Underwater antifouling paint and preparation method thereof

Abstract

The invention relates to the field of coatings, in particular to underwater antifouling paint and a preparation method thereof.The underwater antifouling paint comprises 2-5 parts of chlorinated rubber, 1-3 parts of chlorinated polyether resin, 1-2 parts of zinc acrylate resin, 35-50 parts of an antifouling agent, 9-12 parts of compound rosin, 2-5 parts of a flexibilizer, 1-3 parts of a stabilizer, 2-5 parts of a defoaming agent, 0.1-0.5 part of a dispersing agent, 2-3 parts of a thixotropic agent and 15-25 parts of a solvent; the antifouling agent comprises cuprous oxide, an organic antifouling agent and a natural biological antifouling agent; the compound rosin comprises gum rosin and rosin maleic anhydride polyol ester; the toughening agent is prepared from sorbitan fatty acid ester and tricresyl phosphate; the stabilizer comprises zinc oxide and polyoxyethylene fatty alcohol ether. The underwater antifouling paint disclosed by the invention has relatively high adhesive force, flexibility, impact resistance, water resistance and excellent antifouling property, and is suitable for ship bottoms and underwater facilities.

Description

Technical Field

[0001] The invention relates to the field of coatings, and in particular to an underwater antifouling paint and a preparation method thereof. Background Art

[0002] In underwater antifouling paint, the release speed and uniformity of the antifouling agent are key. If the antifouling agent is released too quickly, the antifouling cycle will be shortened. If the release is uneven, local antifouling effects may be poor. Traditional chlorinated rubber antifouling paint is a dissolving antifouling paint made of chlorinated rubber as the skeleton, rosin as the slow-release agent, and antifouling agents such as cuprous oxide. As the rosin resin continues to dissolve in water, the paint film is constantly renewed, and the antifouling agent contained in it will be continuously released to play an antifouling role. However, due to the excessive amount of chlorinated rubber, the paint film forms a saponification layer, which continuously reduces the seepage rate of the antifouling agent and even causes copper ions to form insoluble salts such as basic copper carbonate, further reducing the seepage rate until the antifouling coating fails.

[0003] In addition, due to the poor mechanical properties of traditional chlorinated rubber antifouling paints such as adhesion, flexibility and stability, the paint film cannot effectively resist the scouring and erosion of water flow. Therefore, the chlorinated rubber antifouling paints currently used generally have a short lifespan. Summary of the invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the deficiencies and defects in the prior art, thereby providing an underwater antifouling paint with high paint film flexibility and stability and strong adhesion and a preparation method thereof.

[0005] To solve the above problems: The present invention provides an underwater antifouling paint, comprising the following components in parts by weight: 2-5 parts of chlorinated rubber, 1-3 parts of chloroether resin, 1-2 parts of zinc acrylate resin, 35-50 parts of antifouling agent, 9-12 parts of compound rosin, 2-5 parts of toughening agent, 1-3 parts of stabilizer, 2-5 parts of defoaming agent, 0.1-0.5 parts of dispersant, 2-3 parts of thixotropic agent, 15-25 parts of solvent; The antifouling agents include cuprous oxide, organic antifouling agents and natural biological antifouling agents; The compound rosin includes gum rosin and rosin maleic anhydride polyol ester; The toughening agent includes sorbitan fatty acid ester and tricresyl phosphate; The stabilizer includes zinc oxide and polyoxyethylene fatty alcohol ether.

[0006] In the present invention, a single chlorinated rubber is used as the film-forming substance of the antifouling paint, which gives the paint film a certain adhesion and quick-drying property, but the flexibility of the paint film is relatively poor, and a saponification layer is easily formed to continuously reduce the permeability of the antifouling agent; a single zinc acrylate resin is used as the film-forming substance, which can prevent marine organisms from attaching to the hull and underwater facilities, and the pollution to the marine environment is small, but the viscosity of the zinc acrylate resin is large, the paint film drying time is long, which affects the construction efficiency, and the paint film has poor corrosion resistance. The present invention uses chlorinated rubber, chloroether resin and zinc acrylate resin as the main carrier of the antifouling paint. The three are intertwined to form a slow-release channel of the antifouling agent and a relatively stable physical barrier, while adjusting the diffusion rate of the antifouling agent to avoid the loss of the antifouling agent in a non-use state. In addition, during use, the antifouling agent wrapped in the paint film is gradually exposed and released by continuously updating the paint film surface, thereby achieving a stable antifouling effect for a long time and extending the antifouling life.

[0007] In the present invention, cuprous oxide is an antifouling agent widely used in antifouling paints. It releases copper ions by slowly dissolving in water to form a toxic water layer on the surface of the paint film, and has the ability of sterilization, algae removal and anti-biological attachment. However, the unstable copper ion seepage rate will affect the antifouling effect and life of the coating. By introducing an organic antifouling agent, a natural biological antifouling agent and cuprous oxide for compounding, the organic antifouling agent and the natural biological antifouling agent are filled between cuprous oxide particles to form a slow-release carrier, and the release rates are coordinated with each other, thereby improving the broad-spectrum bactericidal and antibacterial ability of the antifouling paint, being able to effectively prevent a variety of microorganisms from breeding and attaching on the surface of the antifouling paint, improving the antifouling performance of the coating, making the release of cuprous oxide slower and more lasting, being able to ensure that the antifouling performance of the antifouling agent is stably exerted, and extending the service life of the antifouling paint.

[0008] In the present invention, the compounded rosin is a compound of gum rosin and rosin maleic anhydride polyol ester. The slightly soluble property of gum rosin in seawater is conducive to the release of antifouling agents, but when gum rosin is used as a coating matrix, there are problems of too fast release speed and insufficient mechanical properties of the coating. The compounded rosin in the present invention is a compound of gum rosin and rosin maleic anhydride polyol ester, which has structural characteristics including ester groups, carboxyl groups, hydroxyl groups, and multiple cyclic structures, and can adjust the microstructure and porosity of antifouling paints, form a relatively stable permeation layer in seawater, control the dissolution rate of gum rosin, thereby slowing down the release rate of antifouling agents, so that the antifouling agents are released more evenly during the service life of the coating, thereby achieving better antifouling effects.

[0009] In the present invention, tricresyl phosphate is used as a toughening agent and can be inserted between polymer molecular chains to improve the flexibility of the paint film. However, in the antifouling paint, using too much tricresyl phosphate will affect the permeability of the paint film and is not conducive to the release of the antifouling agent. By introducing sorbitan fatty acid ester and compounding with tricresyl phosphate, the uniform dispersion of tricresyl phosphate in the antifouling paint is promoted, and the wetting and spreading of the paint film on the surface of the substrate are promoted, the internal stress of the antifouling paint is reduced, and the flexibility and impact resistance of the antifouling paint are further improved, so that the paint film is not easy to crack or peel off when subjected to external force, and the sedimentation and stratification of the antifouling agent are avoided, the uniformity, stability and density of the paint film are improved, and the flatness and water resistance of the paint film are improved. The introduction of sorbitan fatty acid ester controls the distribution and migration speed of the antifouling agent in the paint film, realizes the regulation of the release rate of the antifouling agent, and enables the antifouling paint to maintain a stable antifouling effect for a long time.

[0010] In the present invention, zinc oxide is used as a stabilizer to improve the hardness and antifouling performance of the antifouling paint, but zinc oxide is easy to agglomerate, resulting in uneven dispersion in the coating, thereby affecting the performance of the paint film. In the present invention, after the polyoxyethylene fatty alcohol ether is compounded with zinc oxide, it is wrapped on the surface of zinc oxide particles to reduce the surface energy of the zinc oxide particles, thereby avoiding the phenomenon of unstable performance in local areas caused by uneven dispersion of zinc oxide, making the formed paint film more uniform and dense, and improving the hardness and toughness of the paint film. The compounded stabilizer is not only less toxic and can reduce the pollution of the antifouling paint to the environment, but also can play a regulatory role in the release of the antifouling agent in the antifouling paint by improving the chemical stability of the antifouling paint and adjusting the pore structure and diffusion performance of the paint film.

[0011] Preferably, the organic antifouling agent includes copper pyridinethione and / or 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one; and the natural biological antifouling agent includes one or more of capsaicin, gingerol and chitosan.

[0012] Preferably, the mass ratio of cuprous oxide, organic antifouling agent and natural biological antifouling agent is (8-15):(1-2):(1-3); the mass ratio of gum rosin and rosin maleic anhydride polyol ester is (2-5):1; the mass ratio of sorbitan fatty acid ester and tricresyl phosphate is 1:(3-9); the mass ratio of zinc oxide and polyoxyethylene fatty alcohol ether is (4-9):1.

[0013] In the present invention, in order to ensure the antifouling effect while reducing the usage of cuprous oxide and further reduce the negative impact on the marine ecological environment, the mass ratio of cuprous oxide, organic antifouling agent and natural biological antifouling agent is (8-15): (1-2): (1-3).

[0014] In the present invention, the higher the mass ratio of gum rosin to rosin maleic anhydride polyol ester, the lower the flexibility of the paint film, the higher the brittleness of the paint film, and the paint film is prone to cracking when subjected to external force, affecting its antifouling effect; the lower the mass ratio of gum rosin to rosin maleic anhydride polyol ester, the higher the water resistance, flexibility and impact resistance of the paint film, but the dissolution rate is too slow, which is not conducive to the release of the antifouling agent and also affects the antifouling effect. An appropriate compounding ratio can improve the adhesion of the paint film, balance the hardness and toughness of the paint film, improve the antifouling effect, and extend the service life of the paint film. Therefore, the mass ratio of gum rosin to rosin maleic anhydride polyol ester is (2-5):1.

[0015] In the present invention, in order to improve the flexibility of the paint film and avoid the influence of the toughening agent on the antifouling performance, and ensure that the antifouling paint maintains a stable antifouling effect for a long time, the mass ratio of the sorbitan fatty acid ester to tricresyl phosphate is 1: (3-9).

[0016] In the present invention, in order to better improve the performance of the antifouling paint and reduce environmental pollution, the mass ratio of zinc oxide to polyoxyethylene fatty alcohol ether is (4-9):1.

[0017] Preferably, the sorbitan fatty acid ester includes one or more of Span-60, Span-80 and Span-85; the polyoxyethylene fatty alcohol ether is selected from one or more of AEO-9, MOA-9 and Parga O.

[0018] Preferably, the chlorinated rubber is selected from one or more of S-20, CRF20 and CR-20; the chloroether resin is MP-45; and the zinc acrylate resin is SPZn-100 and / or H100Z.

[0019] In the present invention, in order to control the release rate of the antifouling agent, improve the antifouling effect, ensure the smoothness of the coating surface, and improve the water resistance and adhesion of the coating, the acrylate zinc resin is SPZn-100 and / or H100Z.

[0020] Preferably, the chlorine content in the chlorinated rubber is 64-68%, and the chlorine content in the chloroether resin is 42-46%.

[0021] In the present invention, the higher the chlorine content of the chlorinated rubber and the chloroether resin, the better the antifouling effect, hardness and water resistance of the coating, but too high a chlorine content increases the rigidity of the molecular chain, reduces the flexibility and impact resistance of the coating, and affects the marine environment; the lower the chlorine content of the chlorinated rubber and the chloroether resin, the better the flexibility, but the slower the drying speed and the worse the antifouling effect, therefore, the chlorine content in the chlorinated rubber is 64-68%, and the chlorine content in the chloroether resin is 42-46%.

[0022] Preferably, the defoaming agent is a fluorine-free resin defoaming agent, and the fluorine-free resin defoaming agent is one or more of BYK-052, Tego-810, HY-5300 and TEGO Foamex 825; the dispersant is one or more of BYK-190, EFKA-4010 and SN-5027; the thixotropic agent is one or more of organic bentonite, polyamide wax, fumed silica, and hydrogenated castor oil; the solvent is one or more of xylene, 100# gasoline, butyl acetate, n-butanol, methyl ethyl ketone, isopropanol, and butyl acetate.

[0023] The present invention also provides a method for preparing the underwater antifouling paint, comprising the following preparation steps: (1) mixing and stirring a solvent, chlorinated rubber, chloroether resin, zinc acrylate resin, and compound rosin to obtain a first mixed material; (2) adding a thixotropic agent, a dispersant, a defoaming agent, and a toughening agent to the first mixture, mixing and stirring, to obtain a second mixture; (3) adding an antifouling agent and a stabilizer to the second mixture, mixing and stirring to obtain a third mixture, adding a solvent to the third mixture, mixing evenly and filtering to obtain the underwater antifouling paint.

[0024] Preferably, the mixing and stirring speed in step (1) is 1000-1500 r / min; the fineness of the third mixed material in step (3) is less than 40 µm, and the viscosity of the third mixed material after adding the solvent is 100-120 KU.

[0025] Preferably, the mixing and stirring time in step (1) is 20 minutes; and the mixing and stirring time in step (2) is 30-40 minutes.

[0026] The technical solution of the present invention has the following advantages: 1. The underwater antifouling paint provided by the present invention overcomes the adverse effects of single chlorinated rubber or single zinc acrylate resin as a film-forming substance by using chlorinated rubber, chloroether resin and zinc acrylate resin as film-forming substances, enhances the chemical stability and physical properties of the paint film through synergistic effects, and adopts a compound of cuprous oxide with an organic antifouling agent and a natural biological antifouling agent, thereby not only improving the antifouling performance, but also being able to maintain a stable antifouling effect for a long time, extending the antifouling life, and improving the paint film performance of the antifouling paint, enhancing the flexibility, adhesion and water resistance of the paint film, and improving the durability of the antifouling paint, so that it can better resist the scouring and erosion of water flow, and when the paint film is impacted or expands and contracts due to temperature changes, it can remain intact without breaking.

[0027] 2. The underwater antifouling paint provided by the present invention adopts a compound of gum rosin and rosin maleic anhydride polyol ester, which can not only better control the release rate of the antifouling agent, but also enhance the adhesion between the antifouling paint and the substrate, improve the leveling performance of the antifouling paint, make the paint film surface smoother, and form a balance between hardness and toughness in the paint film, so that the paint film can resist the scouring of water flow and the scratching of aquatic organisms, and avoid brittle cracking due to excessive hardness, thereby extending the service life of the paint film.

[0028] 3. The underwater antifouling paint provided by the present invention introduces sorbitan fatty acid ester and tricresol phosphate as a toughening agent, which promotes the uniform dispersion of tricresol phosphate in the antifouling paint, promotes the wetting and spreading of the paint film on the surface of the substrate, reduces the internal stress of the antifouling paint, enhances the flexibility of the paint film, and improves the impact resistance and crack resistance of the paint film. The introduction of sorbitan fatty acid ester effectively avoids the sedimentation and stratification of the antifouling paint, improves the uniformity, stability and density of the paint film, and prevents the penetration and erosion of water by forming a hydrophobic layer, thereby improving the water resistance of the paint film and avoiding the swelling, softening and blistering of the paint film due to long-term contact with seawater.

[0029] 4. The underwater antifouling paint provided by the present invention uses polyoxyethylene fatty alcohol ether and zinc oxide as a stabilizer, which avoids the phenomenon of uneven dispersion of zinc oxide leading to unstable performance in local areas, making the formed paint film more uniform and dense, which not only improves the hardness and toughness of the paint film, but also allows the antifouling agent to be released slowly and evenly over a long period of time. The introduction of polyoxyethylene fatty alcohol ether also improves the cohesion of the paint layer by interacting with other ingredients, enhances the adhesion between the paint film and the substrate, and prolongs the antifouling cycle. DETAILED DESCRIPTION

[0030] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0031] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially. Example 1

[0032] The present invention provides an underwater antifouling paint, comprising the following components in parts by weight: 2 parts of chlorinated rubber S-20, 3 parts of chlorinated rubber CRF20, 3 parts of chloroether resin MP-45, 1 part of zinc acrylate resin SPZn-100, 1 part of zinc acrylate resin H100Z, 30 parts of cuprous oxide, 2 parts of copper pyridinethione (organic antifouling agent), 2 parts of 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of capsaicin (natural biological antifouling agent), 3 parts of gingerol (natural biological antifouling agent), 10 parts of gum rosin, 2 parts of rosin maleic anhydride polyol alcohol ester, 0.2 parts of Span-80 (toughener), 0.3 parts of Span-60 (toughener), 4.5 parts of tricresyl phosphate (toughener), 2.7 parts of zinc oxide (stabilizer), 0.3 parts of AEO-9 (stabilizer), 5 parts of BYK-052 (defoaming agent), 0.2 parts of BYK-190 (dispersant), 0.3 parts of EFKA-4010 (dispersant), 3 parts of organic bentonite (thixotropic agent), 10 parts of ethyl acetate (solvent), 10 parts of n-butanol (solvent).

[0033] The method for preparing the underwater antifouling paint comprises: (1) Add 10 parts of ethyl acetate (solvent) into a dispersion kettle, add 2 parts of S-20 (chlorinated rubber), 3 parts of CRF20 (chlorinated rubber), 3 parts of MP-45 (chloroether resin), 1 part of SPZn-100 (zinc acrylate resin) and 1 part of H100Z (zinc acrylate resin) with stirring, then add 10 parts of gum rosin and 2 parts of rosin maleic anhydride polyol ester (compounded rosin) dissolved in 5 parts of n-butanol in advance, adjust the speed to 1500r / min, disperse for 20 minutes, and obtain a first mixed material; (2) Add 3 parts of organic bentonite (thixotropic agent), 0.2 parts of BYK-190 (dispersant), 0.3 parts of EFKA-4010 (dispersant), 5 parts of BYK-052 (defoaming agent), 0.2 parts of Span-80 (toughening agent), 0.3 parts of Span-60 (toughening agent), and 4.5 parts of tricresyl phosphate (toughening agent) to the first mixture, and continue stirring for 40 minutes until the mixture is uniform, to obtain a second mixture; (3) Add 30 parts of cuprous oxide (antifouling agent), 2 parts of copper pyridinethione (organic antifouling agent), 2 parts of 4,5-dichloro-2-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of capsaicin (natural biological antifouling agent), 3 parts of gingerol (natural biological antifouling agent), 2.7 parts of zinc oxide (stabilizer), and 0.3 parts of AEO-9 (stabilizer) to the second mixture, and stir until the fineness is less than 40 μm to form a slurry, that is, to obtain a third mixture, add 5 parts of n-butanol (solvent) to the third mixture to adjust the viscosity to 100-120 KU, and filter to obtain the underwater antifouling paint. Example 2

[0034] The present invention provides an underwater antifouling paint, comprising the following components in parts by weight: 4 parts of chlorinated rubber CR-20, 2 parts of chloroether resin MP-45, 1 part of zinc acrylate resin H100Z, 40 parts of cuprous oxide, 5 parts of copper pyridinethione (organic antifouling agent), 5 parts of capsaicin (natural biological antifouling agent), 8 parts of gum rosin, 2 parts of rosin maleic anhydride polyol ester, 1 part of Span-80 (toughening agent), 3 parts of tricresol phosphate (toughening agent), 2.5 parts of zinc oxide (stabilizer), 0.5 parts of MOA-9 (stabilizer), 2 parts of Tego-810 (defoaming agent), 0.3 parts of EFKA-4010 (dispersant), 2 parts of polyamide wax (thixotropic agent), 25 parts of xylene (solvent).

[0035] The method for preparing the underwater antifouling paint comprises: (1) Add 10 parts of xylene (solvent) into a dispersion kettle, add 4 parts of CR-20 (chlorinated rubber), 2 parts of MP-45 (chloroether resin), and 1 part of H100Z (zinc acrylate resin) with stirring, and then add 8 parts of gum rosin and 2 parts of rosin maleic anhydride polyol ester (compounded rosin) dissolved in 10 parts of xylene in advance, adjust the speed to 1000 r / min, and disperse for 20 minutes to obtain a first mixed material; (2) Add 2 parts of polyamide wax (thixotropic agent), 0.3 parts of EFKA-4010 (dispersant), 2 parts of Tego-810 (defoaming agent), 1 part of Span-80 (toughening agent), and 3 parts of tricresol phosphate (toughening agent) to the first mixture, and continue stirring for 30 minutes until the mixture is uniformly stirred to obtain a second mixture; (3) Add 40 parts of cuprous oxide (antifouling agent), 5 parts of copper pyrithione (organic antifouling agent), 5 parts of capsaicin (natural biological antifouling agent), 2.5 parts of zinc oxide (stabilizer), and 0.5 parts of MOA-9 (stabilizer) to the second mixture, and stir until the fineness is less than 40 μm to form a slurry, that is, to obtain a third mixture, add 5 parts of xylene (solvent) to the third mixture to adjust the viscosity to 100-120 KU, and filter to obtain the underwater antifouling paint. Example 3

[0036] The present invention provides an underwater antifouling paint, comprising the following components in parts by weight: 2 parts of chlorinated rubber CRF20, 1 part of chloroether resin MP-45, 1 part of zinc acrylate resin H100Z, 30 parts of cuprous oxide, 2 parts of 4,5-dichloro-2-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of chitosan (natural biological antifouling agent), 6 parts of gum rosin, 3 parts of rosin maleic anhydride polyol ester, 0.4 parts of Span-85 (toughening agent), 1.6 parts of tricresol phosphate (toughening agent), 0.8 parts of zinc oxide (stabilizer), 0.1 parts of permethrin O (stabilizer), 0.1 parts of AEO-9 (stabilizer), 2 parts of HY-5300 (defoaming agent), 2 parts of TEGO Foamex 825 (defoaming agent), 0.1 parts of SN-5027 (dispersant), 2 parts of fumed silica (thixotropic agent), and 15 parts of methyl ethyl ketone (solvent).

[0037] The method for preparing the underwater antifouling paint comprises: (1) Add 5 parts of methyl ethyl ketone (solvent) into a dispersion kettle, add 2 parts of CRF20 (chlorinated rubber), 1 part of MP-45 (chloroether resin), and 1 part of H100Z (zinc acrylate resin) with stirring, and then add 6 parts of gum rosin and 3 parts of rosin maleic anhydride polyol ester (compounded rosin) dissolved in 5 parts of methyl ethyl ketone in advance, adjust the speed to 1300r / min, and disperse for 20 minutes to obtain a first mixed material; (2) Add 2 parts of fumed silica (thixotropic agent), 0.1 parts of SN-5027 (dispersant), 2 parts of HY-5300 (defoaming agent), 2 parts of TEGO Foamex 825 (defoaming agent), 0.4 parts of Span-85 (toughening agent), and 1.6 parts of tricresol phosphate (toughening agent) to the first mixture, and continue stirring for 35 minutes until the mixture is uniform, to obtain a second mixture; (3) Add 30 parts of cuprous oxide (antifouling agent), 2 parts of 4,5-dichloro-2-octyl-4-isothiazoline-3-one (organic antifouling agent), 3 parts of chitosan (natural biological antifouling agent), 0.8 parts of zinc oxide (stabilizer), 0.1 parts of perchlorate O (stabilizer), and 0.1 parts of AEO-9 (stabilizer) to the second mixture, and stir until the fineness is less than 40 μm to form a slurry, thereby obtaining a third mixture. Add 5 parts of methyl ethyl ketone (solvent) to the third mixture to adjust the viscosity to 100-120 KU, and filter to obtain the underwater antifouling paint.

[0038] Comparative Example 1 This comparative example provides an underwater antifouling paint, which is different from Example 2 in that, in this comparative example, the chlorinated rubber CR-20 and the chloroether resin MP-45 are replaced by an equal amount of zinc acrylate resin H100Z, and the organic antifouling agent copper pyrithione and the natural biological antifouling agent capsaicin are replaced by an equal amount of cuprous oxide.

[0039] Comparative Example 2 This comparative example provides an underwater antifouling paint, which is different from Example 2 in that an equal amount of gum rosin is used to replace rosin maleic anhydride polyol ester in this comparative example.

[0040] Comparative Example 3 This comparative example provides an underwater antifouling paint, which is different from Example 2 in that the sorbitan fatty acid ester Span-80 is replaced by an equal amount of tricresyl phosphate in this comparative example.

[0041] Comparative Example 4 This comparative example provides an underwater antifouling paint, which is different from Example 2 in that the polyoxyethylene fatty alcohol ether MOA-9 is replaced by an equal amount of zinc oxide in this comparative example.

[0042] In the present invention, the performance of the underwater antifouling paints prepared in Examples 1-3 and Comparative Examples 1-4 was tested according to the performance indicators in Table 1, and the test results are shown in Table 1.

[0043] Table 1 Performance test indicators of coatings and underwater antifouling paint performance test results

[0044] As can be seen from Table 1, the underwater antifouling paints provided by the present invention have excellent antifouling performance, antifouling life, adhesion, flexibility, impact resistance and water resistance, and are suitable for ship bottoms and marine underwater facilities.

[0045] By comparing Comparative Example 1 and Example 2, it is found that the use of a single zinc acrylate resin and a single antifouling agent cuprous oxide not only has limited antifouling effect, but also has poor mechanical properties of the paint film. The use of a compounded film-forming substance and a compounded antifouling agent can improve the antifouling performance and antifouling life, reduce the drying time of the antifouling paint, and the flexibility, water resistance, impact resistance and adhesion of the antifouling coating are outstanding.

[0046] By comparing Comparative Example 2 and Example 2, it is found that the introduction of rosin maleic anhydride polyol ester and gum rosin enhances the antifouling performance of the antifouling paint, improves the antifouling effect, and is beneficial to enhancing the adhesion between the antifouling paint and the substrate, and improving the impact resistance and other properties of the paint film.

[0047] By comparing Comparative Example 3 and Example 2, it is found that the introduction of the compound of sorbitan fatty acid ester and tricresyl phosphate not only enhances the flexibility of the paint film, improves the impact resistance of the paint film, improves the water resistance, but also significantly improves the storage stability of the antifouling paint.

[0048] By comparing Comparative Example 4 and Example 2, it is found that the use of a stabilizer compounded with polyoxyethylene fatty alcohol ether and zinc oxide improves the flexibility of the paint film, enhances the adhesion between the paint film and the substrate, improves the water resistance of the paint film, and improves the antifouling performance.

[0049] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the present invention.

Claims

1. An underwater antifouling paint, characterized in that: The following components are included by weight: 2-5 parts of chlorinated rubber, 1-3 parts of chloroether resin, 1-2 parts of zinc acrylate resin, 35-50 parts of antifouling agent, 9-12 parts of compound rosin, 2-5 parts of toughening agent, 1-3 parts of stabilizer, 2-5 parts of defoaming agent, 0.1-0.5 parts of dispersant, 2-3 parts of thixotropic agent, 15-25 parts of solvent; The antifouling agents include cuprous oxide, organic antifouling agents and natural biological antifouling agents; The compound rosin includes gum rosin and rosin maleic anhydride polyol ester; The toughening agent includes sorbitan fatty acid ester and tricresyl phosphate; The stabilizer includes zinc oxide and polyoxyethylene fatty alcohol ether.

2. An underwater antifouling paint according to claim 1, characterized in that: The organic antifouling agent includes copper pyrithione and / or 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one; The natural biofouling agent includes one or more of capsaicin, gingerol and chitosan.

3. An underwater antifouling paint according to claim 1 or 2, characterized in that: The mass ratio of cuprous oxide, organic antifouling agent and natural biological antifouling agent is (8-15): (1-2): (1-3); The mass ratio of the gum rosin to the rosin maleic anhydride polyol ester is (2-5):1; The mass ratio of the sorbitan fatty acid ester to tricresyl phosphate is 1:(3-9); The mass ratio of zinc oxide to polyoxyethylene fatty alcohol ether is (4-9):

1.

4. An underwater antifouling paint according to claim 3, characterized in that: The sorbitan fatty acid ester includes one or more of Span-60, Span-80 and Span-85; The polyoxyethylene fatty alcohol ether is selected from one or more of AEO-9, MOA-9 and Pingpingjia O.

5. An underwater antifouling paint according to claim 1, characterized in that: The chlorinated rubber is selected from one or more of S-20, CRF20 and CR-20; The chloroether resin is MP-45; The zinc acrylate resin is SPZn-100 and / or H100Z.

6. An underwater antifouling paint according to claim 5, characterized in that: The chlorine content of the chlorinated rubber is 64-68%, and the chlorine content of the chloroether resin is 42-46%.

7. An underwater antifouling paint according to claim 1, characterized in that: The defoamer is a fluorine-free resin defoamer, and the fluorine-free resin defoamer is one or more of BYK-052, Tego-810, HY-5300 and TEGO Foamex 825; The dispersant is one or more of BYK-190, EFKA-4010 and SN-5027; The thixotropic agent is one or more of organic bentonite, polyamide wax, fumed silica, and hydrogenated castor oil; The solvent is one or more of xylene, 100# gasoline, butyl acetate, n-butanol, methyl ethyl ketone, isopropanol, and butyl acetate.

8. The method for preparing the underwater antifouling paint according to any one of claims 1 to 7, characterized in that: The method comprises the following preparation steps: (1) mixing and stirring a solvent, chlorinated rubber, chloroether resin, zinc acrylate resin, and compound rosin to obtain a first mixed material; (2) adding a thixotropic agent, a dispersant, a defoaming agent, and a toughening agent to the first mixture, mixing and stirring, to obtain a second mixture; (3) adding an antifouling agent and a stabilizer to the second mixture, mixing and stirring to obtain a third mixture, adding a solvent to the third mixture, mixing evenly and filtering to obtain the underwater antifouling paint.

9. The method for preparing underwater antifouling paint according to claim 8, characterized in that: The mixing and stirring speed in step (1) is 1000-1500 r / min; The fineness of the third mixed material in step (3) is less than 40 µm, and the viscosity of the third mixed material after adding the solvent is 100-120 KU.

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