbon resin: 5 parts

[0152] Nano-titanium carbide: 22 parts

[0153] Graphene: 4 parts

[0154] Polymer dispersant: 1 part

[0155] Polyamide curing agent: 10 parts

[0156] Environmentally friendly solvent: 15 parts.

[0157] 2. Performance Testing:

[0158] (1) Resistance to robotic cleaning: In natural seawater, using a robotic cleaning device, after a 1-hour rotation test, the weight loss was 1 mg. Figure 4 Photo c shows that the coating surface has no obvious peeling, cracks and wear marks, and has excellent scratch resistance.

[0159] (2) Abrasion resistance: Tested with a Taber abrasion tester, the weight loss was 10 mg after 1000 revolutions with a 500g load, indicating excellent abrasion resistance.

[0160] (3) Antifouling performance: After immersion in natural seawater for 6 months, a large number of marine organisms attached to the surface, and the antifouling performance decreased significantly compared with Examples 1-4 and Comparative Examples 1-2. This indicates that the antifouling agent has a better antifouling effect than fluorocarbon resin. See the photos. Figure 2 c.

[0161] (4) Adhesion: Cross-cut test, adhesion reached level 0, see photo. Figure 4 c.

[0162] This article uses specific examples to illustrate the inventive concept in detail. The description of the above embodiments is only for the purpose of helping to understand the core idea of ​​the present invention. It should be noted that any obvious modifications, equivalent substitutions or other improvements made by those skilled in the art without departing from the inventive concept should be included within the protection scope of the present invention.

Claims

1. A super abrasion anti-fouling coating suitable for cleaning of underwater robots of ships, characterized in that It contains the main components and its mass fraction is: Epoxy resin 40-60 parts Fluorocarbon resin 4-6 parts Organic silane modified nano hard wear-resistant filler 12-18 parts Barrier filler 4-8 parts Environment-friendly antifouling agent 2-6 parts Polyamide curing agent 10-15 parts High molecular dispersant 1-3 parts Environment-friendly solvent 10-20 parts; Among them, the organic silane modified nano hard wear-resistant filler is one or several of nano alumina, nano titanium carbide and nano silicon carbide with Mohs hardness not less than 9; the barrier filler is boron carbide and / or graphene; the fluorocarbon resin is polytetrafluoroethylene-vinyl ether resin and / or polyacrylate-fluorinated polysiloxane copolymer.

2. The super wear-resistant antifouling paint according to claim 1, characterized in that The components also include one or more of leveling agent, defoaming agent and pigment.

3. The super wear-resistant antifouling paint according to claim 1, characterized by The environment-friendly antifouling agent is copper pyrithione and / or bromopyrrole nitrile.

4. The super wear-resistant antifouling paint according to claim 1, characterized by The environment-friendly solvent is one or several mixtures of xylene, n-butanol, dimethyl carbonate, butyl acetate or the like.

5. The super wear-resistant antifouling paint according to claim 1, characterized in that The epoxy resin is bisphenol A type.

6. The super wear-resistant antifouling paint according to claim 1, characterized by The high molecular dispersant is BYK-161 and SOLSPERSE 32500.

7. A method for producing the super wear-resistant antifouling paint according to claim 1, characterized by It includes the following steps: (1) batching: weigh each raw material according to the proportion; (2) pre-mixing: mix epoxy resin, fluorocarbon resin, dispersant and environment-friendly solvent together in a stirred tank and stir uniformly; (3) filler modification: add nano hard wear-resistant filler and barrier filler into organic solvent, add organic silane coupling agent, stir at 60-80℃ for 2-3 hours, then filter and dry to obtain modified filler; (4) adding filler: add the modified nano hard wear-resistant filler of step (3) into the stirred tank after pre-mixing of step (2) and stir to ensure uniform dispersion of the filler; (5) adding antifouling agent: add environment-friendly antifouling agent into the mixture and continue to stir until uniform, then introduce into a basket sand mill and grind to the required fineness; (6) filtration: filter the ground paint to remove grinding medium and impurities and package; (7) curing agent: prepare and filter the curing agent separately and package.

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