An environmentally friendly strippable coating composition having an anti-biofouling function and a coating layer thereof

Abstract

The application provides an environment-friendly strippable coating composition with marine biofouling prevention function and a coating thereof, and belongs to the technical field of functional protective coating. The strippable acrylate film-forming emulsion is used as a main film-forming material, which can enhance the tensile strength of the coating, reduce the adhesion between the coating and the interface, and be beneficial to the overall peeling of the coating from the interface; the rosin tackifying emulsion can increase the viscosity of the coating, control the release rate of the antifouling agent, and improve the antifouling period effect; the water-based antifouling slurry can avoid VOC release and ensure excellent antifouling performance. The coating provided by the application is completely water-based, environment-friendly, has no VOC release in the construction and use process, and has stable and excellent antifouling performance. Meanwhile, the coating has high tensile strength and is easy to peel off as a whole. When the antifouling coating on the surface of an underwater vehicle, an underwater precision instrument or marine equipment fails or has more marine organisms attached, the coating can be peeled off together with the marine organisms attached to the surface, and subsequent respraying construction is facilitated.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional protective coating technology, in particular to an environmentally friendly strippable coating composition with marine biofouling prevention function and a coating layer thereof. BACKGROUND

[0002] Marine biofouling has been a major problem restricting the development and utilization of marine resources. Underwater vehicles, underwater precision instruments, marine equipment and the like are often subject to the attachment of marine organisms in seawater, affecting their performance. Coating marine antifouling paint is an important way to solve marine biofouling, and is also the simplest and most economical effective method.

[0003] However, the commonly used marine antifouling paint at present is basically solvent-based antifouling paint, which has a high VOC content and emits a large amount of organic solvent during coating, causing serious pollution to the operators and the environment. In addition, once the traditional antifouling paint is fouled, its antifouling performance will decrease significantly, and if the antifouling performance is to be restored, the paint needs to be re-sprayed, which is a tedious and time-consuming process. SUMMARY

[0004] Therefore, the purpose of the present application is to provide an environmentally friendly strippable coating composition with marine biofouling prevention function and a coating layer thereof. The environmentally friendly strippable coating composition with marine biofouling prevention function provided by the present application is green, has good antifouling properties and good strippability, and can be stripped and replaced in time after the coating fails or is damaged, ensuring good antifouling effect on the surface and the convenience of maintenance.

[0005] In order to achieve the above-mentioned purpose of the application, the present application provides the following technical solutions:

[0006] The present application provides an environmentally friendly strippable coating composition with marine biofouling prevention function, which comprises the following components in mass parts:

[0007] 20-40 parts of strippable acrylate film-forming emulsion;

[0008] 10-20 parts of rosin tackifying emulsion;

[0009] 40-60 parts of water-based antifouling slurry;

[0010] 1-5 parts of additives;

[0011] 1-5 parts of water;

[0012] The strippable acrylate film-forming emulsion is a mixture of silicone oil modified acrylate emulsion and waxy additives; the mass ratio of the silicone oil modified acrylate emulsion to the waxy additives is 4-5:1.

[0013] Preferably, the silicone oil modified acrylate emulsion comprises the following components by mass percentage:

[0014] dodecafluoroheptyl methacrylate 5~10%;

[0015] vinyl silicone monomer 3~7%;

[0016] acrylate monomer 30~40%;

[0017] acrylic acid 0.5~1.5%;

[0018] emulsifier 1~2%;

[0019] initiator 0.3~0.6%;

[0020] sodium bicarbonate 0.05~0.1%;

[0021] pH regulator 0.3~0.5%;

[0022] the balance is water.

[0023] Preferably, the vinyl silicone monomer comprises polydimethylsiloxane with a vinyl group at each end of the molecular chain.

[0024] The acrylate monomer comprises one or more of methyl methacrylate, butyl acrylate and isooctyl acrylate.

[0025] The initiator comprises a persulfate initiator.

[0026] The emulsifier comprises one or more of an anionic emulsifier, a cationic emulsifier and a nonionic emulsifier.

[0027] The pH regulator comprises ammonia water with a mass concentration of 25~28%.

[0028] Preferably, the waxy auxiliary agent is white mineral oil and / or liquid paraffin.

[0029] The solid content of the strippable acrylate film-forming emulsion is 45~55%.

[0030] Preferably, the rosin tackifier emulsion is an aqueous dispersion of emulsified natural rosin, and the solid content of the rosin tackifier emulsion is 50~60%.

[0031] Preferably, the water-based antifouling slurry comprises the following components by mass percentage:

[0032] antifouling agent 40~60%;

[0033] pigment and filler 8~15%;

[0034] Thickening agent 0.5~1%;

[0035] Water-based wetting dispersant 0.5~1%;

[0036] The balance is water.

[0037] Preferably, the antifouling agent comprises a main antifouling agent and an auxiliary antifouling agent;

[0038] The main antifouling agent comprises cuprous oxide and / or copper; the auxiliary antifouling agent comprises one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, diuron and zineb;

[0039] The mass ratio of the main antifouling agent to the auxiliary antifouling agent is 5~7:1.

[0040] Preferably, the pigment filler comprises one or more of polytetrafluoroethylene micro powder, organic bentonite, iron oxide red, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talc powder;

[0041] The fineness of the water-based antifouling slurry is ≤40 µm.

[0042] Preferably, the auxiliary agent comprises a water-based leveling agent, a water-based defoaming agent and an antifreezing agent, and the mass ratio of the water-based leveling agent, the water-based defoaming agent and the antifreezing agent is 1:(1~2):(2~4).

[0043] The present application provides a coating layer formed by film-forming of the above-mentioned environmentally friendly strippable coating composition with the function of preventing marine biofouling.

[0044] The application provides an environment-friendly strippable coating composition with marine biofouling resistance, which comprises 20-40 parts of strippable acrylate film-forming emulsion, 10-20 parts of rosin tackifying emulsion, 40-60 parts of water-based antifouling slurry, 1-5 parts of additives, and 1-5 parts of water; the strippable acrylate film-forming emulsion is a mixture of silicone oil modified acrylate emulsion and waxy additives. In the application, the strippable acrylate film-forming emulsion as the main film-forming material of the coating can enhance the tensile strength of the coating, reduce the adhesion between the coating and the interface, and facilitate the overall peeling of the coating from the interface. Specifically, the strippable acrylate film-forming emulsion can reduce the surface energy of the resin due to the modification of silicone oil, and can reduce the adhesion of the resin to the surface of the substrate due to its lubricating properties. The waxy additives will gradually migrate to the surface of the film during use, gradually forming a wax film on the surface of the film. This film can prevent the coating surface from sticking together, and also has the simultaneous effects of wear resistance and scratch resistance, further reducing the adhesion of the film-forming material to the surface of the substrate and improving the strippability. In the application, the rosin tackifying emulsion can increase the viscosity of the coating, control the release rate of the antifouling agent, and improve the antifouling period of the coating. The water-based antifouling slurry can avoid VOC release and ensure excellent antifouling performance. The environment-friendly strippable coating provided by the application is completely water-based, environmentally friendly, and has no VOC release during construction and use, and has stable and excellent antifouling performance. At the same time, the coating has high tensile strength and is easy to peel off as a whole. When the antifouling coating on the surface of the underwater vehicle, underwater precision instrument or marine equipment fails or has more marine organisms attached, the coating can be peeled off together with the attached marine organisms, facilitating subsequent respraying.

[0045] Further, the water-based antifouling slurry used in the application comprises 40-60% of antifouling agent, 8-15% of pigment and filler, 0.5-1% of thickening agent, and 0.5-1% of water-based wet dispersant. The antifouling agent used in the application comprises a main antifouling agent and an auxiliary antifouling agent; the main antifouling agent comprises cuprous oxide and / or copper; and the auxiliary antifouling agent comprises one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron and zineb. The antifouling agent used in the application does not add toxic antifouling agents such as organotin. By using the main antifouling agent and the auxiliary antifouling agent together, the antifouling agent is gradually released from the paint film, driving away the fouling organisms adhering to the surface of the paint film, and improving the antifouling period of the coating.

[0046] The results of the examples show that the environment-friendly strippable coating with marine biofouling resistance obtained by the application has a VOC content of less than 70 g / L, a static plate test in the sea for 4 months, a fouling area on the surface of the sample plate of less than 10%, and the coating peels off as a whole, is easy to peel off, the substrate is free of residues, and the paint film is free of damage. BRIEF DESCRIPTION OF DRAWINGS

[0047] Figure 1 Pre-stripping state of the strippable coating prepared for Example 1;

[0048] Figure 2 Post-stripping state of the strippable coating prepared for Example 1. DETAILED DESCRIPTION

[0049] The present application provides an environmentally-friendly strippable coating composition with anti-marine biofouling function, comprising the following components in mass fraction:

[0050] 20-40 parts of strippable acrylate film-forming emulsion;

[0051] 10-20 parts of rosin tackifying emulsion;

[0052] 40-60 parts of water-based antifouling slurry;

[0053] 1-5 parts of auxiliary agent;

[0054] 1-5 parts of water.

[0055] Unless otherwise specified, the sources of the raw materials used in the present application are commercially available.

[0056] The environmentally-friendly strippable coating composition with anti-marine biofouling function provided by the present application comprises 20-40 parts of strippable acrylate film-forming emulsion, which can be 20 parts, 25 parts, 30 parts, 35 parts or 40 parts in specific embodiments. In the present application, the strippable acrylate film-forming emulsion is a mixture of silicone oil modified acrylate emulsion and waxy auxiliary agent.

[0057] In the present application, the silicone oil modified acrylate emulsion preferably comprises the following mass percentage of raw materials for preparation:

[0058] 5-10% of dodecafluoroheptyl methacrylate;

[0059] 3-7% of vinyl silicone oil monomer;

[0060] 30-40% of acrylate monomer;

[0061] 0.5-1.5% of acrylic acid;

[0062] 1-2% of emulsifier;

[0063] 0.3-0.6% of initiator;

[0064] 0.05-0.1% of sodium bicarbonate;

[0065] 0.3-0.5% of pH adjuster;

[0066] The balance is water.

[0067] The silicone oil modified acrylate emulsion preferably includes 5-10% of dodecafluoroheptyl methacrylate in terms of mass percentage, and more preferably 6-8%. In the present application, the monomer can be copolymerized with other monomers such as acrylic acid and acrylate in the resin synthesis, to reduce the surface energy of the resin, improve the hydrophobicity and stain resistance of the coating under water, ensure the chemical stability, weather resistance, hydrolysis resistance and strong hydrophobicity of the coating, thereby reducing the phenomena such as powdering, cracking and gloss reduction of the coating film caused by monomer hydrolysis.

[0068] The silicone oil modified acrylate emulsion preferably includes 3-7% of vinyl silicone oil monomer in terms of mass percentage, and more preferably 4-6%. In the present application, the vinyl silicone oil monomer preferably includes polydimethylsiloxane with one vinyl group at each end of the molecular chain. As a specific embodiment of the present application, the vinyl silicone oil monomer is one or more of Laiyang Dayi V401-500, V401-1000, V401-2000 and V401-2500.

[0069] The silicone oil modified acrylate emulsion preferably includes 30-40% of acrylate monomer in terms of mass percentage, and more preferably 35%. In the present application, the acrylate monomer preferably includes one or more of methyl methacrylate, butyl acrylate and isooctyl acrylate.

[0070] The silicone oil modified acrylate emulsion preferably includes 0.5-1.5% of acrylic acid in terms of mass percentage, and more preferably 1%.

[0071] The silicone oil modified acrylate emulsion preferably includes 1-2% of emulsifier in terms of mass percentage, and more preferably 1.5%. In the present application, the emulsifier preferably includes one or more of anionic emulsifier, cationic emulsifier and non-ionic emulsifier. In the present application, the anionic emulsifier preferably includes one or more of sodium stearate, sodium dodecyl sulfate, sodium dodecyl sulfonate and sodium dodecyl benzene sulfonate; the cationic emulsifier preferably includes one or more of dodecyl ammonium chloride, cetyltrimethylammonium chloride and cetylpyridinium bromide; and the non-ionic emulsifier preferably includes one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and octadecylamine polyoxyethylene ether.

[0072] The silicone oil modified acrylate emulsion preferably includes 0.3-0.6% of initiator in terms of mass percentage, and more preferably 0.4-0.5%. In the present application, the initiator is preferably a persulfate initiator, and more preferably one or more of ammonium persulfate, potassium persulfate and sodium persulfate.

[0073] The silicone oil modified acrylate emulsion preferably includes 0.05-0.1% of sodium bicarbonate in terms of mass percentage, preferably 0.06-0.08%. In the present application, the sodium bicarbonate functions to adjust the pH value of the emulsion and keep the pH value of the system relatively stable.

[0074] The silicone oil modified acrylate emulsion preferably includes 0.3-0.5% of pH value regulator in terms of mass percentage, preferably 0.4%. In the present application, the pH value regulator preferably includes ammonia water, and the mass concentration of the ammonia water is preferably 25-28%.

[0075] In the present application, the preparation method of the silicone oil modified acrylate emulsion preferably includes the following steps:

[0076] (1) Emulsify the mixture of dodecafluoroheptyl methacrylate, vinyl silicone oil monomer, acrylate monomer, acrylic acid, emulsifier and the first part of water to obtain a monomer emulsion;

[0077] (2) Dissolve the initiator in the second part of water to obtain an initiator aqueous solution;

[0078] (3) Mix the sodium bicarbonate, the remaining water, part of the monomer emulsion and part of the initiator aqueous solution, and then heat to 80-81°C, continue to stir for 50-100 min to obtain a seed emulsion;

[0079] (4) Under the condition of 80-81°C, add the remaining monomer emulsion and the remaining initiator aqueous solution into the seed emulsion, and then heat for 50-70 min after the addition is completed, heat to 87-89°C and heat for 50-70 min, and then cool to 50-55°C, add the pH value regulator into the obtained system to obtain the silicone oil modified acrylate emulsion.

[0080] In the present application, the first part of water preferably accounts for 10-15% of the total amount of water. In the present application, the temperature of the emulsification is preferably 80°C, and the time is preferably 60 min; the emulsification is preferably carried out under stirring, and the stirring rate is preferably 500 r / min.

[0081] In the present application, the mass concentration of the initiator aqueous solution is preferably 5-10%.

[0082] In the present application, part of the monomer emulsion preferably accounts for 25-35% of the total amount of the monomer emulsion; and part of the initiator aqueous solution preferably accounts for 12-18% of the total amount of the initiator aqueous solution.

[0083] In the present application, the waxy assistant is preferably white mineral oil and / or liquid paraffin. In the present application, the white mineral oil is preferably white mineral oil emulsion, as a specific embodiment of the present application, the white mineral oil emulsion is purchased from Dongguan Xiangtao, model VJ989. In the present application, the liquid paraffin is preferably liquid paraffin emulsion, as a specific embodiment of the present application, the liquid paraffin emulsion is purchased from Foshan Hongsheng Chemical Co., Ltd., model YT-RH.

[0084] In the present application, the mass ratio of the silicone oil modified acrylic ester emulsion and the waxy assistant in the strippable acrylic ester film-forming emulsion is preferably 4-5:1.

[0085] In the present application, the solid content of the strippable acrylic ester film-forming emulsion is preferably 45-55%, and in specific embodiments, the solid content can be 45%, 50% or 55%. In the present application, the viscosity of the strippable acrylic ester film-forming emulsion (measured by a Stormer viscometer at 25°C) is preferably 58 KU, the pH value is preferably 6-7, and the fineness is preferably 10-20 μm.

[0086] In the present application, the strippable acrylic ester film-forming emulsion can reduce the surface energy of the resin due to the modification of silicone oil, and can reduce the adhesion of the resin to the surface of the substrate due to its lubricating properties. The waxy assistant will gradually migrate to the surface of the film during the use of the film, and gradually form a wax film on the surface of the film. This film can make the surface of the coating resistant to adhesion, and at the same time produce synchronous effects such as wear resistance and scratch resistance, further reducing the adhesion of the film-forming material to the surface of the substrate and improving the strippability. In the present application, the strippable acrylic ester film-forming emulsion as the main film-forming material of the coating can enhance the tensile strength of the coating and reduce the adhesion of the coating to the interface, which is beneficial to the overall peeling of the coating from the interface.

[0087] As a specific embodiment of the present application, the strippable acrylic ester film-forming emulsion, in terms of mass percentage, is composed of: silicone oil modified acrylic ester emulsion 65%, waxy assistant 15%, and the balance is deionized water, with a solid content of 46%.

[0088] Based on the mass fraction of the strippable acrylic ester film-forming emulsion, the environmentally friendly strippable coating composition provided by the present application with the function of preventing marine biofouling comprises 10-20 parts of rosin tackifying emulsion, and in specific embodiments, it can be 10 parts, 12 parts, 15 parts, 18 parts or 20 parts. In the present application, the rosin tackifying emulsion is an aqueous dispersion of emulsified natural rosin, and the solid content of the rosin tackifying emulsion is preferably 50-60%, and in specific embodiments, the solid content can be 50%, 55% or 60%.

[0089] In the present application, the rosin tackifying emulsion can increase the viscosity of the coating, control the release rate of the antifouling agent, and improve the antifouling period of the coating.

[0090] As a specific embodiment of the present application, the rosin tackifying emulsion is preferably SNOWTACK 780G rosin emulsion produced by Shanghai Sangjing Chemical Co., Ltd., with a solid content of 55%.

[0091] The environmentally friendly strippable coating composition with marine biofouling resistance provided by the present application comprises 40-60 parts of the water-based antifouling slurry, and in specific embodiments, can be 40 parts, 45 parts, 50 parts, 55 parts, or 60 parts, based on the mass of the strippable acrylate film-forming emulsion. In the present application, the water-based antifouling slurry preferably comprises the following raw materials in the following mass percentages:

[0092] antifouling agent 40-60%, pigment and filler 8-15%, thickening agent 0.5-1%, water-based wetting dispersant 0.5-1%, and the balance being water; more preferably, the preparation raw materials comprise the following mass percentages: antifouling agent 45-55%, pigment and filler 10-13%, thickening agent 0.6-0.8%, water-based wetting dispersant 0.6-0.8%, and the balance being water.

[0093] In the present application, the antifouling agent preferably comprises a main antifouling agent and an auxiliary antifouling agent, the main antifouling agent preferably comprises cuprous oxide and / or copper, and the copper is preferably copper powder; in the present application, when cuprous oxide and copper are used in combination, the mass ratio of cuprous oxide to copper is preferably 7-9:1. In the present application, the auxiliary antifouling agent preferably comprises one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, diuron, and zineb, and when the auxiliary antifouling agent is a mixture of two or more components, the present application does not make special limitations on the proportion of each component; in the present application, the mass ratio of the main antifouling agent to the auxiliary antifouling agent is preferably 5-7:1, and in specific embodiments, can be 5:1, 6:1, or 7:1.

[0094] In the present application, the main antifouling agent cuprous oxide releases cuprous ions (Cu + ) in seawater through hydrolysis, has bactericidal effect, can inactivate low-level marine organisms, prevent marine organisms from adhering to the coating surface, and has high and rapid antifouling effect; the copper powder has reducing property, can reduce cuprous ions (Cu +oxidation, and avoid losing the antifouling and bactericidal effects after oxidation. Although the antifouling effects of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-ketone, diuron and zineb are not as efficient and rapid as cuprous oxide, they have good stability to oxidation and hydrolysis, high stability, and long-lasting antifouling effect, and are more broad-spectrum, efficient, low-toxic and environmentally friendly antifouling agents. The present application gives the coating high and long-lasting antifouling properties through the synergistic effect of the main antifouling agent and the auxiliary antifouling agent.

[0095] In the present application, the antifouling agent can be gradually released from the paint film to repel the fouling organisms adhering to the surface of the paint film, which is beneficial to improve the antifouling period effect of the coating.

[0096] In the present application, the color filler includes one or more of polytetrafluoroethylene powder, organic bentonite, red iron oxide, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talc powder. In the present application, the color filler can increase the volume of the coating, adjust the matte degree, and is beneficial to reduce the cost.

[0097] In the present application, the thickening agent preferably includes thickening agent DeuRheo WT-105A and hydroxyethyl cellulose, and the mass ratio of the thickening agent DeuRheo WT-05A and hydroxyethyl cellulose is preferably 20-30:1, and in a specific embodiment, it can be 20:1, 25:1 or 30:1. In the present application, the solid content of the DeuRheo WT-105A is preferably 48-52%, and the main component is an associated polyurethane thickening agent. In the present application, the thickening agent can increase the viscosity of the coating, prevent sagging during construction, and is beneficial to improve the coating performance of the coating.

[0098] In the present application, the water-based wetting dispersant preferably includes one or more of NUOSPERSE FX 365 (Hempel), BYK156 (BYK-Chemie) and BYK152 (BYK-Chemie), and more preferably NUOSPERSE FX 365, BYK156 or BYK152. In the present application, the water-based wetting dispersant can improve the interfacial action of the antifouling agent, color filler and emulsion, and is beneficial to improve the dispersion stability of the antifouling agent and color filler in the coating.

[0099] The water used for preparing the water-based antifouling slurry in the present application is not particularly limited, and deionized water is preferably used.

[0100] In the present application, the fineness of the water-based antifouling slurry is preferably ≤40 µm, and specifically can be 20 µm, 30 µm or 40 µm.

[0101] In the present application, the preparation method of the water-based antifouling slurry preferably includes the following steps:

[0102] The antifouling agent, the pigment and filler, the thickening agent, the water-based wetting dispersant and water are mixed and then ball milled to obtain the water-based antifouling slurry.

[0103] In the present application, the mixing preferably comprises: mixing the thickening agent, the water-based wetting dispersant and water uniformly, and then adding the antifouling agent and the pigment and filler, and stirring and dispersing for 25-35 min under the condition of 800-1000 r / min.

[0104] The ball milling in the present application is not particularly limited, and can ensure that the fineness of the finally obtained water-based antifouling slurry is ≤40 µm.

[0105] Based on the mass fraction of the strippable acrylate film-forming emulsion, the environmentally friendly strippable coating composition with the marine biofouling prevention function provided in the present application comprises 1-5 parts of an auxiliary agent, which can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts in the specific embodiment. In the present application, the auxiliary agent preferably comprises a water-based leveling agent, a water-based defoaming agent and an antifreezing agent, and the mass ratio of the water-based leveling agent, the water-based defoaming agent and the antifreezing agent is preferably 1: (1-2): (2-4).

[0106] In the present application, the water-based leveling agent preferably comprises at least one of water-based leveling agents WCT 2490, BYK375 and DC57, and more preferably water-based leveling agent WCT 2490, BYK375 or DC57; the water-based leveling agent can prevent the paint film from having shrinkage holes, and is conducive to improving the leveling performance of the paint film.

[0107] In the present application, the water-based defoaming agent preferably comprises at least one of water-based defoaming agents DA PRO AP7010, BYK025 and DC65, and more preferably water-based defoaming agent DA PRO AP7010, BYK025 or DC65; the water-based defoaming agent can eliminate the air bubbles in the coating, and is conducive to improving the appearance of the paint film and the construction performance of the coating.

[0108] In the present application, the antifreezing agent preferably comprises ethylene glycol and / or propylene glycol; the antifreezing agent can lower the freezing point of the water-based coating, and is conducive to improving the storage stability of the water-based coating in a low-temperature environment.

[0109] Based on the mass fraction of the strippable acrylate film-forming emulsion, the environmentally friendly strippable coating composition with the marine biofouling prevention function provided in the present application comprises 1-5 parts of water. In the present application, the water in the coating is preferably deionized water.

[0110] In the present application, the preparation method of the environmentally friendly strippable coating composition with the marine biofouling prevention function preferably comprises the following steps:

[0111] A peelable acrylic film-forming emulsion, rosin tackifying emulsion, water-based antifouling slurry, additives, and water are mixed and filtered to obtain an environmentally friendly peelable coating composition with antifouling properties against marine biofouling.

[0112] In this invention, the mixing is preferably carried out by stirring; this invention does not have any special requirements for the filtration method, and any filtration method well known in the art can be used.

[0113] This invention provides a coating obtained by forming a film from the above-mentioned environmentally friendly peelable coating composition with anti-marine biofouling function. In this invention, the film-forming method preferably includes one or more of spraying, brushing, and roller coating. In this invention, the coating thickness is preferably 100μm~150μm. The environmentally friendly peelable coating with anti-marine biofouling function provided by this invention is mainly applied to the surfaces of underwater vehicles, underwater precision instruments, and marine equipment. When the antifouling coating on the surface of underwater vehicles, underwater precision instruments, or marine equipment fails or a large amount of marine organisms adhere to it, the coating along with the attached marine organisms can be peeled off, facilitating subsequent recoating.

[0114] The following detailed description, in conjunction with embodiments, illustrates the environmentally friendly peelable coating composition and its coating with anti-marine biofouling function provided by the present invention, but these should not be construed as limiting the scope of protection of the present invention.

[0115] Example 1

[0116] Preparation of water-based antifouling slurry:

[0117] Weigh 38g of deionized water, 0.5g of thickener DeuRheo WT-105A, 0.025g of hydroxyethyl cellulose, and 0.8g of aqueous wetting and dispersing agent BYK156, mix them in a dispersion tank, add 44g of cuprous oxide, 4g of diuron, 3.2g of zineb, and 9.5g of pigments and fillers (7g of polytetrafluoroethylene micro powder and 2.5g of organic bentonite), stir and disperse at 900r / min for 30min, and then ball mill the resulting mixture using a QM-3SP2 planetary ball mill until the slurry fineness is less than 40µm to obtain an aqueous slurry.

[0118] Preparation of environmentally friendly peelable coatings with anti-marine biofouling properties:

[0119] 30.0g of the peelable acrylate film-forming emulsion, 15.0g of the SNOWTACK 780G rosin tackifying emulsion, 45.0g of the water-based antifouling slurry, 2.5g of propylene glycol, 0.8g of the water-based leveling agent WCT 2490, 1.2g of the water-based defoaming agent DA PRO AP7010, and 5.5g of deionized water are weighed out, dispersed under stirring at 300r / min for 30min, filtered, and an environmentally friendly peelable coating with a marine biofouling function is obtained.

[0120] The peelable acrylate film-forming emulsion is a mixture of a silicone oil modified acrylate emulsion and a waxy aid; the mass ratio of the silicone oil modified acrylate emulsion to the waxy aid is 4.5:1; the waxy aid is a mixture of white mineral oil and liquid paraffin, and the mass ratio of white mineral oil to liquid paraffin is 2:1.

[0121] The silicone oil modified acrylate emulsion comprises the following mass percentage of raw materials:

[0122] dodecafluoroheptyl methacrylate 6%;

[0123] vinyl silicone monomer 3%;

[0124] acrylate monomer 35%;

[0125] acrylic acid 1%;

[0126] emulsifier sodium dodecyl sulfate 1.5%;

[0127] initiator ammonium persulfate 0.5%;

[0128] sodium bicarbonate 0.1%;

[0129] pH regulator ammonia water 0.4%;

[0130] the balance is water.

[0131] The preparation method of the silicone oil modified acrylate emulsion is as follows:

[0132] (1) 6% dodecafluoroheptyl methacrylate, 3% vinyl silicone (V401-2000), 35% acrylate monomer (methyl methacrylate: butyl acrylate = 2:1), 1% acrylic acid, 1.5% sodium dodecyl sulfate, and 7% water are mixed and dispersed and emulsified at a speed of 200r / min for 10min to obtain a monomer emulsion;

[0133] (2) 0.5% ammonium persulfate is dissolved in 5% water to obtain an initiator aqueous solution;

[0134] (3) 0.1% sodium bicarbonate, 40.5% water, part of the monomer emulsion (30% of the total amount) and part of the initiator aqueous solution (15% of the total amount) are mixed by stirring (500 r / min) and heated to 80°C, and then the temperature is kept constant for 60 min while continuing to stir, to obtain a seed emulsion;

[0135] (4) Under the condition of 80°C, the remaining monomer emulsion (70% of the total amount) and the remaining initiator aqueous solution (85% of the total amount) are added dropwise into the seed emulsion, and the dropping is completed within 1.5-2 h. After the dropping is completed, the temperature is kept constant for 60 min, then the temperature is raised to 87°C and kept constant for 55 min, then the temperature is lowered to 55°C, 0.4% ammonia water is added to the obtained system to adjust the pH value to 6-7, to obtain a silicone oil modified acrylate emulsion.

[0136] (5) The waxy aid is added to the silicone oil modified acrylate emulsion at 55°C, and stirred and dispersed for 30 min, and then naturally cooled to room temperature. The peelable acrylate film-forming emulsion can be obtained by filtering and packaging.

[0137] Example 2

[0138] The water-based antifouling slurry is prepared according to the method of Example 1;

[0139] Preparation of the environmentally friendly peelable coating with marine biofouling resistance:

[0140] 31.0 g of the peelable acrylate film-forming emulsion, 11.0 g of SNOWTACK 780G rosin tackifier emulsion, 50.0 g of the water-based antifouling slurry, 3.0 g of propylene glycol, 0.8 g of water-based leveling agent WCT 2490, 1.2 g of water-based defoamer DA PRO AP7010 and 3 g of deionized water are stirred and dispersed at 300 r / min for 30 min, and then filtered to obtain the environmentally friendly peelable coating with marine biofouling resistance.

[0141] The peelable acrylate film-forming emulsion is a mixture of silicone oil modified acrylate emulsion and waxy aid; the mass ratio of the silicone oil modified acrylate emulsion to the waxy aid is 4:1; the waxy aid is a mixture of white mineral oil and liquid paraffin, and the mass ratio of white mineral oil to liquid paraffin is 2:1;

[0142] The silicone oil modified acrylate emulsion comprises the following mass percentage of raw materials:

[0143] Methyl dodecafluoroheptyl acrylate 8%;

[0144] Vinyl silicone monomer 5%;

[0145] Acrylate monomer 37%;

[0146] Acrylic acid 0.8%;

[0147] Emulsifier Sodium stearate 1%;

[0148] Initiator Ammonium persulfate 0.3%;

[0149] Sodium bicarbonate 0.1%;

[0150] pH regulator Ammonia water 0.4%;

[0151] The rest is water.

[0152] The preparation method of the silicone oil modified acrylate emulsion is as follows:

[0153] (1) 8% methacrylic acid dodecafluoroheptyl ester, 5% vinyl silicone oil (V401-2000), 37% acrylate monomer (methyl methacrylate: isooctyl acrylate = 3:1), 0.8% acrylic acid, 1% sodium stearate and 6% water are mixed and dispersed and emulsified at a speed of 300 r / min for 10 min to obtain a monomer emulsion;

[0154] (2) 0.3% ammonium persulfate is dissolved in 3% water to obtain an initiator aqueous solution;

[0155] (3) 0.1% sodium bicarbonate, 38.4% water, part of the monomer emulsion (32% of the total amount) and part of the initiator aqueous solution (17% of the total amount) are mixed by stirring (500 r / min) and then heated to 81°C, and the temperature is kept constant while continuing to stir for 60 min to obtain a seed emulsion;

[0156] (4) Under the condition of 81°C, the remaining monomer emulsion (68% of the total amount) and the remaining initiator aqueous solution (83% of the total amount) are added dropwise into the seed emulsion, and the dropping is completed within 1.5-2h, and then the temperature is kept constant for 60 min after the dropping is completed, and then the temperature is raised to 88°C and kept constant for 50 min, and then the temperature is lowered to 50°C, and 0.4% ammonia water is added to the obtained system to adjust the pH value to 6-7 to obtain a silicone oil modified acrylate emulsion.

[0157] (5) According to the mass ratio of the silicone oil modified acrylate emulsion to the waxy auxiliary agent (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 2:1) is 4:1, the waxy auxiliary agent is added into the silicone oil modified acrylate emulsion at 50°C, and stirred and dispersed for 30 min, and then naturally cooled to room temperature, and then discharged, filtered and packaged to obtain a strippable acrylate film forming emulsion.

[0158] Example 3

[0159] Preparation of water-based antifouling slurry:

[0160] Take 40.5g deionized water, 0.6g thickening agent DeuRheo WT-105A, 0.02g hydroxyethyl cellulose and 0.9g water-based wet dispersant BYK156, mix uniformly in a dispersion cylinder, add 40g cuprous oxide, 7g copper pyrithione, 11g pigment and filler (7g polytetrafluoroethylene powder, 2g zinc oxide, 2g organic bentonite), disperse at 900r / min for 30min, then use QM-3SP2 planetary ball mill to ball mill the obtained mixture, to a slurry fineness of less than 40µm, to obtain a water-based slurry.

[0161] Preparation of environmentally friendly strippable coating with anti-marine biofouling function:

[0162] Take 40.5g deionized water, 0.6g thickening agent DeuRheo WT-105A, 0.02g hydroxyethyl cellulose and 0.9g water-based wet dispersant BYK156, mix uniformly in a dispersion cylinder, add 40g cuprous oxide, 7g copper pyrithione, 11g pigment and filler (7g polytetrafluoroethylene powder, 2g zinc oxide, 2g organic bentonite), disperse at 900r / min for 30min, then use QM-3SP2 planetary ball mill to ball mill the obtained mixture, to a slurry fineness of less than 40µm, to obtain a water-based slurry.

[0163] The strippable acrylic ester film-forming emulsion is a mixture of silicone oil modified acrylic ester emulsion and waxy auxiliary agent; the mass ratio of the silicone oil modified acrylic ester emulsion to the waxy auxiliary agent is 5:1; the waxy auxiliary agent is a mixture of white mineral oil and liquid paraffin, and the mass ratio of white mineral oil to liquid paraffin is 1:2;

[0164] The silicone oil modified acrylic ester emulsion comprises the following mass percentage of raw materials:

[0165] Methyl methacrylate dodecafluoroheptyl ester 9%;

[0166] Vinyl silicone oil monomer 6%;

[0167] Acrylate monomer 32%;

[0168] Acrylic acid 1.2%;

[0169] Emulsifier fatty alcohol polyoxyethylene ether 1.7%;

[0170] Initiator potassium persulfate 0.5%;

[0171] Sodium bicarbonate 0.1%;

[0172] pH regulator ammonia water 0.5%;

[0173] The rest is water.

[0174] The preparation method of the silicone oil modified acrylic ester emulsion is:

[0175] (1) 9% dodecafluoroheptyl methacrylate, 6% vinyl silicone oil (V401-2000), 32% acrylate monomer (methyl methacrylate: butyl acrylate: isooctyl acrylate = 2:1:1), 1.2% acrylic acid, 1.7% fatty alcohol polyoxyethylene ether and 7% water were mixed and dispersed and emulsified at a speed of 500 r / min for 10 min to obtain a monomer emulsion;

[0176] (2) 0.5% potassium persulfate was dissolved in 5% water to obtain an initiator aqueous solution;

[0177] (3) 0.1% sodium bicarbonate, 37% water, part of the monomer emulsion (35% of the total amount) and part of the initiator aqueous solution (15% of the total amount) were mixed by stirring (500 r / min) and then heated to 80°C, and the temperature was kept constant while continuing to stir for 70 min to obtain a seed emulsion;

[0178] (4) The remaining monomer emulsion (65% of the total amount) and the remaining initiator aqueous solution (85% of the total amount) were added dropwise to the seed emulsion at 81°C, and the dropping was completed within 1.5-2 h. After the dropping was completed, the temperature was kept constant for 60 min, then the temperature was increased to 87°C and kept constant for 60 min, then the temperature was decreased to 53°C, 0.5% ammonia water was added to the obtained system to adjust the pH value to 6-7, and a silicone oil modified acrylate emulsion was obtained.

[0179] (5) The waxy aid (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 1:2) was added to the silicone oil modified acrylate emulsion at 53°C, and stirred and dispersed for 30 min, then naturally cooled to room temperature, and the peelable acrylate film-forming emulsion was obtained by filtering and packaging.

[0180] Example 4

[0181] The water-based antifouling slurry was prepared according to the method of Example 3;

[0182] Preparation of an environmentally friendly peelable coating with marine biofouling resistance:

[0183] 25.0 g of the peelable acrylate film-forming emulsion, 10.0 g of SNOWTACK 780G rosin tackifier emulsion, 55.0 g of the water-based antifouling slurry, 2.5 g of propylene glycol, 0.8 g of water-based leveling agent WCT 2490, 1.2 g of water-based defoamer DA PRO AP7010 and 5.5 g of deionized water were stirred and dispersed at 300 r / min for 30 min, and then filtered to obtain an environmentally friendly peelable coating with marine biofouling resistance.

[0184] The peelable acrylate film-forming emulsion is a mixture of a silicone oil modified acrylate emulsion and a waxy auxiliary agent; the mass ratio of the silicone oil modified acrylate emulsion to the waxy auxiliary agent is 5:1; the waxy auxiliary agent is a mixture of white mineral oil and liquid paraffin, and the mass ratio of the white mineral oil to the liquid paraffin is 3:1;

[0185] The silicone oil modified acrylate emulsion comprises the following mass percentage of raw materials:

[0186] dodecafluoroheptyl methacrylate 5%;

[0187] vinyl silicone monomer 7%;

[0188] acrylate monomer 31%;

[0189] acrylic acid 0.6%;

[0190] emulsifier dodecyl ammonium chloride 1.6%;

[0191] initiator potassium persulfate 0.4%;

[0192] sodium bicarbonate 0.075%;

[0193] pH regulator ammonia water 0.325%;

[0194] the rest is water.

[0195] The preparation method of the silicone oil modified acrylate emulsion is as follows:

[0196] (1) 5% dodecafluoroheptyl methacrylate, 7% vinyl silicone oil (V401-2000), 31% acrylate monomer (methyl methacrylate: butyl acrylate: isooctyl acrylate = 1:2:1), 0.6% acrylic acid, 1.6% dodecyl ammonium chloride and 8% water are mixed and dispersed and emulsified at a speed of 400 r / min for 10 min to obtain a monomer emulsion;

[0197] (2) 0.4% potassium persulfate is dissolved in 4% water to obtain an initiator aqueous solution;

[0198] (3) 0.075% sodium bicarbonate, 42% water, part of the monomer emulsion (25% of the total amount) and part of the initiator aqueous solution (12% of the total amount) are mixed by stirring (600 r / min) and then heated to 81°C, and the temperature is kept constant for 65 min while continuing to stir to obtain a seed emulsion;

[0199] (4) Under the condition of 81℃, the remaining monomer emulsion (75% of the total amount) and the remaining initiator aqueous solution (88% of the total amount) are added dropwise into the seed emulsion, and the dropping is completed within 1.5-2h. After the dropping is completed, the system is kept at 60min, and then the temperature is raised to 88℃ and kept for 60min. After that, the temperature is lowered to 55℃, 0.325% ammonia water is added into the obtained system to adjust the pH value to 6-7, and a silicone oil modified acrylate emulsion is obtained.

[0200] (5) The waxy aid (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 3:1) is added into the silicone oil modified acrylate emulsion at 55℃ at a mass ratio of 5:1, and the mixture is stirred and dispersed for 30min. Then, the mixture is naturally cooled to room temperature, and the peelable acrylate film-forming emulsion is obtained.

[0201] Comparative Example 1

[0202] The water-based antifouling slurry is prepared according to Example 1.

[0203] The peelable coating with the function of preventing marine biofouling is prepared according to Example 1. In the preparation, an equal amount of the peelable acrylate film-forming emulsion is replaced by a water-based acrylate emulsion without silicone oil modification and without the addition of a waxy aid, and the peelable performance of the coating is tested under the same conditions.

[0204] The water-based acrylate emulsion comprises the following mass percentage of raw materials:

[0205] Methyl methacrylate 14%;

[0206] Methyl methacrylate 14%;

[0207] Methyl methacrylate 14%;

[0208] Methyl methacrylate 14%;

[0209] Methyl methacrylate 14%;

[0210] Methyl methacrylate 14%;

[0211] Methyl methacrylate 14%;

[0212] Methyl methacrylate 14%;

[0213] Methyl methacrylate 14%;

[0214] Methyl methacrylate 14%;

[0215] The preparation method of the water-based acrylate emulsion is as follows:

[0216] (1) 10% methacrylic acid dodecyl fluoride ester, 14% methyl methacrylate, 10% butyl acrylate, 8% isooctyl acrylate, 0.6% acrylic acid, 1.6% dodecyl ammonium chloride and 8% water were mixed and dispersed and emulsified at a speed of 400 r / min for 10 min to obtain a monomer emulsion;

[0217] (2) 0.4% potassium persulfate was dissolved in 4% water to obtain an initiator aqueous solution;

[0218] (3) 0.075% sodium bicarbonate, 43% water, part of the monomer emulsion (25% of the total amount) and part of the initiator aqueous solution (12% of the total amount) were mixed by stirring (600 r / min) and then heated to 81°C, and the temperature was kept constant for 65 min while continuing to stir, to obtain a seed emulsion;

[0219] (4) Under the condition of 81°C, the remaining monomer emulsion (75% of the total amount) and the remaining initiator aqueous solution (88% of the total amount) were added dropwise into the seed emulsion, and the dropping was completed within 1.5-2 h. After the dropping was completed, the temperature was kept constant for 60 min, then the temperature was increased to 88°C and kept constant for 60 min, then the temperature was decreased to 55°C, 0.325% ammonia water was added to the obtained system to adjust the pH value to 6-7, to obtain a water-based acrylate emulsion. After natural cooling to room temperature, the water-based acrylate film-forming emulsion was obtained, which was discharged, filtered and packaged.

[0220] Evaluation of physical and chemical properties, peeling performance and antifouling performance

[0221] (1) The VOC content of the environmentally friendly strippable coating with marine biofouling resistance prepared in Examples 1-4 and Comparative Example 1 was determined according to the method in GB 18582-2008;

[0222] (2) The environmentally friendly strippable coating with marine biofouling resistance prepared in Examples 1-4 and Comparative Example 1 was sprayed on the surface of the substrate plate to form a paint film, and the performance of the paint film was tested as follows:

[0223] The flexibility of the paint film was tested according to GB / T 1731-2020;

[0224] The impact resistance of the paint film was tested according to GB / T 1732-2020;

[0225] The strippable coating was cut into samples according to GB / T 2792-2014, and the 180° peeling strength test was performed.

[0226] (3) The environmentally friendly strippable coating with the anti-marine biofouling function prepared in Examples 1-4 and Comparative Example 1 was sprayed on a low-carbon steel plate (200 mm x 300 mm x 2 mm) with an epoxy anticorrosive primer (80-100 microns) to make a sample plate, and the sample plate was fully cured at room temperature for 2 days, and then was placed at a depth of 1 meter under seawater for a static real sea plate test, and the test period was 4 months, and the test site was in the Nan'ao sea area of Shenzhen.

[0227] The coating obtained in Example 1 was sprayed on a steel plate with an epoxy primer, and the surface stripping could be performed after 24 hours. The pre-stripping state of the strippable coating prepared in Example 1 is shown in Figure 1 , and the post-stripping state is shown in Figure 2 . As can be seen from Figure 1 and Figure 2 , the coating can be easily stripped as a whole, the substrate is free of residues, and the paint film is free of damage.

[0228] The physicochemical properties and anti-fouling performance data of the environmentally friendly strippable coating with the anti-marine biofouling function in Examples 1-4 and Comparative Example 1 are shown in Table 1.

[0229] Table 1 Physicochemical properties, stripping performance and anti-fouling performance evaluation test results

[0230]

[0231] As can be seen from Table 1, the environmentally friendly strippable coating with the anti-marine biofouling function provided by the present application has good physicochemical properties, stable strippable performance and excellent anti-marine biofouling performance; the VOC content of the coating is less than 70 g / L, and the coating is environmentally friendly.

[0232] The above only describes the preferred embodiments of the present application, and it should be noted that for those skilled 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 environmentally friendly peelable coating composition with anti-marine biofouling function, characterized in that, Based on parts by mass, it includes the following components: 20-40 parts of peelable acrylate film-forming emulsion; 10-20 parts of rosin thickening emulsion; 40-60 parts of water-based antifouling slurry; 1-5 parts of auxiliary agent; 1-5 parts water; The peelable acrylate film-forming emulsion is a mixture of silicone oil-modified acrylate emulsion and wax additives; the mass ratio of the silicone oil-modified acrylate emulsion to the wax additives is 4~5:

1. The waxy additive is white mineral oil and / or liquid paraffin; The silicone oil-modified acrylate emulsion comprises the following raw materials in weight percentage: Dodecafluoroheptyl methacrylate 5-10%; Vinyl silicone monomers 3-7%; 30-40% acrylate monomers; Acrylic acid 0.5~1.5%; Emulsifier 1~2%; Initiator 0.3~0.6%; Sodium bicarbonate 0.05~0.1%; pH adjuster 0.3~0.5%; The remainder is water; The vinyl silicone oil monomers include polydimethylsiloxane with a vinyl group at each end of the molecular chain; The acrylate monomers include one or more of methyl methacrylate, butyl acrylate and isooctyl acrylate; The water-based antifouling slurry comprises the following components by weight percentage: Antifouling agent 40-60%; Pigments and fillers 8~15%; Thickener 0.5~1%; Aqueous wetting and dispersing agent 0.5~1%; The remainder is water; The antifouling agent includes a primary antifouling agent and an auxiliary antifouling agent; The primary antifouling agent includes cuprous oxide and / or copper; the secondary antifouling agent includes one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, diuron, and zineb. The mass ratio of the primary antifouling agent to the secondary antifouling agent is 5~7:

1.

2. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that, The initiator includes persulfate initiators; The emulsifier includes one or more of anionic emulsifiers, cationic emulsifiers, and nonionic emulsifiers; The pH adjuster includes ammonia water, and the mass concentration of the ammonia water is 25-28%.

3. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that, The solid content of the peelable acrylate film-forming emulsion is 45-55%.

4. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that, The rosin thickening emulsion is a water-soluble dispersion of emulsified natural rosin, and the solid content of the rosin thickening emulsion is 50-60%.

5. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that, The pigments and fillers include one or more of the following: polytetrafluoroethylene micro powder, organobentonite, iron oxide red, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder, and talc powder. The fineness of the water-based antifouling slurry is ≤40 µm.

6. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that, The additives include water-based leveling agents, water-based defoamers, and antifreeze agents, and the mass ratio of the water-based leveling agents, water-based defoamers, and antifreeze agents is 1:(1~2):(2~4).

7. The coating obtained by forming a film from the environmentally friendly peelable coating composition with anti-marine biofouling function according to any one of claims 1 to 6.

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