CN110684421A - Surface microstructure self-polishing antifouling coating and preparation method thereof - Google Patents

Abstract

The invention relates to the technical field of marine antifouling, and provides a surface microstructure self-polishing antifouling coating and a preparation method thereof in order to solve the problems that the conventional self-polishing antifouling coating cuprous oxide antifouling agent has large usage amount, the surface microstructure coating is difficult to construct on the surface of a ship, and the antifouling effect of the coating is difficult to play due to the damage of marine microorganisms and inorganic matters on the surface, wherein the surface microstructure self-polishing antifouling coating comprises the following components in parts by weight: 20-30 parts of resin, 1-3 parts of microgel balls, 1-2 parts of a cross-linking agent, 2-3 parts of a plasticizer, 4-5 parts of cuprous oxide, 2-3 parts of copper pyrithione, 5-8 parts of terpene and 5-8 parts of an organic solvent. The invention utilizes the synergistic antifouling effect of the surface microstructure and the self-polishing antifouling agent, enhances the antifouling effect of the surface of the coating, greatly reduces the using amount of the antifouling agent in the formula of the existing self-polishing antifouling coating, and reduces the influence on the marine environment.

Description

Surface microstructure self-polishing antifouling coating and preparation method thereof

Technical Field

The invention relates to the technical field of marine antifouling, in particular to a surface microstructure self-polishing antifouling coating and a preparation method thereof.

Background

Marine fouling refers to the attachment and growth of marine organisms on the surface exposed in seawater, which causes great harm to marine ships and marine facilities, and not only increases the frictional resistance of ships, reduces the speed of navigation, increases the fuel consumption, and causes the aging damage, coating damage and steel corrosion of turbines, but also has the problems of influencing heat transfer, increasing the energy consumption of equipment and the like. According to foreign statistical analysis, marine biofouling can cause the fuel consumption of ships to increase by more than 40%, and the total amount of the marine biofouling and the marine biofouling is about 700 ten thousand tons of fuel consumed each year in the world, so that the economic loss can reach nearly billion dollars, and CO is increased₂21000 million tons of gas and SO₂560 million tons of gas.

The application of antifouling paints is recognized as the most economical, effective and commonly used method of antifouling. The global sea area of 1 month in 2008 prohibits the use of the antifouling paint containing organotin biocidal materials, and the prohibition of tributyltin antifouling paint promotes the environmental development of the antifouling paint towards the environment-friendly paint without organic tin, low cuprous oxide content, heavy metal bactericide and bactericide.

At present, the environment-friendly antifouling paint mainly comprises a self-polishing antifouling coating, a low-surface-energy fouling desorption antifouling paint, a microstructure surface coating, a hydrogel antifouling technology and the like, but the methods have different degrees of limitations, for example, the self-polishing antifouling coating has to use a certain amount of antifouling agent to achieve a better antifouling effect, and the antifouling agent generally has certain toxicity and can damage marine environment and ecology after being used for a long time; the coating of the desorptable elastomer has high cost and poor bonding force with the substrate, and generally needs an intermediate coating, so the coating is difficult; for coatings with surface microstructures, the deposition of marine microorganisms and minerals on the surface makes the microstructures easily destroyed and lose their antifouling effect due to the complexity of marine environment.

The Chinese patent literature discloses a self-polishing antifouling paint, the application publication number of which is CN105482702A, the self-polishing antifouling paint disclosed by the invention is composed of resin, an antifouling agent, graphene micro-sheets, pigment and filler, a dispersing agent, organic bentonite and an organic solvent, although the antifouling paint has the advantages of high antifouling efficiency and low VOC (volatile organic compounds), the using amount of the antifouling agent is up to 50-55 parts per 100 parts by mass, and the using amount of cuprous oxide is 30-35%, so that the marine environment can still be damaged when a large amount of the antifouling paint is used.

The invention discloses a method for manufacturing a bionic micro-nano structure surface material with a marine antifouling function, and the application publication number of the method is CN 101792534A.

Disclosure of Invention

The invention provides a self-polishing antifouling coating which can greatly reduce the using amount of an antifouling agent and continuously regenerate a surface microstructure, aiming at solving the problems that the existing self-polishing antifouling coating is large in using amount of a cuprous oxide antifouling agent, a surface microstructure coating is difficult to construct on the surface of a ship, and the coating is damaged due to the deposition of marine microorganisms and inorganic matters on the surface so that the antifouling effect is difficult to realize.

The invention also provides a preparation method of the surface microstructure self-polishing antifouling coating, which has simple steps, easily controlled process conditions and easy industrial production.

In order to achieve the purpose, the invention adopts the following technical scheme:

the surface microstructure self-polishing antifouling coating comprises the following components in parts by weight: 20-30 parts of resin, 1-3 parts of microgel balls, 1-2 parts of a cross-linking agent, 2-3 parts of a plasticizer, 4-5 parts of cuprous oxide, 2-3 parts of copper pyrithione, 5-8 parts of terpene and 5-8 parts of an organic solvent.

The cuprous oxide and the copper pyrithione are powdery solids and antifouling agents, and the terpene is flaky solids and is industrial products.

In the antifouling coating obtained by adopting the formula, the microgel spheres are dispersed in the coating, a microstructure with a convex surface is formed due to water absorption and expansion, the microstructure is continuously regenerated due to polishing of the polishing resin, the antifouling effect of the microstructure is continuously exerted, and the phenomenon that the microstructure is damaged and loses the antifouling effect due to the deposition of marine microorganisms and inorganic matters on the surface of the coating caused by a complex marine environment is avoided. 500-time observation of an ultra-depth-of-field microscope shows that in the artificial seawater soaking process, the surface of the self-polishing antifouling coating with the surface microstructure always has a convex microstructure along with continuous polishing of the coating, and the size of the microstructure is about 1-2 μm. An indoor chlorella antifouling performance evaluation test shows that the microstructure and the antifouling agent have a synergistic antifouling effect. The synergistic antifouling effect of the surface microstructure and the antifouling agent enhances the antifouling effect of the surface of the coating, and can reduce the using amount of the antifouling agent of the existing self-polishing coating by 50-60 percent, thereby reducing the influence on the marine environment. The cross-linking reaction of the resin and the micro gel balls in the surface micro-structure self-polishing antifouling coating enables the coating to form a network structure, improves the water resistance of the coating, and is beneficial to prolonging the service life of the coating.

Preferably, the resin is an acrylate resin.

Preferably, the acrylate resin is a ternary random copolymer synthesized by free radical polymerization of two acrylate monomers and acrylic acid.

Preferably, the preparation method of the resin comprises the following steps: firstly, adding a solvent into a four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, wherein the solvent is dimethylbenzene or a mixed solvent of the dimethylbenzene and n-butyl alcohol (the mass ratio is 7: 3-9: 1), the stirring speed is controlled to be 150-200 r/min, nitrogen is introduced to remove oxygen for 30 minutes, and then the solvent is heated to 85 ℃ and the constant nitrogen pressure is kept. And then dropwise adding the mixed solution of the acrylate monomer, acrylic acid and azodiisobutyronitrile into the solvent at a constant speed by using a semi-automatic dropwise adding device, wherein the dropwise adding time is controlled to be 3-4 hours. And after the dropwise addition is finished, continuing the heat preservation reaction for 3-4 hours.

Preferably, the microgel spheres are polyacrylamide-methacrylic acid microgel spheres; the particle size of the micro gel spheres is 0.5-0.7 mu m, and the excessive or insufficient particle size is not beneficial to exerting the antifouling effect of the microstructure of the antifouling coating.

Preferably, the polyacrylamide-methacrylic acid microgel spheres are prepared according to the following method:

introducing nitrogen into a first N-butyl alcohol solution dissolved with acrylamide, N' -methylene bisacrylamide, methacrylic acid, a dispersing agent and azobisisobutyronitrile under the condition of stirring, heating to 70-80 ℃, and reacting for 1-2 hours; and then continuously dropwise adding a second N-butyl alcohol solution dissolved with acrylamide, N' -methylene bisacrylamide, methacrylic acid, a dispersing agent and azobisisobutyronitrile into the mixture by a semi-automatic sample injection device within 8-10 h, and continuously reacting for 10-12 h under heat preservation after dropwise adding is finished to obtain the polyacrylamide-methacrylic acid microgel balls.

Preferably, the mass ratio of the acrylamide, the N, N' -methylene bisacrylamide, the methacrylic acid, the dispersant, the azobisisobutyronitrile and the N-butyl alcohol in the first N-butyl alcohol solution is (15-21): (0.14-0.16): (7.5-10.5): (30-45): (0.5-0.7): (920-950).

Preferably, the mass ratio of acrylamide and methacrylic acid in the second n-butanol solution to the corresponding components in the first n-butanol solution is 12: 1; the mass ratio of azodiisobutyronitrile in the second n-butanol solution to the corresponding components in the first n-butanol solution is 1: 0.6; the mass ratio of N, N' -methylene bisacrylamide in the second N-butanol solution to the corresponding components in the first N-butanol solution is 12.5: 1; the mass ratio of the dispersing agent in the second n-butanol solution to the corresponding components in the first n-butanol solution is 1 (0.2-0.3); the mass ratio of n-butanol in the second n-butanol solution to the corresponding components in the first n-butanol solution is 1 (1.2-1.6).

Preferably, the dispersing agent is a ternary random copolymer synthesized by free radical polymerization of acrylic acid and two monomers of methyl methacrylate, tert-butyl methacrylate, butyl acrylate and ethyl acrylate.

Preferably, the crosslinker is a trifunctional aziridine crosslinker.

Preferably, the plasticizer is dibutyl phthalate or chlorinated paraffin.

Preferably, the organic solvent is selected from one or a mixture of two of xylene and n-butanol.

Preferably, the mass ratio of the xylene to the n-butanol is 7: 3-9: 1.

A preparation method of a surface microstructure self-polishing antifouling coating comprises the following steps:

(1) dissolving the microgel balls into resin according to the proportion, and stirring at the rotating speed of 600 revolutions per minute for 10-20 minutes; the step adopts a lower rotating speed because the micro gel balls have better compatibility with resin and are easy to disperse;

(2) then adding copper pyrithione, and stirring at the rotating speed of 3000 rpm for 20-30 minutes; controlling the rotation rate to favor the dispersion of copper pyrithione, too low a rotation rate will result in larger particles of copper pyrithione present in the mixture, which are not uniformly dispersed; the rotating speed is too high, the temperature of the mixture rises too fast, the volatilization of the solvent is accelerated, and the dispersion is not facilitated;

(3) then adding plasticizer, terpene and cuprous oxide, and stirring at the rotating speed of 2000 rpm for 20-40 minutes; the rotating speed is controlled to be beneficial to uniformly dispersing the added components in the mixture, and the rotating speed is too low to cause non-uniform dispersion;

(4) finally, adding a cross-linking agent and an organic solvent, and stirring for 30-50 minutes at the rotating speed of 800 revolutions per minute to obtain a mixed coating; controlling the rotating speed is beneficial to the crosslinking reaction of the crosslinking agent, the microspheres and the resin; the rotation speed is too high, so that the volatilization of the solvent is accelerated, and the reaction is not facilitated;

(5) and coating the mixed coating on the surface of a material to be protected to obtain the self-polishing antifouling coating with the surface microstructure.

In the preparation method of the surface microstructure self-polishing antifouling coating, the stirring speed of each link is very critical, and the surface microstructure self-polishing antifouling coating with excellent performance can be obtained only by strictly following the process parameters.

Therefore, the invention has the following beneficial effects:

(1) the surface microstructure of the self-polishing antifouling coating has the synergistic antifouling effect of the surface microstructure and the antifouling agent, so that the antifouling effect of the surface of the coating is enhanced, the using amount of the antifouling agent in the formula of the existing self-polishing antifouling coating is greatly reduced, and the influence on the marine environment is reduced; the cross-linking reaction of the resin and the micro gel spheres enables the coating to form a network structure, improves the water resistance of the coating, and is beneficial to achieving a long-acting antifouling effect;

(2) the preparation method has simple steps, easily controlled process conditions and easy industrial production.

Detailed Description

The technical solution of the present invention is further specifically described below by way of specific examples.

In the present invention, all the equipment and materials are commercially available or commonly used in the art, and the methods in the following examples are conventional in the art unless otherwise specified.

Example 1

(1) Preparation of resin: firstly, adding 180g of xylene solvent into a 500mL four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, controlling the stirring speed to be 150 r/min, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 85 ℃, and keeping constant nitrogen pressure; then, a mixed solution of 117.2g of tert-butyl methacrylate, 40g of triisopropyl methacrylate silicone grease, 2.8g of acrylic monomer and 1.28g of azobisisobutyronitrile is dropwise added into the solvent at a constant speed by a semi-automatic dropwise adding device, wherein the dropwise adding time is controlled to be 3 hours; after the dropwise addition is finished, the reaction is continued for 4 hours under heat preservation;

(2) preparing microspheres: adding a mixed solution containing 1.8g of acrylamide, 0.016g of N, N' -methylene bisacrylamide, 0.9g of methacrylic acid, 3.6g of self-made dispersant, 0.06g of azobisisobutyronitrile and 110g of N-butyl alcohol into a 500mL four-neck flask provided with a stirrer, a reflux condenser, a semi-automatic sample injection device and a vent pipe, introducing nitrogen for 30 minutes to remove residual oxygen in the solution, heating to 75 ℃, and reacting for 1 hour to obtain white solution; then, a mixed solution containing 21.6g of acrylamide, 0.2g of N, N' -methylenebisacrylamide, 9.8g of methacrylic acid, 15.2g of a dispersing agent, 0.1g of azobisisobutyronitrile and 70g of N-butanol was continuously added dropwise to the reaction solution in 8 hours by a semi-automatic sample injection device; after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 10 hours to obtain stable white emulsion, namely microgel sphere solution; the particle size of the microgel balls is 0.5-0.6 mu m; the dispersant used in the step is ternary random copolymer synthesized by acrylic acid, methyl methacrylate and ethyl acrylate through free radical polymerization;

(3) preparing a surface microstructure self-polishing antifouling coating: firstly, dissolving 18g of microgel balls in 150g of resin, stirring at 600 rpm for 10-20 minutes to uniformly disperse the microspheres, then adding 12g of copper pyrithione into a container, stirring at 3000 rpm for 20-30 minutes, then sequentially adding 12g of dibutyl phthalate, 30g of terpene and 24g of cuprous oxide into the container, stirring at 2000 rpm for 30 minutes, finally adding 12g of trifunctional aziridine crosslinking agent and 42g of xylene, stirring at 800 rpm for reaction for 30 minutes, and finally coating the prepared mixture on the surface of a material to obtain the surface microstructure self-polishing antifouling coating.

Example 2

(1) Preparation of resin: firstly, adding a mixed solvent mass ratio (7:3) of 180 dimethylbenzene and n-butanol into a 500mL four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, controlling the stirring rotation speed to be 160 revolutions, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 85 ℃, and keeping constant nitrogen pressure; then, a mixed solution of 123g of methyl methacrylate, 54g of tributyl methacrylate, 3g of acrylic monomer and 1.28g of azobisisobutyronitrile is dropwise added into the solvent at a constant speed by a semi-automatic dropwise adding device, wherein the dropwise adding time is controlled to be 4 hours; after the dropwise addition is finished, the reaction is continued for 4 hours under heat preservation;

(2) preparing microspheres: a mixed solution containing 2.2g of acrylamide, 0.016g of N, N' -methylenebisacrylamide, 1.1g of methacrylic acid, 4g of a self-made dispersant, 0.06g of azobisisobutyronitrile and 100g of N-butanol is added into a 500mL four-neck flask provided with a stirrer, a reflux condenser, a semi-automatic sample injection device and a vent pipe, nitrogen is introduced for 30 minutes to remove residual oxygen in the solution, the temperature is raised to 70 ℃, and the solution turns white after reaction for 1.5 hours. Then, a mixed solution in which 26.4g of acrylamide, 0.2g of N, N' -methylenebisacrylamide, 12.1g of methacrylic acid, 18.8g of a dispersant, 0.1g of azobisisobutyronitrile and 80g of N-butanol were dissolved was continuously dropped into the reaction solution through a semi-automatic sampling device within 9 hours. After the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 11 hours to obtain stable white emulsion, namely microgel sphere solution; the particle size of the microgel balls is 0.5-0.6 mu m; the dispersant used in the step is ternary random copolymer synthesized by acrylic acid, methyl methacrylate and butyl acrylate through free radical polymerization;

(3) preparing a surface microstructure self-polishing antifouling coating: firstly, dissolving 9g of microspheres in 180g of resin, stirring at 600 rpm for 10-20 minutes to uniformly disperse the microspheres, then adding 18g of copper pyrithione into a container, stirring at 3000 rpm for 20-30 minutes, then sequentially adding 15g of chlorinated paraffin, 30g of terpene and 24g of cuprous oxide into the container, stirring at 2000 rpm for 30 minutes, finally adding 9g of trifunctional aziridine crosslinking agent and 30g of mixed solution of xylene and n-butanol (mass ratio of 9:1), stirring at 800 rpm for reaction for 40 minutes, and finally coating the prepared mixture on the surface of a material to obtain the surface microstructure self-polishing antifouling coating.

Example 3

(1) Preparation of resin: firstly, adding 180g of mixed solvent (mass ratio is 9:1) of dimethylbenzene and n-butanol into a four-neck flask provided with a stirrer, a reflux condensing device, a semi-automatic sampling device and a vent pipe, controlling the stirring speed to be 200 revolutions, introducing nitrogen to remove oxygen for 30 minutes, heating the solvent to 85 ℃, and keeping constant nitrogen pressure. Then, a mixed solution of 128.6g of tert-butyl methacrylate, 28.8g of triisopropyl silicone acrylate, 2.6g of acrylic monomer and 1.28g of azobisisobutyronitrile is dropwise added into the solvent at a constant speed by a semi-automatic dropwise adding device, wherein the dropwise adding time is controlled to be 3.5 hours; after the dropwise addition is finished, the reaction is continued for 3.5 hours under heat preservation;

(2) preparing microspheres: a mixed solution containing 2g of acrylamide, 0.016g of N, N' -methylenebisacrylamide, 1g of methacrylic acid, 5g of self-made dispersing agent, 0.06g of azobisisobutyronitrile and 105g of N-butyl alcohol is added into a 500mL four-neck flask provided with a stirrer, a reflux condenser, a semi-automatic sample injection device and a vent pipe, nitrogen is introduced for 30 minutes to remove residual oxygen in the solution, the temperature is raised to 80 ℃, and the solution turns white after reaction for 1.5 hours. Then, a mixed solution in which 24g of acrylamide, 0.2g of N, N' -methylenebisacrylamide, 13.2g of methacrylic acid, 18.2g of a dispersing agent, 0.1g of azobisisobutyronitrile and 75g of N-butanol are dissolved is continuously dropped into the reaction solution within 10 hours through a semi-automatic sample injection device; after the mixed solution is dripped, the mixed solution is continuously subjected to heat preservation reaction for 12 hours to obtain stable white emulsion, namely microgel sphere solution; the particle size of the microgel balls is 0.6-0.7 mu m; the dispersant used in the step is ternary random copolymer synthesized by acrylic acid, tert-butyl methacrylate and ethyl acrylate through free radical polymerization;

(3) preparing a surface microstructure self-polishing antifouling coating: firstly dissolving 12g of microspheres in 120g of resin, stirring for 10-20 minutes at 600 revolutions to uniformly disperse the microspheres, then adding 12g of copper pyrithione into a container, dispersing for 20-30 minutes at 3000 revolutions, then sequentially adding 12g of chlorinated paraffin, 42g of terpene and 30g of cuprous oxide into the container, dispersing for 30 minutes at 2000 revolutions, finally adding 6g of trifunctional aziridine crosslinking agent and 30g of mixed solution of xylene and n-butyl alcohol (mass ratio of 8:2), stirring for reacting for 50 minutes at 800 revolutions, and finally coating the prepared mixture on the surface of a material to obtain the self-polishing antifouling coating with the surface microstructure.

Example 4

Example 4 differs from example 1 in that: the surface microstructure self-polishing antifouling coating comprises the following components in proportion: 120g of resin, 6g of microgel balls, 6g of trifunctional aziridine crosslinking agent, 12g of dibutyl phthalate, 30g of cuprous oxide, 12g of copper pyrithione, 30g of terpene, 21g of xylene and 9g of n-butyl alcohol, and the rest processes are completely the same.

Example 5

Example 5 differs from example 1 in that: the surface microstructure self-polishing antifouling coating comprises the following components in proportion: 180g of resin, 15g of microgel balls, 12g of trifunctional aziridine crosslinking agent, 18g of dibutyl phthalate, 24g of cuprous oxide, 18g of copper pyrithione, 48g of terpene, 43.2g of xylene and 4.8g of n-butyl alcohol, and the rest processes are completely the same.

Comparative example 1

Comparative example 1 differs from example 1 in that no antifouling agent was added to the composition and the remaining process conditions were exactly the same.

Comparative example 2

Comparative example 2 differs from example 1 in that no microspheres were added to the composition; the rest process conditions are completely the same.

Comparative example 3

Comparative example 3 differs from example 1 in that the components are not added with microspheres and antifouling agent; the rest process conditions are completely the same.

Comparative example 4

Comparative example 4 differs from example 1 in that no crosslinking agent was added to the composition; the rest process conditions are completely the same.

The performance indexes of the surface microstructure self-polishing antifouling coatings prepared in the examples 1 to 5 and the antifouling coatings prepared in the comparative examples 1 to 4 are detected as follows:

1) the surface roughness test method comprises the following steps: drying the prepared coatings of examples 1-5 and comparative examples 1-4 at room temperature, then placing the coatings on an object stage of a super-depth-of-field microscope for observation under 500 times, taking 7 photos, calculating the surface roughness by using software carried by an instrument and taking an average value;

2) water resistance test method: immersing the dried coating examples 1-5 and comparative examples 1-4 in an artificial seawater tank with a cover, obliquely placing the coating close to the side to immerse the coating into the water, keeping a certain flow rate of the internal water body by a pump, starting a heating system, keeping the water temperature at 23-25 ℃ and the pH at 7.8-8.2, replacing the artificial seawater every 48 hours, taking out a test sample after 20 days, soaking the test sample in deionized water for 5 minutes, slightly wiping the test sample by a paper towel to remove residual water on the surface, checking the state of the surface coating, and evaluating the antifouling sample according to the water resistance grade standard of the surface 1.

TABLE 1 evaluation of Water resistance

Grade	Density of foaming	Grade	Size of blister
				0	Bubble-free	S0	No visible bubble under 10 times magnifying glass
1	Few, a few bubbles	S1	Visible bubbles under a 10 times magnifying glass
				2	With a small amount of bubbles	S2	Bubbles visible under normal vision
3	With a moderate amount of bubbles	S3	Bubble less than or equal to 0.5mm
				4	There are moreNumber of bubbles	S4	Bubbles of > 0.5mm and < 5mm
5	Dense bubble	S5	Bubble of not less than 5mm

3) The antifouling performance test method comprises the following steps:

shaking up chlorella solution cultured to exponential growth phase, pouring into a self-made sterilized algae culture container (the length, width and height of the inner dimension are 10cm), immersing prepared antifouling coatings of examples 1-5 and comparative examples 1-4 into the chlorella solution, placing the container obliquely and side by side, coating one side of the container downwards, covering a cover which is provided with air holes on the surface and is covered with a sterile sealing film, carefully moving the container into an illumination incubator, controlling the temperature at 25 ℃, the light-dark ratio at 12:12 and the illumination intensity at 3500lx, standing and culturing for 1 day, taking out the sample plate, laying flat, observing the adhesion condition of the surface by using an inverted fluorescence microscope after the surface of the sample plate is dried, taking fluorescence pictures of 7 points at different positions on the surface of the sample plate, the algae attachment area was calculated by image processing software and averaged, and the antifouling sample was evaluated with the attachment ratio as an evaluation index of antifouling performance with reference to the antifouling performance rating scale of table 2.

TABLE 2 antifouling Performance rating

Grade of antifouling Properties	Evaluation index	Chlorella attachment ratio (%)
			First stage	Good antifouling performance	≤0.5％
Second stage	General antifouling properties	More than 0.5 percent and less than or equal to 1.5 percent
			Three-stage	Poor antifouling performance	More than 1.5 percent and less than 3 percent
Four stages	Poor antifouling performance	≥3％

The results are shown in Table 3:

TABLE 3 test results

As can be seen from Table 3, the surface microstructure self-polishing antifouling coating has good water resistance, can greatly reduce the using amount of an antifouling agent, and has little influence on marine environment. Comparing the test data of example 1 and comparative examples 1, 2, 3, it can be seen that the claimed formulation is an integral and that the microgel spheres are critical to the formation of the microstructure; meanwhile, the micro gel balls and the antifouling agent play a synergistic antifouling role, the antifouling effect of the surface of the coating is enhanced, and the using amount of the antifouling agent in the formula of the existing self-polishing antifouling coating is reduced. Comparing example 1 with comparative example 4, the addition of the crosslinking agent improves the water resistance of the coating layer, which is advantageous for prolonging the service life of the coating layer.

The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.

Claims (10)

1. The self-polishing antifouling coating with the surface microstructure is characterized by comprising the following components in parts by weight: 20-30 parts of resin, 1-3 parts of microgel balls, 1-2 parts of a cross-linking agent, 2-3 parts of a plasticizer, 4-5 parts of cuprous oxide, 2-3 parts of copper pyrithione, 5-8 parts of terpene and 5-8 parts of an organic solvent.

2. The surface microstructure self-polishing antifouling coating of claim 1, wherein the resin is an acrylate resin.

3. The surface microstructure self-polishing antifouling coating as claimed in claim 2, wherein the acrylate resin is a ternary random copolymer synthesized by two acrylate monomers and acrylic acid through a free radical polymerization reaction.

4. The surface microstructure self-polishing antifouling coating according to claim 1, wherein the microgel spheres are polyacrylamide-methacrylic acid microgel spheres; the particle size of the micro gel ball is 0.5-0.7 mu m.

5. The surface microstructure self-polishing antifouling coating according to claim 4, wherein the polyacrylamide-methacrylic acid microgel spheres are prepared according to the following method:

introducing nitrogen into a first N-butyl alcohol solution dissolved with acrylamide, N' -methylene bisacrylamide, methacrylic acid, a dispersing agent and azobisisobutyronitrile under the condition of stirring, heating to 70-80 ℃, and reacting for 1-2 hours; continuously dropwise adding a second N-butyl alcohol solution dissolved with acrylamide, N' -methylene bisacrylamide, methacrylic acid, a dispersing agent and azobisisobutyronitrile in 8-10 h through a semi-automatic sample injection device, and continuously reacting for 10-12 h under heat preservation after dropwise adding is finished to obtain polyacrylamide-methacrylic acid microgel spheres;

the adding mass ratio of acrylamide, N' -methylene bisacrylamide, methacrylic acid, a dispersing agent, azobisisobutyronitrile and N-butyl alcohol in the first N-butyl alcohol solution is (15-21): 0.14-0.16): 7.5-10.5): 30-45: (0.5-0.7): 920-950;

the mass ratio of acrylamide and methacrylic acid in the second n-butanol solution to the corresponding components in the first n-butanol solution is 12: 1; the mass ratio of azodiisobutyronitrile in the second n-butanol solution to the corresponding components in the first n-butanol solution is 1: 0.6; the mass ratio of N, N' -methylene bisacrylamide in the second N-butanol solution to the corresponding components in the first N-butanol solution is 12.5: 1; the mass ratio of the dispersing agent in the second n-butanol solution to the corresponding components in the first n-butanol solution is 1 (0.2-0.3); the mass ratio of n-butanol in the second n-butanol solution to the corresponding components in the first n-butanol solution is 1 (1.2-1.6).

6. The surface microstructure self-polishing antifouling coating according to claim 1, wherein the crosslinking agent is a trifunctional aziridine crosslinking agent.

7. The surface microstructure self-polishing antifouling coating according to claim 1, wherein the plasticizer is dibutyl phthalate or chlorinated paraffin.

8. The self-polishing antifouling coating with surface microstructure as claimed in claim 1, wherein the organic solvent is selected from one or a mixture of xylene and n-butanol.

9. The surface microstructure self-polishing antifouling coating as claimed in claim 8, wherein the mass ratio of xylene to n-butanol is 7: 3-9: 1.

10. A method of producing a surface microstructured self-polishing anti-soiling coating according to any of claims 1 to 9, characterized in that it comprises the following steps:

(1) dissolving the microgel balls into resin according to the proportion, and stirring at the rotating speed of 600 revolutions per minute for 10-20 minutes;

(2) then adding copper pyrithione, and stirring at the rotating speed of 3000 rpm for 20-30 minutes;

(3) then adding plasticizer, terpene and cuprous oxide, and stirring at the rotating speed of 2000 rpm for 20-40 minutes;

(4) finally, adding a cross-linking agent and an organic solvent, and stirring for 30-50 minutes at the rotating speed of 800 revolutions per minute to obtain a mixed coating;

(5) and coating the mixed coating on the surface of a material to be protected to obtain the self-polishing antifouling coating with the surface microstructure.