Water-based antifouling paint for shielding fouling by utilizing hydration layer as well as preparation method and application of water-based antifouling paint

Abstract

The invention provides a water-based antifouling coating for shielding fouling by utilizing a hydration layer as well as a preparation method and application of the water-based antifouling coating, and relates to the technical field of antifouling coatings. The invention provides a water-based antifouling coating for shielding fouling by using a hydration layer. The water-based antifouling coating comprises the following components in percentage by mass: 1-10% of a hydrophilic macromolecular component, 30-50% of a water-based self-polishing emulsion, 40-50% of water-based slurry and the balance of water. Hydrophilic macromolecular components in the water-based antifouling paint provided by the invention can form a hydration layer to physically shield fouling adhesion, so that broad-spectrum antifouling is realized; the hydration effect process of the water-based self-polishing emulsion containing the organosilicon self-polishing component is regulated, controlled and updated at the micron scale level; the antifouling capability of an interface hydration layer is kept for a long time; the water-based slurry improves the mechanical property and the scouring resistance of the coating and supports the antifouling property of the coating. The water-based antifouling paint for shielding fouling by using the hydration layer provided by the invention is excellent in antifouling effect and low in VOC (Volatile Organic Compounds) and antifouling agent content.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of antifouling coatings, in particular to a water-based antifouling coating for shielding fouling by hydration layer and a preparation method and application thereof. BACKGROUND

[0002] The equipment used in the marine fishery and transportation industries is affected by biological fouling attachment, resulting in problems such as shortened service life and increased operation and maintenance costs, which seriously affect the deep development and utilization of marine resources. At present, coating is the most economical and effective antifouling means. In recent years, with the increasing restrictions on the use of high-biological-hazard antifouling agents and volatile organic compounds (VOCs) worldwide, environmental protection and greenness have become the main trend of marine antifouling technology. Therefore, it is urgent to develop low-toxicity and low-VOC water-based antifouling coating technology.

[0003] At present, there are few public reports on mature low-toxicity and low-VOC water-based antifouling coating technology. Existing researches mostly use different water-based resins in combination with antifouling agents. Excessive use of antifouling agents can lead to toxin accumulation in organisms, seriously threatening fish food safety and marine ecological balance. In order to reduce the use of coating antifouling agents, a low surface energy coating of the detachment type is proposed. Related technology discloses a low surface energy antifouling coating based on water-based silicone modified resin, but the coating does not have long-term antifouling ability. SUMMARY

[0004] Therefore, the purpose of the present application is to provide a water-based antifouling coating for shielding fouling by hydration layer and a preparation method and application thereof. The water-based antifouling coating provided by the present application has excellent antifouling effect and can achieve long-term antifouling.

[0005] In order to achieve the above-mentioned purpose of the application, the following technical solutions are provided: The present application provides a water-based antifouling coating for shielding fouling by hydration layer, which comprises the following components by mass percentage: 1-10% of a hydrophilic macromolecular component, 30-50% of a water-based self-polishing emulsion, 40-50% of a water-based slurry, and the balance of water; The hydrophilic macromolecular component is a powder particulate hydrophilic macromolecular polymer, and the weight average molecular weight of the hydrophilic macromolecular polymer is 2000-100000, the solubility in artificial seawater at 23℃ is <12g / L, and the water absorption is >0.1wt%; The water-based self-polishing emulsion is obtained by polymerization reaction of the following raw materials by mass percentage: 3-10% of a silane ester-based monomer, 10-20% of a vinyl unsaturated monomer, 0.1-0.5% of an initiator, 0.5-1% of an emulsifier, 0.1-0.3% of an alkaline buffer, 0.1-0.5% of a plasticizer, and the balance of water; The aqueous slurry comprises the following components in mass fraction: thickening agent 0.01-0.05 parts, aqueous wetting dispersant 0.5-2.5 parts, antifouling agent 20-40 parts, aqueous bentonite 0.1-0.3 parts and water 40-60 parts.

[0006] Preferably, the hydrophilic groups of the hydrophilic macromolecule polymer comprise one or more of hydroxyl, amino, carboxyl, amide and polyvinyl.

[0007] Preferably, the hydrophilic macromolecule polymer comprises one or more of alcohol polymer, acrylic polymer and acrylic derivative polymer.

[0008] Preferably, the acrylsilane monomer comprises one or more of triisopropyl methacrylsilane and / or triisopropyl acrylsilane; the vinyl unsaturated monomer comprises one or more of methyl methacrylate, butyl acrylate, methacrylic acid, acrylamide, acrylic acid, acrylonitrile, styrene, vinyl acetate and methacryloyl ethyl sulfobetaine.

[0009] Preferably, the preparation method of the aqueous self-polishing emulsion comprises the following steps: mixing the acrylsilane monomer, the vinyl unsaturated monomer, the emulsifier and the first part of water to obtain a monomer emulsion; mixing the initiator with the second part of water to obtain an initiator solution; mixing the alkaline buffer, the remaining water and part of the monomer emulsion, adding part of the initiator solution thereto, performing a first polymerization reaction to obtain a seed emulsion; the temperature of the first polymerization reaction is 70-90℃; adding the remaining monomer emulsion and the remaining initiator solution to the seed emulsion, performing a second polymerization reaction, cooling the obtained reaction liquid to room temperature, adding a plasticizer thereto to obtain the aqueous self-polishing emulsion; the temperature of the second polymerization reaction is 80-100℃.

[0010] Preferably, the antifouling agent comprises one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron and zineb.

[0011] Preferably, the aqueous antifouling coating further comprises the following components in mass percentage: aqueous leveling agent 0.2-0.6%, aqueous defoaming agent 0.4-1.2%, film-forming aid 0.4-1.2%.

[0012] The present application provides a preparation method of the aqueous antifouling coating for shielding fouling by using hydration layer as described in the above technical solutions, comprising the following steps: Mixing the hydrophilic macromolecular component, the water-based self-polishing emulsion, the water-based slurry and water to obtain the water-based antifouling coating for shielding fouling by hydration layer.

[0013] The application provides application of the water-based antifouling coating for shielding fouling by hydration layer or the water-based antifouling coating for shielding fouling by hydration layer prepared by the preparation method in the surface protection of marine equipment.

[0014] Preferably, the marine equipment comprises a culture net cage.

[0015] The application provides a water-based antifouling coating for shielding fouling by hydration layer, which comprises the following components in mass percentage: 1-10% of a hydrophilic macromolecular component, 30-50% of a water-based self-polishing emulsion, 40-50% of a water-based slurry and the balance of water; the water-based self-polishing emulsion is obtained by polymerization of the following components in mass percentage: 3-10% of a silane acrylate monomer, 10-20% of a vinyl unsaturated monomer, 0.1-0.5% of an initiator, 0.5-1% of an emulsifier, 0.1-0.3% of an alkaline buffer and the balance of water; and the water-based slurry comprises the following components in mass percentage: 0.01-0.05 parts of a thickening agent, 0.5-2.5 parts of a water-based wetting dispersant, 20-40 parts of an antifouling agent, 0.1-0.3 parts of a water-based bentonite and 40-60 parts of water. The main antifouling components of the water-based antifouling coating provided by the application are the hydrophilic macromolecular component and the water-based self-polishing emulsion containing a silicone self-polishing component, and the mechanism is that a dense high-energy barrier hydration layer is formed by the interfacial hydration effect of the hydrophilic macromolecular component, so that fouling is difficult to break through, physical shielding resistance is achieved in the initial adhesion stage of fouling, and strong and broad-spectrum antifouling is achieved; the hydrolysis self-polishing performance of the water-based self-polishing emulsion controls and updates the hydration effect process in the micron scale level, and long-acting interface hydration layer antifouling ability is maintained. In addition, the water-based slurry can improve the mechanical properties and erosion resistance of the coating, and support the antifouling performance of the coating. The water-based antifouling coating provided by the application shields fouling by controllable interfacial hydration effect to achieve antifouling, and has excellent antifouling effect, can achieve long-acting antifouling, and the VOC and antifouling agent contents in the coating are low, which effectively avoids the excessive use of traditional coating antifouling agents; and the water-based antifouling coating also has excellent mechanical properties.

[0016] The results of the embodiments show that the water-based antifouling paint provided by the present application has excellent antifouling performance. After 120 days of real sea static hanging piece, there is no obvious fouling attachment on the surface of the netting of the culture net cage, which shows excellent long-acting anti-biofouling characteristics. The VOC content is low (less than 30 g / L), and there is no toxic agent such as organic tin, which is friendly to the environment and has good film-forming properties. The surface drying time of the paint film is 1-2 hours, the real drying time is 12 hours, the adhesion of the paint film after film formation can reach level 1 (GB / T 1720-2020), the flexibility can reach 1 mm (GB / T 1731-2020), the impact resistance is greater than 50 kg·cm (GB / T 1732-2020), there is no blistering and falling after soaking in artificial seawater for 120 days, the self-polishing rate of the paint film is stable, and the average polishing rate is 0.26-0.32 microns / day. BRIEF DESCRIPTION OF DRAWINGS

[0017] Figure 1 The results of the shallow sea static hanging plate experiment of the sample coated with the water-based marine antifouling paint using the water layer to shield fouling obtained in embodiments 1-6 and the blank sample. DETAILED DESCRIPTION

[0018] The present application provides a water-based antifouling paint using a water layer to shield fouling, which comprises the following components by mass percentage: 1-10% of a hydrophilic macromolecular component, 30-50% of a water-based self-polishing emulsion, 40-50% of a water-based slurry, and the balance of water; The hydrophilic macromolecular component is a powder particulate hydrophilic macromolecular polymer, and the weight average molecular weight of the hydrophilic macromolecular polymer is 2000-100000, the solubility in artificial seawater at 23°C is <12 g / L, and the water absorption is >0.1 wt%; The water-based self-polishing emulsion is obtained by polymerization reaction of the following preparation raw materials by mass percentage: 3-10% of a silane ester-based monomer, 10-20% of a vinyl unsaturated monomer, 0.1-0.5% of an initiator, 0.5-1% of an emulsifier, 0.1-0.3% of an alkaline buffer, 0.1-0.5% of a plasticizer, and the balance of water; The water-based slurry comprises the following components by mass fraction: 0.01-0.05 parts of a thickening agent, 0.5-2.5 parts of a water-based wet dispersant, 20-40 parts of an antifouling agent, 0.1-0.3 parts of a water-based bentonite, and 40-60 parts of water.

[0019] In the present application, the raw materials involved are commercially available products well known in the art unless otherwise specified.

[0020] The water-based antifouling paint provided by the present application includes 1-10% of a hydrophilic macromolecular component, preferably 2-9%, and more preferably 4-8%, which can be 5% or 8%, in terms of mass percentage. In the present application, the hydrophilic macromolecular component is a powder particulate hydrophilic macromolecular polymer (i.e., the hydrophilic macromolecular component is directly added in the form of powder particles), and in the embodiments of the present application, the particle size of the hydrophilic macromolecular polymer is 0.02-120 µm. If the particle size is too small, the hydrophilic macromolecular polymer cannot be fully hydrated, and if the particle size is too large, the hydrophilic macromolecular polymer swells in water, which can cause surface state deterioration. The weight average molecular weight of the hydrophilic macromolecular polymer is 2000-100000 (preferably 3000-50000, which can be 3000 or 10000), the solubility in artificial seawater at 23°C is <12 g / L (preferably <10 g / L), and the water absorption is >0.1 wt% (preferably >1 wt%). In the present application, the particle size refers to the weight average particle size obtained by light scattering; the solubility is the solubility obtained by drying and weighing the hydrophilic macromolecular polymer at room temperature under reduced pressure in artificial seawater specified in ASTM D1141-98; and the water absorption is obtained by the following method: 1 g of hydrophilic macromolecular polymer particles dried at room temperature under vacuum is accurately weighed and added to 50 g of artificial seawater prepared according to ASTM D1141-98, stirred at 23°C for 5 h, then filtered, washed the residue, weighed and calculated.

[0021] In the present application, the hydrophilic macromolecular polymer has strong hydrophilicity and low solubility, which is suitable for exerting the antifouling performance of the hydration layer. If the solubility exceeds 12 g / L, the solubility of the hydrophilic macromolecular polymer is too high, which is easily dissolved in water (such as seawater) and flows out from the surface of the coating film; if the water absorption is <0.1 wt%, the hydrophilic macromolecular polymer has low hydrophilicity in water, which cannot be fully hydrated, and the antifouling shielding effect is inhibited; if the molecular weight is less than 2000, the film-forming property of the coating film will be reduced, and if the molecular weight exceeds 100000, the storage stability of the obtained coating is poor and not practical.

[0022] In the present application, the hydrophilic groups of the hydrophilic macromolecule polymer preferably include one or more of hydroxyl, amino, carboxyl, amide and polyvinyl; the hydrophilic macromolecule polymer further preferably includes one or more of alcohol polymer, acrylic polymer and acrylic derivative polymer, the alcohol polymer preferably includes polyvinyl alcohol (PVA) and / or polyethylene glycol (PEG); the acrylic polymer preferably includes polyacrylic acid and / or sodium polyacrylate. In the embodiments of the present application, the hydrophilic macromolecule polymer is preferably an acrylic polymer. In the present application, the hydrophilic macromolecule polymer has an appropriate amount of hydrophilic groups and cross-linkable characteristics, in which the hydrophilic functional groups can increase the water absorption amount and facilitate the generation of hydration effect, while too high hydrophilicity can accelerate the dissolution, and the solubility can be adjusted by physical cross-linking, i.e. the hydrophilic macromolecule polymer can be physically cross-linked to control the solubility by hydrogen bonding, particle interaction, etc. while having strong hydrophilicity.

[0023] In the present application, the hydrophilic macromolecule component generates a strong hydration layer, shields fouling adhesion, and provides a broad-spectrum antifouling effect of the antifouling coating.

[0024] In mass percentage, the water-based antifouling coating for shielding fouling by using a hydration layer provided by the present application includes 30-50%, preferably 33-45%, more preferably 35-42%, which can be 35% or 40% of the water-based self-polishing emulsion.

[0025] In the present application, the water-based self-polishing emulsion is obtained by polymerization reaction of raw materials including 3-10% of silane acrylate monomer, 10-20% of vinyl unsaturated monomer, 0.1-0.5% of initiator, 0.5-1% of emulsifier, 0.1-0.3% of alkaline buffer, 0.1-0.5% of plasticizer and the balance of water.

[0026] In the present application, the raw materials of the water-based self-polishing emulsion include 3-10%, preferably 5-9%, which can be 6%, 7%, 8% or 9% of silane acrylate monomer in mass percentage; the silane acrylate monomer preferably includes triisopropyl methyl methacrylate and / or triisopropyl acrylate, more preferably triisopropyl methyl methacrylate. In the present application, the silane acrylate monomer can undergo hydrolysis reaction in water to regulate the performance of the hydration layer.

[0027] In the present application, the preparation raw material of the water-based self-polishing emulsion includes 10-20% of vinyl unsaturated monomer in mass percentage, preferably 12-18%, which can be 14% or 15%; the vinyl unsaturated monomer preferably includes one or more of methyl methacrylate, butyl acrylate, methacrylic acid, acrylamide, acrylic acid, acrylonitrile, styrene, vinyl acetate and methacryloyl ethyl sulfobetaine, more preferably methyl methacrylate, butyl acrylate, acrylic acid, styrene and methacryloyl ethyl sulfobetaine, wherein the mass ratio of the methyl methacrylate, butyl acrylate, acrylic acid, styrene and methacryloyl ethyl sulfobetaine is preferably (3.5-9.5):(1.5-5):(0.2-0.8):(1.2-3.2):1, which can be 6.5:3.75:0.5:2.25:1; the methyl methacrylate, butyl acrylate and styrene can improve the water resistance of the coating, and the acrylic acid and methacryloyl ethyl sulfobetaine can improve the interfacial hydration properties of the coating. In the present application, the double bonds in the vinyl unsaturated monomer can polymerize the monomers into high molecular chains during emulsion polymerization, thereby obtaining an emulsion with a certain function.

[0028] In the present application, the preparation raw material of the water-based self-polishing emulsion includes 0.1-0.5% of initiator in mass percentage, preferably 0.2-0.5%, more preferably 0.35-0.5%; the initiator is preferably a persulfate initiator, more preferably includes ammonium persulfate and / or potassium persulfate, and further preferably is ammonium persulfate.

[0029] In the present application, the preparation raw material of the water-based self-polishing emulsion includes 0.5-1% of emulsifier in mass percentage, preferably 0.6-0.9%, more preferably 0.7-0.8%; the emulsifier preferably includes two of sodium dodecyl sulfate, sodium cetyl sulfate, cetyltrimethylammonium chloride, dodecylpyridinium chloride, alkylphenol polyoxyethylene ether-10 (OP-10) and ceteareth-10, more preferably sodium dodecyl sulfate and alkylphenol polyoxyethylene ether-10, wherein the mass ratio of the sodium dodecyl sulfate and alkylphenol polyoxyethylene ether-10 is preferably 1:2. The use of the compounded emulsifier in the present application can effectively avoid the defect of poor emulsion stability caused by charge effect.

[0030] In the present application, the preparation raw material of the water-based self-polishing emulsion includes 0.1-0.3% of alkaline buffer in mass percentage, preferably 0.15-0.25%, which can be 0.2%. In the present application, the alkaline buffer preferably includes one or more of sodium hydroxide, potassium hydroxide, sodium acetate, triethanolamine, sodium carbonate and sodium bicarbonate, more preferably sodium carbonate or sodium bicarbonate. In the present application, the alkaline buffer can make the emulsion polymerization more stable.

[0031] In the present application, the preparation raw material of the water-based self-polishing emulsion includes 0.1-0.5% of plasticizer, preferably 0.15-0.5%, more preferably 0.35-0.5% by mass percentage; the plasticizer preferably includes one or more of dioctyl phthalate, dibutyl phthalate, tricresyl phosphate and triphenyl phosphate, more preferably dioctyl phthalate. In the present application, the plasticizer serves to improve the flexibility, adhesion and durability of the coating film.

[0032] In the present application, the preparation raw material of the water-based self-polishing emulsion includes water in excess, and the water is preferably deionized water.

[0033] In the present application, the water-based self-polishing emulsion is a water-based self-polishing emulsion containing a silicone self-polishing component, and has a pH value of preferably 6-8, more preferably 7-7.5, and a mean particle size of latex particles of preferably 200-500 nm, more preferably 200-250 nm.

[0034] In the present application, the preparation method of the water-based self-polishing emulsion preferably includes the following steps: mixing a silane acrylate monomer, a vinyl unsaturated monomer, an emulsifier and a first portion of water to obtain a monomer emulsion; mixing an initiator and a second portion of water to obtain an initiator solution; mixing a basic buffer, the remaining water and part of the monomer emulsion, adding part of the initiator solution thereto, and performing a first polymerization reaction to obtain a seed emulsion; adding the remaining monomer emulsion and the remaining initiator solution to the seed emulsion, performing a second polymerization reaction, cooling the obtained reaction liquid to room temperature, adding a plasticizer thereto, and obtaining the water-based self-polishing emulsion.

[0035] In the present application, the mass of the first portion of water preferably accounts for 50-70%, more preferably 53-60% of the total mass of water required for preparing the water-based self-polishing emulsion; the mixing of the silane acrylate monomer, the vinyl unsaturated monomer, the emulsifier and the first portion of water is preferably performed under stirring, and the stirring speed is preferably 500-700 r / min, more preferably 550-600 r / min, and the time is preferably 25-45 min, more preferably 30-35 min.

[0036] In the present application, the mass of the second portion of water preferably accounts for 6-6.5% of the total mass of water required for preparing the water-based self-polishing emulsion.

[0037] In the present application, the mass of the partial monomer emulsion preferably accounts for 18-30% of the total mass of the monomer emulsion, more preferably 19-28%; the mass of the partial initiator solution preferably accounts for 9-20% of the total mass of the initiator solution, more preferably 9-12%. In the present application, the mixing of the basic buffer, the remaining water and the partial monomer emulsion is preferably carried out under stirring, the stirring speed is preferably 400-600 r / min, more preferably 500-600 r / min, and the time is preferably 30-60 min, more preferably 30-55 min. In the present application, the temperature of the first polymerization reaction is preferably 70-90℃, further preferably 80-85℃, and can be 81℃. The present application does not have special requirements for the time of the first polymerization reaction, and the solution becomes blue after the latex particles are stably formed, at which time the latex particle size is 180-220 nm. In the present application, by adding the initiator in stages, the polymerization reaction is continuously initiated, and the desired emulsion is obtained by controlling the rate, avoiding rapid polymerization and obtaining the desired product. In the present application, after the first polymerization reaction is completed, the stirring is preferably continued for 0.5-1 h, which can be 30-45 min, and the stirring speed is preferably 400-600 r / min, which can be 500-550 r / min. The stirring can make the seed emulsion obtained by the first polymerization reaction uniformly dispersed, facilitate the second polymerization reaction by dropwise adding the remaining monomer emulsion and the remaining initiator solution, and also prevent local polymerization of the emulsion, while making the solution temperature distribution more uniform (the polymerization reaction is an exothermic reaction).

[0038] In the present application, the adding mode of the remaining monomer emulsion and the remaining initiator solution is preferably dropwise addition, and the dropwise addition rate is 1-2 h to add the remaining monomer emulsion and the remaining initiator solution, and the system temperature is maintained at 70-90℃ during the dropwise addition. In the present application, the temperature of the second polymerization reaction is preferably 80-100℃, further preferably 80-90℃; the time of the second polymerization reaction is preferably 1-2.5 h, and the time of the second polymerization reaction is calculated from the start of the dropwise addition of the remaining monomer emulsion and the remaining initiator solution. In the present application, the second polymerization reaction is more preferably a staged temperature rising reaction, which preferably includes: first rising to 80-85℃ for 0.5-1.5 h, and then continuously rising to 86-90℃ for 0.5-1 h. In the present application, the second polymerization reaction is the constant speed period of emulsion polymerization, during which the system maintains a stable chain growth environment by rising the temperature.

[0039] Preferably, the reaction solution is first cooled to 50-60°C (53-56°C), and the pH value of the reaction solution is adjusted to 6-8, and then the plasticizer is added to the reaction solution cooled to room temperature. In the present application, the pH adjuster used to adjust the pH value of the reaction solution is preferably ammonia, triethylamine or ethylenediamine, and more preferably saturated ammonia. By adjusting the pH value, the stability of the system is maintained, and the formation of gel is inhibited. In the present application, after the plasticizer is added, the obtained emulsion is preferably subjected to stirring and filtration to obtain the water-based self-polishing emulsion containing the silicone self-polishing component. In the present application, the stirring time is preferably 5-15 min, and more preferably 8-12 min. The present application does not have special requirements for the filtration mode, and the filtration mode commonly used in the art can be used, such as filtration with gauze.

[0040] In the present application, the water-based self-polishing emulsion contains acrylsilane monomers, which are hydrolyzed in seawater to regulate and update the hydration effect process and long-acting maintain the interface hydration layer antifouling ability.

[0041] The water-based antifouling coating provided by the present application for shielding fouling by using a hydration layer contains 40-50% of the water-based slurry, preferably 40-48%, and more preferably 40-46%, which can be 40%, 42%, 43% or 46%. In the present application, the water-based slurry contains the following components in mass fraction: 0.01-0.05 parts of thickening agent, 0.5-2.5 parts of water-based wetting dispersant, 20-40 parts of antifouling agent, 0.1-0.3 parts of water-based bentonite and 40-60 parts of water.

[0042] In the present application, the water-based slurry contains 20-40 parts of the antifouling agent in mass fraction, preferably 25-35 parts, which can be 30, 31, 32, 33, 34 or 35 parts. In the present application, the antifouling agent preferably contains one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron and zineb, and in the embodiments of the present application, the antifouling agent is copper pyrithione and zineb, and the mass ratio of the copper pyrithione to the zineb is 1:1. In the present application, the antifouling agent is used with the hydrophilic macromolecular component to form a hydration layer that can remove marine animals and plants such as barnacles, mussels and algae, and can achieve the effect of broad-spectrum and long-acting antifouling.

[0043] In the present application, the water-based slurry includes thickening agent 0.01-0.05 parts by mass of the anti-fouling agent, more preferably 0.02-0.04 parts, which can be 0.02, 0.03 or 0.04 parts. In the present application, the thickening agent preferably includes one or more of associative polyurethane thickening agent, sodium carboxymethyl cellulose and hydroxyethyl cellulose, and the model number of the associative polyurethane thickening agent is preferably DeuRheo WT-105A; when the thickening agent preferably includes associative polyurethane thickening agent, sodium carboxymethyl cellulose and hydroxyethyl cellulose, the mass ratio of the associative polyurethane thickening agent, sodium carboxymethyl cellulose and hydroxyethyl cellulose is preferably (8-12):(0.8-1.2):(0.8-1.2), more preferably 10:1:1. In the present application, the thickening agent ensures the thickening effect of the system, so that the pigments and fillers do not settle during storage, prolonging the shelf life of the paint.

[0044] In the present application, the water-based slurry includes water-based wet dispersant 0.5-2.5 parts by mass of the anti-fouling agent, preferably 0.8-2 parts, more preferably 1-1.7 parts, which can be 1.5, 1.6 or 1.7 parts. In the present application, the water-based wet dispersant is preferably PL-20, AC 8892, BYK156 or BYK152.

[0045] In the present application, the water-based slurry includes water-based bentonite 0.1-0.3 parts by mass of the anti-fouling agent, preferably 0.15-0.25 parts, which can be 0.2 or 0.25 parts. In the present application, the water-based bentonite has a thickening effect, and in the present application, the model of the water-based bentonite is OPTIGEL-WX of BYK.

[0046] In the present application, the water-based slurry includes water 40-60 parts by mass of the anti-fouling agent, which can be 45, 50, 53 or 55 parts. In the present application, the water is preferably deionized water.

[0047] In the present application, the water-based slurry further preferably includes pigments and fillers 5-30 parts by mass of the anti-fouling agent, which can be 9, 12, 14, 15, 20, 25 or 27 parts. In the present application, the pigments and fillers preferably include one or more of red iron oxide, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talc powder. In the present application, the pigments and fillers are specifically red iron oxide, zinc oxide and barium sulfate, or red iron oxide, zinc oxide and talc powder. In the present application, the presence of the pigments and fillers improves the color of the coating, making the coated product more beautiful.

[0048] In the present application, the water-based slurry can mix the components uniformly. In the embodiments of the present application, the water-based slurry is preferably prepared by the following method: mixing water, thickening agent, water-based wetting dispersant and water-based bentonite, carrying out first grinding, adding antifouling agent (when the water-based slurry also contains pigments and fillers, pigments and fillers are also added at this time) to the obtained slurry, carrying out second grinding, to obtain the water-based slurry. In the present application, the grinding balls used in the first grinding and the second grinding are preferably zirconia beads, the time of the first grinding is preferably 30 min, and the time of the second grinding is preferably 0.5-1 h, more preferably 0.5-0.75 h, specifically to make the fineness of the slurry <50 μm.

[0049] In the present application, the water-based slurry can improve the mechanical properties, the erosion resistance of the coating, and the long-acting support of the antifouling performance of the coating, and the small amount of antifouling agent contained further improves the antifouling effect of the antifouling coating.

[0050] In mass percentage, the water-based antifouling coating for shielding fouling by hydration layer provided by the present application preferably further comprises the following components in mass percentage: water-based leveling agent 0.2-0.6% (preferably 0.3-0.5%, more preferably 0.3-0.45%), water-based defoaming agent 0.4-1.2% (preferably 0.5-1.0%, more preferably 0.5-0.9%), film-forming aid 0.4-1.2% (preferably 0.6-1.0%, more preferably 0.7-0.9%). In the present application, the water-based leveling agent is preferably WSI 2490 (Guangzhou Teswi Chemical Co., Ltd.), BYK375 or DC57; the water-based leveling agent can make the coating better level and form a film. In the present application, the water-based defoaming agent is preferably DAPRO AP 7010, BYK025 or DC65, more preferably DAPRO AP 7010 or BYK025; the water-based defoaming agent can reduce the bubbles of the coating and improve its stability. In the present application, the film-forming aid is preferably ethylene glycol ethyl ether, ethylene glycol butyl ether or 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, more preferably ethylene glycol butyl ether or ethylene glycol ethyl ether; the film-forming aid makes the antifouling coating better form a film and improves its weather resistance.

[0051] In mass percentage, the water-based antifouling coating for shielding fouling by hydration layer provided by the present application comprises water in balance, and the water is preferably deionized water.

[0052] The VOC content of the water-based antifouling coating for shielding fouling by hydration layer provided by the present application is <35 g / L, preferably 10-20 g / L, and further preferably 13-19 g / L.

[0053] The water-based antifouling paint provided by the present application contains a hydrophilic macromolecular component and a water-based self-polishing emulsion containing a silicone self-polishing component, which can be uniformly distributed in the paint film during the film forming process, and the hydrophilic macromolecular component and the self-polishing component provide a sustained and stable hydration effect. Specifically, the hydrophilic macromolecular component rapidly hydrates in water (such as seawater) to form a stable interfacial strong hydration layer, and the acrylate silane ester monomer slowly hydrolyzes in seawater. The interfacial hydration layer effect and the hydrolysis reaction occur simultaneously on the micron scale, and the self-polishing emulsion component slowly peels off under the shearing action of seawater. The hydrophilic macromolecular component continuously stabilizes the strong hydration layer as the emulsion peels off, realizes controllable hydration of the interface, self-renews the interfacial hydration layer for long-term maintenance, and resists fouling and adhesion in a broad spectrum; the water-based slurry supports the mechanical properties and erosion resistance of the coating, and synergistically improves the antifouling effect (the long-term support of the strong hydration hydrophilic macromolecular component and the antifouling performance of the silicone self-polishing emulsion, and the small amount of antifouling agent contained therein further improves the antifouling effect of the antifouling paint). The present application uses the physical shielding effect of the hydration layer for antifouling, and the comprehensive action of each component exhibits excellent antifouling properties. The use of water-based raw materials as coating components reduces the use of antifouling agents, especially heavy metal antifouling agents, and VOC emissions, reduces the biological hazard risk, and protects the ecological environment.

[0054] The present application provides a preparation method of the water-based antifouling paint using a hydration layer to shield fouling as described in the above technical solutions, comprising the following steps: Mixing the hydrophilic macromolecular component, the water-based self-polishing emulsion, the water-based slurry, and water to obtain the water-based antifouling paint using a hydration layer to shield fouling.

[0055] The present application does not have special requirements for the mixing method, and the mixing method known in the art can be used, such as stirring mixing. The mixing is preferably followed by filtration.

[0056] In the present application, when the water-based antifouling paint using a hydration layer to shield fouling further comprises a water-based leveling agent, a water-based defoaming agent, and a film-forming aid, the preparation method of the water-based antifouling paint is preferably: First mixing the hydrophilic macromolecular component, the water-based self-polishing emulsion, the water-based slurry, the film-forming aid, and water to obtain a mixed solution; Second mixing the mixed solution with the water-based leveling agent and the water-based defoaming agent to obtain the water-based antifouling paint.

[0057] In the present application, the first mixing is preferably carried out under stirring, the stirring rate is preferably 200-300 r / min, more preferably 250-300 r / min, further preferably 280-300 r / min, and the stirring time is preferably 0.5-1 h, more preferably 0.5-0.75 h. In the present application, the second mixing is preferably carried out under stirring, the stirring rate is preferably 150-250 r / min, more preferably 180-230 r / min, further preferably 190-210 r / min, and the stirring time is preferably 0.5-1 h, more preferably 0.5-0.75 h.

[0058] The present application provides the application of the water-based antifouling paint for shielding fouling by using a hydration layer in the surface protection of marine equipment, which is prepared by the above technical scheme or the preparation method.

[0059] In the present application, the marine equipment preferably comprises a culture net cage, and specifically can be a culture net cage netting. In the embodiments of the present application, the water-based antifouling paint is also referred to as a water-based marine antifouling paint. In application, the water-based antifouling paint is sprayed on the surface of the marine equipment to be protected, and is fully solidified at room temperature, and the spraying thickness is preferably 60-400 μm, and can be 100-200 μm.

[0060] The present application directly blends a hydrophilic macromolecular particle with strong hydration characteristics, a hydrolysable water-based self-polishing emulsion and other components to obtain a water-based antifouling paint, the coating film of which can form a stable fouling shielding layer by hydration, and performs physical antifouling without relying on antifouling agents, and has the characteristics of low toxicity and low VOC.

[0061] In order to further illustrate the present application, the water-based antifouling paint for shielding fouling by using a hydration layer, the preparation method and the application thereof provided by the present application are described in detail below with reference to examples, but they should not be understood as limiting the protection scope of the present application.

[0062] Example 1 A water-based antifouling paint for shielding fouling by using a hydration layer, and the preparation method is as follows: (1) Selection of hydrophilic macromolecular component 100 g of polyacrylic acid powder with a weight average molecular weight of 3000 is taken for standby.

[0063] (2) Preparation of water-based self-polishing emulsion Mix 90 g of deionized water, 4.5 g of styrene, 7.5 g of butyl acrylate, 13 g of methyl methacrylate, and 1 g of acrylic acid, 12 g of triisopropyl methacrylate silicate, 2 g of methacryl ethyl sulfobetaine, 1 g of OP-10, and 0.5 g of sodium dodecyl sulfate, stir at 600 r / min for 30 min at room temperature to obtain a monomer emulsion.

[0064] Mix 1 g of ammonium persulfate with 10 g of deionized water to obtain an initiator solution.

[0065] Mix 30 g of monomer emulsion, 0.4 g of sodium bicarbonate, and 55 g of deionized water, put it into a four-necked flask, and mechanically stir at 600 r / min at room temperature. After 0.5 h, add 1 mL of initiator solution, and heat to 81 ℃ while stirring. After the latex particles are stable and form, the system turns blue, and then stir for another 0.5 h. Then add the remaining monomer emulsion and the remaining initiator solution, and dropwise add for 1 h at 81 ℃. Heat to 88 ℃ for 1 h, then cool to 55 ℃, and adjust the solution pH to 7 by dropwise adding ammonia. Cool to room temperature, add 1 g of dioctyl phthalate, stir for 10 min, filter with gauze, and package to obtain a water-based self-polishing emulsion with a solid content of 20% and a latex particle size of 200-250 nm.

[0066] (3) Preparation of water-based slurry Mix 265 g of deionized water, 0.126 g of sodium carboxymethyl cellulose, 8.72 g of dispersant PL-20 (Clariant), and 1.25 g of water-based bentonite (OPTIGEL-WX), add zirconium oxide beads, and mechanically grind at 600 r / min for 30 min. Then add 83.1 g of Zineb, 33.23 g of red iron oxide, 62.3 g of zinc oxide, 41.53 g of barium sulfate, and 83.1 g of copper pyrithione, and continue to grind for 30 min. The slurry fineness is less than 50 μm, and a water-based slurry with a solid content of 50.8% is obtained.

[0067] (4) Preparation of water-based marine antifouling coating using hydration layer to shield fouling Mix 40 g of water-based self-polishing emulsion, 43 g of water-based slurry, 5 g of polyacrylic acid, 0.7 g of ethylene glycol butyl ether, and 10.5 g of deionized water, stir and disperse at 300 r / min for 30 min, adjust the stirring speed to 200 r / min, add 0.3 g of water-based leveling agent WSI2490 (Guangzhou Teswi Chemical Co., Ltd.) and 0.5 g of water-based defoamer DAPRO AP 7010, and stir for 30 min. Filter to obtain a water-based marine antifouling coating using hydration layer to shield fouling, which has a solid content of 36%.

[0068] The tested paint film adhesion is 1 level (GB / T 1720-2020), flexibility is 1 mm (GB / T 1731-2020), impact resistance is greater than 50 kg·cm (GB / T 1732-2020), no blistering and falling off in artificial seawater (prepared according to ASTM D1141-98) for 120 days (the paint film thickness is 200 μm), the average polishing rate of the paint film is 0.28 microns / day, and the VOC content is 20.2 g / L.

[0069] Example 2 (1) The selection of hydrophilic macromolecules, the preparation of water-based self-polishing emulsion and the preparation of water-based slurry are the same as those in Example 1.

[0070] (2) Preparation of water-based marine antifouling coating for shielding fouling by hydration layer Mix 35 g of water-based self-polishing emulsion, 46 g of water-based slurry, 5 g of polyacrylic acid, 0.7 g of ethylene glycol butyl ether and 12.5 g of deionized water, stir and disperse at 300 r / min for 30 min, adjust the speed to 200 r / min, add 0.3 g of water-based leveling agent WSI2490 (Guangzhou Tesi Chemical Co., Ltd.) and 0.5 g of water-based defoaming agent DAPRO AP 7010, stir for 30 min, filter, and obtain a water-based marine antifouling coating for shielding fouling by hydration layer, which has a solid content of 36.5%.

[0071] The tested paint film adhesion is 1 level (GB / T 1720-2020), flexibility is 1 mm (GB / T 1731-2020), impact resistance is greater than 50 kg·cm (GB / T 1732-2020), no blistering and falling off in artificial seawater (prepared according to ASTM D1141-98) for 120 days (the paint film thickness is 200 μm), the average polishing rate of the paint film is 0.32 microns / day, and the VOC content is 14.8 g / L.

[0072] Example 3 (1) The selection of hydrophilic macromolecules, the preparation of water-based self-polishing emulsion and the preparation of water-based slurry are the same as those in Example 1.

[0073] (2) Preparation of water-based marine antifouling coating for shielding fouling by hydration layer Mix 40 g of the waterborne self-polishing emulsion, 40 g of the waterborne slurry, 8 g of polyacrylic acid, 0.7 g of ethylene glycol butyl ether, and 10.5 g of deionized water, stir and disperse at 300 r / min for 30 min, adjust the speed to 200 r / min, add 0.3 g of the waterborne leveling agent WSI2490 (Guangzhou Teswi Chemical Co., Ltd.) and 0.5 g of the waterborne defoamer DAPRO AP 7010, stir for 30 min, filter, and obtain the waterborne marine antifouling coating using the hydration layer to shield fouling, which has a solid content of 37.5%.

[0074] Tested, the paint film adhesion is 1 level (GB / T 1720-2020), the flexibility is 1 mm (GB / T 1731-2020), the impact resistance is greater than 50 kg·cm (GB / T 1732-2020), there is no blistering and peeling after immersion in artificial seawater (prepared according to ASTM D1141-98) for 120 days, the average polishing rate of the paint film is 0.28 microns / day, and the VOC content is 23.1 g / L.

[0075] Example 4 The preparation of the waterborne self-polishing emulsion, the preparation of the waterborne slurry, and the preparation of the waterborne marine antifouling coating using the hydration layer to shield fouling are the same as in Example 1, except that the selection of the hydrophilic macromolecular component: take 100 g of polyacrylic acid powder with a weight average molecular weight of 10000.

[0076] Tested, the paint film adhesion is 1 level (GB / T 1720-2020), the flexibility is 1 mm (GB / T 1731-2020), the impact resistance is greater than 50 kg·cm (GB / T 1732-2020), there is no blistering and peeling after immersion in artificial seawater (prepared according to ASTM D1141-98) for 120 days, the average polishing rate of the paint film is 0.28 microns / day, and the VOC content is 23.1 g / L.

[0077] Example 5 The preparation of the waterborne self-polishing emulsion, the preparation of the waterborne slurry, and the preparation of the waterborne marine antifouling coating using the hydration layer to shield fouling are the same as in Example 1, except that the selection of the hydrophilic macromolecular component: take 100 g of polyacrylic acid powder with a weight average molecular weight of 10000.

[0078] Tested, the paint film adhesion is 1 level (GB / T 1720-2020), the flexibility is 1 mm (GB / T 1731-2020), the impact resistance is greater than 50 kg·cm (GB / T 1732-2020), there is no blistering and peeling after immersion in artificial seawater (prepared according to ASTM D1141-98) for 120 days, the average polishing rate of the paint film is 0.28 microns / day, and the VOC content is 23.1 g / L.

[0079] Example 6 (1) The selection of the hydrophilic macromolecular component and the preparation of the aqueous slurry are the same as in Example 1.

[0080] (2) Preparation of the aqueous self-polishing emulsion Take 84 g of deionized water, 4.5 g of styrene, 7.5 g of butyl acrylate, 13 g of methyl methacrylate, and 1 g of acrylic acid, 18 g of triisopropyl methyl methacrylate, 2 g of methacryl ethyl sulfobetaine, 1 g of OP-10, and 0.5 g of sodium dodecyl sulfate, mix at room temperature for 30 min at 600 r / min, and get the monomer emulsion.

[0081] Mix 1 g of ammonium persulfate with 10 g of deionized water to get the initiator solution.

[0082] Take 30 g of monomer emulsion, 0.4 g of sodium bicarbonate, and 55 g of deionized water, mix in a four-necked flask, and stir mechanically at room temperature at 600 r / min. After 0.5 h, add 1 mL of initiator solution, and heat to 81 ℃ while stirring. After the latex particles are stable and form, the system turns blue, and stir for another 0.5 h. Then add the remaining monomer emulsion and the remaining initiator solution, and dropwise add for 1 h at 81 ℃. Heat to 88 ℃ for 1 h, then cool to 55 ℃, and dropwise add ammonia water to adjust the solution pH to 7. Cool to room temperature, add 1 g of dioctyl phthalate, and stir for 10 min. Filter with gauze, and package to get the aqueous self-polishing emulsion containing silicone self-polishing components, with a solid content of 25% and a latex particle size of 200-250 nm.

[0083] (3) Preparation of the water-based marine antifouling paint using hydration layer to shield fouling Mix 40 g of the aqueous self-polishing emulsion, 43 g of the aqueous slurry, 5 g of polyacrylic acid, 0.7 g of ethylene glycol butyl ether, and 10.5 g of deionized water, and stir to disperse at 300 r / min for 30 min. Adjust the stirring speed to 200 r / min, add 0.3 g of the water-based leveling agent WSI2490 (Guangzhou Teswi Chemical Co., Ltd.) and 0.5 g of the water-based defoamer DAPRO AP 7010, and stir for 30 min. Filter to get the water-based marine antifouling paint using hydration layer to shield fouling, with a solid content of 38%.

[0084] Test results show that the paint film adhesion is 1 level (GB / T 1720-2020), the flexibility is 1 mm (GB / T 1731-2020), the impact resistance is greater than 50 kg·cm (GB / T 1732-2020), there is no blistering and peeling after immersion in artificial seawater (prepared according to ASTM D1141-98) for 120 days (the paint film thickness is 200 μm), the average polishing rate of the paint film is 0.26 microns / day, and the VOC content is 24.7 g / L.

[0085] Antifouling performance evaluation: The water-based marine antifouling paint for shielding fouling by using hydration layer obtained in Examples 1-6 was sprayed on a nylon netting (400x400mm) to make a sample sheet (spraying thickness of 200μm), and after being fully cured at room temperature for 2 days, a shallow sea static hanging sheet test was performed; at the same time, a nylon netting of the same size was selected as a blank control. The two sample sheets were placed at a depth of 2 meters under seawater for a static real sea hanging sheet test, the test time was from March 2025 to June 2025, and the test site was the Beibu Gulf sea area in the north of Leizhou, Zhanjiang City, China.

[0086] The sample sheets were photographed at 120 days of static hanging board, respectively, to observe the surface morphology and the degree of fouling organism attachment of the sample sheets, and the results are shown in Figure 1 . Figure 1 The results of the shallow sea static hanging board test of the sample sheet coated with the water-based marine antifouling paint for shielding fouling by using hydration layer obtained in Examples 1-6 and the blank sample sheet are shown in the Figure 1 . As can be seen from the figure, after 120 days of shallow sea static hanging board test of the blank sample sheet, various fouling organisms were attached to the surface of the sample sheet, mainly barnacles, forming a fouling community, and the fouling was serious, while after 120 days of static hanging board test of the sample sheet sprayed with the antifouling paint obtained in Examples 1-6, no obvious fouling attachment was observed on the surface of the sample sheet, and no blistering and peeling occurred, indicating excellent antifouling performance. Therefore, it can be seen that the water-based marine antifouling paint for shielding fouling by using hydration layer provided by the present application has very excellent antifouling performance and shows a broad-spectrum antifouling effect, and the antifouling effect is long-lasting.

[0087] The above description is only a preferred embodiment of the present application, and does not limit the present application in any form. It should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. An aqueous antifouling paint for shielding against fouling by means of a hydration layer, characterized in that, The water-based antifouling coating comprises the following components in the following mass percentages: The hydrophilic macromolecular component is a powder particulate hydrophilic macromolecular polymer, the weight average molecular weight of the hydrophilic macromolecular polymer is 2000-100000, the solubility in artificial seawater at 23℃ is <12g / L, and the water absorption is >0.1wt%; The water-based self-polishing emulsion is obtained by polymerization reaction of the following raw materials in the following mass percentages: 3-10% of a silane acrylate monomer, 10-20% of a vinyl unsaturated monomer, 0.1-0.5% of an initiator, 0.5-1% of an emulsifier, 0.1-0.3% of an alkaline buffer, 0.1-0.5% of a plasticizer, and the balance of water; The water-based slurry comprises the following components in the following mass percentages: 0.01-0.05 parts of a thickening agent, 0.5-2.5 parts of a water-based wet dispersant, 20-40 parts of an antifouling agent, 0.1-0.3 parts of a water-based bentonite, and 40-60 parts of water. The hydrophilic group of the hydrophilic macromolecular polymer comprises one or more of a hydroxyl group, an amino group, a carboxyl group, an amide group, and a polyvinyl group.

2. The water-based antifouling paint according to claim 1, characterized by, The hydrophilic macromolecular polymer comprises one or more of an alcohol polymer, an acrylic polymer, and an acrylic derivative polymer.

3. The water-based antifouling paint according to claim 2, characterized by The silane acrylate monomer comprises triisopropyl methacrylate silane and / or triisopropyl acrylate silane; the vinyl unsaturated monomer comprises one or more of methyl methacrylate, butyl acrylate, methacrylic acid, acrylamide, acrylic acid, acrylonitrile, styrene, vinyl acetate, and methacryloyl ethyl sulfobetaine.

4. The water-based antifouling paint according to claim 1, characterized by, The preparation method of the water-based self-polishing emulsion comprises the following steps:

5. The water-based antifouling paint according to claim 1 or 4, characterized in that, Mixing the silane acrylate monomer, the vinyl unsaturated monomer, the emulsifier, and the first part of water to obtain a monomer emulsion; Mixing the initiator and the second part of water to obtain an initiator solution; Mixing the alkaline buffer, the remaining water, and part of the monomer emulsion, adding part of the initiator solution thereto, and performing a first polymerization reaction to obtain a seed emulsion; the temperature of the first polymerization reaction is 70-90℃; Adding the remaining monomer emulsion and the remaining initiator solution to the seed emulsion, performing a second polymerization reaction, cooling the obtained reaction liquid to room temperature, and adding the plasticizer thereto to obtain the water-based self-polishing emulsion; the temperature of the second polymerization reaction is 80-100℃. The antifouling agent comprises one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron, and zineb.

6. The water-based antifouling paint according to claim 1, characterized by, The water-based antifouling coating further comprises the following components in the following mass percentages: 0.2-0.6% of a water-based leveling agent, 0.4-1.2% of a water-based defoaming agent, and 0.4-1.2% of a film-forming aid.

7. The water-based antifouling paint according to claim 1, characterized by, The method comprises the following steps:

8. The method for producing the water-based antifouling paint using a hydration layer to shield fouling according to any one of claims 1 to 7, characterized in that, Mixing the hydrophilic macromolecular component, the water-based self-polishing emulsion, the water-based slurry, and water to obtain the water-based antifouling coating that shields fouling by a hydration layer. ​ 9. The use of the water-based antifouling coating for shielding marine fouling by hydration layer according to any one of claims 1 to 7 or prepared by the method according to claim 8 for the protection of surfaces of marine equipment.

10. Use according to claim 9, characterized in that, The marine equipment includes a farming net cage.

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