A self-polishing zinc-acrylic antifouling paint and a method for preparing the same

Abstract

The present application relates to the field of paint, in particular to a kind of self-polishing zinc-acrylic antifouling paint and preparation method thereof.The self-polishing zinc-acrylic antifouling paint includes: zinc-acrylic resin 30-40 parts, polyvinyl isobutyl ether resin 5-10 parts, rosin 10-15 parts, wetting dispersant 1-1.5 parts, defoaming agent 0.5-1.0 parts, toughening agent 5-8 parts, thixotropic agent 1.5-4 parts, antifouling agent 20-35 parts, filler 5-10 parts, pigment 3-6 parts, solvent 10-20 parts;The antifouling agent includes inorganic antifouling agent, capsaicin and cucurbituril [7];The toughening agent includes polytetrahydrofuran ether glycol and dioctyl sebacate;The rosin includes hydrogenated rosin and maleic rosin pentaerythritol ester.The capsaicin in the self-polishing zinc-acrylic antifouling paint of the present application can realize controlled release, and the antifouling paint has excellent performance of effective antifouling, long-acting antifouling and storage stability.

Description

Technical Field

[0001] This invention relates to the field of coatings, specifically to a self-polishing zinc acrylic antifouling paint and its preparation method. Background Technology

[0002] When ships navigate at sea, the attachment of organisms such as barnacles, algae, and marine bacteria increases drag and accelerates hull corrosion. Currently, self-polishing antifouling coatings are the mainstream choice for ocean-going vessels, relying on seawater hydrolysis to release copper ions for antifouling. To improve the broad-spectrum antifouling effect, existing technologies attempt to introduce natural capsaicin for synergistic antifouling, utilizing capsaicin to repel larvae and inhibit biofilm formation, thus compensating for the shortcomings of copper ions in controlling copper-resistant microorganisms. However, capsaicin is a polar small molecule without a long-lasting binding structure, and it dissolves rapidly in seawater, resulting in an initial burst of release followed by depletion of effective components. The release rate cannot be synchronously controlled with the self-polishing process of the coating film, making it difficult to achieve a stable and long-lasting effect for 3-5 years. Simply adding capsaicin to increase the amount increases the overall polarity of the system, leading to increased water absorption, easier copper salt complexation and precipitation, and decreased coating storage stability. In addition, current zinc acrylate antifouling systems also suffer from problems such as easy plasticizer migration, insufficient adaptability to different sea areas, and generally poor anti-settling and workability of thixotropic systems.

[0003] In summary, current technologies cannot achieve controlled release of capsaicin from antifouling paints, and there are problems in simultaneously achieving effective antifouling, long-lasting antifouling, and storage stability. Summary of the Invention

[0004] Therefore, the technical problem to be solved by the present invention is to overcome the deficiencies and defects in the prior art, thereby providing a self-polishing zinc acrylate antifouling paint with controllable release of capsaicin and effective antifouling, long-lasting antifouling and storage stability, as well as its preparation method.

[0005] To solve the above problems: This invention provides a self-polishing zinc acrylic antifouling paint, comprising the following components by weight: Zinc acrylate resin 30-40 parts, polyvinyl isobutyl ether resin 5-10 parts, rosin 10-15 parts, wetting and dispersing agent 1-1.5 parts, defoamer 0.5-1.0 parts, toughening agent 5-8 parts, thixotropic agent 1.5-4 parts, antifouling agent 20-35 parts, filler 5-10 parts, pigment 3-6 parts, solvent 10-20 parts; The antifouling agent comprises an inorganic antifouling agent, capsaicin and cucurbita[7]; The toughening agent includes polytetrahydrofuran ether diol and dioctyl sebacate; The rosin includes hydrogenated rosin and pentaerythritol ester of maleic rosin.

[0006] Preferably, the inorganic antifouling agent is in a mass ratio of (17-26):(3-9) to the total mass of capsaicin and cucurbita[7], wherein the mass ratio of cucurbita[7] to capsaicin is (2-2.5):1; the inorganic antifouling agent is selected from one or more of cuprous oxide, zinc oxide, and cuprous thiocyanate.

[0007] Preferably, the zinc acrylate resin is selected from one or more of SPZn-100, SPZn-300, and H100Z; the polyvinyl isobutyl ether resin is selected from one or two of LUT-I60 and LUT-I30.

[0008] Preferably, the polytetrahydrofuran ether diol is selected from one or both of PTMEG-2000 and PTMEG-1000; the dioctyl sebacate is selected from one or more of DOS99, JIAAO DOS, and DOS100.

[0009] Preferably, the hydrogenated rosin is selected from one or more of H100, H200, and QL-H601; The acid value of the maleic rosin pentaerythritol ester is ≤25 mgKOH / g, and the maleic rosin pentaerythritol ester is selected from one or more of MRP1205, M120, and MR-120.

[0010] Furthermore, the mass ratio of the polytetrahydrofuran ether diol to dioctyl sebacate is (2-4):1.

[0011] Furthermore, the mass ratio of the hydrogenated rosin to maleic rosin pentaerythritol ester is (1.5-2):1.

[0012] Preferably, the wetting and dispersing agent is selected from one or more of BYK AT-204, HH2015, CANFAIR 163A, BYK-163, EFKA-4060, and WinSperse 3193; The defoamer is a silicone-free defoamer, and the silicone-free defoamer is selected from one or more of Deqian 5500, CANFAIR 554, and EFKA 2020; The thixotropic agent is a compound of organobentonite, polyamide wax and hydrophobic fumed silica. The hydrophobic fumed silica is selected from one or two of R202 and R974. The compounding ratio of organobentonite, polyamide wax and hydrophobic fumed silica is 5:3:2. The filler is selected from one or more of barium sulfate, talc powder, wollastonite powder, calcined kaolin, and quartz powder; The pigment is selected from one or more of titanium dioxide, iron oxide red, and iron oxide yellow; The solvent is selected from one or more of mixed xylene, S-100, and S-150.

[0013] The present invention also provides a method for preparing the self-polishing zinc acrylate antifouling paint, comprising the following preparation steps: S1: Add the solvent, zinc acrylate resin, polyvinyl isobutyl ether resin, rosin, and toughening agent into the dispersion vessel in the predetermined weight proportions, heat to 50°C and stir at low speed for 20-30 minutes until completely dissolved, then cool to below 40°C to obtain the first mixture. S2: Add wetting and dispersing agent and defoamer to the first mixture and stir at low speed for 10 minutes; then add organic bentonite and hydrophobic fumed silica and disperse and pre-activate at high speed; then add filler and pigment, disperse at medium speed for 10 minutes and then transfer to a sand mill to grind to a fineness ≤40μm to obtain the second mixture; S3: Add inorganic antifouling agent, cucurbita[7] and capsaicin to the second mixture, stir at low speed for 20-30 minutes to obtain the third mixture; S4: Add polyamide wax to the third mixture and disperse and activate at high speed for 15-30 minutes; adjust to the working viscosity using solvent, filter and discharge to obtain self-polishing acrylic zinc antifouling paint.

[0014] Preferably, the low speed in steps S1-S4 is 300-500 r / min, the medium speed is 600-1000 r / min, and the high speed is 1200-1500 r / min.

[0015] The technical solution of this invention has the following advantages: 1. The resin provided by this invention is a compound of zinc acrylate resin and polyvinyl isobutyl ether resin. Zinc acrylate resin alone has high molecular polarity and strong hydrophilicity, resulting in excessively fast polishing rates during low-speed navigation. Furthermore, the high rigidity of zinc acrylate resin alone makes the formed paint film prone to cracking. Therefore, a compound of zinc acrylate resin and polyvinyl isobutyl ether resin is used as the film-forming resin for the antifouling paint. Polyvinyl isobutyl ether resin molecules are flexible and have low rotational resistance within the ether bonds on the molecular chain. When compounded with zinc acrylate resin, it weakens the strong intermolecular forces of zinc acrylate, effectively lowering the glass transition temperature and synergistically improving the crack resistance of the paint film. Additionally, polyvinyl isobutyl ether resin can prevent water molecules from entering the molecular interior without restriction, further regulating the polishing rate. Moreover, the addition of polyvinyl isobutyl ether resin exhibits excellent compatibility with various additives and rosin components, preventing filler and copper salt sedimentation and agglomeration, improving the stability of the antifouling paint, and balancing the tension gradient on the wet film surface, thereby eliminating defects such as pinholes and craters.

[0016] 2. The antifouling agent provided by the present invention is a compound of inorganic antifouling agent, cucurbita[7] and capsaicin. The inorganic antifouling agent is the main antifouling component and capsaicin is the auxiliary antifouling component. It can make up for the antifouling shortcomings of the inorganic antifouling agent. However, capsaicin is easy to be lost during static soaking and its release is not controlled. It is easily washed away by seawater in dynamic rinsing environment, resulting in a short antifouling life. Therefore, cucurbita[7] is added to control the release of capsaicin. The overall structure of cucurbita[7] is a symmetrical hollow barrel shape. The inner cavity is composed of a large number of methylene and hydrocarbon skeletons, which have a strong affinity for long alkyl groups. It can coat the hydrophobic long alkyl chain at the tail end of the capsaicin molecule. The long alkyl chain is closely attached to the inner cavity wall, which greatly reduces the interfacial energy of the system and forms a stable spatial configuration. In addition, cucurbita[7] has a ring of carbonyl groups at both ends, which can form hydrogen bonds with the amide group at the front end of the capsaicin molecule chain. Moreover, the polar molecular size at the front end of the capsaicin molecule chain is larger than the inner cavity diameter of cucurbita[7] and cannot enter the cavity. Therefore, during the production and storage stage, the rigid macrocycle of cucurbita[7] completely wraps the hydrophobic long alkyl chain in capsaicin, isolating it from air, ultraviolet light, trace amounts of free acid and copper ions in the system. It structurally blocks the oxidation and complexation inactivation pathway of capsaicin and solves the problem of free capsaicin storage failure. After the paint film is soaked in water, it can achieve reversible dissociation and slow release. Seawater is more polar than amide groups and replaces capsaicin NH to form water-cucurbita[7] hydrogen bonds. At the same time, water continuously seeps into the coating, and the hydrophobic carbon chain of capsaicin spontaneously comes out of the cavity and works synergistically with inorganic antifouling agents to play an antifouling role. After the water is removed, the hydrogen bonds are restored, and capsaicin can be re-encapsulated, thus achieving long-term antifouling. In static sea areas, cucurbita[7] can slow down the release rate of capsaicin in static sea areas by encapsulating capsaicin through cavities. During high-speed navigation of ships, the rigid cucurbita[7] structure can resist the shearing force of sand and gravel, ensuring the stable release of capsaicin. The combination of cucurbita[7] and capsaicin can achieve the dual effects of storage and locking and slow release of seawater, overcoming the defects of short-term antifouling and uncontrollable release of single capsaicin. Furthermore, by combining it with inorganic antifouling agents, long-term synergistic antifouling can be achieved, extending the antifouling life of the antifouling paint.

[0017] 3. The rosin provided by this invention is a compound of hydrogenated rosin and pentaerythritol maleate. The self-polishing of the paint film depends on the hydrolysis of zinc carboxylate on the side chain of zinc acrylate in water. The hydrogenated rosin in the system provides free carboxyl groups, acting as polishing promoters, improving resin hydrolysis efficiency, and ensuring sufficient polishing effect. However, prolonged static immersion in seawater leads to excessively rapid hydrolysis and severe damage to the paint film. Therefore, a compound of hydrogenated rosin and pentaerythritol maleate is used as the rosin for antifouling paint. Pentaerythritol maleate has almost no free carboxyl groups, which can reduce the overall acid value of the system, weaken the hydrophilicity of the paint film, and slow down excessive polishing under static conditions. This effectively matches the different working conditions of ships in motion and static environments, solving the problem of the inability to adjust the polishing rate of a single raw material. Furthermore, the compound of hydrogenated rosin and pentaerythritol maleate can increase the surface hardness of the paint film, reducing scratches caused by external substances during navigation. Simultaneously, the compound can further improve the compatibility between resins, resulting in a paint film free of gloss spots and delamination, and improving the storage stability of the coating.

[0018] 4. The toughening agent provided by this invention is a compound of polytetrahydrofuran ether glycol and dioctyl sebacate. Dioctyl sebacate has a short molecular chain, which easily interweaves between resin macromolecular chains, reducing the interaction forces between resins. However, using dioctyl sebacate alone as a toughening agent may lead to brittleness of the paint film over time, and small molecules easily migrate to the paint film surface and are washed away by seawater, affecting the wear resistance and polishing rate of the antifouling paint. Therefore, polytetrahydrofuran ether glycol and dioctyl sebacate are used as toughening agents for the antifouling paint. Polytetrahydrofuran ether glycol is a linear polyether with long chains, allowing the molecular chains to extend freely and exhibiting high flexibility. It entangles with zinc acrylate resin and rosin to form a network structure, locking in dioctyl sebacate, inhibiting the loss of small molecules, and enhancing the flexibility and wear resistance of the paint film. Simultaneously, the flexible network can disperse impact force, improving the impact resistance, crack resistance, and adhesion of the paint film. The compound of the two in the system achieves a balance between hardness and flexibility. Detailed Implementation

[0019] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0020] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0021] This invention provides a self-polishing zinc acrylic antifouling paint, comprising the following components by weight: Zinc acrylate resin 30-40 parts, polyvinyl isobutyl ether resin 5-10 parts, rosin 10-15 parts, wetting and dispersing agent 1-1.5 parts, defoamer 0.5-1.0 parts, toughening agent 5-8 parts, thixotropic agent 1.5-4 parts, antifouling agent 20-35 parts, filler 5-10 parts, pigment 3-6 parts, solvent 10-20 parts; wherein the antifouling agent includes inorganic antifouling agent, cucurbita[7] and capsaicin; the toughening agent includes polytetrahydrofuran ether diol and dioctyl sebacate; the rosin includes hydrogenated rosin and pentaerythritol ester of maleic rosin.

[0022] The resin provided by this invention is a compound of zinc acrylate resin and polyvinyl isobutyl ether resin. Zinc acrylate resin alone has high molecular polarity and strong hydrophilicity, resulting in excessively fast polishing rates during low-speed navigation. Furthermore, the high rigidity of zinc acrylate resin makes the formed paint film prone to cracking. Therefore, a compound of zinc acrylate resin and polyvinyl isobutyl ether resin is used as the film-forming resin for antifouling paint. Polyvinyl isobutyl ether resin has good molecular flexibility and low rotational resistance within the ether bonds of its molecular chain. When compounded with zinc acrylate resin, it weakens the strong intermolecular forces of zinc acrylate, effectively lowering the glass transition temperature and synergistically improving the crack resistance of the paint film. Moreover, polyvinyl isobutyl ether resin can prevent water molecules from entering the molecular interior without restriction, further regulating the polishing rate. In addition, the addition of polyvinyl isobutyl ether resin has excellent compatibility with various additives and rosin components, preventing filler and copper salt sedimentation and agglomeration, improving the stability of the antifouling paint, and balancing the tension gradient on the wet film surface, thereby eliminating defects such as pinholes and craters.

[0023] Preferably, the zinc acrylate resin is selected from one or more of SPZn-100, SPZn-300, and H100Z; and the polyvinyl isobutyl ether resin is selected from one or two of LUT-I60 and LUT-I30.

[0024] The antifouling agent provided by this invention uses a combination of inorganic antifouling agent, cucurbita[7] and capsaicin. The inorganic antifouling agent is the main antifouling component, and capsaicin is the auxiliary antifouling component. This can make up for the shortcomings of inorganic antifouling agent. However, capsaicin is easily lost during static soaking and its release is not controlled. It is easily washed away by seawater in dynamic rinsing environment, resulting in a short antifouling life. Therefore, cucurbita[7] is added to control the release of capsaicin. The overall structure of cucurbita[7] is a symmetrical hollow barrel shape. The inner cavity is composed of a large number of methylene and hydrocarbon skeletons, which have a strong affinity for long alkyl groups. It can coat the hydrophobic long alkyl chain at the tail end of the capsaicin molecule. The long alkyl chain is closely attached to the inner cavity wall, which greatly reduces the interfacial energy of the system and forms a stable spatial configuration. In addition, cucurbita[7] has a ring of carbonyl groups at both ends, which can form hydrogen bonds with the amide group at the front end of the capsaicin molecule chain. Furthermore, the polar molecular size at the front end of the capsaicin molecule chain is larger than the inner cavity diameter of cucurbita[7] and cannot enter the cavity. Therefore, during the production and storage stage, the rigid macrocycle of cucurbita[7] completely wraps the hydrophobic long alkyl chain in capsaicin, isolating it from air oxygen, ultraviolet light, trace amounts of free acid and copper ions in the system. This structurally blocks the oxidation and complexation inactivation pathway of capsaicin, solving the problem of free capsaicin storage failure. After the paint film is soaked in water, it can achieve reversible dissociation and slow release. Seawater is more polar than amide groups, which replace capsaicin NH to form water-cucurbita[7] hydrogen bonds. Water continuously penetrates into the coating, and the hydrophobic carbon chain of capsaicin spontaneously comes out of the cavity and plays an antifouling role with inorganic antifouling agents. After water is removed, the hydrogen bonds are restored, and capsaicin can be encapsulated again, thus achieving long-term antifouling. In static sea areas, cucurbita[7] can slow down the release of capsaicin in static sea areas by encapsulating capsaicin through cavities. During high-speed navigation of ships, the rigid cucurbita[7] structure can resist the shearing force of sand and gravel, ensuring the stable release of capsaicin. The combination of cucurbita[7] and capsaicin can achieve the dual effects of storage and locking and slow release of seawater, overcoming the defects of short-term antifouling and uncontrollable release of single capsaicin. Furthermore, by combining it with inorganic antifouling agents, long-term synergistic antifouling can be achieved, extending the antifouling life of the antifouling paint.

[0025] In this antifouling system, inorganic antifouling agent is the main antifouling component, and capsaicin is the auxiliary antifouling component, which can reduce the overall amount of inorganic antifouling agent. Cucurbita[7] can regulate the release of capsaicin. If the amount of inorganic antifouling agent is too large, it will easily accelerate the oxidation of rosin and resin, and the coating will easily change color during storage. If the amount is too small, the amount of copper ion leaching will be insufficient, and it will not be able to effectively inhibit barnacles, mussels and other substances. If the amount of capsaicin exceeds the upper limit of cucurbita[7], the release of a large amount of free capsaicin will be uncontrolled. If the amount is too small, it will not be able to form a complete antibacterial barrier, and will accelerate the polishing imbalance. Cucurbita[7] needs to be moderately excessive to ensure that capsaicin can be effectively encapsulated and prevent polar small molecules in the system from occupying the cavity of cucurbita[7]. Moreover, since cucurbita[7] is a strongly polar water-soluble macrocyclic ring, adding too much will increase the water absorption rate of the paint film, which will lead to an accelerated hydrolysis rate of zinc acrylate resin. Therefore, the compounding ratio of the inorganic antifouling agent with the sum of the masses of cucurbitacin[7] and capsaicin is (17-26):(3-9), wherein the mass ratio of cucurbitacin[7] to capsaicin is (2-2.5):1.

[0026] Furthermore, the inorganic antifouling agent is selected from one or more of cuprous oxide, zinc oxide, and cuprous thiocyanate.

[0027] The toughening agent provided by this invention is a compound of polytetrahydrofuran ether glycol and dioctyl sebacate. Dioctyl sebacate has a short molecular chain, which easily intercalates between resin macromolecular chains, reducing the intermolecular forces. However, using dioctyl sebacate alone as a toughening agent may lead to brittleness of the paint film over time, and small molecules easily migrate to the paint film surface and are washed away by seawater, affecting the wear resistance and polishing rate of the antifouling paint. Therefore, polytetrahydrofuran ether glycol and dioctyl sebacate are used as toughening agents for the antifouling paint. Polytetrahydrofuran ether glycol is a linear polyether with long chains; its molecular chains can extend freely and are highly flexible. It entangles with zinc acrylate resin and rosin to form a network structure, locking in dioctyl sebacate, inhibiting the loss of small molecules, and enhancing the flexibility and wear resistance of the paint film. Simultaneously, the flexible network can disperse impact force, improving the impact resistance, crack resistance, and adhesion of the paint film. The compounding of the two in the system achieves a balance between hardness and flexibility. The short molecular chain and high hydroxyl content of polytetrahydrofuran ether diol lead to increased water absorption of the paint film. After long-term use, the paint film lacks toughness and is prone to cracking. Furthermore, the hydroxyl groups more easily coordinate with copper and zinc ions to form precipitates. Conversely, excessively long molecular chains cause entanglement between molecules, hindering water penetration into the paint film and resulting in insufficient release of copper ions and capsaicin. On the other hand, a low hydroxyl content leads to insufficient interaction with zinc acrylate resin and rosin, reducing the adhesion of the paint film to the substrate and making it prone to peeling and flaking in alternating wet and dry environments. Preferably, the polytetrahydrofuran ether diol is selected from one or both of PTMEG-2000 and PTMEG-1000; and the dioctyl sebacate is selected from one or more of DOS99, JIAAODOS, and DOS100.

[0028] Insufficient amounts of polytetrahydrofuran ether glycol and dioctyl sebacate result in a hardened and brittle paint film with low flexibility and poor processing flow, leading to pinholes during spraying. Excessive amounts of either compound increase the number of free small molecules and hydroxyl groups, weakening the film's erosion resistance. Furthermore, excessive dioctyl sebacate weakens the intermolecular forces of zinc acrylate, impairing the film's polishing rate. Therefore, the optimal mass ratio of polytetrahydrofuran ether glycol to dioctyl sebacate is (2-4):1.

[0029] The rosin provided by this invention is a compound of hydrogenated rosin and pentaerythritol maleate. The self-polishing of the paint film depends on the hydrolysis of zinc carboxylate on the side chain of zinc acrylate in water. Hydrogenated rosin in the system provides free carboxyl groups, acting as polishing promoters, improving resin hydrolysis efficiency, and ensuring sufficient polishing effect. However, prolonged static immersion in seawater leads to excessively rapid hydrolysis and severe damage to the paint film. Therefore, a compound of hydrogenated rosin and pentaerythritol maleate is used as the rosin for antifouling paint. Pentaerythritol maleate has almost no free carboxyl groups, which can reduce the overall acid value of the system, weaken the hydrophilicity of the paint film, and slow down over-polishing under static conditions. This effectively matches the different working conditions of ships in motion and static environments, solving the problem of the inability to adjust the polishing rate of a single raw material. Furthermore, the compound of hydrogenated rosin and pentaerythritol maleate can increase the surface hardness of the paint film, reducing scratches caused by external substances during navigation. Simultaneously, the compound further improves the compatibility between the resins, resulting in a paint film free of gloss spots and delamination, and improving the storage stability of the coating.

[0030] Selecting hydrogenated rosin with high hydrogenation saturation and low double bond content can improve the oxidation resistance of the paint film and prevent oxidation and blackening of copper salts during long-term storage. Selecting maleic rosin pentaerythritol ester with high esterification degree and high softening point can increase the erosion resistance and stability of the paint film. Therefore, the hydrogenated rosin is selected from one or more of H100, H200, and QL-H601; the acid value of the maleic rosin pentaerythritol ester is ≤25 mgKOH / g, and the maleic rosin pentaerythritol ester is selected from one or more of MRP1205, M120, and MR-120. Of course, a higher proportion of hydrogenated rosin will lead to stronger hydrophilicity of the paint film and a faster overall polishing rate, while a higher proportion of maleic rosin pentaerythritol ester will lead to a slower overall polishing rate. Therefore, the mass ratio of hydrogenated rosin to maleic rosin pentaerythritol ester is (1.5-2):1.

[0031] The wetting and dispersing agent is selected from one or more of BYK AT-204, HH2015, CANFAIR 163A, BYK-163, EFKA-4060, and WinSperse 3193; the defoamer is a silicone-free defoamer, selected from one or more of Deqian 5500, CANFAIR 554, and EFKA 2020; the thixotropic agent is a compound of organobentonite, polyamide wax, and hydrophobic fumed silica, with the hydrophobic fumed silica selected from one or both of R202 and R974; the compounding ratio of organobentonite, polyamide wax, and hydrophobic fumed silica is 5:3:2. The filler is selected from one or more of barium sulfate, talc, wollastonite, calcined kaolin, and quartz powder; the pigment is selected from one or more of titanium dioxide, iron oxide red, and iron oxide yellow; the solvent is selected from one or more of mixed xylene, S-100, and S-150.

[0032] The present invention also provides a method for preparing the self-polishing zinc acrylate antifouling paint, comprising the following preparation steps: S1: Add the solvent, zinc acrylate resin, polyvinyl isobutyl ether resin, rosin, and toughening agent into the dispersion vessel in the predetermined weight proportions, heat to 50°C and stir at low speed for 20-30 minutes until completely dissolved, then cool to below 40°C to obtain the first mixture. S2: Add wetting and dispersing agent and defoamer to the first mixture and stir at low speed for 10 minutes; then add organic bentonite and hydrophobic fumed silica and disperse and pre-activate at high speed; then add filler and pigment, disperse at medium speed for 10 minutes and then transfer to a sand mill to grind to a fineness ≤40μm to obtain the second mixture; S3: Add inorganic antifouling agent, cucurbita[7] and capsaicin to the second mixture, stir at low speed for 20-30 minutes to obtain the third mixture; S4: Add polyamide wax to the third mixture and disperse and activate at high speed for 15-30 minutes; adjust to the working viscosity using solvent, filter and discharge to obtain self-polishing acrylic zinc antifouling paint.

[0033] Preferably, the low speed in steps S1-S4 is 300-500 r / min, the medium speed is 600-1000 r / min, and the high speed is 1200-1500 r / min.

[0034] Example 1 This invention provides a self-polishing zinc acrylic antifouling paint, comprising the following components by weight: 30 parts zinc acrylate resin H100Z, 5 parts polyvinyl isobutyl ether resin LUT-I60, 6 parts hydrogenated rosin H100, 4 parts maleic rosin pentaerythritol ester MRP1205, 17 parts cuprous oxide (inorganic antifouling agent), 1 part capsaicin, 2 parts cucurbita[7], 3.4 parts polytetrahydrofuran ether diol PTMEG-2000 (toughening agent), 1.7 parts dioctyl sebacate DOS99 (toughening agent), 1 part BYKAT-204 (wetting and dispersing agent), 0.5 parts Deqian 5500 (defoamer), 0.75 parts organic bentonite (thixotropic agent), 0.45 parts polyamide wax (thixotropic agent), 0.3 parts hydrophobic fumed silica R202 (thixotropic agent), 5 parts talc (filler), 3 parts iron oxide red (pigment), 10 parts mixed xylene (solvent).

[0035] The preparation method of the above-mentioned self-polishing zinc acrylate antifouling paint includes: S1: Add 8 parts of mixed xylene, 30 parts of zinc acrylate resin H100Z, 5 parts of polyvinyl isobutyl ether resin LUT-I60, 6 parts of hydrogenated rosin H100, 4 parts of maleic rosin pentaerythritol ester MRP1205, 3.4 parts of polytetrahydrofuran ether diol PTMEG-2000, and 1.7 parts of dioctyl sebacate DOS99 to a dispersion vessel in the predetermined weight parts, heat to 50℃, adjust the speed to 300 r / min, stir for 20 min until completely dissolved, and cool to below 40℃ to obtain the first mixture; S2: Add 1 part BYK AT-204 and 0.5 parts Deqian 5500 to the first mixture, adjust the speed to 300 r / min, and stir for 10 min; then add 0.75 parts organic bentonite and 0.3 parts hydrophobic fumed silica R202, adjust the speed to 1200 r / min, and disperse and pre-activate; then add 5 parts talc and 3 parts iron oxide red, adjust the speed to 600 r / min, disperse for 10 min, and then transfer to a sand mill to grind to a fineness ≤40 μm to obtain the second mixture; S3: Add 17 parts cuprous oxide, 1 part capsaicin and 2 parts cucurbita[7] to the second mixture, adjust the rotation speed to 300 r / min, stir for 20 min, and obtain the third mixture; S4: Add 0.45 parts of polyamide wax to the third mixture, adjust the rotation speed to 1200 r / min, and disperse and activate for 15 min; use 2 parts of mixed xylene to adjust to the working viscosity, filter and discharge to obtain self-polishing acrylic zinc antifouling paint.

[0036] Example 2 This invention provides a self-polishing zinc acrylic antifouling paint, comprising the following components by weight: 40 parts of zinc acrylate resin SPZn-100, 10 parts of polyvinyl isobutyl ether resin LUT-I30, 10 parts of hydrogenated rosin H200, 5 parts of maleic rosin pentaerythritol ester M120, 26 parts of zinc oxide (inorganic antifouling agent), 2.5 parts of capsaicin, 6.5 parts of cucurbita[7], 6.4 parts of polytetrahydrofuran ether diol PTMEG-2000 (toughening agent), 1.6 parts of dioctyl sebacate JIAA0 DOS (toughening agent), 1.5 parts of EFKA-4060 (wetting and dispersing agent), 1.0 parts of CANFAIR 554 (defoamer), 2 parts of organic bentonite (thixotropic agent), 1.2 parts of polyamide wax (thixotropic agent), 0.8 parts of hydrophobic fumed silica R974 (thixotropic agent), 10 parts of barium sulfate (filler), 6 parts of titanium dioxide (pigment), and 20 parts of S-100 (solvent).

[0037] The preparation method of the above-mentioned self-polishing zinc acrylate antifouling paint includes: S1: 18 parts S-100, 40 parts zinc acrylate resin SPZn-100, 10 parts polyvinyl isobutyl ether resin LUT-I30, 10 parts hydrogenated rosin H200, 5 parts maleic rosin pentaerythritol ester M120, 6.4 parts polytetrahydrofuran ether diol PTMEG-2000, and 1.6 parts dioctyl sebacate JIAA0 DOS are added to a dispersion vessel in the predetermined weight parts, heated to 50°C, and stirred for 30 minutes until completely dissolved. The mixture is then cooled to below 40°C to obtain the first mixture. S2: Add 1.5 parts EFKA-4060 and 1.0 parts CANFAIR 554 to the first mixture, adjust the speed to 500 r / min, and stir for 10 min; then add 2 parts organic bentonite and 0.8 parts hydrophobic fumed silica R974, adjust the speed to 1500 r / min, and disperse and pre-activate; then add 10 parts barium sulfate and 6 parts titanium dioxide, adjust the speed to 1000 r / min, disperse for 10 min, and then transfer to a sand mill to grind to a fineness ≤40 μm to obtain the second mixture; S3: Add 26 parts zinc oxide, 2.5 parts capsaicin and 6.5 parts cucurbita[7] to the second mixture, adjust the rotation speed to 500 r / min, stir for 30 min, and obtain the third mixture; S4: Add 1.2 parts of polyamide wax to the third mixture, adjust the rotation speed to 1500 r / min, and disperse and activate for 30 min; use 2 parts of S-100 to adjust to the application viscosity, filter and discharge to obtain self-polishing acrylic zinc antifouling paint.

[0038] Example 3 This invention provides a self-polishing zinc acrylic antifouling paint, comprising the following components by weight: 35 parts of zinc acrylate resin SPZn-300, 8 parts of polyvinyl isobutyl ether resin LUT-I60, 8 parts of hydrogenated rosin QL-H601, 4 parts of maleic rosin pentaerythritol ester MR-120, 24 parts of cuprous oxide (inorganic antifouling agent), 2 parts of capsaicin, 4 parts of cucurbita[7], 4.5 parts of polytetrahydrofuran ether diol PTMEG-1000 (toughening agent), 1.5 parts of dioctyl sebacate DOS100 (toughening agent), 1.2 parts of BYK-163 (wetting and dispersing agent), 0.8 parts of EFKA 2020 (defoamer), 1.5 parts of organic bentonite (thixotropic agent), 0.9 parts of polyamide wax (thixotropic agent), 0.6 parts of hydrophobic fumed silica R202 (thixotropic agent), 7 parts of quartz powder (filler), 4 parts of titanium dioxide (pigment), and 15 parts of S-150.

[0039] The preparation method of the above-mentioned self-polishing zinc acrylate antifouling paint includes: S1: 13 parts S-150, 35 parts zinc acrylate resin SPZn-300, 8 parts polyvinyl isobutyl ether resin LUT-I60, 8 parts hydrogenated rosin QL-H601, 4 parts maleic rosin pentaerythritol ester MR-120, 4.5 parts polytetrahydrofuran ether diol PTMEG-1000, and 1.5 parts dioctyl sebacate DOS100 are added to a dispersion vessel in the predetermined weight parts, heated to 50°C, and stirred for 25 minutes at a speed of 400 r / min until completely dissolved. The mixture is then cooled to below 40°C to obtain the first mixture. S2: Add 1.2 parts BYK-163 and 0.8 parts EFKA 2020 to the first mixture, adjust the speed to 400 r / min, and stir for 10 min; then add 1.5 parts organic bentonite and 0.6 parts hydrophobic fumed silica R202, adjust the speed to 1300 r / min, and disperse and pre-activate; then add 7 parts quartz powder and 4 parts titanium dioxide, adjust the speed to 800 r / min, disperse for 10 min, and then transfer to a sand mill to grind to a fineness ≤40 μm to obtain the second mixture; S3: Add 24 parts cuprous oxide, 2 parts capsaicin, and 4 parts cucurbita[7] to the second mixture, adjust the rotation speed to 400 r / min, stir for 25 min, and obtain the third mixture; S4: Add 0.9 parts of polyamide wax to the third mixture, adjust the rotation speed to 1300 r / min, and disperse and activate for 20 min; use 2 parts of S-150 to adjust to the application viscosity, filter and discharge to obtain self-polishing acrylic zinc antifouling paint.

[0040] Comparative Example 1 This comparative example provides a self-polishing zinc acrylic antifouling paint. The difference from Example 1 is that the antifouling component of this comparative example does not contain cucurbita[7], and the antifouling component only contains equal amounts of cuprous oxide and capsaicin.

[0041] Comparative Example 2 This comparative example provides a self-polishing zinc acrylate antifouling paint. The difference from Example 1 is that this comparative example uses an equal amount of dioctyl sebacate (DOS99) instead of polytetrahydrofuran ether diol (PTMEG-2000).

[0042] Comparative Example 3 This comparative example provides a self-polishing zinc acrylate antifouling paint. The difference from Example 1 is that this comparative example uses an equal amount of zinc acrylate resin H100Z to replace polyvinyl isobutyl ether resin LUT-I60.

[0043] Comparative Example 4 This comparative example provides a self-polishing zinc acrylate antifouling paint. The difference from Example 1 is that this comparative example uses an equal amount of hydrogenated rosin H100 to replace maleic rosin pentaerythritol ester MRP1205.

[0044] In this invention, the performance of the self-polishing zinc acrylic antifouling paints prepared in Examples 1-3 and Comparative Examples 1-4 was tested according to the performance indicators in Table 1, and the test results are shown in Table 1.

[0045] Table 1 Performance test indicators of coatings and performance test results of self-polishing zinc acrylic antifouling paint

[0046] As shown in Table 1, the self-polishing acrylic zinc antifouling paint provided by the present invention has the characteristics of stable storage, high polishing rate adaptability, long antifouling life, high adhesion, good flexibility and strong impact resistance, and is suitable for antifouling of ship bottoms and marine underwater facilities.

[0047] Comparing Comparative Example 1 and Example 1, it was found that adding cucurbita[7] to the self-polishing zinc acrylic antifouling paint can regulate the release of capsaicin. When combined with inorganic antifouling agents, it can improve the antifouling performance and extend the antifouling life. Moreover, the antifouling coating has outstanding performance in shallow sea immersion, dynamic simulation experiments and abrasion rate detection, and also improves the storage stability of the antifouling paint.

[0048] Comparing Comparative Example 2 and Example 1, it was found that the addition of polytetrahydrofuran ether diol to the self-polishing zinc acrylate antifouling paint enhanced adhesion, flexibility, and impact resistance, and passed the dynamic simulation experiment.

[0049] Comparing Comparative Example 3 and Example 1, it was found that the addition of polyvinyl isobutyl ether resin to the self-polishing zinc acrylic antifouling paint enhanced the flexibility of the paint film and improved the storage stability of the antifouling paint, which was also verified by dynamic simulation experiments.

[0050] Comparing Comparative Example 4 and Example 1, it was found that the addition of maleic rosin pentaerythritol ester to the self-polishing zinc acrylate antifouling paint resulted in superior performance in terms of adhesion, flexibility, impact resistance, shallow sea immersion, dynamic simulation experiments, and abrasion rate. Furthermore, it improved the storage stability of the antifouling paint. Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A self-polishing zinc acrylic anti-fouling paint, characterized in that, The product comprises the following components by weight: 30-40 parts zinc acrylate resin, 5-10 parts polyvinyl isobutyl ether resin, 10-15 parts rosin, 1-1.5 parts wetting and dispersing agent, 0.5-1.0 parts defoamer, 5-8 parts toughening agent, 1.5-4 parts thixotropic agent, 20-35 parts antifouling agent, 5-10 parts filler, 3-6 parts pigment, and 10-20 parts solvent. The antifouling agent comprises an inorganic antifouling agent, capsaicin and cucurbita[7]; The toughening agent includes polytetrahydrofuran ether diol and dioctyl sebacate; The rosin includes hydrogenated rosin and pentaerythritol ester of maleic rosin.

2. The self-polishing zinc acrylic antifouling paint according to claim 1, characterized in that, The inorganic antifouling agent is in the mass ratio of capsaicin and cucurbita[7] to (17-26):(3-9), wherein the mass ratio of cucurbita[7] to capsaicin is (2-2.5):1; the inorganic antifouling agent is selected from one or more of cuprous oxide, zinc oxide, and cuprous thiocyanate.

3. The self-polishing zinc acrylic antifouling paint according to claim 1, characterized in that, The zinc acrylate resin is selected from one or more of SPZn-100, SPZn-300, and H100Z; The polyvinyl isobutyl ether resin is selected from one or both of LUT-I60 and LUT-I30.

4. The self-polishing zinc acrylic antifouling paint according to claim 1, characterized in that, The polytetrahydrofuran ether diol is selected from one or both of PTMEG-2000 and PTMEG-1000; the dioctyl sebacate is selected from one or more of DOS99, JIAAO DOS, and DOS100.

5. The self-polishing zinc acrylic antifouling paint according to claim 4, characterized in that, The mass ratio of the polytetrahydrofuran ether diol to dioctyl sebacate is (2-4):

1.

6. The self-polishing zinc acrylic antifouling paint according to claim 1, characterized in that, The hydrogenated rosin is selected from one or more of H100, H200, and QL-H601; The acid value of the maleic rosin pentaerythritol ester is ≤25 mgKOH / g, and the maleic rosin pentaerythritol ester is selected from one or more of MRP1205, M120, and MR-120.

7. The self-polishing zinc acrylic antifouling paint according to claim 6, characterized in that, The mass ratio of the hydrogenated rosin to the maleic rosin pentaerythritol ester is (1.5-2):

1.

8. The self-polishing zinc acrylic antifouling paint according to claim 1, characterized in that, The wetting and dispersing agent is selected from one or more of BYK AT-204, HH2015, CANFAIR 163A, BYK-163, EFKA-4060, and WinSperse 3193; The defoamer is a silicone-free defoamer, and the silicone-free defoamer is selected from one or more of Deqian 5500, CANFAIR 554, and EFKA 2020; The thixotropic agent is a compound of organobentonite, polyamide wax and hydrophobic fumed silica. The hydrophobic fumed silica is selected from one or two of R202 and R974. The compounding ratio of organobentonite, polyamide wax and hydrophobic fumed silica is 5:3:

2. The filler is selected from one or more of barium sulfate, talc powder, wollastonite powder, calcined kaolin, and quartz powder; The pigment is selected from one or more of titanium dioxide, iron oxide red, and iron oxide yellow; The solvent is selected from one or more of mixed xylene, S-100, and S-150.

9. The method for preparing the self-polishing zinc acrylate antifouling paint according to any one of claims 1-8, characterized in that, Includes the following steps: S1: Add the solvent, zinc acrylate resin, polyvinyl isobutyl ether resin, rosin, and toughening agent into the dispersion vessel in the predetermined weight proportions, heat to 50°C and stir at low speed for 20-30 minutes until completely dissolved, then cool to below 40°C to obtain the first mixture. S2: Add wetting and dispersing agent and defoamer to the first mixture and stir at low speed for 10 minutes; then add organic bentonite and hydrophobic fumed silica and disperse and pre-activate at high speed; then add filler and pigment, disperse at medium speed for 10 minutes and then transfer to a sand mill to grind to a fineness ≤40μm to obtain the second mixture; S3: Add inorganic antifouling agent, cucurbita[7] and capsaicin to the second mixture, stir at low speed for 20-30 minutes to obtain the third mixture; S4: Add polyamide wax to the third mixture and disperse and activate at high speed for 15-30 minutes; adjust to the working viscosity using solvent, filter and discharge to obtain self-polishing acrylic zinc antifouling paint.

10. The method for preparing the self-polishing zinc acrylate antifouling paint according to claim 9, characterized in that, In steps S1-S4, the low speed is 300-500 r / min, the medium speed is 600-1000 r / min, and the high speed is 1200-1500 r / min.

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