Antifouling self-cleaning fluorocarbon finish paint as well as preparation method and application thereof

Abstract

The invention provides an antifouling self-cleaning fluorocarbon finish paint as well as a preparation method and application thereof, and particularly relates to the technical field of special coatings. The antifouling self-cleaning fluorocarbon finish paint is composed of a component A and a component B in a ratio of (80-87): 16, the component A is prepared from the following components in parts by weight: 560 to 580 parts of fluorocarbon resin, 30 to 35 parts of a first solvent, 20 to 40 parts of a second solvent, 180 to 220 parts of titanium dioxide, 90 to 110 parts of filler, 11 to 20 parts of a light stabilizer, 3 to 5 parts of a thickening agent and 13 to 28 parts of an auxiliary agent; the component B comprises the following components in parts by weight: 20-22 parts of fluorocarbon resin, 4-5 parts of a chain extender, 15-20 parts of a diamine curing agent, 15-20 parts of a polyamine curing agent and 25-35 parts of a second solvent. According to the finishing paint, on the basis of enhancing the self-cleaning capability, the weather resistance of a coating is improved, and the aging and damage of the coating are delayed, so that the service life of the coating is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of special coating, in particular to a kind of antifouling self-cleaning fluorocarbon finish and its preparation method and application. BACKGROUND

[0002] Bridge tower as the key load-bearing part of bridge structure, long-term exposure in complex and changeable natural environment, in addition to be subjected to sunlight, rain and wind erosion, temperature changes and other climatic factors, as well as industrial waste gas, automobile exhaust and other corrosive media, if the bridge is in marine environment, it will also be subjected to high salt fog, tidal immersion, sea water splashing and other special conditions erosion-chloride ions in seawater and other corrosive components can accelerate the corrosion of tower matrix, long-term attachment of salt fog can also damage the coating structure. At the same time, the tower surface also needs to have certain decorative to maintain the overall beauty of the bridge. Therefore, the coating used in tower area has strict requirements: it needs to have excellent weather resistance to resist the aging, chalking and discoloration of coating caused by long-term outdoor environment, and it needs to resist the coating degradation caused by salt fog in marine environment; it needs to have good corrosion resistance, especially to resist chloride ions and other corrosive media, to prevent the corrosion damage of steel or concrete matrix; it also needs to have certain mechanical properties, such as impact resistance and abrasion resistance, to cope with possible external force, and the adhesion of coating should be strong to firmly combine with the matrix and not easy to fall off in dynamic environment such as tide.

[0003] However, the existing bridge tower area coating still has many defects: some coatings have insufficient weather resistance, and have easy coating cracking and peeling phenomenon under long-term ultraviolet irradiation and temperature and humidity cycle, and in high-salt marine environment, the degradation rate will be further accelerated; some anticorrosive coatings have good initial anticorrosive effect, but are difficult to resist chloride ion penetration for a long time, and their anticorrosive performance decays quickly with the extension of use time, especially in marine environment, it is difficult to meet the long-term protection needs of tower; some coatings have high requirements for environmental conditions during construction, such as specific temperature and humidity environment, otherwise the coating quality will be affected, which not only increases the construction difficulty and cost, but also limits its application scenarios in complex climate or marine environment, and it is difficult to meet the actual needs of efficient and stable construction of bridge tower area, especially in marine environment.

[0004] Therefore, the present application is proposed. SUMMARY

[0005] The present application aims to provide a kind of antifouling self-cleaning fluorocarbon finish and its preparation method and application, to alleviate at least one of the above technical problems in the prior art.

[0006] To solve the above technical problems, the present application adopts the following technical scheme: The first aspect of the present application provides a kind of anti-fouling self-cleaning fluorocarbon finish, by single storage and when using according to (80~87):16 A component and B component of group are formed; The A component includes fluorocarbon resin 560~580 parts by weight, first solvent 30~35 parts, second solvent 20~40 parts, titanium white 180~220 parts, filler 90~110 parts, light stabilizer 11~20 parts, thickening agent 3~5 parts and auxiliary agent 13~28 parts by weight; The B component includes fluorocarbon resin 20~22 parts by weight, chain extender 4~5 parts, diamine curing agent 15~20 parts, polyamine curing agent 15~20 parts and second solvent 25~35 parts.

[0007] Further, the auxiliary agent includes at least one of leveling agent, anti-settling agent, dispersant and defoaming agent.

[0008] Preferably, the B component further includes stabilizer 8~12 parts.

[0009] Preferably, the stabilizer includes at least one of benzyl alcohol, ethylbenzyl alcohol, propylene glycol methyl ether.

[0010] Further, the auxiliary agent includes at least one of leveling agent 6~8 parts, anti-settling agent 1~5 parts, dispersant 1~5 parts and defoaming agent 5~10 parts.

[0011] Further, the brand of fluorocarbon resin includes at least one of ZU201, ZB-F500.

[0012] Preferably, the first solvent includes at least one of butyl acetate, dibasic acid ester (DBP).

[0013] Preferably, the second solvent includes at least one of dimethylbenzene, toluene, isobutyl alcohol, cyclohexanol.

[0014] Preferably, the filler includes at least one of aluminum clay, talc powder, glass flake, quartz powder and precipitated barium sulfate.

[0015] Preferably, the brand of light stabilizer includes at least one of TINUVIN 292, TINUVIN 1130.

[0016] Preferably, the thickening agent includes at least one of polyamide wax, polyethylene wax, fumed silica, hydrogenated castor oil.

[0017] Further, the chain extender includes at least one of propylene glycol.

[0018] Preferably, the diamine curing agent includes at least one of m-xylylenediamine, p-xylylenediamine.

[0019] Preferably, the polyamine curing agent comprises at least one of polyoxypropylene triamine and diethylene triamine.

[0020] Further, the pigments are used to partially replace titanium dioxide in the anti-fouling self-cleaning fluorocarbon topcoat.

[0021] Preferably, the pigments comprise at least one of red iron oxide, molybdenum-chromium red, carbon black, black iron oxide, aniline black, yellow iron oxide, bismuth vanadate, chromium yellow, phthalocyanine blue, cobalt blue and ultramarine blue.

[0022] The second aspect of the present application provides a preparation method of the anti-fouling self-cleaning fluorocarbon topcoat, and the preparation method of the A component is as follows: adding fluorocarbon resin, a first solvent, a second solvent and a thickening agent to stir uniformly to obtain a pre-solution; then adding titanium dioxide and a filler in the pre-solution, increasing the stirring speed and increasing the temperature, then decreasing the stirring speed and keeping the temperature to obtain a first semi-finished product, and finally adding an additive and a light stabilizer to mix uniformly to obtain the A component.

[0023] and / or, The preparation method of the B component is as follows: mixing a chain extender, part of the second solvent, a diamine curing agent and an optional stabilizer uniformly, then adding fluorocarbon resin to stir uniformly and stand to obtain a semi-finished product; and finally adding a polyamine curing agent and the remaining second solvent in the semi-finished product to mix uniformly to obtain the B component.

[0024] Further, in the preparation method of the A component, the stirring speed for obtaining the pre-solution is 400-700 rpm.

[0025] Preferably, the stirring speed is increased to 800-1500 rpm and the temperature is increased to 60-65°C.

[0026] Preferably, the stirring speed is decreased to 400-700 rpm.

[0027] Preferably, in the preparation method of the B component, the standing time is 48-96 h.

[0028] The third aspect of the present application provides an application of the anti-fouling self-cleaning fluorocarbon topcoat in the industrial protection field.

[0029] Further, the industrial protection field includes coastal bridges, port machinery, offshore wind power piles, ships and offshore oil platforms.

[0030] Preferably, the coastal bridges include bridge pylon towers.

[0031] Preferably, the bridge pylon towers include cable-stayed bridge main towers or cable anchorage zones.

[0032] Compared with the prior art, the present application has at least the following beneficial effects: The anti-fouling self-cleaning fluorocarbon finish provided by the application can significantly improve the self-cleaning efficiency of the coating: by virtue of the super-hydrophobic property of the finish, the contact angle of water droplets and dirt on the surface of the coating is greatly increased, the residence time of the water droplets on the surface is effectively shortened, and the removal of the dirt is accelerated, which directly prolongs the cleaning cycle of the surface of the building, reduces the maintenance frequency and cleaning cost. Meanwhile, the addition of the new super-hydrophobic fluorocarbon resin enhances the self-cleaning ability and further improves the weather resistance of the coating, which can resist the influence of adverse environments such as ultraviolet radiation, acid rain erosion and sharp temperature changes, delays the aging and damage of the coating, thereby prolonging the service life of the coating and reducing the long-term maintenance requirements. In addition, the reduction of the cleaning frequency caused by the self-cleaning function can also reduce the use of chemical cleaning agents, further reducing the impact on the environment.

[0033] In the preparation method provided by the application, the A component is prepared by adding raw materials step by step, which not only ensures the sufficient dispersion of solid particles, but also avoids the damage of high temperature to the additives and light stabilizers, thereby improving the stability of the component; the preparation steps of the B component reduce the advance reaction of the curing agent and the resin, thereby ensuring the storage stability. The overall process steps are clear, the uniform mixing of each component is realized by controlling the rotation speed and temperature, the performance stability of the coating is ensured, and the operation is simple, which is suitable for industrial production.

[0034] The anti-fouling self-cleaning fluorocarbon finish provided by the application is applied in the field of industrial protection. In view of the advantages of the anti-fouling self-cleaning fluorocarbon finish, it can be applied in the port industry to effectively protect equipment, storage tanks and the like from corrosion caused by industrial waste gas and seawater splashing, reduce corrosion damage, reduce the use of cleaning agents, meet environmental protection requirements, realize the dual benefits of long-term protection and reduced maintenance cost. DETAILED DESCRIPTION

[0035] To make the objectives, technical solutions and advantages of the present application clearer, the technical solutions in the embodiments of the present application will be described below in conjunction with the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The components of the embodiments of the present application can be arranged and designed in various different configurations.

[0036] The first aspect of the present application provides an anti-fouling self-cleaning fluorocarbon finish, which is composed of A component and B component stored separately and used according to the ratio of (80-87):16; The A component includes fluorocarbon resin 560-580 parts, first solvent 30-35 parts, second solvent 20-40 parts, titanium dioxide 180-220 parts, filler 90-110 parts, light stabilizer 11-20 parts, thickening agent 3-5 parts and additive 13-28 parts by weight; The B component comprises 20-22 parts by weight of fluorocarbon resin, 4-5 parts of chain extender, 15-20 parts of diamine curing agent, 15-20 parts of polyamine curing agent and 25-35 parts of second solvent.

[0037] The anti-fouling self-cleaning fluorocarbon finish provided by the application can significantly improve the self-cleaning efficiency of the coating: by virtue of the super-hydrophobic property of the finish, the contact angle of water droplets and dirt on the coating surface is greatly increased, effectively shortening the residence time of water droplets on the surface and accelerating the removal of dirt, which directly prolongs the cleaning cycle of the building surface and reduces the maintenance frequency and cleaning cost. At the same time, the addition of the new super-hydrophobic resin fluorocarbon resin further improves the weather resistance of the coating on the basis of enhancing the self-cleaning ability, and can resist the influence of ultraviolet radiation, acid rain erosion, and drastic changes in temperature and other harsh environments, delaying the aging and damage of the coating, thereby prolonging the service life of the coating and reducing the long-term maintenance requirements. In addition, the reduction in cleaning frequency brought about by the self-cleaning function can also reduce the use of chemical cleaning agents, further reducing the impact on the environment.

[0038] In the above-mentioned anti-fouling self-cleaning fluorocarbon finish, the fluorocarbon resin of the A component forms a coating film with high crosslinking density, excellent physical and mechanical properties and chemical medium resistance; the fluorocarbon resin in the B component and the polyamine curing agent form a pre-reaction body, which can produce more reactive groups. When the A and B components are mixed in proportion, a tight reaction system can be formed, and a coating with high thickness and no sagging can be formed.

[0039] (80-87): 16 is the mass ratio of the A component and the B component, typically but not limitedly, the anti-fouling self-cleaning fluorocarbon finish is composed of the A component and the B component which are separately stored and used in a mass ratio of (80-87): 16; for example, the mass ratio can be 80:16, 81:16, 82:16, 83:16, 84:16, 85:16, 86:16 or 87:16, or any ratio within the range of 80-87:16.

[0040] Typically but not exclusively, the weight parts of each raw material in the A component, typically but not exclusively, the fluorocarbon resin may be 560 parts, 565 parts, 570 parts, 575 parts, or 580 parts, or any value within the range of 560-580 parts; the first solvent may be 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, or 35 parts, or any value within the range of 30-35 parts; the second solvent may be 20 parts, 25 parts, 30 parts, 35 parts, or 40 parts, or any value within the range of 20-40 parts; the titanium dioxide may be 180 parts, 190 parts, 200 parts, 210 parts, or 220 parts, or any value within the range of 180-220 parts; the filler may be 90 parts, 95 parts, 100 parts, 105 parts, or 110 parts, or any value within the range of 90-110 parts; the light stabilizer may be 11 parts, 13 parts, 15 parts, 17 parts, 19 parts, or 20 parts, or any value within the range of 11-20 parts; the thickening agent may be 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts, or any value within the range of 3-5 parts; the auxiliary agent may be 13 parts, 16 parts, 19 parts, 22 parts, 25 parts, or 28 parts, or any value within the range of 13-28 parts.

[0041] Typically but not exclusively, the weight parts of each raw material in the B component, typically but not exclusively, the fluorocarbon resin may be 20 parts, 20.5 parts, 21 parts, 21.5 parts, or 22 parts, or any value within the range of 20-22 parts; the chain extender may be 4 parts, 4.2 parts, 4.5 parts, 4.8 parts, or 5 parts, or any value within the range of 4-5 parts; the diamine curing agent may be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts, or any value within the range of 15-20 parts; the polyamine curing agent may be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, or 20 parts, or any value within the range of 15-20 parts; the second solvent may be 25 parts, 27 parts, 30 parts, 33 parts, or 35 parts, or any value within the range of 25-35 parts.

[0042] Further, the auxiliary agent includes at least one of a leveling agent, an anti-settling agent, a dispersing agent, and a defoaming agent.

[0043] Preferably, the B component further includes a stabilizer 8-12 parts.

[0044] Typically but not exclusively, the stabilizer may be 8 parts, 9 parts, 10 parts, 11 parts, or 12 parts, or any value within the range of 8-12 parts.

[0045] Preferably, the stabilizer includes at least one of benzyl alcohol, ethyl benzyl alcohol, propylene glycol methyl ether. The stabilizer participates in the chain extension reaction, and plays the role of reaction stabilizer. When the concentration of stabilizer in the system is low, the reaction is slow or the reaction is terminated. When the amount of stabilizer is more than 12 parts, the chain extension reaction continues; when the amount of stabilizer is less than 8 parts, the chain extension reaction is terminated.

[0046] Further, the auxiliary agent includes at least one of 6-8 parts of a leveling agent, 1-5 parts of an anti-settling agent, 1-5 parts of a dispersing agent, and 5-10 parts of a defoaming agent.

[0047] Typically but not limitedly, the leveling agent may be, for example, 6 parts, 6.5 parts, 7 parts, 7.5 parts, or 8 parts, or any value within the range of 6-8 parts; the anti-settling agent may be, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any value within the range of 1-5 parts; the dispersing agent may be, for example, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, or any value within the range of 1-5 parts; the defoaming agent may be, for example, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, or any value within the range of 5-10 parts; the auxiliary agent may use any one of the above leveling agent, anti-settling agent, dispersing agent, and defoaming agent alone, or any combination of two, three, or all four thereof in any proportion.

[0048] Further, the fluorocarbon resin includes at least one of ZU201.

[0049] The ZU201 resin contains C-F bonds with bond energies as high as 486 kJ / mol, so it is difficult for the C-F bonds to break under the action of ultraviolet light, showing super-long weather resistance, durability, and chemical resistance, and being able to resist ultraviolet rays, rain, and other natural environmental erosion for a long time, maintaining the stability and aesthetics of the coating. The ZU201 resin contains a large number of carbon-fluorine bonds in its molecular structure, and this bond is one of the strongest single bonds known. The high bond energy of the carbon-fluorine bond makes the resin extremely difficult to be destroyed in a chemical environment, so it has extremely high resistance to most chemical reagents. In addition, the side chain structure of the ZU201 resin is simple, without functional groups that are easy to attack, further enhancing its chemical stability.

[0050] The coating skillfully combines the advantages of super-hydrophobic technology and fluorocarbon coating, and has excellent self-cleaning function and weather resistance. Specifically, by introducing a new super-hydrophobic resin ZU201 into the coating, a super-hydrophobic structure can be formed on the surface of the coating, which can effectively resist the adhesion of pollutants such as water and oil stains, thereby realizing high-efficiency self-cleaning effect; at the same time, the addition of fluorocarbon resin not only improves the weather resistance of the coating, so that it can maintain stable performance in various complex environmental conditions, but also enhances the adhesion of the coating, further ensuring the durability of the protection effect. In summary, the anti-fouling and self-cleaning fluorocarbon topcoat coating of the present application can not only improve the aesthetic appearance of buildings, but also significantly reduce maintenance costs, and therefore has a wide application prospect.

[0051] Preferably, the first solvent includes at least one of butyl acetate and dibasic acid ester (DBP).

[0052] Preferably, the second solvent includes at least one of dimethylbenzene, toluene, isobutyl alcohol, and cyclohexanol.

[0053] Preferably, the filler includes at least one of aluminum clay, talcum powder, glass flake, quartz powder, and precipitated barium sulfate.

[0054] Preferably, the light stabilizer includes at least one of TINUVIN 292 and TINUVIN 1130.

[0055] Preferably, the thickening agent includes at least one of polyamide wax, polyethylene wax, fumed silica, and hydrogenated castor oil.

[0056] Further, the chain extender includes at least one of propylene glycol.

[0057] Preferably, the diamine curing agent includes at least one of m-xylylenediamine and p-xylylenediamine.

[0058] Preferably, the polyamine curing agent includes at least one of polyoxypropylene triamine and diethylene triamine.

[0059] Polyoxypropylene triamine has an oxidized propane as a basic repeating segment in the main chain structure, and it is a three-amine with polypropylene glycol as the main chain. In the system reaction with fluorocarbon resin, the reaction rate is uniform, the anti-sagging property is good, and the elongation and strength of the anti-fouling and self-cleaning fluorocarbon topcoat can be increased.

[0060] Further, the anti-fouling and self-cleaning fluorocarbon topcoat uses pigments to partially replace titanium dioxide. Titanium dioxide has a dual role of pigment and filler in the formula, which can provide sufficient hiding power and adjust the color of the coating. In specific implementation, other pigments can be used to partially replace titanium dioxide according to the required appearance color of the product.

[0061] Preferably, the pigments include at least one of red iron oxide, molybdate red, carbon black, black iron oxide, aniline black, yellow iron oxide, bismuth vanadate, chrome yellow, phthalocyanine blue, cobalt blue, and ultramarine blue.

[0062] The second aspect of the present application provides a preparation method of the anti-fouling self-cleaning fluorocarbon finish, and the preparation method of the A component is as follows: adding fluorocarbon resin, a first solvent, a second solvent and a thickening agent to stir uniformly to obtain a pre-solution; then adding titanium dioxide and a filler in the pre-solution, increasing the rotating speed and increasing the temperature, then decreasing the rotating speed and keeping the temperature to obtain a first semi-finished product, and finally adding an additive and a light stabilizer to mix uniformly to obtain the A component.

[0063] and / or, The preparation method of the B component is as follows: mixing a chain extender, part of the second solvent, a diamine curing agent and an optional stabilizer uniformly, then adding fluorocarbon resin to stir uniformly and stand to obtain a semi-finished product; finally adding a polyamine curing agent and the remaining second solvent in the semi-finished product to mix uniformly to obtain the B component.

[0064] In the preparation method, the A component is prepared by adding raw materials step by step, which not only ensures the sufficient dispersion of solid particles, but also avoids the damage of high temperature to the additive and the light stabilizer, thereby improving the stability of the component; the preparation steps of the B component reduce the early reaction of the curing agent and the resin, thereby ensuring the storage stability. The overall process steps are clear, the components are uniformly mixed by controlling the rotating speed and the temperature, the performance stability of the paint is ensured, the operation is simple, and the method is suitable for industrial production.

[0065] In the preparation method of the B component, the chain extender and the diamine curing agent are first subjected to chain extension reaction, then the fluorocarbon resin is added for pre-reaction, so as to promote the intermediate chain addition of the amine group of the fluorocarbon resin; the intermediate chain can continue to undergo curing reaction during construction, thereby ensuring the continuity and integrity of the curing process. At the same time, by adding the polyamine curing agent, the number of amine groups in the curing agent is increased, which can further promote the curing reaction, improve the reaction activity of the paint film, and finally enhance the corrosion resistance of the coating.

[0066] Further, in the preparation method of the A component, the stirring rotating speed for obtaining the pre-solution is 400-700 rpm. Typically but not limitedly, the stirring rotating speed for obtaining the pre-solution may be, for example, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm or 700 rpm, or any value within the range of 400-700 rpm.

[0067] Preferably, the rotating speed is increased to 800-1500 rpm and the temperature is increased to 60-65 ℃. Increasing the rotating speed temporarily reduces the viscosity of the system, and high temperature intensifies the molecular thermal motion, so that the thickening agent is completely dissolved in the system.

[0068] Typically but not exclusively, the increased rotational speed can be, for example, 800 rpm, 900 rpm, 1000 rpm, 1100 rpm, 1200 rpm, 1300 rpm, 1400 rpm or 1500 rpm, or any value within the range of 800-1500 rpm; the increased temperature can be, for example, 70℃, 72℃, 75℃, 78℃, 80℃, 82℃, 84℃ or 85℃, or any value within the range of 70-85℃. Preferably, the rotational speed is decreased to 400-700 rpm. Typically but not exclusively, the decreased rotational speed can be, for example, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm or 700 rpm, or any value within the range of 400-700 rpm.

[0069] Preferably, in the preparation method of the B component, the standing time is 48-96 h, and the resin undergoes chain extension reaction during the standing process.

[0070] Typically but not exclusively, the standing time can be, for example, 48 h, 54 h, 60 h, 66 h, 72 h, 78 h, 84 h, 90 h or 96 h, or any value within the range of 48-96 h.

[0071] The third aspect of the present application provides the application of the anti-fouling self-cleaning fluorocarbon finish in the industrial protection field.

[0072] The application of the anti-fouling self-cleaning fluorocarbon finish in the industrial protection field provided by the present application, due to the advantages of the anti-fouling self-cleaning fluorocarbon finish, makes it possible to effectively protect equipment, storage tanks and the like from corrosion caused by industrial waste gas and seawater splashing, reduce corrosion damage, reduce the use of cleaning agents, meet environmental protection requirements, achieve the dual benefits of long-term protection and reduced maintenance costs.

[0073] Further, the industrial protection field includes coastal bridges, port machinery, offshore wind power piles, ships and offshore oil platforms.

[0074] Preferably, the coastal bridge includes a bridge pylon.

[0075] Preferably, the bridge pylon includes a cable-stayed bridge main tower or a cable anchor area.

[0076] The present application will be further described in detail below in combination with examples and comparative examples.

[0077] Example 1 The present example provides an anti-fouling self-cleaning fluorocarbon finish, and the preparation steps are as follows: (1) Add butyl acetate 30 parts, ZU201 resin 560 parts, BYK-P-104S 6 parts, xylene 20 parts, and polyamide wax powder 3 parts in sequence under stirring at 600 rpm for 20 min to obtain a pre-solution.

[0078] (2) Add titanium dioxide 180 parts and barium sulfate 90 parts in sequence in the pre-solution, increase the stirring speed to 1200 rpm to make the temperature in the container reach 72°C, then reduce the stirring speed to 600 rpm and keep for 30 min to obtain a semi-finished product of component A.

[0079] (3) Add TINUVIN 292 3 parts, TINUVIN 1130 8 parts, BYK-355 6 parts, BYK-410 1 part, BYK-182 1 part, and EFKA 2020 5 parts in the semi-finished product of component A under stirring at 600 rpm for 20 min to obtain component A.

[0080] (4) First, add benzyl alcohol 10.4 parts, xylene 15.5 parts, isobutyl alcohol 5.5 parts, propylene glycol 4.8 parts, and m-xylylenediamine 16.7 parts under stirring at 600 rpm for 10 min. Then, add ZU201 resin 21 parts gradually, stir uniformly, and then stand for 72 h to obtain a semi-finished product of component B. After standing, stir the semi-finished product of component B at 600 rpm for 5 min, then add polyoxypropylene triamine 16.1 parts and xylene 7.2 parts in sequence, and stir at 600 rpm for 20 min to obtain component B.

[0081] (5) The mass ratio of component A to component B is 5:1.

[0082] Example 2 The present embodiment provides a stain-resistant self-cleaning fluorocarbon finish, which is different from example 1 in that in component A, butyl acetate 35 parts, ZU201 resin 580 parts, BYK-P-104S 9 parts, titanium dioxide 220 parts, barium sulfate 110 parts, xylene 40 parts, TINUVIN 292 6 parts, TINUVIN 1130 14 parts, BYK-355 8 parts, BYK-410 5 parts, BYK-182 5 parts, EFKA 2020 10 parts, and polyamide wax powder 5 parts are used; the remaining raw materials and preparation steps are the same as those in example 1, and will not be repeated here.

[0083] Example 3 The present embodiment provides a stain-resistant self-cleaning fluorocarbon finish, which is different from example 1 in that the amount of titanium dioxide used in component A is 90 parts; the remaining raw materials and preparation steps are the same as those in example 1, and will not be repeated here.

[0084] Example 4 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the amount of titanium dioxide in the A component is 270 parts, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0085] Embodiment 5 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the ZU201 resin is replaced by Dalian Zhenbang ZB-F500, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0086] Embodiment 6 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the mass ratio of the A component to the B component is 87:16, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0087] Embodiment 7 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the amount of benzyl alcohol in the B component is 5 parts, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0088] Embodiment 8 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the amount of benzyl alcohol in the B component is 15 parts, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0089] Embodiment 9 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the B component does not contain benzyl alcohol, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0090] Embodiment 10 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the content of m-xylylenediamine in the B component is 15 parts, and the content of polyoxypropylene triamine is 20 parts, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0091] Embodiment 11 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the content of m-xylylenediamine in the B component is 20 parts, and the content of polyoxypropylene triamine is 5 parts, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0092] Embodiment 12 The embodiment provides an antifouling self-cleaning fluorocarbon finish, which is different from the embodiment 1 in that the standing time in the step (4) is 48 h, and the remaining raw materials and preparation steps are the same as those of the embodiment 1, which are not described herein again.

[0093] Example 13 This example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, the standing time in step (4) is 96h, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0094] Example 14 This example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, the standing time in step (4) is 24h, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0095] Comparative Example 1 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, the amount of polyamide wax powder is 1 part, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0096] Comparative Example 2 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, the amount of polyamide wax powder is 7 parts, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0097] Comparative Example 3 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, does not contain polyamide wax powder, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0098] Comparative Example 4 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, does not contain propylene glycol, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0099] Comparative Example 5 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, the amount of m-xylylenediamine is 32.8 parts, does not use polyoxypropylene triamine, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0100] Comparative Example 6 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, the amount of polyoxypropylene triamine is 32.8 parts, does not use m-xylylenediamine, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0101] Comparative Example 7 This comparative example provides a kind of anti-fouling self-cleaning fluorocarbon finish, different from example 1, does not add ZU201 resin in B component, the rest of raw materials and preparation steps are identical with example 1, will not be described here.

[0102] Comparative Example 8 This comparative example provides a stain-resistant, self-cleaning fluorocarbon topcoat. Unlike Example 1, TINUVIN292 and TINUVIN1130 are not added to component A. The remaining raw materials and preparation steps are the same as in Example 1, and will not be repeated here.

[0103] Comparative Example 9 This comparative example provides a topcoat, a high-durability, low-surface-energy composite coating provided by Changtao New Materials, a CT-H type hydrophobic protective coating.

[0104] Experimental Example 1 The performance of the antifouling self-cleaning fluorocarbon topcoats obtained in the examples and comparative examples was tested. The specific process and method are as follows.

[0105] Specimen preparation and testing methods: carried out in accordance with GB / T1727-1992.

[0106] (1) Solid content test: conducted in accordance with GB / T1725-2007.

[0107] (2) Anti-sagging performance test: conducted according to GB9264-88 method.

[0108] (3) Abrasion resistance test: conducted according to GB / T1768 method.

[0109] (4) Water contact angle test: Performed according to ISO 19403-2:2017.

[0110] (5) Adhesion test: The test shall be conducted in accordance with ISO4624 or ASTM4541 standards. The instrument used is AT-A automatic pull-out tester. The iron plate is sandblasted and the film thickness is 150 micrometers. The film is tested after natural drying for 24 hours.

[0111] (6) Salt spray resistance test: conducted in accordance with GB / T1771 method.

[0112] (7) Water resistance test: conducted in accordance with GB / T1733 method.

[0113] (8) Weather resistance test: conducted in accordance with GB / T9274 method.

[0114] The test results are shown in Table 1.

[0115] Table 1 Performance Data of Antifouling and Self-Cleaning Fluorocarbon Topcoat

[0116] As shown in Table 1, in terms of basic performance indicators, the solid content of all examples and comparative examples is concentrated in the range of 54% to 70%, which is in line with the conventional solid content range in the coating industry. Furthermore, the solid content of Examples 1-14 is mostly between 54% and 59%, indicating good overall stability. Only Comparative Example 7 (component B does not contain fluorocarbon resin) has a solid content that rises to 70% due to missing components, deviating from the normal range. Regarding anti-sagging performance, the anti-sagging thickness of Examples 1-14 is mostly between 255μm and 285μm, meeting the anti-sagging requirements of industrial protective coatings. The amount of thickener has a significant impact on this performance—the anti-sagging thickness of Comparative Example 1 (1 part polyamide wax) and Comparative Example 3 (no polyamide wax) is 240μm and 210μm respectively, significantly lower than that of Example 1 (3 parts polyamide wax, 275μm), confirming the key role of the thickener in improving the anti-sagging ability of the coating. While Comparative Example 2 (7 parts polyamide wax) has an anti-sagging thickness of 310μm, exhibiting excessive anti-sagging properties, it did not affect other core performance characteristics.

[0117] In terms of functional performance indicators, salt water resistance and salt spray resistance showed extremely strong consistency. Examples 1-14 and Comparative Examples 1-3 and 8-9 all achieved 4200h of salt water resistance and salt spray resistance. Only Comparative Example 7 (without component B fluorocarbon resin) saw a sharp drop in both indicators to 2000h due to the lack of fluorocarbon resin, while Comparative Example 8 (without TINUVIN light stabilizer) dropped to 3000h. This fully demonstrates that the weather resistance advantage of fluorocarbon resin and the anti-aging effect of light stabilizer are the core components ensuring the long-term corrosion resistance of the coating. Regarding abrasion resistance, the abrasion amount in Examples 1-14 was mostly between 43mg and 56mg. Comparative Example 7, due to the lack of fluorocarbon resin, had an abrasion amount of 70mg, resulting in a significant decrease in abrasion resistance. Examples 4 (270 parts titanium dioxide) and 5 (ZB-F500 replacing ZU201) showed slightly higher abrasion amounts than Example 1, reflecting the slight influence of excessive titanium dioxide or differences in fluorocarbon resin grade on abrasion resistance, but overall, the results remained excellent.

[0118] The water contact angle is a key indicator for measuring self-cleaning performance. Examples 1-2 and 8-9 have water contact angles of 150°, demonstrating outstanding superhydrophobicity. Examples 3 (90 parts titanium dioxide) and 6 (A / B ratio 87:16) have water contact angles of 140°, Examples 4 and 10-14 have water contact angles of 120°~125°, Example 5 (ZB-F500 resin) has a water contact angle of 100°, and Comparative Examples 1 and 4 (without chain extender) have a water contact angle of 105°. It can be seen that ZU201 fluorocarbon resin, reasonable titanium dioxide dosage, and A / B component ratio are key to ensuring superhydrophobic performance. Replacing the resin grade, excessive titanium dioxide, or missing components will lead to a decrease in self-cleaning performance. Regarding adhesion, Examples 1-9, 12-14 and Comparative Examples 1-3, 9 all reached level 0 (optimal), while Comparative Examples 4 (without chain extender) and 5-6 (single curing agent) dropped to level 1, and Comparative Example 7 dropped to level 2. This indicates that the synergistic effect of chain extender and composite curing agent (diamine + polyamine) is the core to ensure a strong bond between the coating and the substrate. The absence or simplification of components will significantly weaken the adhesion.

[0119] Furthermore, the performance of Comparative Example 9 (commercially available CT-H type coating) is basically the same as that of Example 1. However, the water contact angle is 130° and the abrasion resistance is 51mg, which is slightly lower than that of Example 1 (150° and 43mg). This indicates that the coating of the present invention is superior to commercially available similar products in terms of self-cleaning and abrasion resistance, and its overall performance reaches the advanced level in the industry.

[0120] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A self-cleaning, anti-fouling fluorocarbon topcoat, characterized in that, It consists of component A and component B, which are stored separately and used in a ratio of (80~87):16; Component A comprises, by weight, 560-580 parts of fluorocarbon resin, 30-35 parts of the first solvent, 20-40 parts of the second solvent, 180-220 parts of titanium dioxide, 90-110 parts of filler, 11-20 parts of light stabilizer, 3-5 parts of thickener, and 13-28 parts of additives. Component B comprises, by weight, 20-22 parts of fluorocarbon resin, 4-5 parts of chain extender, 15-20 parts of diamine curing agent, 15-20 parts of polyamine curing agent, and 25-35 parts of second solvent.

2. The anti-fouling self-cleaning fluorocarbon topcoat according to claim 1, characterized in that, The additives include at least one of leveling agents, anti-settling agents, dispersants, and defoamers; Preferably, component B further includes 8-12 parts of a stabilizer; Preferably, the stabilizer includes at least one of benzyl alcohol, ethylbenzyl alcohol, and propylene glycol methyl ether.

3. The anti-fouling self-cleaning fluorocarbon topcoat according to claim 2, characterized in that, The additives include at least one of the following: 6-8 parts leveling agent, 1-5 parts anti-settling agent, 1-5 parts dispersant, and 5-10 parts defoamer.

4. The anti-fouling self-cleaning fluorocarbon topcoat according to any one of claims 1 to 3, characterized in that, The fluorocarbon resin grades include at least one of ZU201; Preferably, the first solvent includes at least one of butyl acetate and divalent ester; Preferably, the second solvent includes at least one of xylene, toluene, isobutanol, and cyclohexanol; Preferably, the filler comprises at least one of alumina clay, talc powder, glass flakes, quartz powder, and precipitated barium sulfate; Preferably, the light stabilizer is selected from at least one of TINUVIN 292 and TINUVIN 1130; Preferably, the thickener includes at least one of polyamide wax, polyethylene wax, fumed silica, and hydrogenated castor oil.

5. The anti-fouling self-cleaning fluorocarbon topcoat according to any one of claims 1 to 3, characterized in that, The chain extender includes propionol; Preferably, the diamine curing agent includes at least one of m-phenylenediamine and p-phenylenediamine; Preferably, the polyamine curing agent includes at least one of polyoxypropylene triamine and diethylenetriamine.

6. The anti-fouling self-cleaning fluorocarbon topcoat according to any one of claims 1 to 3, characterized in that, Use pigments to partially replace titanium dioxide; Preferably, the pigment includes at least one of iron oxide red, molybdenum chrome red, carbon black, iron oxide black, aniline black, iron oxide yellow, bismuth vanadate, chrome yellow, phthalocyanine blue, cobalt blue, and ultramarine.

7. A method for preparing the antifouling self-cleaning fluorocarbon topcoat according to any one of claims 1 to 6, characterized in that, The preparation method of component A is as follows: add fluorocarbon resin, first solvent, second solvent and thickener and stir evenly to obtain a pre-solution; then add titanium dioxide and filler to the pre-solution and increase the rotation speed and temperature, then decrease the speed and keep the temperature to obtain a first semi-finished product; finally add additives and light stabilizer and mix evenly to obtain component A. And / or, The preparation method of component B is as follows: the chain extender, part of the second solvent, diamine curing agent and optional stabilizer are mixed evenly, and then fluorocarbon resin is added, stirred evenly and allowed to stand to obtain a semi-finished product; finally, polyamine curing agent and the remaining second solvent are added to the semi-finished product and mixed evenly to obtain component B.

8. The preparation method according to claim 7, characterized in that, In the preparation method of component A, the stirring speed for obtaining the pre-dissolved material is 400~700 rpm; Preferably, the rotation speed is increased to 800~1500 rpm and the temperature is increased to 60~65℃; Preferably, the speed is reduced to 400~700 rpm; Preferably, in the preparation method of component B, the standing time is 48-96 hours.

9. The application of the antifouling self-cleaning fluorocarbon topcoat according to any one of claims 1 to 6 in the field of industrial protection.

10. The application according to claim 9, characterized in that, The industrial protection areas include coastal bridges, port machinery, offshore wind turbines, ships, and offshore oil platforms. Preferably, the coastal bridge includes bridge towers; Preferably, the bridge tower includes the main tower of a cable-stayed bridge or the cable anchorage zone.

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