Flexible wave-transparent antifouling paint as well as preparation method and application thereof

Abstract

The invention relates to the technical field of antifouling paint, in particular to flexible wave-transparent antifouling paint as well as a preparation method and application thereof. On the basis of the existing antifouling paint, the wave-transparent performance of the paint is improved by adding the hollow glass beads, and the chlorosulfonated polyethylene is further added, so that the matching performance between the paint and an antenna housing is improved, and finally, the antifouling paint which is relatively good in wave-transparent performance and excellent in matching performance with the antenna housing is obtained. Therefore, the technical problem of poor wave permeability of the existing antifouling paint is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antifouling coatings, and further relates to a flexible wave-transparent antifouling coating, a preparation method and application thereof. BACKGROUND

[0002] The harm caused by marine biofouling to ships and underwater facilities is attracting more and more attention. Marine biofouling will increase the resistance of ships sailing, resulting in reduced speed and increased fuel consumption. On the other hand, it will accelerate the corrosion of metal and shorten the service life of ships and marine facilities. Among the methods for solving marine biofouling, the use of antifouling coatings is the most widely used and effective measure.

[0003] Antifouling coatings have the effect of preventing marine organisms from adhering. The principle is that as the resin in the coating layer slowly hydrolyzes, the antifouling agent with the effect of killing marine organisms in the coating layer is gradually released, thereby achieving the effect of inhibiting the adhesion of marine organisms.

[0004] The radome is a medium soft shell for protecting the antenna, and needs to have good wave-transparent performance to achieve high transmission and low loss of electromagnetic waves in the medium soft shell. In the field of underwater electromagnetic wave communication, marine fouling organisms such as barnacles, mussels, and seaweed will adhere and grow on the surface of the radome, greatly affecting the wave-transparent performance. The commonly used antifouling agents, cuprous oxide and cuprous thiocyanate, have poor wave-transparent performance and require a high amount of addition. When prepared into antifouling coatings and coated on the surface of the radome, although they can prevent marine organisms from adhering, the low wave-transparent performance of the coating itself also reduces the transmission efficiency of electromagnetic waves in the radome medium soft shell. SUMMARY

[0005] In order to solve the technical problem of poor wave-transparent performance of the existing antifouling coatings using cuprous oxide and cuprous thiocyanate as antifouling agents, the present application provides a flexible wave-transparent antifouling coating, a preparation method and application thereof.

[0006] On the basis of the existing antifouling coatings, the present application adds hollow glass microspheres to improve the wave-transparent performance of the coating, thereby obtaining an antifouling coating with good wave-transparent performance. However, this antifouling coating cannot form a good match with the radome. Therefore, the present application further adds chlorosulfonated polyethylene to the antifouling coating, thereby improving the matching performance between the coating and the radome, and ultimately obtaining an antifouling coating with good wave-transparent performance and excellent matching performance with the radome.

[0007] The present application aims to provide a flexible wave-transparent antifouling coating.

[0008] The flexible wave-transparent antifouling coating contains resin, filler, chlorosulfonated polyethylene solution, anti-settling agent, diluent, hollow glass microspheres, and antifouling agent.

[0009] The flexible wave-transparent antifouling coating adds hollow glass beads and chlorosulfonated polyethylene solution to the existing antifouling coating. The addition of hollow glass beads significantly improves the wave-transparent performance of the coating. The addition of chlorosulfonated polyethylene solution not only improves the matching performance between the coating and the radome, but also improves the wave-transparent performance of the coating to a certain extent.

[0010] The "good matching performance between the coating and the radome" means that the coating deforms with the substrate and does not crack due to large deformation of the substrate. In summary, the coating does not peel off from the substrate due to changes in the external environment, and is firmly attached to the surface of the substrate to form a good match.

[0011] The resin can be selected from any one or more than one resin that can be used in antifouling coatings. As a preferred solution, the resin is selected from at least one of zinc acrylate resin, copper acrylate resin, and disproportionated rosin resin. Among them, the zinc acrylate resin can be prepared by any one of the methods disclosed in CN103897092B. Compared with other available resins, the resin of the preferred solution can gradually dissolve in water, and the antifouling agent components in the coating are fully released, preventing marine fouling organisms from attaching and growing on its surface.

[0012] Among them, rosin resin is a natural product; the molecular weight of zinc acrylate resin and copper acrylate resin is between 5000 and 20000, preferably between 10000 and 16000.

[0013] The solid content of the resin can be selected within a wide range. As a preferred solution, the solid content of the resin is 40-60wt%, preferably 48-52wt%.

[0014] The filler can be selected from any one or more than one filler that can be used in antifouling coatings. As a preferred solution, the filler is selected from at least one of zinc oxide, polytetrafluoroethylene powder, talc powder, feldspar powder, and silicon dioxide; more preferably, polytetrafluoroethylene powder.

[0015] The amount of the filler can be selected within a wide range. As a preferred solution, the amount of the filler is 1-5 parts by weight based on 25 parts by weight of the resin; for example, it can be 2 parts by weight, 3 parts by weight, 4 parts by weight, and any two values between 1 and 5 parts by weight and any interval between the two values.

[0016] The solvent of the chlorosulfonated polyethylene solution can be selected within a wide range. As a preferred solution, the solvent of the chlorosulfonated polyethylene solution is selected from at least one of xylene, trimethylbenzene, butyl acetate, and methyl isobutyl ketone.

[0017] The solid content of the chlorosulfonated polyethylene solution can be selected within a wide range. As a preferred solution, the solid content of the chlorosulfonated polyethylene solution is 15-25 wt%, such as 15 wt%, 18 wt%, 20 wt%, 23 wt%, 25 wt%, and any two values and the interval between any two values within 15-25 wt%, and more preferably 20 wt%.

[0018] The number average molecular weight of the chlorosulfonated polyethylene resin can be selected within a wide range. However, the higher the molecular weight of the chlorosulfonated polyethylene resin, the more difficult it is to dissolve, and the production process is difficult. The viscosity of the coating after dissolving the high molecular weight resin is larger, and more solvent needs to be added, resulting in a lower solid content of the coating. The lower the molecular weight, the better the processability, but it is easy to cause the strength of the coating to decrease. Therefore, as a preferred solution, the number average molecular weight of the chlorosulfonated polyethylene resin is 30000-100000, such as 40000, 50000, 60000, 70000, 80000, 90000, and any two values and the interval between any two values within 30000-100000, and more preferably 40000-70000.

[0019] The chlorine content of the chlorosulfonated polyethylene can be selected within a wide range. As a preferred solution, the chlorine content of the chlorosulfonated polyethylene is 20-50 wt%, and more preferably 30-40 wt%.

[0020] The amount of the chlorosulfonated polyethylene solution can be selected within a wide range. The amount of the chlorosulfonated polyethylene solution will significantly affect the performance of the antifouling coating. If the amount of the chlorosulfonated polyethylene solution is too low, the flexibility and wave permeability of the antifouling coating will decrease. If the amount of the chlorosulfonated polyethylene solution is increased, the wave permeability and flexibility of the coating will increase, but the antifouling performance will decrease; the possible reason is that the chlorosulfonated polyethylene does not hydrolyze when it comes into contact with seawater, and if the amount is too high, the hydrolysis effect of the coating will be poor, the release rate of the antifouling agent will be insufficient, and marine organisms will be attached. Therefore, as a preferred solution, the amount of the chlorosulfonated polyethylene solution is 40-55 parts by weight based on 25 parts by weight of the resin; for example, it can be 40 parts by weight, 42 parts by weight, 45 parts by weight, 48 parts by weight, 50 parts by weight, 52 parts by weight, 55 parts by weight, and any two values and the interval between any two values within 40-55 parts by weight.

[0021] The anti-settling agent can be selected from any one or more than one anti-settling agent that can be used in antifouling coatings. As a preferred solution, the anti-settling agent is selected from at least one of polyamide wax, organic bentonite, and fumed silica.

[0022] The amount of the anti-settling agent can be selected within a wide range. As a preferred embodiment, the amount of the anti-settling agent is 0.5-1 parts by weight, for example 0.5 parts by weight, 0.7 parts by weight, 1 part by weight, and any two values between 0.5 and 1 parts by weight and the interval between any two values.

[0023] The diluent can be selected from any one or more of the diluents that can be used in antifouling paints. As a preferred embodiment, the diluent is at least one of xylene, trimethylbenzene, butyl acetate, and methyl isobutyl ketone.

[0024] The amount of the diluent can be selected within a wide range. As a preferred embodiment, the amount of the diluent is 3-10 parts by weight, for example 3 parts by weight, 7 parts by weight, 10 parts by weight, and any two values between 3 and 10 parts by weight and the interval between any two values, based on 25 parts by weight of the resin.

[0025] The particle size of the hollow glass microbeads can be selected within a wide range. However, if the particle size of the hollow glass microbeads is too large, the shielding performance of the coating layer will decrease, moisture will penetrate into the interface between the coating layer and the substrate, and the matching performance of the coating layer will decrease. If the particle size of the hollow glass microbeads is too small, the specific surface area will be too large, and the overall flowability of the coating will be worse. Therefore, as a preferred embodiment, the particle size of the hollow glass microbeads is 5-100 μm, preferably 20-50 μm.

[0026] The wall thickness of the hollow glass microbeads is usually 1-2 μm.

[0027] The amount of the hollow glass microbeads can be selected within a wide range. As a preferred embodiment, the amount of the hollow glass microbeads is 1-8 parts by weight, for example 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, and any two values between 1 and 8 parts by weight and the interval between any two values, based on 100 parts by weight of the flexible, wave-transparent, antifouling coating.

[0028] The antifouling agent can be selected from any one or more than one antifouling agent that can be used in antifouling paint. On the basis of the existing antifouling paint using cuprous oxide, cuprous thiocyanate and other copper salts as antifouling agents, the addition of hollow glass microbeads can improve the wave permeability of the antifouling paint, but the wave permeability needs to be further improved. In the present application, a specific organic antifouling agent is used as the main antifouling agent, and a specific organic antifouling agent is used as the auxiliary antifouling agent. Through the cooperation of the main antifouling agent and the auxiliary antifouling agent, good antifouling effect is achieved under the condition of less use of antifouling agent. Compared with the antifouling paint added with cuprous oxide, cuprous thiocyanate and other copper salt antifouling agents, the antifouling agent used in the antifouling paint with two or more organic antifouling agents is significantly reduced in amount and further improves the wave permeability. Therefore, as a preferred solution, the antifouling agent is selected from two or more organic antifouling agents. As a more preferred solution, the antifouling agent comprises a main antifouling agent and an auxiliary antifouling agent.

[0029] The main antifouling agent is selected from at least one of pyridine triphenyl boron, bromopyrrole nitrile and 4,5-dichloro-N-octyl-4-isothiazoline-3-ketone.

[0030] The auxiliary antifouling agent is selected from at least one of chlorothalonil (2,4,5,6-tetrachloro-1,3-benzene dicyan), copper pyrithione, zinc pyrithione and zineb (zinc ethylene bis dithiocarbamate).

[0031] Through the synergistic effect between the main antifouling agent and the auxiliary antifouling agent, the antifouling performance of the antifouling paint is significantly improved, and the amount of the antifouling agent is reduced. In addition, the main antifouling agent and the auxiliary antifouling agent have less effect on the wave permeability than the heavy metal antifouling agent such as cuprous oxide; that is, under the condition that the other components and the amount of the antifouling paint remain unchanged, the wave permeability of the paint can be improved by replacing the cuprous oxide, cuprous thiocyanate and other copper salt antifouling agents with an equal amount of the antifouling agent composed of the main antifouling agent and the auxiliary antifouling agent.

[0032] The mass ratio of the main antifouling agent to the auxiliary antifouling agent in the antifouling agent can be selected within a wide range. As a preferred solution, the mass ratio of the main antifouling agent to the auxiliary antifouling agent in the antifouling agent is 10: (1-10), for example, it can be 10:1, 10:2, 10:3, 10:4, 10:5, 10:6, 10:7, 10:8, 10:9, 10:10, and when the mass ratio of the main antifouling agent is 10, the mass ratio of the auxiliary antifouling agent is any value between 1 and 10 and any interval between any two values; more preferably, it is 10: (1-5).

[0033] The particle size of the antifouling agent can be selected within a wide range. As a preferred solution, the particle size of the antifouling agent is not more than 80 μm.

[0034] The amount of the antifouling agent can be selected within a wide range. As a preferred solution, the amount of the antifouling agent is 15-20 parts by weight, for example 15 parts by weight, 18 parts by weight, 20 parts by weight, and any two values between 15 and 20 and the interval between any two values, based on 25 parts by weight of the resin.

[0035] As a preferred solution, the antifouling coating is composed of the following components, based on 100 parts by weight of the total weight of the antifouling coating: Resin 15-25 parts by weight; Filler 1-5 parts by weight; Chlorosulfonated polyethylene solution 40-55 parts by weight; Anti-settling agent 0.5-1 parts by weight; Diluent 3-10 parts by weight; Hollow glass microbeads 1-8 parts by weight; Antifouling agent 15-20 parts by weight.

[0036] The antifouling coating can be prepared by existing methods, for example, one-step method. However, compared with the antifouling coating prepared by one-step method, the antifouling coating prepared by two-step method (adding hollow glass microbeads later) has higher wave transmission performance.

[0037] The second object of the present application is to provide a preparation method of the antifouling coating according to the first object of the present application.

[0038] The preparation method comprises: In the first step, the components except for the hollow glass microbeads are stirred uniformly and ground to a fineness of ≤80 μm; In the second step, the hollow glass microbeads are added and stirred uniformly to obtain the antifouling coating.

[0039] The third object of the present application is to provide the surface antifouling application of the antifouling coating according to the first object of the present application or the antifouling coating prepared by the method according to the second object of the present application in the field of underwater electromagnetic wave communication.

[0040] Compared with the prior art, the present application has the following advantages: The present application adds hollow glass microbeads and chlorosulfonated polyethylene on the basis of resin, filler, anti-settling agent, diluent and antifouling agent, and finally obtains an antifouling coating with better wave transmission performance and excellent matching performance with radomes.

[0041] The antifouling coating provided by the present application can form a good match with the materials used in underwater electromagnetic wave communication, such as radomes, has good adhesion, no powdering and cracking phenomenon during coating application, no gelation phenomenon during coating storage, is easy to construct, and the prepared coating has both antifouling and wave transmission performance, and has high practical application value. DETAILED DESCRIPTION

[0042] The following will be specifically described in combination with specific examples. It is necessary to point out here that the following examples are only used for further illustration of the present application and cannot be understood as a limitation on the protection scope of the present application. Some non-essential improvements and adjustments made by those skilled in the art according to the content of the present application still fall within the protection scope of the present application.

[0043] The raw materials used in the examples and comparative examples of the present application are all commercially available products except for the zinc acrylate resin.

[0044] The zinc acrylate resin is prepared by the method described in paragraphs 0070-0074 of the specification of Chinese patent CN103897092B; The pyridine triphenyl boron is from Macklin; The chlorothalonil is from Balingwei Technology Co., Ltd.; The chlorosulfonated polyethylene is from CSM30 (4010); The polyamide wax is from Hainms P200X; The hollow glass microbeads have a particle size of 20 μm; The solvent of the chlorosulfonated polyethylene solution is xylene, and the solid content is 20 wt%.

[0045] Example 1 In the first step, 20 parts of zinc acrylate resin, 18 parts of pyridine triphenyl boron, 2 parts of chlorothalonil, 3 parts of zinc oxide, 45 parts of chlorosulfonated polyethylene solution, 0.5 part of polyamide wax, 3 parts of xylene, and 3.5 parts of butyl acetate are mixed and dispersed at 500 r / min for 0.5 h, and then ground to a fineness of 70 μm.

[0046] In the second step, 5 parts of hollow glass microbeads are added, and then dispersed at 500 r / min for 0.5 h to obtain an antifouling coating with a fineness of 70 μm.

[0047] The coating is solidified on the surface of the medium soft shell to form a coating layer, and the test results of the coating layer are shown in Table 1.

[0048] Example 2 In the first step, 8 parts of disproportionated rosin resin, 10 parts of copper acrylate resin, 15 parts of bromopyrrole nitrile, 3 parts of copper pyrithione, 2 parts of talc, 50 parts of chlorosulfonated polyethylene solution, 1 part of organic bentonite, 2 parts of trimethylbenzene, and 1 part of methyl isobutyl ketone are mixed and dispersed at 500 r / min for 0.5 h, and then ground to a fineness of 75 μm.

[0049] In the second step, 8 parts of hollow glass microbeads are added, and then dispersed at 500 r / min for 0.5 h to obtain an antifouling coating with a fineness of 70 μm.

[0050] The medium is solidified on the surface of the soft shell into a coating layer, and the test results of the coating layer are shown in Table 1.

[0051] Example 3 In the first step, 25 parts by weight of disproportionated rosin resin, 10 parts by weight of 4, 5-dichloro-N-octyl-4-isothiazolin-3-one, 5 parts by weight of zinc omethioate, 3 parts by weight of polytetrafluoroethylene powder, 2 parts by weight of silicon dioxide, 40 parts by weight of chlorosulfonated polyethylene solution, 0.7 parts by weight of fumed silica, and 9.3 parts by weight of ethyl acetate are mixed and dispersed at 500 r / min for 0.5 h, and then ground to a fineness of 70 μm.

[0052] In the second step, 5 parts by weight of hollow glass microbeads are added, and the mixture is again dispersed at 500 r / min for 0.5 h to obtain an antifouling coating with a fineness of 70 μm.

[0053] The medium is solidified on the surface of the soft shell into a coating layer, and the test results of the coating layer are shown in Table 1.

[0054] Example 4 In the first step, 5 parts by weight of copper acrylate resin, 10 parts by weight of disproportionated rosin resin, 6 parts by weight of pyridine triphenyl boron, 6 parts by weight of 4, 5-dichloro-N-octyl-4-isothiazolin-3-one, 3 parts by weight of chlorothalonil, 3 parts by weight of zinc omethioate, 4 parts by weight of zinc oxide, 55 parts by weight of chlorosulfonated polyethylene solution, 1 part by weight of organic bentonite, and 6 parts by weight of mesitylene are mixed and dispersed at 500 r / min for 0.5 h, and then ground to a fineness of 75 μm.

[0055] In the second step, 1 part by weight of hollow glass microbeads is added, and the mixture is again dispersed at 500 r / min for 0.5 h to obtain an antifouling coating with a fineness of 70 μm.

[0056] The medium is solidified on the surface of the soft shell into a coating layer, and the test results of the coating layer are shown in Table 1.

[0057] Example 5 In the first step, 25 parts by weight of disproportionated rosin resin, 10 parts by weight of 4, 5-dichloro-N-octyl-4-isothiazolin-3-one, 5 parts by weight of zinc omethioate, 3 parts by weight of polytetrafluoroethylene powder, 2 parts by weight of silicon dioxide, 5 parts by weight of chlorosulfonated polyethylene solution, 0.7 parts by weight of fumed silica, and 9.3 parts by weight of ethyl acetate are mixed and dispersed at 500 r / min for 0.5 h, and then ground to a fineness of 70 μm.

[0058] In the second step, 5 parts by weight of hollow glass microbeads are added, and the mixture is again dispersed at 500 r / min for 0.5 h to obtain an antifouling coating with a fineness of 70 μm.

[0059] The medium is solidified on the surface of the soft shell into a coating layer, and the test results of the coating layer are shown in Table 1.

[0060] Example 6 First step, by weight parts, dismutation rosin resin 25 parts, 4,5-dichloro-N-octyl-4- isothiazolin-3-ketone 10 parts, Zineb 5 parts, polytetrafluoroethylene powder 3 parts, silicon dioxide 2 parts, chlorosulfonated polyethylene solution 70 parts, fumed silica 0.7 parts, ethyl acetate 9.3 parts mixed after stirring dispersion at 500 r / min for 0.5 h, grinding to fineness 70 μm.

[0061] Second step, by weight parts, adding hollow glass microspheres 5 parts, stirring dispersion again at 500 r / min for 0.5 h, preparing anti-fouling coating with fineness 70 μm.

[0062] Curing into coating on the surface of medium soft shell, the test results of the coating are shown in Table 1.

[0063] Example 7 First step, by weight parts, dismutation rosin resin 25 parts, 4,5-dichloro-N-octyl-4- isothiazolin-3-ketone 15 parts, polytetrafluoroethylene powder 3 parts, silicon dioxide 2 parts, chlorosulfonated polyethylene solution 40 parts, fumed silica 0.7 parts, ethyl acetate 9.3 parts mixed after stirring dispersion at 500 r / min for 0.5 h, grinding to fineness 70 μm.

[0064] Second step, by weight parts, adding hollow glass microspheres 5 parts, stirring dispersion again at 500 r / min for 0.5 h, preparing anti-fouling coating with fineness 70 μm.

[0065] Curing into coating on the surface of medium soft shell, the test results of the coating are shown in Table 1.

[0066] Example 8 First step, by weight parts, dismutation rosin resin 25 parts, Zineb 15 parts, polytetrafluoroethylene powder 3 parts, silicon dioxide 2 parts, chlorosulfonated polyethylene solution 40 parts, fumed silica 0.7 parts, ethyl acetate 9.3 parts mixed after stirring dispersion at 500 r / min for 0.5 h, grinding to fineness 70 μm.

[0067] Second step, by weight parts, adding hollow glass microspheres 5 parts, stirring dispersion again at 500 r / min for 0.5 h, preparing anti-fouling coating with fineness 70 μm.

[0068] Curing into coating on the surface of medium soft shell, the test results of the coating are shown in Table 1.

[0069] Example 9 First step, by weight parts, dismutation rosin resin 25 parts, cuprous oxide 15 parts, polytetrafluoroethylene powder 3 parts, silicon dioxide 2 parts, chlorosulfonated polyethylene solution 40 parts, fumed silica 0.7 parts, ethyl acetate 9.3 parts mixed after stirring dispersion at 500 r / min for 0.5 h, grinding to fineness 70 μm.

[0070] Second step, add 5 parts of hollow glass beads by weight fraction, stir and disperse again at 500 r / min for 0.5 h, and prepare an antifouling coating with a fineness of 70 μm.

[0071] Solidify on the surface of the medium soft shell into a coating layer, and the test results of the coating layer are shown in Table 1.

[0072] Example 10 Different from Example 1, the antifouling coating is prepared by grinding after mixing all components uniformly in one step. The rest of the conditions are the same.

[0073] Comparative Example 1 Different from Example 9, it does not contain chlorosulfonated polyethylene solution. The rest of the conditions are the same.

[0074] Comparative Example 2 Different from Example 9, it does not add hollow glass beads and does not contain chlorosulfonated polyethylene solution. The rest of the conditions are the same.

[0075] Performance test The antifouling coatings prepared in Examples 1-10 and the coatings prepared in Comparative Examples 1-2 are respectively solidified on the surface of the medium soft shell into a coating layer. The coating layer is tested for electric constant, dielectric loss, shallow sea immersion, and flexibility. The test results are shown in Table 1.

[0076] The flexibility is tested by using “GB / T 1731-2020 Paint film, putty film flexibility determination method”. The flexibility of 1 mm, 2 mm, and 5 mm means that the paint film is bent on a column with a diameter of 1 mm, 2 mm, and 5 mm, and the paint film does not crack or damage, which means that the paint film flexibility is 1 mm, 2 mm, and 5 mm. Among them, the smaller the value of flexibility, the better the flexibility, for example, the flexibility of 1 mm is better than the flexibility of 2 mm.

[0077] The shallow sea immersion test is tested by using “GB / T 5370-2007 Antifouling paint sample shallow sea immersion test method”.

[0078] Dielectric constant and dielectric loss: tested by using a vector network analyzer, frequency 10 GHz. Reference standard IEC61189-2-721.

[0079] Table 1

[0080] Compared with Comparative Example 2, the dielectric constant and dielectric loss of Comparative Example 1 are both reduced (the wave permeability is improved). The only difference between Comparative Example 1 and Comparative Example 2 is that Comparative Example 1 adds hollow glass beads on the basis of Comparative Example 2. It is indicated that the addition of hollow glass beads can improve the wave permeability of the coating; however, the obtained anti-fouling coating cannot form good matching performance with the radome (“cracking and falling off”, reduced flexibility).

[0081] Compared with Comparative Example 1, the dielectric constant of Example 9 is reduced (the wave permeability is improved), the coating changes from “cracking and falling off” to “no physical damage”, and the flexibility is improved (the matching performance is better). Hollow glass beads are added in the coatings of Example 9 and Comparative Example 1, and the addition amount of the hollow glass beads is the same. The difference between Example 9 and Comparative Example 1 is that Example 9 adds chlorosulfonated polyethylene solution. It is indicated that the further addition of chlorosulfonated polyethylene solution in the anti-fouling coating containing hollow glass beads can not only improve the wave permeability of the coating, but also improve the matching performance of the coating with the radome (the coating changes from “cracking and falling off” to “no physical damage”, and the flexibility is improved).

[0082] The difference between Examples 3, 5 and 6 is only that the addition amount of the chlorosulfonated polyethylene solution is different; among them, the addition amount of the chlorosulfonated polyethylene solution in Examples 5, 3 and 6 is increased in turn. The dielectric constant and dielectric loss of Examples 5, 3 and 6 are reduced in turn, the flexibility of Examples 3 and 6 is higher than that of Example 5, and (in Examples 5, 3 and 6, the wave permeability and flexibility of Example 6 are the best); however, the coating surface of Example 6 appears marine bio-attachment (the coating surfaces of Examples 5 and 3 are free of marine bio-attachment). It is indicated that with the increase of the amount of chlorosulfonated polyethylene solution, the wave permeability and flexibility of the coating are improved, but the anti-fouling performance is reduced.

[0083] The difference between Examples 3, 7, 8 and 9 is only that the anti-fouling agents used are different. Among them, the surfaces of Examples 7, 8 and 9 are attached with marine organisms, and the surface of Example 3 is free of marine bio-attachment; compared with Examples 7, 8 and 9, the dielectric constant and dielectric loss of Example 3 are reduced. It is indicated that the anti-fouling coating prepared by using the anti-fouling agent of Example 3 has better anti-fouling effect and better wave permeability.

[0084] The difference between Example 1 and Example 10 is only that the preparation methods are different. Compared with Example 1, the dielectric constant and dielectric loss of Example 10 are increased (the wave permeability is reduced). It is indicated that under the condition that the raw materials are the same, the preparation method of Example 1 can further improve the wave permeability of the coating compared with the preparation method of Example 10.

[0085] As can be seen from the test results of the examples in Table 1, the coating provided by the present application has reduced dielectric constant and dielectric loss. Replacing the preferred anti-fouling agent (selected from two or more organic anti-fouling agents) with heavy metal cuprous oxide, the anti-fouling coating prepared by one-step method, and the absence of hollow glass microsphere component, will increase the dielectric constant and dielectric loss of the coating; the anti-fouling coating with low content of chlorosulfonated polyethylene solution has a hard texture, which is difficult to match the deformation of the substrate, and the coating on the surface of the soft shell medium substrate cracks.

Claims

1. A flexible wave-transparent antifouling coating, comprising a resin, a filler, a chlorosulfonated polyethylene solution, an anti-settling agent, a diluent, hollow glass microbeads, and an antifouling agent. 2.The flexible wave-transparent antifouling coating according to claim 1, wherein the resin is at least one selected from the group consisting of zinc acrylate resin, copper acrylate resin, and disproportionated rosin resin; or / and, the solid content of the resin is 40-60 wt%, preferably 48-52 wt%. 3.The flexible wave-transparent antifouling coating according to claim 1, wherein the filler is at least one selected from the group consisting of zinc oxide, polytetrafluoroethylene powder, talc powder, feldspar powder, and silicon dioxide, preferably polytetrafluoroethylene powder; or / and, the amount of the filler is 1-5 parts by weight based on 25 parts by weight of the resin. 4.The flexible wave-transparent antifouling coating according to claim 1, wherein the amount of the chlorosulfonated polyethylene solution is 40-55 parts by weight based on 25 parts by weight of the resin; or / and, the solvent of the chlorosulfonated polyethylene solution is at least one selected from the group consisting of xylene, trimethylbenzene, butyl acetate, and methyl isobutyl ketone; or / and, the solid content of the chlorosulfonated polyethylene solution is 15-25 wt%, more preferably 20 wt%; or / and, the number average molecular weight of the chlorosulfonated polyethylene resin is 30,000-100,000, more preferably 40,000-70,000; or / and, the chlorine content of the chlorosulfonated polyethylene is 20-50 wt%, more preferably 30-40 wt%. 5.The flexible wave-transparent antifouling coating according to claim 1, wherein the anti-settling agent is at least one selected from the group consisting of polyamide wax, organic bentonite, and fumed silica; or / and, the amount of the anti-settling agent is 0.5-1 parts by weight based on 25 parts by weight of the resin. 6.The flexible wave-transparent antifouling coating according to claim 1, wherein the diluent is at least one selected from the group consisting of xylene, trimethylbenzene, butyl acetate, and methyl isobutyl ketone; or / and, the amount of the diluent is 3-10 parts by weight based on 25 parts by weight of the resin. 7.The flexible wave-transparent antifouling coating according to claim 1, wherein the particle size of the hollow glass microbeads is 5-100 μm, preferably 20-50 μm; or / and, the amount of the hollow glass microbeads is 1-8 parts by weight based on 100 parts by weight of the flexible wave-transparent antifouling coating. 8.The flexible wave-transparent antifouling coating according to claim 1, wherein the amount of the antifouling agent is 15-20 parts by weight based on 25 parts by weight of the resin; the particle size of the antifouling agent is not more than 80 μm; or / and, the antifouling agent is selected from two or more kinds of organic antifouling agents; preferably, the antifouling agent comprises a main antifouling agent and an auxiliary antifouling agent; the mass ratio of the main antifouling agent to the auxiliary antifouling agent in the antifouling agent is 10: (1-10) ; or / and, the main antifouling agent is at least one selected from the group consisting of pyridine triphenyl boron, bromopyrrole nitrile, and 4,5-dichloro-N-octyl-4-isothiazoline-3-ketone; or / and, the auxiliary antifouling agent is at least one selected from the group consisting of chlorothalonil, copper pyrithione, zinc pyrithione, and zineb. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 9. A method for preparing the antifouling paint according to any one of claims 1-8, comprising: a first step of grinding the components except the hollow glass microspheres to a fineness of ≤80 μm after stirring uniformly according to the weight parts; a second step of adding the hollow glass microspheres and stirring uniformly to obtain the antifouling paint.

10. The antifouling paint according to any one of claims 1-8 or prepared by the method according to claim 9 for surface antifouling applications in the field of underwater electromagnetic wave communication.

Images