Self-polishing antifouling paint as well as preparation method and application thereof

Abstract

The invention relates to a self-polishing antifouling coating and a preparation method and application thereof, the self-polishing antifouling coating is composed of a component A and a component B. The component A is composed of water-based acrylic acid self-polishing antifouling resin, an antifouling agent and pigment filler, and the component B is a cross-linking agent; in water, the self-polishing antifouling paint is provided with a hydrogel microlayer with the thickness of 50-200 microns on the surface of a coating on the surface of a base material. The hydrogel microlayer enables the surface of the antifouling coating to be smoother, the drag reduction performance of the coating is improved, the film forming performance, the adhesion performance, the slow release performance and the drag reduction performance on a base material are good, the polishing performance is stable, and the excellent algae adsorption inhibition capacity and the real sea antifouling capacity are shown.

Description

[Technical field]

[0001] The present invention relates to the technical field of marine fouling organism control, and more specifically, to a self-polishing antifouling coating, a preparation method of the self-polishing antifouling coating, and a use of the self-polishing antifouling coating. [Background technology]

[0002] Water-based antifouling paint uses water as a dispersion system. Compared with oil-based self-polishing antifouling paints that use volatile and toxic organic solvents such as xylene, butanol, and butyl acetate as dispersants (content up to about 30%), water-based antifouling paints do not release or only release a small amount of volatile organic matter during use, and are more environmentally friendly. In water-based self-polishing antifouling paints, the self-polishing resin has two main functions: ① As a film-forming material, it loads the pigments and fillers in the paint; ② Through stable hydrolysis polishing, the coating thickness reduction rate is more stable, the surface is smoother, and it helps to release the antifouling agent stably.

[0003] Hydrogel is a gel system formed by a type of aqueous polymer with a bulk network structure that dissolves in water but does not swell. Hydrogel can have a considerable inhibitory ability on the attachment of marine fouling organisms through the hydration layer on its surface. The surface instability caused by its low elasticity film is also not conducive to the attachment of marine fouling organisms. If the characteristics of hydrogel are compounded on the water-based self-polishing antifouling resin, it will help to improve the antifouling performance of the self-polishing antifouling coating. At the same time, the presence of the hydrogel layer helps to further reduce the viscous resistance of the coating to the water body and improve the drag reduction performance of the coating; the presence of the hydrogel layer also provides a certain buffer for the coating to release antifouling agents or ions into the water body, which helps the slow release of the above substances, thereby increasing the service life of the coating.

[0004] The present invention is based on the summary of the prior art, through a large number of experimental studies and analyses, and imparts a hydrogel microlayer to the surface of a water-based acrylic self-polishing antifouling resin and an antifouling coating prepared with the resin to improve the performance of the material, thereby completing the present invention. [Summary of the invention]

[0005] [Technical issues to be solved]

[0006] The object of the present invention is to provide a self-polishing antifouling coating.

[0007] Another object of the present invention is to provide a method for preparing the self-polishing antifouling coating.

[0008] Another object of the present invention is to provide use of the self-polishing antifouling coating.

[0009] [Technical solution]

[0010] The present invention is achieved through the following technical solutions.

[0011] The invention relates to a self-polishing antifouling coating, which is composed of component A and component B in a weight ratio of 100:0.1-0.5, wherein component A is composed of 10-50 weight parts of water-based acrylic self-polishing antifouling resin, 10-60 weight parts of antifouling agent and 1-30 weight parts of pigment filler, and component B is a cross-linking agent; in water, the coating surface of the self-polishing antifouling coating on the surface of a substrate has a hydrogel microlayer with a thickness of 50-200 μm.

[0012] According to a preferred embodiment of the present invention, the water-based acrylic self-polishing antifouling resin is prepared by the following preparation steps:

[0013] A. Preparation of monomer mixture

[0014] 10-100% of sodium hydroxide based on the molar amount of the unsaturated organic acid and 30-200% of water are mixed evenly, and then 3-20% of the unsaturated organic acid based on the total molar amount of the following monomers is added, mixed evenly, and dissolved to obtain a NaAA solution;

[0015] Under stirring with a magnetic stirrer, the total amount of the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer in moles is 1:20-30 to the volume of the NaAA solution in milliliters, and the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer are sequentially added to the NaAA solution in a molar ratio of 70-95:5-25:2-15 to obtain the monomer mixture;

[0016] B. Preparation of initiator solution

[0017] At room temperature, 0.5-2.0% of the aqueous initiator, 0-1.0% of the oily initiator and 30-200% of deionized water, based on the molar amount of the unsaturated organic acid, are mixed uniformly to obtain the initiator solution;

[0018] C. Preparation of water-based acrylic self-polishing antifouling resin

[0019] In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 90-270% ethanol and 10-30% deionized water are added based on the total weight of the above monomers, and then the monomer mixture obtained in step A and the initiator solution obtained in step B are added, and the addition amount thereof is 5-10% of their respective volumes; then, the remaining monomer mixture solution is heated to a temperature of 65-85° C. under a stirring speed of 50-500 rpm;

[0020] When blue light appears in the reaction system, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 0.5 to 1.5 hours, and the temperature is maintained at 65 to 85° C. for 0.4 to 0.6 hours; then, 0.01 to 0.02% of the above-mentioned initiator solution based on the total mass of all monomers is continued to be added, and the temperature is maintained at 60 to 70° C. for 0.8 to 1.2 hours, and then cooled to room temperature to obtain a white emulsion of water-based acrylic self-polishing antifouling resin.

[0021] According to another preferred embodiment of the present invention, in the preparation step A and the preparation step B, the unsaturated organic acid is acrylic acid, methacrylic acid or a mixture thereof.

[0022] According to another preferred embodiment of the present invention, in the preparation step A, the oily acrylic monomer is one or more oily acrylic monomers selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate; the water-based monomer is acrylamide, hydroxyacrylamide, unsaturated organic acid or a mixture thereof, wherein the hydroxyacrylamide is N-hydroxymethylacrylamide, N-hydroxyethylacrylamide or N-hydroxypropylacrylamide; the acrylic silicone self-polishing monomer is acryloxytriisopropylsilane, methacryloxytriisopropylsilane, γ-methacryloxypropyltrimethoxysilane or a mixture thereof.

[0023] According to another preferred embodiment of the present invention, in the preparation step B, the aqueous initiator is azobisisobutylimidazoline hydrochloride, azobisisopropylimidazoline, azobisisobutylamidine hydrochloride, potassium persulfate or ammonium persulfate; the oily initiator is azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl benzoyl peroxide or methyl ethyl ketone peroxide.

[0024] According to another preferred embodiment of the present invention, the antifouling agent is one or more antifouling agents selected from Cu2O, copper pyrithione, zinc pyrithione, thiophanate-methyl, diuron or 4,5-dichloro-2-octyl-4-isothiazoline-3-one.

[0025] According to another preferred embodiment of the present invention, the pigment filler is one or more pigment fillers selected from ZnO, TiO2, Fe2O3, talc, molybdenum red, nano-silicon dioxide, kaolin, Al2O3 or activated carbon.

[0026] The invention also relates to a method for preparing the self-polishing antifouling coating.

[0027] The preparation steps of the preparation method are as follows:

[0028] Under room temperature, a white emulsion-like water-based acrylic self-polishing antifouling resin, an antifouling agent and a pigment and filler are uniformly mixed in a mass ratio of 10-50:10-60:1-30, and a coating rapid dispersion tester is used to grind and disperse the mixture for 0.4-1.0 h at a stirring speed of 2000-5000 rpm. When the fineness of the ground material is measured by a scraper fineness meter and is less than 50 μm, component A is obtained;

[0029] When the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is a hydroxyl group, a carboxyl group or an amino group, aziridine, tetramethoxymethyl glycoluril, glutaraldehyde, formaldehyde, phthalaldehyde, epichlorohydrin or triethoxysilane cross-linking agent is used as component B;

[0030] The amount of component B is 3-20% based on the molar amount of the cross-linking functional group hydroxyl, carboxyl or amino group contained in the water-based acrylic self-polishing antifouling resin in component A; the aqueous solution obtained by dissolving component B in water in a ratio of 1:20-80 in grams of component B to milliliters of water is uniformly mixed with component A to obtain the self-polishing antifouling coating;

[0031] The self-polishing antifouling paint is brushed onto the surface of a substrate to obtain a water-based acrylic self-polishing antifouling paint coating having a hydrogel microlayer in water, wherein the thickness of the hydrogel microlayer is 50-200 μm.

[0032] According to another preferred embodiment of the present invention, when the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is an alkoxysilyl group, tetraethoxysilane, silane coupling agent A-171, silane coupling agent KH-550, silane coupling agent KH-560 or silane coupling agent KH-570 cross-linking agent is used as component B; the amount of component B is 3 to 20% based on the molar amount of the cross-linking functional group alkoxysilyl group contained in the water-based acrylic self-polishing antifouling resin in component A.

[0033] The present invention also relates to the use of the self-polishing antifouling coating or the self-polishing antifouling coating prepared by the preparation method in the field of marine fouling organism control.

[0034] The present invention will be described in more detail below.

[0035] The invention prepares a water-based acrylic self-polishing resin containing a hydroxyl group, a carboxyl group or an amine group that can be cross-linked with a cross-linking agent, or an alkoxysilyl group that can self-cross-link. The resin is compounded with an antifouling agent and a pigment filler to form a water-based acrylic self-polishing antifouling coating. A component B cross-linking agent is added before the coating is applied, mixed evenly, and coated on a substrate. After the water-based acrylic self-polishing antifouling coating is in contact with water, an extremely thin hydrogel microlayer can be formed on its surface. The presence of the hydrogel microlayer improves the antifouling and drag-reducing performance of the water-based self-polishing antifouling coating and slows down the release rate of the antifouling agent.

[0036] The invention relates to a self-polishing antifouling coating, which is composed of component A and component B in a weight ratio of 100:0.1-0.5, wherein component A is composed of 10-50 weight parts of water-based acrylic self-polishing antifouling resin, 10-60 weight parts of antifouling agent and 1-30 weight parts of pigment filler, and component B is a cross-linking agent; in water, the coating surface of the self-polishing antifouling coating on the surface of a substrate has a hydrogel microlayer with a thickness of 50-200 μm.

[0037] In the self-polishing antifouling coating of the present invention, component A is composed of 10-50 parts by weight of waterborne acrylic self-polishing antifouling resin, 10-60 parts by weight of antifouling agent and 1-30 parts by weight of pigment filler. The waterborne acrylic self-polishing antifouling resin will be described in detail in the following part.

[0038] The basic function of the antifouling agent in the self-polishing antifouling coating of the present invention is to significantly improve the antifouling performance, durability and environmental friendliness of the coating, while improving the use effect and economic benefit of the coating.

[0039] The antifouling agent used in the present invention is one or more antifouling agents selected from Cu2O, copper pyrithione, zinc pyrithione, thiophanate-methyl, diuron or 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, all of which are products currently sold on the market, such as copper pyrithione sold under the trade name of Omedin Copper by Tianjin Damao Chemical Reagent Company and diuron sold under the trade name of Diuron by Shanghai Aladdin Biochemical Technology Co., Ltd.

[0040] The basic function of the pigments and fillers in the self-polishing antifouling coating of the present invention is to provide color and hiding power, improve the physical properties, rheological properties and weather resistance of the coating, and synergize with other ingredients to enhance the antifouling performance.

[0041] The pigments and fillers used in the present invention are one or more pigments and fillers selected from ZnO, TiO2, Fe2O3, talc, molybdenum red, nano-silicon dioxide, kaolin, Al2O3 or activated carbon, all of which are products currently sold on the market, such as ZnO sold under the trade name Tiandun Zinc by Beijing Tiandun New Materials Technology Co., Ltd. and talc sold under the trade name Tiandun Talc by Beijing Tiandun New Materials Technology Co., Ltd.

[0042] In the present invention, component A is composed of 10 to 50 parts by weight of water-based acrylic self-polishing antifouling resin, 10 to 60 parts by weight of antifouling agent and 1 to 30 parts by weight of pigments and fillers. When the amount of antifouling agent and pigments and fillers is within the range, if the content of water-based acrylic self-polishing antifouling resin is less than 10 parts by weight, it will affect the dispersibility and binding force of the antifouling agent, thereby reducing the antifouling effect of the coating and increasing the risk of biological attachment; if the content of water-based acrylic self-polishing antifouling resin is higher than 50 parts by weight, it will lead to a decrease in the ratio of antifouling agent and pigments and fillers, affecting their functionality, such as antifouling performance and hiding power; therefore, it is reasonable for the content of water-based acrylic self-polishing antifouling resin to be 10 to 50 parts by weight, preferably 16 to 55 parts by weight, and more preferably 24 to 48 parts by weight;

[0043] When the amount of the water-based acrylic self-polishing antifouling resin and the pigment filler is within the range, if the content of the antifouling agent is less than 10 parts by weight, the antifouling performance of the coating will be significantly reduced, and it will not be able to effectively resist biological attachment, such as algae and marine organisms; if the content of the antifouling agent is higher than 60 parts by weight, the overall structure of the coating will become fragile, affecting its mechanical properties, and easily causing peeling or damage; therefore, the content of the antifouling agent is appropriately 10 to 60 parts by weight, preferably 18 to 52 parts by weight, and more preferably 25 to 45 parts by weight;

[0044] When the amount of water-based acrylic self-polishing antifouling resin and antifouling agent is within the described range, if the content of pigments and fillers is less than 1 part by weight, the covering ability of the coating will be insufficient and the substrate may not be effectively covered; if the content of pigments and fillers is higher than 30 parts by weight, the coating will become fragile, reduce its mechanical strength and toughness, and easily crack or peel off; therefore, it is appropriate for the content of pigments and fillers to be 1 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 9 to 20 parts by weight.

[0045] Preferably, component A is composed of 16 to 55 parts by weight of water-based acrylic self-polishing antifouling resin, 18 to 52 parts by weight of antifouling agent and 5 to 25 parts by weight of pigments and fillers.

[0046] More preferably, component A is composed of 24 to 48 parts by weight of an aqueous acrylic self-polishing antifouling resin, 25 to 45 parts by weight of an antifouling agent and 9 to 20 parts by weight of a pigment and filler.

[0047] The main function of component B in the self-polishing antifouling coating of the present invention is to react with the carboxyl group, hydroxyl group or amine group in the antifouling resin to form a three-dimensional network structure of the acrylic self-polishing antifouling resin polymer. When the coating is exposed to water, the hydrophilic groups such as the hydroxyl group, amine group, carboxyl group and carboxyl anion generated by hydrolysis in the acrylic self-polishing antifouling resin polymer absorb water under the constraint of the three-dimensional network to form a hydrogel microlayer on the surface of the coating.

[0048] Component B is a crosslinking agent. When the crosslinking functional group of the water-based acrylic self-polishing antifouling resin is a hydroxyl group, a carboxyl group or an amine group, component B is selected from aziridine, tetramethoxymethyl glycoluril, glutaraldehyde, formaldehyde, phthalaldehyde, epichlorohydrin or triethoxysilane crosslinking agent, all of which are products currently sold on the market, such as the aziridine crosslinking agent sold by Shanghai Aladdin Biochemical Technology Co., Ltd. under the trade name trifunctional aziridine crosslinking agent;

[0049] When the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is an alkoxysilyl group, component B is selected from tetraethoxysilane, silane coupling agent A-171, silane coupling agent KH-550, silane coupling agent KH-560 or silane coupling agent KH-570 cross-linking agent, all of which are products currently sold on the market, such as silane coupling agent A-171 sold by Qingdao Datang Chemical Co., Ltd. under the trade name vinyl trimethoxy silane.

[0050] The self-polishing antifouling coating of the present invention is composed of component A and component B in a weight ratio of 100:0.1-0.5. If the weight ratio of component A to component B is less than 100:0.5, the cross-linking effect of the cross-linking agent is insufficient, and an obvious hydrogel microlayer structure cannot be formed; if the weight ratio of component A to component B is greater than 100:0.1, the cross-linking structure of the hydrogel is too much, affecting the mechanical properties and adhesion ability of the coating. Therefore, it is desirable that the weight ratio of component A to component B is 100:0.1-0.5, preferably 100:0.1-0.4, and more preferably 100:0.2-0.4.

[0051] The self-polishing antifouling coating of the present invention was applied on the surface of the substrate and then placed in seawater for 7 days and 14 days. The coating was then taken out and analyzed by scanning electron microscope. The analysis results are listed in the attached figure. Figure 2 , the figure clearly shows that the microlayer on the coating surface is a hydrogel microlayer, and its thickness is 50 to 200 μm.

[0052] In the present invention, the water-based acrylic self-polishing antifouling resin is obtained by the following preparation steps:

[0053] A. Preparation of monomer mixture

[0054] 10-100% of sodium hydroxide based on the molar amount of the unsaturated organic acid and 30-200% of water are mixed evenly, and then 3-20% of the unsaturated organic acid based on the total molar amount of the following monomers is added, mixed evenly, and dissolved to obtain a NaAA solution;

[0055] According to the present invention, the main role of the unsaturated organic acid in the preparation of the water-based self-polishing antifouling resin is that it can provide cross-linking sites and react with the cross-linking agent to obtain a cross-linked network structure, thereby promoting the formation of a hydrogel microlayer; in addition, the unsaturated organic acid can react with NaOH to form an unsaturated acid sodium salt, thereby affecting the polymerization reaction rate of the water-based acrylic self-polishing antifouling resin.

[0056] The unsaturated organic acid used in the present invention is acrylic acid, methacrylic acid or a mixture thereof, which are all products currently sold on the market, such as acrylic acid sold by Tianjin Damao Chemical Reagent Company under the trade name of acrylic acid.

[0057] In this step, when the amount of sodium hydroxide and water is within the range, if the amount of unsaturated organic acid is less than 3%, sufficient cross-linking sites cannot be provided, affecting the formation of the hydrogel microlayer; if the amount of unsaturated organic acid is higher than 20%, the cross-linking of the hydrogel on the coating surface is too large, the water absorption rate of the hydrogel is low, and the hydrogel is easy to become brittle, crack and fall off; therefore, the amount of unsaturated organic acid is appropriately 3-20%, preferably 5-18%, and more preferably 8-15%.

[0058] When the dosage of unsaturated organic acid and water is within the described range, if the dosage of sodium hydroxide is less than 10%, the number of gel particles generated by the polymerization reaction is large, and the reaction rate is too fast, which is prone to violent polymerization; if the dosage of sodium hydroxide is higher than 100%, the latex particles in the polymerization process of the water-based acrylic self-polishing antifouling resin emulsion will be too large, the polymerization rate will be too fast, and the stability of the emulsion will be affected; therefore, it is reasonable to use 10-100% of sodium hydroxide, preferably 25-90%.

[0059] When the dosage of the unsaturated organic acid and sodium hydroxide is within the range, if the dosage of water is less than 30%, the temperature drops slowly, and the large amount of heat released by the neutralization reaction will destroy the balance of the reaction system; if the dosage of water is higher than 200%, it is easy to cause the emulsion concentration to be too low, which is not conducive to increasing the solid content of the emulsion; therefore, it is appropriate for the dosage of water to be 30-200%, preferably 55-175%, and more preferably 75-150%.

[0060] In this step, under the stirring of a magnetic stirrer, the total amount of the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer in moles is 1:20-30 to the volume of the NaAA solution in milliliters, and the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer are sequentially added to the NaAA solution in a molar ratio of 70-95:5-25:2-15 to obtain the monomer mixture;

[0061] In the present invention, the oily acrylic monomer should be understood as an acrylic monomer containing an oil group (such as a long-chain alkyl group, an aromatic group, an alkoxy group, etc.) in its molecular structure.

[0062] The main function of oily acrylic monomers in waterborne acrylic self-polishing antifouling coatings is to provide good adhesion of the coating to the substrate;

[0063] The oily acrylic monomer used in the present invention is one or more oily acrylic monomers selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate, all of which are products currently sold on the market, such as butyl acrylate sold by Tianjin Tianjiao Chemical Co., Ltd. under the trade name butyl acrylate.

[0064] In the present invention, a water-based monomer should be understood as a monomer containing polar groups (such as hydroxyl groups, carboxyl groups, amide groups, etc.) in its molecular structure, which enables it to interact with water.

[0065] The role of water-based monomers in water-based acrylic self-polishing antifouling coatings is to provide hydroxyl, carboxyl or amine groups to form hydrogel microlayers to participate in the cross-linking reaction of the cross-linking agent and the self-cross-linking reaction, thereby promoting the formation of a cross-linking network of the coating.

[0066] The aqueous monomer used in the present invention is acrylamide, hydroxyacrylamide, unsaturated organic acid or a mixture thereof, wherein the hydroxyacrylamide is N-hydroxymethylacrylamide, N-hydroxyethylacrylamide or N-hydroxypropylacrylamide; the unsaturated organic acid is acrylic acid, methacrylic acid or a mixture thereof; all of them are products currently sold on the market, such as N-hydroxypropylacrylamide sold by Qingdao Datang Chemical Co., Ltd. under the trade name N-hydroxypropylacrylamide, and hydroxyethylacrylate sold by Sinopharm Chemical Reagent Co., Ltd. under the trade name hydroxyethylacrylate.

[0067] In the present invention, the acrylic silicone self-polishing monomer should be understood as a functional monomer having chemical hydrolysis or biodegradation characteristics in seawater.

[0068] The main function of the acrylic silicone self-polishing monomer in the water-based acrylic self-polishing antifouling coating is to provide a good polishing effect for the coating formed by the self-polishing antifouling coating, and further enhance the anti-fouling adhesion performance of the coating;

[0069] The acrylic organosilicon self-polishing monomer used in the present invention is acryloxy triisopropyl silane, methacryloxy triisopropyl silane, γ-methacryloxy propyl trimethoxy silane or a mixture thereof, all of which are products currently sold on the market, such as the methacryloxy triisopropyl silane sold by Wuhan Yuancheng Technology Development Co., Ltd. under the trade name of methacryloxy triisopropyl silane.

[0070] In the present invention, when the amount of the water-based monomer and the acrylic silicone self-polishing monomer is within the range, if the amount of the oily acrylic monomer is less than 70%, the adhesion performance of the water-based acrylic self-polishing antifouling resin on the substrate is significantly reduced; if the amount of the oily acrylic monomer is higher than 95%, the emulsion will be unstable and the viscosity of the resin emulsion will be affected; therefore, the amount of the oily acrylic monomer is appropriately 70-95%, preferably 75-90%, and more preferably 80-85%.

[0071] When the amount of oily acrylic monomer and acrylic silicone self-polishing monomer is within the range, if the amount of water-based monomer is less than 5%, the cross-linkable groups are small and it is not conducive to the formation of hydrogel microlayer and hydrogel network structure; if the amount of water-based monomer is higher than 25%, it will cause the water resistance of the coating to decrease and fall off; therefore, the amount of water-based monomer is suitable to be 5-25%, preferably 8-22%, and more preferably 10-18%.

[0072] When the amount of oily acrylic monomer and water-based monomer is within the range, if the amount of acrylic silicone self-polishing monomer is less than 2%, the polishing performance of the coating is significantly reduced, thereby hindering the release of the antifouling agent in the coating into the seawater and affecting the antifouling performance of the coating; if the amount of acrylic silicone self-polishing monomer is higher than 15%, the coating exhibits a large self-polishing abrasion rate, accelerates the release of the antifouling agent, and affects the antifouling effect of the coating; therefore, it is appropriate to use 2-15% of the acrylic silicone self-polishing monomer, preferably 4-12%, and more preferably 6-10%.

[0073] In this step, the ratio of the total amount of oily acrylic monomers, water-based monomers and acrylic silicone self-polishing monomers in moles to the volume of the NaAA solution in milliliters is 1:20 to 30. If the ratio of the total amount of these monomers to the volume of the NaAA solution is greater than 1:20, it will lead to incomplete reaction or insufficient crosslinking, thereby affecting the performance and stability of the final product; if the ratio of the total amount of these monomers to the volume of the NaAA solution is less than 1:30, it will lead to excessive crosslinking, increase viscosity, affect the workability of the coating, and even cause the strength and durability of the final product to decrease; therefore, the ratio of the total amount of these monomers to the volume of the NaAA solution is 1:20 to 30, preferably 1:22 to 28, and more preferably 1:24 to 26.

[0074] B. Preparation of initiator solution

[0075] At room temperature, 0.5-2.0% of the aqueous initiator, 0-1.0% of the oily initiator and 30-200% of deionized water, based on the molar amount of the unsaturated organic acid, are mixed uniformly to obtain the initiator solution;

[0076] In the present invention, an aqueous initiator should be understood as an initiator having water-soluble or hydrophilic properties.

[0077] The main function of the aqueous initiator in the preparation of the self-polishing antifouling resin of the present invention is to promote the occurrence of polymerization reaction, generate free radicals, thereby initiating the polymerization of acrylic ester monomers, forming a cross-linked structure, and enhancing the performance and durability of the coating.

[0078] The aqueous initiator used in the present invention is azobisisobutylimidazoline hydrochloride, azobisisopropylimidazoline, azobisisobutylamidine hydrochloride, potassium persulfate or ammonium persulfate, all of which are products currently sold on the market, such as azobisisobutylamidine hydrochloride (AIBA) sold by Tianjin Damao Chemical Reagent Company under the trade name azobisisobutylamidine hydrochloride;

[0079] In the present invention, an oily initiator should be understood as an initiator having hydrophobic or lipophilic properties.

[0080] The main function of the oily initiator in the preparation of the self-polishing antifouling resin of the present invention is to promote the occurrence of polymerization reaction, initiate the polymerization of acrylic ester monomers by generating free radicals, and form a cross-linked network structure, thereby enhancing the durability, flexibility and antifouling performance of the coating.

[0081] The oily initiator used in the present invention is azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl benzoyl peroxide or methyl ethyl ketone peroxide, all of which are currently sold on the market, such as azobisisobutyronitrile (AIBN) sold under the trade name azobisisobutyronitrile by Tianjin Damao Chemical Reagent Company;

[0082] In this step, when the amount of the oily initiator and the deionized water is within the range, if the amount of the water-based initiator is less than 0.5%, less free radicals will be generated at the beginning of the polymerization reaction, the polymerization reaction will be unstable or not initiated, and the water-based monomer will be difficult to participate in the polymerization reaction; if the amount of the water-based initiator is higher than 2.0%, more free radicals will be generated in the polymerization reaction, the average particle size of the latex particles will be small, and the prepolymerization time will be significantly prolonged;

[0083] When the amount of aqueous initiator and deionized water is within the above range, the present invention may not use an oily initiator while ensuring that the polymerization reaction proceeds smoothly and the generated resin has good properties; if the amount of the oily initiator is higher than 1.0%, it is easy to initiate polymerization of the oily monomer, produce more gel, and affect the heat dissipation of the reaction; therefore, it is reasonable to use an amount of the oily initiator of 0 to 1%, preferably 0.2 to 0.8%;

[0084] When the amount of oily initiator and aqueous initiator is within the range, if the amount of deionized water is less than 30%, the polymerization reaction is not sufficient, thereby affecting the crosslinking degree and final performance of the resin, resulting in decreased durability and adhesion of the coating; if the amount of deionized water is higher than 200%, the system is too diluted, affecting the rate and efficiency of the polymerization reaction, and may even cause the activity of the initiator to decrease, so that the performance of the resin cannot meet the expected requirements; therefore, it is appropriate to use 30-200% of deionized water, preferably 55-175%, and more preferably 80-145%.

[0085] C. Preparation of water-based acrylic self-polishing antifouling resin

[0086] In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 90-270% ethanol and 10-30% deionized water are added based on the total weight of the above monomers, and then the monomer mixture obtained in step A and the initiator solution obtained in step B are added, and the addition amount thereof is 5-10% of their respective volumes; then, the remaining monomer mixture solution is heated to a temperature of 65-85° C. under a stirring speed of 50-500 rpm;

[0087] In this step, the main purpose of first adding 90-270% ethanol and 10-30% deionized water is to improve the solubility and stability of the reaction system, promote the effective dispersion of the oily initiator and the water-based initiator, and thus ensure the smooth progress of the polymerization reaction. It is not advisable to use ethanol and deionized water in amounts exceeding the above range, because too high an ethanol content may lead to instability of the system, affecting the crosslinking degree and mechanical properties of the resin, while too much deionized water may make the system too diluted, reduce the polymerization efficiency, and ultimately affect the performance and application effect of the resin.

[0088] The main purpose of adding 5-10% of the monomer mixture obtained in step A and 5-10% of the initiator solution obtained in step B is to allow the initiator to slowly decompose and initiate the polymerization reaction during the subsequent heating process, so that the polymerization reaction can be initiated more stably.

[0089] When blue light appears in the reaction system, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 0.5 to 1.5 hours, and the temperature is maintained at 65 to 85° C. for 0.4 to 0.6 hours; then, 0.01 to 0.02% of the above-mentioned initiator solution based on the total mass of all monomers is continued to be added, and the temperature is maintained at 60 to 70° C. for 0.8 to 1.2 hours, and then cooled to room temperature to obtain a white emulsion of water-based acrylic self-polishing antifouling resin.

[0090] The appearance of blue light in the reaction system indicates a stable dispersion state and good uniformity, indicating that the polymerization reaction has been successfully carried out and that the generated resin has a suitable cross-linking structure and physical properties.

[0091] After adding the remaining monomer mixture solution and the remaining initiator solution, the temperature is maintained at 65-85°C for 0.4-0.6h. When the reaction (maintenance) time is within the range, if the reaction temperature is lower than 65°C, the polymerization reaction rate may slow down, resulting in incomplete reaction; if the reaction temperature is higher than 85°C, the polymerization reaction may be too rapid, resulting in side reactions or chain termination reactions; therefore, a reaction temperature of 65-85°C is appropriate; when the reaction temperature is within the range, if the reaction time is shorter than 0.4h, the polymerization reaction may not reach the expected conversion rate, resulting in insufficient performance of the resin, bubbles or unevenness; if the reaction time is longer than 0.6h, the properties of the resin may change, such as excessive cross-linking, affecting the flexibility and adhesion of the coating; therefore, a reaction time of 0.4-0.6h is appropriate;

[0092] In this step, continue to add 0.01-0.02% of the above-mentioned initiator solution based on the total mass of all monomers, and maintain it at a temperature of 60-70°C for 0.8-1.2 hours. The basic purpose is to further promote the polymerization reaction, increase the crosslinking degree and molecular weight of the resin, and thus improve the physical properties and durability of the final product.

[0093] The product obtained in this step was tested by conventional infrared spectroscopy. Figure 1 The figure shows characteristic absorption peaks, as well as absorption peaks of other related functional groups. These characteristic peaks are consistent with the structural characteristics of water-based acrylic self-polishing antifouling resin. Figure 2 The results clearly showed that the white emulsion product was a water-based acrylic self-polishing antifouling resin.

[0094] The reaction container, electric stirring device, oil bath pot, drying device, etc. used in the present invention are all chemical equipment or devices commonly used in the field of chemical technology.

[0095] The invention also relates to a method for preparing the self-polishing antifouling coating.

[0096] The preparation steps of the preparation method are as follows:

[0097] Under room temperature, a white emulsion-like water-based acrylic self-polishing antifouling resin, an antifouling agent and a pigment and filler are uniformly mixed in a mass ratio of 10-50:10-60:1-30, and a coating rapid dispersion tester is used to grind and disperse the mixture for 0.4-1.0 h at a stirring speed of 2000-5000 rpm. When the fineness of the ground material is measured by a scraper fineness meter and is less than 50 μm, component A is obtained;

[0098] The white emulsion water-based acrylic self-polishing antifouling resin, antifouling agent, pigment and filler have been described in detail above, so they will not be repeated here.

[0099] The coating rapid dispersion test machine used in the present invention is a product currently sold on the market, such as a product sold by Shanghai Modern Environmental Engineering Technology Co., Ltd. under the trade name SFJ-400 mixer;

[0100] The scraper fineness meter used in the present invention is a product currently sold on the market, such as a product sold by Tianjin Kelian Material Testing Machine Factory under the trade name KLD-1ISO scraper fineness meter.

[0101] When the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is a hydroxyl group, a carboxyl group or an amino group, aziridine, tetramethoxymethyl glycoluril, glutaraldehyde, formaldehyde, phthalaldehyde, epichlorohydrin or triethoxysilane cross-linking agent is used as component B;

[0102] When the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is an alkoxysilyl group, tetraethoxysilane, silane coupling agent A-171, silane coupling agent KH-550, silane coupling agent KH-560 or silane coupling agent KH-570 cross-linking agent is used as component B;

[0103] The amount of component B is 3-20% based on the molar amount of the cross-linking functional group hydroxyl, carboxyl, amino or alkoxysilyl group contained in the water-based acrylic self-polishing antifouling resin in component A; the aqueous solution obtained by dissolving component B in water in a ratio of 1:20-80 in grams of component B to milliliters of water is uniformly mixed with component A to obtain the self-polishing antifouling coating;

[0104] The self-polishing antifouling paint is brushed onto the surface of a substrate to obtain a water-based acrylic self-polishing antifouling paint coating having a hydrogel microlayer in water, wherein the thickness of the hydrogel microlayer is 50-200 μm.

[0105] The present invention also relates to the use of the self-polishing antifouling coating or the self-polishing antifouling coating prepared by the preparation method in the field of marine fouling organism control.

[0106] The present invention investigates the emulsion performance by observing the emulsion state, observes the hydrogel microlayer on the coating surface by SEM, investigates the sustained-release antifouling agent performance of the hydrogel microlayer by the release rate of the antifouling agent DCOIT, investigates the adhesion performance of the water-based self-polishing antifouling coating by a static bubble board method, investigates its self-polishing performance by calculating the self-polishing abrasion rate, investigates its antifouling performance by inhibiting the attachment of proteins and microalgae and actual sea hanging boards, etc. Please refer to the implementation method section for details.

[0107] [Beneficial Effects]

[0108] The beneficial technical effects of the present invention are: first, it has a significant slow-release effect on the release of organic antifouling agents, reducing the amount of antifouling agents used, and thus helping to improve the environmentally friendly performance of antifouling coatings; second, a stable hydration layer is generated on the surface of the coating to make the surface of the antifouling coating smoother, which is beneficial to further improve the drag reduction effect of the water-based self-polishing antifouling coating and reduce the fuel consumption of ships; third, the hydrogel microlayer on the surface of the resin is beneficial to the coating to reduce the adsorption of organic matter such as protein, prevent the occurrence of attachments in the first stage of marine biofouling, and give the coating a new antifouling mechanism. The water-based self-polishing antifouling coating prepared using the water-based self-polishing antifouling resin that can form a hydrogel microlayer as a film-forming material of the present invention has good film-forming performance, adhesion performance, storage stability, and construction performance on the substrate, and shows excellent antifouling effect.

Brief Description of the Drawings

[0109] Figure 1 is an infrared spectrum of the aqueous acrylic self-polishing antifouling resin capable of forming a hydrogel microlayer prepared in Examples 1-4;

[0110] Figure 2 is a morphology analysis diagram of the water-based acrylic self-polishing antifouling resin coating with a hydrogel microlayer prepared in Examples 1-4;

[0111] Figure 3 is a graph showing the antifouling agent release performance test results of the water-based acrylic self-polishing antifouling resin coating with a hydrogel microlayer prepared in Examples 1-4;

[0112] Figure 4 1 is a graph showing the test results of the self-polishing performance and drag reduction performance of the water-based acrylic self-polishing antifouling resin coating with a hydrogel microlayer prepared in Examples 1-4;

[0113] Figure 5 is a graph showing the antifouling performance test results of the water-based acrylic self-polishing antifouling resin coating with a hydrogel microlayer prepared in Examples 1-4;

[0114] Figure 6 and Figure 7is a graph showing the adhesion and polishing performance test results of the water-based self-polishing antifouling coating with a hydrogel microlayer prepared in Examples 5-8;

[0115] Figure 8 The results of the actual sea board test of the water-based self-polishing antifouling coating with a hydrogel microlayer prepared in Examples 5-8; [Specific implementation method]

[0116] The present invention will be better understood through the following examples.

[0117] Example 1: Preparation of the water-based acrylic self-polishing antifouling resin of the present invention

[0118] The implementation of this embodiment is as follows:

[0119] A. Preparation of monomer mixture

[0120] 70% of sodium hydroxide based on the molar amount of the unsaturated organic acid and 85% of water are mixed evenly, and then 20% of acrylic acid unsaturated organic acid based on the total molar amount of the following monomers are added and mixed evenly, and dissolved to obtain a NaAA solution;

[0121] Under stirring with a magnetic stirrer, according to the ratio of the total amount of the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer in moles to the volume of the NaAA solution in milliliters being 1:20, methyl methacrylate oily acrylic monomer, acrylamide water-based monomer and acryloxy triisopropylsilane acrylic silicone self-polishing monomer in a molar ratio of 95:18:6 are sequentially added to the NaAA solution to obtain the monomer mixture;

[0122] B. Preparation of initiator solution

[0123] At room temperature, 1.0% of azobisisobutylimidazoline hydrochloride aqueous initiator, 0.7% of azobisisobutylonitrile oil initiator and 90% of deionized water, based on the molar amount of acrylic acid unsaturated organic acid, are mixed uniformly to obtain the initiator solution;

[0124] C. Preparation of water-based acrylic self-polishing antifouling resin

[0125] In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 90% ethanol and 10% deionized water based on the total weight of the above monomers are added, and then the monomer mixture obtained in step A and the initiator solution obtained in step B are added, and the addition amount thereof is 8% of their respective volumes; then, the remaining monomer mixture solution is heated to a temperature of 78° C. under a stirring speed of 200 rpm;

[0126] When the reaction system emits blue light, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 1.5 hours, and the temperature is maintained at 72° C. for 0.5 hours; then, 0.01% of the above-mentioned initiator solution based on the total weight of all monomers is continued to be added, and the temperature is maintained at 67° C. for 0.9 hours, and then cooled to room temperature to obtain the white emulsion-like water-based acrylic self-polishing antifouling resin of the present invention.

[0127] The water-based acrylic self-polishing antifouling resin prepared in this example was measured at a wavelength of 4000-400 cm using a Fourier transform infrared spectrometer (BRUKER, EQUNINOX55) according to the operating method described in its instruction manual. -1 The infrared spectrum in the range of 1000 nm was used to determine the different functional groups to which these infrared absorption peaks belonged according to the positions and intensities of the characteristic absorption peaks in the infrared spectrum. The test results are listed in the attached figure. Figure 1 (TIPSMA5).

[0128] Example 2: Preparation of the water-based acrylic self-polishing antifouling resin of the present invention

[0129] The implementation of this embodiment is as follows:

[0130] A. Preparation of monomer mixture

[0131] 10% of sodium hydroxide based on the molar amount of the unsaturated organic acid and 30% of water are mixed evenly, and then 3% of methacrylic acid based on the total molar amount of the following monomers are added and mixed evenly, and dissolved to obtain a NaAA solution;

[0132] Under stirring with a magnetic stirrer, according to the ratio of the total amount of oily acrylic monomer, water-based monomer and acrylic silicone self-polishing monomer in moles to the volume of NaAA solution in milliliters being 1:24, ethyl methacrylate oily acrylic monomer, N-hydroxymethyl acrylamide water-based monomer and methacryloxy triisopropyl silane acrylic silicone self-polishing monomer in a molar ratio of 70:5:2 are sequentially added to the NaAA solution to obtain the monomer mixture;

[0133] B. Preparation of initiator solution

[0134] At room temperature, 1.5% of azobisisopropylimidazoline water-based initiator, 0% of azobisisoheptanenitrile oil-based initiator and 140% of deionized water, based on the molar amount of the unsaturated organic acid, are mixed uniformly to obtain the initiator solution;

[0135] C. Preparation of water-based acrylic self-polishing antifouling resin

[0136] In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 135% ethanol and 15% deionized water based on the total weight of the above monomers are added, and then the monomer mixture obtained in step A and the initiator solution obtained in step B are added, and the addition amount thereof is 5% of their respective volumes; then, the remaining monomer mixture solution is heated to a temperature of 65° C. under a stirring speed of 50 rpm;

[0137] When the reaction system emits blue light, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 0.5 h, and the temperature is maintained at 78° C. for 0.4 h; then, 0.02% of the above-mentioned initiator solution based on the total mass of all monomers is continued to be added, and the temperature is maintained at 60° C. for 1.2 h, and then cooled to room temperature to obtain the white emulsion-like water-based acrylic self-polishing antifouling resin of the present invention.

[0138] The water-based acrylic self-polishing antifouling resin prepared in this example was measured at a wavelength of 4000-400 cm using a Fourier transform infrared spectrometer (BRUKER, EQUNINOX55) according to the operating method described in its instruction manual. -1 The infrared spectrum in the range of 1000 nm was used to determine the different functional groups to which these infrared absorption peaks belonged according to the positions and intensities of the characteristic absorption peaks in the infrared spectrum. The test results are listed in the attached figure. Figure 1 (T-HAM1).

[0139] Example 3: Preparation of the water-based acrylic self-polishing antifouling resin of the present invention

[0140] The implementation of this embodiment is as follows:

[0141] A. Preparation of monomer mixture

[0142] 40% of sodium hydroxide based on the molar amount of the unsaturated organic acid is mixed with 200% of water, and then 8% of a mixture of acrylic acid and methacrylic acid (weight ratio 1:1) based on the total molar amount of the following monomers is added and mixed with the unsaturated organic acid to obtain a NaAA solution;

[0143] Under stirring with a magnetic stirrer, the total amount of the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer in moles is 1:26 to the volume of the NaAA solution in milliliters, and a mixture of methyl methacrylate and propyl methacrylate (weight ratio 2:3), the oily acrylic monomer, the acrylic water-based monomer and the γ-methacryloxypropyltrimethoxysilane acrylic silicone self-polishing monomer are sequentially added to the NaAA solution in a molar ratio of 78:12:11 to obtain the monomer mixture;

[0144] B. Preparation of initiator solution

[0145] At room temperature, 2.0% of azobisisobutylamidine hydrochloride aqueous initiator, 0.3% of benzoyl peroxide oily initiator and 30% of deionized water, based on the molar amount of unsaturated organic acid, are mixed uniformly to obtain the initiator solution;

[0146] C. Preparation of water-based acrylic self-polishing antifouling resin

[0147] In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 180% ethanol and 20% deionized water based on the total weight of the above monomers are added, and then the monomer mixture obtained in step A and the initiator solution obtained in step B are added, and the addition amount thereof is 10% of their respective volumes; then, the remaining monomer mixture solution is heated to a temperature of 72° C. under a stirring speed of 350 rpm;

[0148] When the reaction system emits blue light, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 0.8 h, and the temperature is maintained at 65° C. for 0.5 h; then, 0.01% of the above-mentioned initiator solution based on the total mass of all monomers is continued to be added, and the temperature is maintained at 63° C. for 1.1 h, and then cooled to room temperature to obtain the white emulsion-like water-based acrylic self-polishing antifouling resin of the present invention.

[0149] The water-based acrylic self-polishing antifouling resin prepared in this example was measured at a wavelength of 4000-400 cm using a Fourier transform infrared spectrometer (BRUKER, EQUNINOX55) according to the operating method described in its instruction manual. -1 The infrared spectrum in the range of 1000 nm was used to determine the different functional groups to which these infrared absorption peaks belonged according to the positions and intensities of the characteristic absorption peaks in the infrared spectrum. The test results are listed in the attached figure. Figure 1 (T-HAM2)

[0150] Example 4: Preparation of the water-based acrylic self-polishing antifouling resin of the present invention

[0151] The implementation of this embodiment is as follows:

[0152] A. Preparation of monomer mixture

[0153] 100% of sodium hydroxide based on the molar amount of the unsaturated organic acid and 145% of water are mixed evenly, and then 14% of a mixture of acrylic acid and methacrylic acid (weight ratio 2:3) based on the total molar amount of the following monomers are added and mixed evenly, and dissolved to obtain a NaAA solution;

[0154] Under stirring with a magnetic stirrer, according to the ratio of the total amount of oily acrylic monomer, water-based monomer and acrylic silicone self-polishing monomer in moles to the volume of NaAA solution in milliliters being 1:30, ethyl methacrylate and butyl methacrylate (weight ratio 1:2), oily acrylic monomer, a mixture of acrylamide and methacrylic acid (weight ratio 1:1), water-based monomer and a mixture of acryloxy triisopropyl silane and methacryloxy triisopropyl silane (weight ratio 3:1), and acrylic silicone self-polishing monomer in a molar ratio of 86:25:15 are sequentially added to the NaAA solution to obtain the monomer mixture;

[0155] B. Preparation of initiator solution

[0156] At room temperature, 0.5% of the total weight of the above-mentioned monomers as an aqueous initiator of ammonium persulfate, 1.0% of the oily initiator of methyl ethyl ketone peroxide and 200% of deionized water as a molar amount of the unsaturated organic acid are mixed uniformly to obtain the initiator solution;

[0157] C. Preparation of water-based acrylic self-polishing antifouling resin

[0158] In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 270% ethanol and 30% deionized water were added based on the total weight of the above monomers, and then the monomer mixture obtained in step A and the initiator solution obtained in step B were added, and the amount of each of them added was 7% of their respective volumes; then, the remaining monomer mixture solution was heated to a temperature of 85° C. under a stirring speed of 500 rpm;

[0159] When the reaction system emits blue light, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 1.1 hours, and the temperature is maintained at 85° C. for 0.6 hours; then, 0.02% of the above-mentioned initiator solution based on the total weight of all monomers is continued to be added, and the temperature is maintained at 70° C. for 0.8 hours, and then cooled to room temperature to obtain the white emulsion-like water-based acrylic self-polishing antifouling resin of the present invention.

[0160] The water-based acrylic self-polishing antifouling resin prepared in this example was measured at a wavelength of 4000-400 cm using a Fourier transform infrared spectrometer (BRUKER, EQUNINOX55) according to the operating method described in its instruction manual. -1 The infrared spectrum in the range of 1000 nm was used to determine the different functional groups to which these infrared absorption peaks belonged according to the positions and intensities of the characteristic absorption peaks in the infrared spectrum. The test results are listed in the attached figure. Figure 1 (T-HAM3).

[0161] Example 5: Self-polishing antifouling coating of the present invention

[0162] The implementation of this embodiment is as follows:

[0163] The self-polishing antifouling coating is composed of component A and component B in a weight ratio of 100:0.2, wherein component A is composed of 36 parts by weight of the water-based acrylic self-polishing antifouling resin prepared in Example 3, 60 parts by weight of Cu2O antifouling agent and 10 parts by weight of ZnO pigment filler;

[0164] The cross-linking functional group of the water-based acrylic self-polishing antifouling resin is hydroxyl, and component B is aziridine; the amount of component B is 3% based on the molar amount of the cross-linking functional group hydroxyl group contained in the water-based acrylic self-polishing antifouling resin in component A;

[0165] Component B is dissolved in water at a ratio of 1:20 in grams of component B to milliliters of water, and the obtained aqueous solution is then mixed evenly with component A to obtain the self-polishing antifouling coating TM0; according to the GB / T 1728-2007 standard method, in water, the coating surface of the self-polishing antifouling coating on the surface of the substrate has a hydrogel microlayer with a thickness of 50 to 80 μm.

[0166] Example 6: Self-polishing antifouling coating of the present invention

[0167] The implementation of this embodiment is as follows:

[0168] The self-polishing antifouling coating is composed of component A and component B in a weight ratio of 100:0.1, wherein component A is composed of 10 parts by weight of the water-based acrylic self-polishing antifouling resin prepared in Example 1, 10 parts by weight of pyrithione copper antifouling agent and 1 part by weight of TiO2 pigment filler;

[0169] The cross-linking functional group of the water-based acrylic self-polishing antifouling resin is a carboxyl group, and component B is tetramethoxymethyl glycoluril; the amount of component B is 9% based on the molar amount of the cross-linking functional group carboxyl group contained in the water-based acrylic self-polishing antifouling resin in component A;

[0170] Component B is dissolved in water at a ratio of 1:40 in grams of component B to milliliters of water, and the obtained aqueous solution is then mixed evenly with component A to obtain the self-polishing antifouling coating TM1; according to the GB / T 1728-2007 standard method, in water, the coating surface of the self-polishing antifouling coating on the surface of the substrate has a hydrogel microlayer with a thickness of 85 to 115 μm.

[0171] Example 7: Self-polishing antifouling coating of the present invention

[0172] The implementation of this embodiment is as follows:

[0173] The self-polishing antifouling coating is composed of component A and component B in a weight ratio of 100:0.4, wherein component A is composed of 50 parts by weight of the water-based acrylic self-polishing antifouling resin prepared in Example 2, 18 parts by weight of an antifouling agent of a mixture of zinc pyrithione and thiophanate-methyl (weight ratio 1:1), and 30 parts by weight of a pigment and filler of a mixture of talc and molybdenum red (weight ratio 1:2);

[0174] The cross-linking functional group of the water-based acrylic self-polishing antifouling resin is an amine group, and component B is a mixture of epichlorohydrin and phthalaldehyde (weight ratio 1:3); the amount of component B is 20% based on the molar amount of the cross-linking functional group amine group contained in the water-based acrylic self-polishing antifouling resin in component A;

[0175] Component B is dissolved in water at a ratio of 1:60, and the obtained aqueous solution is then mixed evenly with component A to obtain the self-polishing antifouling coating TM2; according to the GB / T 1728-2007 standard method, in water, the coating surface of the self-polishing antifouling coating on the surface of the substrate has a hydrogel microlayer with a thickness of 120 to 150 μm.

[0176] Example 8: Self-polishing antifouling coating of the present invention

[0177] The implementation method of this embodiment is as follows:

[0178] The self-polishing antifouling coating is composed of component A and component B in a weight ratio of 100:0.5, wherein component A is composed of 24 parts by weight of the water-based acrylic self-polishing antifouling resin prepared in Example 4, 42 parts by weight of an antifouling agent of a mixture of diuron and 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one (weight ratio 2:3), and 20 parts by weight of a pigment and filler of a mixture of nano-silicon dioxide and kaolin (weight ratio 1:3);

[0179] The crosslinking functional group of the water-based acrylic self-polishing antifouling resin is an alkoxysilyl group, and component B is a crosslinking agent of a mixture of tetraethoxysilane and silane coupling agent A-171 (weight ratio 1:1); the amount of component B is 15% based on the molar amount of the crosslinking functional group alkoxysilyl group contained in the water-based acrylic self-polishing antifouling resin in component A;

[0180] Component B is dissolved in water at a ratio of 1:80, and the obtained aqueous solution is then mixed evenly with component A to obtain the self-polishing antifouling coating TM3; according to the GB / T 1728-2007 standard method, in water, the coating surface of the self-polishing antifouling coating on the substrate surface has a hydrogel microlayer with a thickness of 170 to 200 μm.

[0181] Application Example 1: Hydrogel Microlayer Test of Self-polishing Antifouling Coating of the Invention

[0182] The implementation method of this application example is as follows:

[0183] Test sample: self-polishing antifouling coating prepared in Examples 5-8;

[0184] Sample treatment: The self-polishing antifouling coating was immersed in seawater for 7 days and 14 days at room temperature, taken out, rinsed with deionized water, freeze-dried for 24 hours at 40°C using a DHC-9140A electric constant temperature blast drying oven, and then the sample was placed in liquid nitrogen to fracture it;

[0185] Test method: A scanning electron microscope (FlexSEM 1000) of Hitachi High-Technologies Corporation was used to observe the surface and cross-section of the hydrogel microlayer of the self-polishing antifouling coating of the present invention. The observation results are listed in the attached figure. Figure 2 middle.

[0186] By the attached Figure 2 It is known that after the self-polishing antifouling coating of the present invention is immersed in seawater for 7 days, the side and surface of the coating are uniform and flat. After immersion for 14 days, the surface of the coating is continuously hydrolyzed, a large number of holes appear on the surface, and wrinkles of different thickness appear on the cross section of the coating in contact with seawater. According to scanning electron microscopy analysis, it is determined that the water-based acrylic self-polishing resin prepared by the present invention has a hydrogelation phenomenon.

[0187] Application Example 2: Antifouling agent release performance test of the self-polishing antifouling coating of the present invention

[0188] The implementation method of this application example is as follows:

[0189] Test sample: self-polishing antifouling coating prepared in Examples 5-8;

[0190] Test substrate: ABS board, ABS board size is 50×50×1mm 3 ;

[0191] Coating method: At room temperature, the water-based acrylic self-polishing antifouling resin of the present invention is compounded with 4,5-dichloro-2-octylisothiazolinone (DCOIT), coated on an ABS plate, dried at room temperature for 2 days, and then further dried in an oven at a temperature of 40° C. for 2 days.

[0192] Detection method: The antifouling agent release performance of the self-polishing antifouling coating of the present invention under static conditions is measured using a U-2800 ultraviolet-visible photometer. Specifically, the dry coating is immersed in 50 mL of filtered and high-temperature sterilized seawater, and the coating is taken out after soaking for a period of time. The sample is rinsed three times with the soaked seawater to remove the DCOIT remaining on the surface. Then, 50 mL of the rinse solution is transferred, and the DCOIT contained in the rinse solution is extracted with 10 mL of hexane, and the absorbance at a wavelength of 290 nm is measured using an ultraviolet spectrophotometer (U-2800, HITACHI). The coating continues to be soaked in seawater.

[0193] According to the DCOIT concentration in the flushing solution, the release rate of DCOIT from the coating was calculated by the following formula:

[0194]

[0195] Where:

[0196] R is the DCOIT release rate of the coating (μg·cm -2 ·d -1 ),

[0197] C is the DCOIT concentration in seawater (μg·mL -1 ),

[0198] D is the immersion time of the coating (d),

[0199] A is the coating surface area (25 cm 2 ).

[0200] From the attached Figure 3 It can be seen that:

[0201] A. The antifouling agent release rate of the water-based acrylic self-polishing antifouling resin of the present invention gradually decreases with the extension of the test time, and in the early stage of the test, its antifouling agent release rate increases with the increase of the cross-linking agent monomer HAM content, and in the later stage of the test, its antifouling agent release rate decreases with the increase of the cross-linking agent monomer HAM content, and its release rate is 0.15-1.0 μg cm -2 ·d -1 ;

[0202] B. The cumulative release of the antifouling agent shows a decreasing trend as the amount of the crosslinking agent monomer increases. In the early stage of the test, the hydrogel microlayer of the self-polishing antifouling coating of the present invention has not yet been completely formed, and the antifouling agent is gradually released as its hydrogel microlayer is hydrolyzed. As time goes by, the hydrogel microlayer is gradually formed, which slows down the release rate of the antifouling agent from the hydrogel microlayer into the seawater. Moreover, as the content of the crosslinking agent monomer increases, the crosslinking density of the hydrogel microlayer increases, and the effect of slowing down the release of the antifouling agent is more obvious.

[0203] Application Example 3: Test on drag reduction performance of hydrogel microlayer of self-polishing antifouling coating of the present invention

[0204] The implementation method of this application example is as follows:

[0205] Sample preparation: The white emulsion-like aqueous acrylic self-polishing antifouling resin prepared in Example 1-4 was uniformly mixed with an aziridine crosslinking agent (weight ratio 2:1), and the mixture was applied on the following rotor by dip coating, and the coating was repeated three times, and dried at room temperature for 2 days; after drying, the following test was performed, and the following test was performed again after soaking in seawater for a period of time;

[0206] Test basis: "Test method for drag reduction performance of antifouling paint" (GB / T 7791-2014).

[0207] Using a cylindrical rotor with a radius of 1 cm and a height of 10 cm as a reference, the drag reduction effect of the coating can be preliminarily determined by measuring the viscosity change before and after coating with a rotational viscometer in seawater with a fixed viscosity.

[0208] Experimental results: The drag reduction results of the self-polishing antifouling coating of the present invention when immersed in seawater for 7 days are as follows: Figure 4 c. Compared with the blank rotor, the rotors with coatings all have a certain drag reduction effect. As the content of the cross-linking agent monomer HAM increases, the hydrogel effect on the surface of the self-polishing antifouling coating becomes more obvious, and the viscous torque of the coating on seawater decreases more significantly. This is because the hydrogel coating has a good drag reduction effect.

[0209] Application Example 4: Self-polishing performance test of the hydrogel microlayer of the self-polishing antifouling coating of the present invention The implementation method of this application example is as follows:

[0210] Test sample: self-polishing antifouling coating prepared in Examples 5-8;

[0211] Test substrate: ABS board, ABS board size is 250×100×1mm 3 ;

[0212] Coating method: The self-polishing antifouling coating of the present invention is evenly coated on the ABS board by a drip coating method;

[0213] Test method: Dry the ABS plate coated with self-polishing antifouling paint for two days at room temperature, then place it in an oven at 40°C to continue drying for two days, weigh it (N1), and fix the ABS plate on a dynamic paddling acceleration simulation device. The specific structure of the device can be found in the document "Dynamic Test Method for Antifouling Performance of Ship Antifouling Paint" (GB / T 7789-2007).

[0214] In each paddling cycle (10 days), the ABS board was taken out, the surface of the ABS board was rinsed with deionized water, and then it was placed in an oven at 40 °C for two days, and the dry weight of the ABS board (N t ), then put the ABS board back into the device to continue dynamic paddling.

[0215] The self-polishing erosion rate (P%) is calculated according to the following formula:

[0216] p%=(N i -N t ) / Sx100%

[0217] Where:

[0218] N i is the dry weight of the water-based self-polishing coating in the i-th cycle,

[0219] N1 is the initial dry weight of the water-based self-polishing coating,

[0220] N t is the dry weight of the water-based self-polishing coating in the tth cycle,

[0221] S is the coating area of ​​water-based self-polishing paint.

[0222] Test results: The polishing property of the self-polishing antifouling coating of the present invention is one of the factors affecting the antifouling effect of the coating. Figure 4 As shown in Figures 4a and 4b, the self-polishing antifouling coating of the present invention exhibits a high self-polishing erosion rate in the early stage of paddling (0-10 days) due to the rapid exudation of oligomers and residual solvents, while the self-polishing erosion rate in the middle and late stages is basically maintained at 7.5×10 -4 ~4.3×10 -4 g cm -2 The self-polishing erosion rate of the coating containing the crosslinking monomer HAM in the later stage is slightly lower than that of the coating TIPSMA5. This is because the addition of the crosslinking monomer HAM further enhances the network structure of the coating surface, and the polymer forms a more obvious hydrogel structure after surface hydrolysis.

[0223] Application Example 5: Protein inhibition performance test of the self-polishing antifouling coating of the present invention

[0224] The implementation method of this application example is as follows:

[0225] Test sample: the self-polishing antifouling coating of the present invention prepared in Examples 5-8;

[0226] Test substrate: glass plate, plate size 20×20×0.15mm 3 ;

[0227] Test method: The ability of the self-polishing antifouling coating of the present invention to inhibit protein adsorption is tested by using a fluorescent protein labeling method;

[0228] At room temperature, a white latex-like water-based acrylic self-polishing antifouling resin was applied to a 20×20×0.15 mm 3 On a glass slide, dry at room temperature for two days, and then dry in an oven at 40°C for two days. -1 The BSA-FITC (fluorescein isothiocyanate labeled bovine serum albumin) solution and the coated glass slide were placed in a tall weighing bottle and shaken at 200 rpm for 6 h in a shaking box in a dark environment, and then washed with 15 mL PBS (phosphate buffer solution) for 30 min.

[0229] Next, the samples were imaged using a fluorescence microscope (Leica DMRDE), and the amount of absorbed protein was quantitatively calculated using the Image J program.

[0230] The protein adsorbed on the coating was normalized, and the protein on the glass slide was counted as 100%. The adsorption rate (A) of the protein on the coating surface was calculated according to the following formula:

[0231]

[0232] Where:

[0233] A i is the protein adsorption area of ​​the coating,

[0234] A0 is the protein adsorbed area of ​​the blank glass slide.

[0235] Test results:

[0236] By the attached Figure 5 It can be seen from Figures 5b and 5c that the protein area attached to the self-polishing antifouling coating of the present invention is significantly less than the protein adsorbed area of ​​the blank glass sheet, and as the HAM content increases, the relative protein coverage area on the surface of the resin coating decreases. This is because as the cross-linking agent monomer content increases, the coating absorbs more water, the surface hydrophilicity is stronger, and the hydration of the hydrogel microlayer is more obvious, thus forming a physical barrier and energy barrier to the protein to prevent protein adhesion.

[0237] Application Example 6: Test on the performance of the self-polishing antifouling coating of the present invention in inhibiting algae attachment

[0238] The implementation method of this application example is as follows:

[0239] Test sample: self-polishing antifouling coating prepared in Examples 5-8;

[0240] Test substrate: ABS board, ABS board size is 50×50×1mm 3 ;

[0241] Coating method: The self-polishing antifouling coating of the present invention is evenly coated on the ABS board by a drip coating method;

[0242] Test method: Author Qu Weigang, title "Comparison of algal cell counting methods in algal growth inhibition experiments", Journal Name: Pesticides, Vol. 52, No. 07, Page 498, describes the evaluation method for the algal adsorption inhibition test;

[0243] Test steps: The algae species and nutrient solution cultured to the exponential growth cycle are formulated into an algae solution with an absorbance of 0.09 at an ultraviolet absorption wavelength of 680nm. The self-polishing antifouling coating of the present invention is placed at the bottom of a culture dish with a diameter of 10cm, with the coating facing up, and then 40mL of algae solution is added and placed in an intelligent artificial climate box (RXZ-380C) for cultivation, and the algae solution is shaken at the same time every day. After 5 days, the coating is removed and the surface is rinsed with nutrient solution to remove algae with weaker surface attachment. Then, 10mL of nutrient solution is used to rinse all algae attached to the surface of the coating into another container, and the absorbance of the rinsing solution at a wavelength of 680nm is measured with an ultraviolet spectrophotometer (U-2800, HITACHI), and the algae concentration is calculated according to the standard curve.

[0244] Test results: Taking Chlorella vulgaris and Nitzschia closterium as examples, the performance of the coating in inhibiting algae adsorption in seawater was determined. Figure 5 a shows that the concentration of algae liquid adsorbed by the self-polishing antifouling coating of the present invention is significantly lower than that of the blank sample, showing good algae inhibition performance, and this performance weakens as the content of the coating antifouling agent decreases. Compared with the blank sample (dashed line in the figure), all coatings show the performance of inhibiting algae adsorption, and the higher the content of cross-linking agent monomer, the lower the concentration of adsorbed algae. This antifouling performance is provided by the self-polishing performance and the hydration layer generated by the microgel surface, and the antifouling performance of the hydration layer is more significant under static test conditions. The higher the content of cross-linking agent monomer, the more obvious the coating hydrogel structure, the more stable the interfacial hydration layer, and the better the antifouling performance.

[0245] Application Example 7: Adhesion and polishing performance test of the self-polishing antifouling coating of the present invention

[0246] The implementation method of this application example is as follows:

[0247] Test sample: water-based acrylic self-polishing antifouling coating coating capable of forming a hydrogel microlayer prepared in Examples 1-4;

[0248] Adhesion performance test basis: "Pull-off adhesion test for paints and varnishes" (GB / T5210-2006), "Determination of salt water resistance of ship coatings - Salt water and hot salt water immersion method" (GB / T10834-2008) and "Dynamic test method for antifouling performance of ship antifouling paint" (GB / T 7789-2007);

[0249] Test substrate: 20mm diameter metal cylinder (for adhesion test); ABS board, ABS board size is 50×50×1mm 3 (for static foam board), 250×100×1mm 3 (for dynamic paddling);

[0250] Coating method: The metal cylinder / ABS plate used in the test was polished with 80-mesh sandpaper, and then the coating was evenly applied on the top surface of the cylinder with an 80μm coater. The water-based acrylic self-polishing antifouling coating resin that can form a hydrogel microlayer of the present invention was evenly applied on the ABS plate by brushing, and then dried in a 40°C oven for 2 days after drying at room temperature; xylene and n-butanol were mixed in a mass ratio of 7:3, and then the polyamide curing agent was diluted (the mass ratio of the solvent to the curing agent was 1:4), and then mixed with epoxy resin in a mass ratio of 1:1 to obtain an adhesive, which was coated on the surface of another cylinder with an 80μm coater, and the cylindrical surface coated with the coating was connected with the cylindrical surface coated with the curing agent, and the adhesion was tested after drying in a 40°C oven for 7 days, and the average value was taken after 6 repetitions;

[0251] Specifically, a method combining static bubble plate and dynamic paddling was used to evaluate the adhesion ability of water-based self-polishing antifouling coatings to substrates in a seawater environment.

[0252] Static bubble board: At room temperature, the prepared coating sample is immersed in seawater. The sample is taken out every 10 days and the surface of the sample is rinsed with deionized water. The excess water on the surface is then gently wiped off with a clean absorbent filter paper. After taking photos and recording, the sample is put back into the seawater for further immersion.

[0253] Dynamic paddling: The prepared coating sample was placed in a dynamic paddling device, and the adhesion of the coating under the impact of seawater was recorded every cycle (10 days). The drum speed was 80 rpm and the device radius was 60 cm. The adhesion performance of the hydrogel coating was compared by observing whether the coating fell off on the substrate and the time and area of ​​the shedding.

[0254] By the attached Figure 6 It can be seen that almost all coatings show an adhesion strength of more than 2.4 MPa. The adhesion of the coatings when used in the ocean was measured by combining the static bubble board and dynamic paddling method. The results are shown in the attached figure. Figure 7As shown in Fig. 7a and Fig. 7b, after 100 days of static bubble board and 50 days of dynamic paddling test, all coatings maintained good adhesion without shedding or bubbling. Pigments, fillers, antifouling agents, etc. in the coating can interact with polar groups such as amide groups and carboxylic acid groups in the resin to form more physical crosslinks, increase the bonding points between the coating and the substrate, and improve the adhesion of the coating. The coating has the potential to achieve long-term adhesion in seawater.

[0255] The self-polishing test results of water-based acrylic self-polishing antifouling coating are shown in the attached Figure 7 As shown in c and 7d, compared with the resin coating, the abrasion rate of the paint coating was significantly reduced in the early stage of paddling, and the abrasion rate was stable at 0.6×10 -4 ~2.0×10 -4 g cm -2 The total wear rate at 50 days also decreased significantly (1.1×10 -3 ~1.6×10 -3 g cm -2 The physical cross-linking of pigments, fillers, antifouling agents, etc. in the coating with the polar groups of the resin, and the cross-linking structure of the hydrogel, prevent the coating polishing material from peeling off into the seawater, and the highly cross-linked network structure reduces the abrasion rate of the coating.

[0256] Application Example 8: Study on the actual sea cladding of the waterborne acrylic self-polishing antifouling coating with a hydrogel microlayer of the present invention

[0257] The implementation method of this application example is as follows:

[0258] Test sample: self-polishing antifouling coating prepared in Examples 5-8;

[0259] Test substrate: PVC board, size 900×300×3mm 3 , blank plate was used as control;

[0260] Test substrate treatment: The PVC board used in the test was evenly polished with 80-grit sandpaper, then cleaned with ethanol and water respectively, and dried at room temperature to constant weight.

[0261] Coating method: conventional coating method, add 10% aziridine crosslinking agent based on carboxyl mole to the self-polishing antifouling coating of the present invention, mix well, and coat 8000 μg on the ABS plate;

[0262] Test basis: "Shallow Sea Immersion Coating Template Test Method" (GB / T5370-2007);

[0263] Test results: The actual sea hanging board test results of the self-polishing antifouling coating of the present invention are listed in the attached Figure 8 middle.

[0264] By the attached Figure 8 It can be seen that after 100 days of real sea antifouling test, the coating of the present invention maintained a good adhesion state, with a small amount of fouling attached to the surface, but significantly less than the blank sample, showing a good antifouling effect. The types and number of marine organisms attached to the surface of the sample on the 65th day gradually decreased with the increase of HAM content, and there was only a part of the biological mucosa on the surface of the sample on the 100th day. This is because the fouling organisms on the surface of the sample are continuously washed and released by seawater under the self-polishing effect of the coating. In addition to preventing the attachment of fouling organisms by self-polishing and releasing antifouling agents, the coating of the present invention can also achieve the purpose of antifouling by self-generating a hydrogel layer on the surface, thereby improving the antifouling performance of the coating.

Claims

1. A self-polishing antifouling coating, characterized in that The invention is composed of component A and component B in a weight ratio of 100:0.1-0.5, wherein component A is composed of 10-50 weight parts of water-based acrylic self-polishing antifouling resin, 10-60 weight parts of antifouling agent and 1-30 weight parts of pigment and filler, and component B is a cross-linking agent. In water, the coating surface of the self-polishing antifouling coating on the surface of the substrate has a hydrogel microlayer with a thickness of 50-200 μm.

2. The self-polishing antifouling coating according to claim 1, characterized in that The water-based acrylic acid self-polishing antifouling resin is prepared by the following preparation steps: A. Preparation of monomer mixture 10-100% of sodium hydroxide based on the molar amount of the unsaturated organic acid and 30-200% of water are mixed evenly, and then 3-20% of the unsaturated organic acid based on the total molar amount of the following monomers is added, mixed evenly, and dissolved to obtain a NaAA solution; Under stirring with a magnetic stirrer, the total amount of the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer in moles is 1:20-30 to the volume of the NaAA solution in milliliters, and the oily acrylic monomer, the water-based monomer and the acrylic silicone self-polishing monomer are sequentially added to the NaAA solution in a molar ratio of 70-95:5-25:2-15 to obtain the monomer mixture; B. Preparation of initiator solution At room temperature, 0.5-2.0% of the aqueous initiator, 0-1.0% of the oily initiator and 30-200% of deionized water, based on the molar amount of the unsaturated organic acid, are mixed uniformly to obtain the initiator solution; C. Preparation of water-based acrylic self-polishing antifouling resin In a four-necked flask equipped with a stirrer, a condenser and a thermometer, 90-270% ethanol and 10-30% deionized water are added based on the total weight of the above monomers, and then the monomer mixture obtained in step A and the initiator solution obtained in step B are added, and the addition amount thereof is 5-10% of their respective volumes; then, the remaining monomer mixture solution is heated to a temperature of 65-85° C. under a stirring speed of 50-500 rpm; When blue light appears in the reaction system, the remaining monomer mixture solution and the remaining initiator solution are added in batches over a period of 0.5 to 1.5 hours, and the temperature is maintained at 65 to 85° C. for 0.4 to 0.6 hours; then, 0.01 to 0.02% of the above-mentioned initiator solution based on the total mass of all monomers is continued to be added, and the temperature is maintained at 60 to 70° C. for 0.8 to 1.2 hours, and then cooled to room temperature to obtain a white emulsion of water-based acrylic self-polishing antifouling resin.

3. The self-polishing antifouling coating according to claim 2, characterized in that In the preparation step A and the preparation step B, the unsaturated organic acid is acrylic acid, methacrylic acid or a mixture thereof.

4. The self-polishing antifouling coating according to claim 2, characterized in that In the preparation step A, the oily acrylic monomer is one or more oily acrylic monomers selected from methyl methacrylate, ethyl methacrylate, propyl methacrylate or butyl methacrylate; the water-based monomer is acrylamide, hydroxyacrylamide, unsaturated organic acid or a mixture thereof, wherein the hydroxyacrylamide is N-hydroxymethylacrylamide, N-hydroxyethylacrylamide or N-hydroxypropylacrylamide; the acrylic silicone self-polishing monomer is acryloxytriisopropylsilane, methacryloxytriisopropylsilane, γ-methacryloxypropyltrimethoxysilane or a mixture thereof.

5. The self-polishing antifouling coating according to claim 2, characterized in that In the preparation step B, the aqueous initiator is azobisisobutylimidazoline hydrochloride, azobisisopropylimidazoline, azobisisobutylamidine hydrochloride, potassium persulfate or ammonium persulfate; the oily initiator is azobisisobutyronitrile, azobisisoheptanenitrile, benzoyl peroxide, tert-butyl benzoyl peroxide or methyl ethyl ketone peroxide.

6. The self-polishing antifouling coating according to claim 1, characterized in that The antifouling agent is one or more antifouling agents selected from Cu2O, copper pyrithione, zinc pyrithione, thiophanate-methyl, diuron or 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one.

7. The self-polishing antifouling coating according to claim 1, characterized in that The pigments and fillers are one or more pigments and fillers selected from ZnO, TiO2, Fe2O3, talcum powder, molybdenum red, nano silicon dioxide, kaolin, Al2O3 or activated carbon.

8. The method for preparing the self-polishing antifouling coating according to claim 2, characterized in that The preparation steps of the preparation method are as follows: Under room temperature, a white emulsion-like water-based acrylic self-polishing antifouling resin, an antifouling agent and a pigment and filler are uniformly mixed in a mass ratio of 10-50:10-60:1-30, and a coating rapid dispersion tester is used to grind and disperse the mixture for 0.4-1.0 h at a stirring speed of 2000-5000 rpm. When the fineness of the ground material is measured by a scraper fineness meter and is less than 50 μm, component A is obtained; When the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is a hydroxyl group, a carboxyl group or an amino group, aziridine, tetramethoxymethyl glycoluril, glutaraldehyde, formaldehyde, phthalaldehyde, epichlorohydrin or triethoxysilane cross-linking agent is used as component B; The amount of component B is 3-20% based on the molar amount of the cross-linking functional group hydroxyl, carboxyl or amino group contained in the water-based acrylic self-polishing antifouling resin in component A; the aqueous solution obtained by dissolving component B in water in a ratio of 1:20-80 in grams of component B to milliliters of water is uniformly mixed with component A to obtain the self-polishing antifouling coating; The self-polishing antifouling paint is brushed onto the surface of a substrate to obtain a water-based acrylic self-polishing antifouling paint coating having a hydrogel microlayer in water, wherein the thickness of the hydrogel microlayer is 50-200 μm.

9. The method for preparing the self-polishing antifouling coating according to claim 8, characterized in that When the cross-linking functional group of the water-based acrylic self-polishing antifouling resin is an alkoxysilyl group, tetraethoxysilane, silane coupling agent A-171, silane coupling agent KH-550, silane coupling agent KH-560 or silane coupling agent KH-570 cross-linking agent is used as component B; The amount of component B used is 3-20% based on the molar amount of the cross-linking functional group alkoxysilyl group contained in the water-based acrylic self-polishing antifouling resin in component A.

10. Use of the self-polishing antifouling coating according to any one of claims 1 to 7 or the self-polishing antifouling coating prepared according to the preparation method according to claim 8 or 9 in the field of marine fouling organism control.

Images