Environment-friendly peelable coating composition with marine organism fouling prevention function and coating layer of environment-friendly peelable coating composition

Abstract

The invention provides an environment-friendly strippable coating composition with a marine organism fouling prevention function and a coating layer of the environment-friendly strippable coating composition, and belongs to the technical field of functional protective coatings. The peelable acrylate film-forming emulsion is used as a main film forming matter, so that the tensile strength of a coating can be enhanced, the bonding force between the coating and an interface is reduced, and the coating can be integrally peeled off from the interface; the rosin tackifying emulsion can increase the viscosity of the coating, control the release rate of the antifouling agent and prolong the antifouling period; the water-based antifouling slurry can avoid VOC release and ensure excellent antifouling performance. The coating provided by the invention is completely aqueous, environment-friendly, free of VOC release in construction and use processes, and stable and excellent in antifouling performance. And meanwhile, the coating is high in tensile strength and easy to peel off integrally, and when the antifouling coating on the surfaces of underwater navigation bodies, underwater precise instruments and marine equipment is invalid or many marine organisms are attached to the surfaces, the coating and the marine organisms attached to the surfaces can be peeled off together, so that subsequent re-spraying construction is facilitated.

Description

Technical Field

[0001] The invention relates to the technical field of functional protective coatings, and in particular to an environmentally friendly peelable coating composition with anti-marine biofouling function and a coating thereof. Background Art

[0002] Marine biofouling has always been a major problem that restricts the development and utilization of marine resources. Underwater navigation objects, underwater precision instruments, marine equipment, etc. often encounter the attachment of marine organisms in seawater, affecting their performance. Applying marine antifouling coatings is an important way to solve marine biofouling, and it is also the simplest, most economical and effective way.

[0003] However, the commonly used marine antifouling coatings are basically solvent-based antifouling coatings, which have high VOC content and volatilize a large amount of organic solvents during the coating process, causing serious pollution to construction workers and the environment. In addition, once the traditional antifouling coating is fouled, its antifouling performance will be significantly reduced. If the antifouling performance is to be restored, it needs to be re-polished and sprayed. The post-processing process is cumbersome, time-consuming and labor-intensive. Summary of the invention

[0004] In view of this, the object of the present invention is to provide an environmentally friendly peelable coating composition with anti-marine biofouling function and a coating thereof. The environmentally friendly peelable coating composition with anti-marine biofouling function provided by the present invention is green and environmentally friendly, has good antifouling properties, and has good peelability. The coating can be peeled off and replaced in time after the coating fails or is damaged, ensuring good antifouling effect of the surface and convenience of maintenance.

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

[0006] The present invention provides an environmentally friendly peelable coating composition with anti-marine biofouling function, which comprises the following components in parts by mass:

[0007]

[0008] The strippable acrylic film-forming emulsion is a mixture of silicone oil-modified acrylic emulsion and a wax auxiliary agent; the mass ratio of the silicone oil-modified acrylic emulsion to the wax auxiliary agent is 4 to 5:1.

[0009] Preferably, the silicone oil-modified acrylate emulsion comprises the following raw materials in percentage by weight:

[0010]

[0011]

[0012] The balance is water.

[0013] Preferably, the vinyl silicone oil monomer includes polydimethylsiloxane with a vinyl group at each end of the molecular chain;

[0014] The acrylic acid ester monomer includes one or more of methyl methacrylate, butyl acrylate and isooctyl acrylate;

[0015] The initiator includes a persulfate initiator;

[0016] The emulsifier includes one or more of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers;

[0017] The pH regulator includes ammonia water, and the mass concentration of the ammonia water is 25-28%.

[0018] Preferably, the wax additive is white mineral oil and / or liquid paraffin;

[0019] The solid content of the strippable acrylic ester film-forming emulsion is 45-55%.

[0020] Preferably, the rosin tackifying emulsion is a water-soluble dispersion of emulsified natural rosin, and the solid content of the rosin tackifying emulsion is 50-60%.

[0021] Preferably, the aqueous antifouling slurry comprises the following components in terms of mass percentage:

[0022]

[0023] The balance is water.

[0024] Preferably, the antifouling agent includes a main antifouling agent and an auxiliary antifouling agent;

[0025] The main antifouling agent includes cuprous oxide and / or copper; the auxiliary antifouling agent includes one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, diuron and mancozeb;

[0026] The mass ratio of the main antifouling agent to the auxiliary antifouling agent is 5 to 7:1.

[0027] Preferably, the pigment and filler include one or more of polytetrafluoroethylene powder, organic bentonite, red iron oxide, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talcum powder;

[0028] The fineness of the aqueous antifouling slurry is ≤40 μm.

[0029] Preferably, the auxiliary agent includes an aqueous leveling agent, an aqueous defoaming agent and an antifreeze agent, and the mass ratio of the aqueous leveling agent, the aqueous defoaming agent and the antifreeze agent is 1:(1-2):(2-4).

[0030] The present invention provides a coating obtained by forming a film of the above-mentioned environmentally friendly peelable coating composition with the function of preventing marine biofouling.

[0031] The invention provides an environmentally friendly strippable coating composition with anti-marine biofouling function, comprising 20-40 parts of a strippable acrylic film-forming emulsion, 10-20 parts of a rosin tackifying emulsion, 40-60 parts of an aqueous antifouling slurry, 1-5 parts of an auxiliary agent, and 1-5 parts of water. The strippable acrylic film-forming emulsion is a mixture of a silicone oil-modified acrylic emulsion and a wax auxiliary agent. In the invention, the strippable acrylic film-forming emulsion is used as the main film-forming material of the coating, which can enhance the tensile strength of the coating, reduce the adhesion between the coating and the interface, and facilitate the overall stripping of the coating from the interface. Specifically, the strippable acrylic film-forming emulsion can reduce the surface energy of the resin due to silicone oil modification, and can reduce the adhesion of the resin to the surface of the substrate due to its lubricating properties, while the wax auxiliary agent will uniformly and gradually migrate to the surface of the film during the use of the film, gradually forming a wax film on the surface of the film, which can make the coating surface anti-adhesive, and at the same time produce synchronous effects such as anti-wear and anti-scratch, further reduce the adhesion of the film-forming material on the surface of the substrate, and improve the strippability. In the present invention, the rosin thickening emulsion can increase the viscosity of the coating, control the release rate of the antifouling agent, and is beneficial to improving the antifouling effect of the coating; the water-based antifouling slurry can avoid VOC release and ensure excellent antifouling performance. The environmentally friendly peelable coating with anti-marine biofouling function provided by the present invention is completely water-based, environmentally friendly, 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 fails or there are many marine organisms attached to the surface of underwater navigation bodies, underwater precision instruments, and marine equipment, the coating can be peeled off together with the marine organisms attached to the surface, which is convenient for subsequent re-spraying construction.

[0032] Further, the aqueous antifouling slurry used in the present invention includes 40-60% of antifouling agent; 8-15% of pigment filler; 0.5-1% of thickener; and 0.5-1% of aqueous wetting dispersant. The antifouling agent used in the present invention includes a main antifouling agent and an auxiliary antifouling agent; the main antifouling agent includes cuprous oxide and / or copper; the auxiliary antifouling agent includes one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, diuron and mancozeb. The antifouling agent used in the present invention does not add toxic antifouling agents such as organic tin. Through the coordinated use of the main antifouling agent and the auxiliary antifouling agent, the antifouling agent is gradually released from the paint film, and the fouling organisms adhering to the surface of the paint film are driven away, which is beneficial to improving the antifouling effect of the coating.

[0033] The results of the embodiments show that the VOC content of the environmentally friendly peelable coating with anti-marine biofouling function obtained by the present invention is less than 70g / L. After static hanging on the sample in the sea for 4 months, the surface fouling area of ​​the sample is less than 10%, and the coating can be peeled off as a whole and easily without any residue on the substrate and without any damage to the paint film. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 The peelable coating prepared in Example 1 is in a state before peeling;

[0035] Figure 2 This is the peelable coating prepared in Example 1 after peeling. DETAILED DESCRIPTION

[0036] The present invention provides an environmentally friendly peelable coating composition with anti-marine biofouling function, which comprises the following components in parts by mass:

[0037]

[0038] Unless otherwise specified, the raw materials used in the present invention are commercially available.

[0039] The environmentally friendly peelable coating composition with anti-marine biofouling function provided by the present invention comprises 20 to 40 parts of a peelable acrylic film-forming emulsion by weight, and in a specific embodiment, it can be 20 parts, 25 parts, 30 parts, 35 parts or 40 parts. In the present invention, the peelable acrylic film-forming emulsion is a mixture of a silicone oil-modified acrylic emulsion and a wax additive.

[0040] In the present invention, the silicone oil-modified acrylate emulsion preferably includes the following raw materials in percentage by weight:

[0041]

[0042] The balance is water.

[0043] In terms of mass percentage, the silicone oil modified acrylic emulsion preferably includes 5-10% dodecafluoroheptyl methacrylate, more preferably 6-8%. In the present invention, the monomer can be copolymerized with other monomers such as acrylic acid and acrylic esters 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 powdering, cracking, gloss reduction and other phenomena of the coating film caused by monomer hydrolysis.

[0044] In terms of mass percentage, the silicone oil-modified acrylic emulsion preferably includes 3-7% of vinyl silicone oil monomers, more preferably 4-6%. In the present invention, the vinyl silicone oil monomers preferably include polydimethylsiloxane with a vinyl group at each end of the molecular chain. As a specific embodiment of the present invention, the vinyl silicone oil monomers are one or more of Laiyang Dayi V401-500, V401-1000, V401-2000 and V401-2500.

[0045] In terms of mass percentage, the silicone oil modified acrylate emulsion preferably includes 30-40% acrylate monomer, more preferably 35%. In the present invention, the acrylate monomer preferably includes one or more of methyl methacrylate, butyl acrylate and isooctyl acrylate.

[0046] In terms of mass percentage, the silicone oil-modified acrylate emulsion preferably includes 0.5-1.5% of acrylic acid, more preferably 1%.

[0047] In terms of mass percentage, the silicone oil modified acrylic emulsion preferably includes 1-2% of emulsifier, more preferably 1.5%. In the present invention, the emulsifier preferably includes one or more of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers. In the present invention, the anionic emulsifier preferably includes one or more of sodium stearate, sodium dodecyl sulfate, sodium dodecyl sulfonate and sodium dodecylbenzene sulfonate; the cationic emulsifier preferably includes one or more of dodecyl ammonium chloride, hexadecyl trimethyl ammonium chloride and hexadecyl pyridinium bromide; the nonionic emulsifier preferably includes one or more of fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester and octadecylamine polyoxyethylene ether.

[0048] In terms of mass percentage, the silicone oil modified acrylate emulsion preferably includes 0.3-0.6% of initiator, more preferably 0.4-0.5%. In the present invention, the initiator is preferably a persulfate initiator, specifically preferably one or more of ammonium persulfate, potassium persulfate, and sodium persulfate.

[0049] In terms of mass percentage, the silicone oil modified acrylate emulsion preferably includes 0.05-0.1% sodium bicarbonate, preferably 0.06-0.08%. In the present invention, the role of the sodium bicarbonate is to adjust the pH value of the emulsion and keep the pH value of the system relatively stable.

[0050] In terms of mass percentage, the silicone oil modified acrylate emulsion preferably includes 0.3-0.5% of pH value adjuster, preferably 0.4%. In the present invention, the pH adjuster preferably includes ammonia water, and the mass concentration of the ammonia water is preferably 25-28%.

[0051] In the present invention, the preparation method of the silicone oil-modified acrylate emulsion preferably comprises the following steps:

[0052] (1) mixing dodecafluoroheptyl methacrylate, vinyl silicone oil monomer, acrylate monomer, acrylic acid, an emulsifier and the first portion of water and emulsifying the mixture to obtain a monomer emulsion;

[0053] (2) dissolving the initiator in the second portion of water to obtain an initiator aqueous solution;

[0054] (3) mixing sodium bicarbonate, remaining water, part of the monomer emulsion and part of the initiator aqueous solution, heating to 80-81° C., and stirring for 50-100 minutes to obtain a seed emulsion;

[0055] (4) at 80-81° C., adding the remaining monomer emulsion and the remaining initiator aqueous solution to the seed emulsion, keeping the temperature for 50-70 min after the addition is completed, raising the temperature to 87-89° C. and keeping the temperature for 50-70 min, then cooling the temperature to 50-55° C., adding a pH adjuster to the obtained system, and obtaining a silicone oil-modified acrylate emulsion.

[0056] In the present invention, the first part of water preferably accounts for 10-15% of the total amount of water. In the present invention, the emulsification temperature is preferably 80°C, the time is preferably 60 minutes; the emulsification is preferably carried out under stirring, and the stirring rate is preferably 500r / min.

[0057] In the present invention, the mass concentration of the initiator aqueous solution is preferably 5-10%.

[0058] In the present invention, the part of the monomer emulsion preferably accounts for 25-35% of the total monomer emulsion; the part of the initiator aqueous solution preferably accounts for 12-18% of the total initiator aqueous solution.

[0059] In the present invention, the wax additive is preferably white mineral oil and / or liquid paraffin. In the present invention, the white mineral oil is preferably a white mineral oil emulsion. As a specific embodiment of the present invention, the white mineral oil emulsion is purchased from Dongguan Xiangtao, model VJ989. In the present invention, the liquid paraffin is preferably a liquid paraffin emulsion. As a specific embodiment of the present invention, the liquid paraffin emulsion is purchased from Foshan Hongsheng Chemical Co., Ltd., model YT-RH.

[0060] In the present invention, in the strippable acrylic film-forming emulsion, the mass ratio of the silicone oil-modified acrylic emulsion to the wax auxiliary agent is preferably 4 to 5:1.

[0061] In the present invention, the solid content of the strippable acrylic film-forming emulsion is preferably 45-55%, and in a specific embodiment, the solid content may be 45%, 50% or 55%. In the present invention, the viscosity of the strippable acrylic film-forming emulsion (measured by Stormer viscometer at 25° C.) is preferably 58 KU, the pH value is preferably 6-7, and the fineness is preferably 10-20 μm.

[0062] In the present invention, the strippable acrylic film-forming emulsion can reduce the surface energy of the resin due to silicone oil modification, and can reduce the adhesion of the resin to the surface of the substrate due to its lubricating properties, and the wax additive will evenly and gradually migrate to the surface of the film during the use of the film, gradually forming a wax film on the surface of the film, which can make the coating surface anti-adhesive, and at the same time produce synchronous effects such as anti-wear and anti-scratch, further reduce the adhesion of the film-forming substance on the surface of the substrate, and improve the strippability. In the present invention, the strippable acrylic film-forming emulsion is used as the main film-forming substance of the coating, which can enhance the tensile strength of the coating, reduce the adhesion between the coating and the interface, and facilitate the overall stripping of the coating from the interface.

[0063] As a specific embodiment of the present invention, the strippable acrylic film-forming emulsion comprises, by weight percentage, 65% silicone oil-modified acrylic emulsion, 15% wax additive, and the balance is deionized water, and the solid content is 46%.

[0064] Based on the mass fraction of the strippable acrylic film-forming emulsion, the environmentally friendly strippable coating composition with anti-marine biofouling function provided by the present invention includes 10 to 20 parts of rosin tackifying emulsion, and in a specific embodiment, it can be 10 parts, 12 parts, 15 parts, 18 parts or 20 parts. In the present invention, the rosin tackifying emulsion is a water-soluble dispersion of emulsified natural rosin, and the solid content of the rosin tackifying emulsion is preferably 50 to 60%, and in a specific embodiment, the solid content can be 50%, 55% or 60%.

[0065] In the present invention, the rosin tackifying emulsion can increase the viscosity of the coating, control the release rate of the antifouling agent, and is beneficial to improving the antifouling effect of the coating.

[0066] As a specific embodiment of the present invention, the rosin tackifying emulsion is preferably SNOWTACK 780G rosin emulsion produced by Shanghai Sangjing Chemical Co., Ltd., and its solid content is 55%.

[0067] Based on the mass fraction of the strippable acrylic film-forming emulsion, the environmentally friendly strippable coating composition with anti-marine biofouling function provided by the present invention includes 40 to 60 parts of an aqueous antifouling slurry, and in a specific embodiment, it can be 40 parts, 45 parts, 50 parts, 55 parts or 60 parts. In the present invention, the aqueous antifouling slurry preferably includes the following raw materials in mass percentage:

[0068] The composition comprises 40-60% antifouling agent, 8-15% pigment and filler, 0.5-1% thickener, 0.5-1% aqueous wetting and dispersing agent, and the balance is water; more preferably, the composition comprises the following raw materials in percentage by weight: 45-55% antifouling agent, 10-13% pigment and filler, 0.6-0.8% thickener, 0.6-0.8% aqueous wetting and dispersing agent, and the balance is water.

[0069] In the present invention, the antifouling agent preferably includes a main antifouling agent and an auxiliary antifouling agent, and the main antifouling agent preferably includes cuprous oxide and / or copper, and the copper is preferably copper powder; in the present invention, when cuprous oxide and copper are used in combination, the mass ratio of cuprous oxide to copper is preferably 7 to 9:1. In the present invention, the auxiliary antifouling agent preferably includes one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, diuron and mancozeb. When the auxiliary antifouling agent is a mixture of two or more components, the present invention does not specifically limit the distribution ratio of each component; in the present invention, the mass ratio of the main antifouling agent to the auxiliary antifouling agent is preferably 5 to 7:1, and in a specific embodiment, it can be 5:1, 6:1 or 7:1.

[0070] In the present invention, the main antifouling agent cuprous oxide releases cuprous ions (Cu + ), which has a bactericidal effect, can inactivate low-level marine organisms, prevent marine organisms from attaching to the coating surface, and has an efficient and rapid antifouling effect; copper powder has a reducing property, which can reduce cuprous ions (Cu + ) to prevent it from losing its antifouling and bactericidal effect after being oxidized. Although the antifouling effects of auxiliary antifouling agents such as copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, diuron and maneb are not as efficient and rapid as cuprous oxide, they have good stability to oxidation and hydrolysis, high stability, and long-lasting antifouling effect. They are more broad-spectrum, efficient, low-toxic, and environmentally friendly antifouling agents. The present invention gives the coating efficient and long-lasting antifouling properties through the synergistic effect of the main antifouling agent and the auxiliary antifouling agent.

[0071] In the present invention, the antifouling agent can be gradually released from the paint film to drive away the fouling organisms adhering to the surface of the paint film, which is beneficial to improving the antifouling effect of the coating.

[0072] In the present invention, the pigments and fillers include one or more of polytetrafluoroethylene powder, organic bentonite, red iron oxide, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talcum powder. In the present invention, the pigments and fillers can increase the volume of the coating, adjust the matte degree, and help reduce costs.

[0073] In the present invention, the thickener preferably includes thickener DeuRheo WT-105A and hydroxyethyl cellulose, and the mass ratio of the thickener DeuRheo WT-05A to hydroxyethyl cellulose is preferably 20 to 30:1, and in a specific embodiment, it can be 20:1, 25:1 or 30:1. In the present invention, the solid content of the DeuRheo WT-105A is preferably 48 to 52%, and the main component is an associative polyurethane thickener. In the present invention, the thickener can increase the viscosity of the coating, prevent sagging during construction, and is conducive to improving the coating performance of the coating.

[0074] In the present invention, the aqueous wetting and dispersing agent preferably includes one or more of NUOSPERSE FX 365 (Hemmingsdeqian), BYK156 (BYK Chemical) and BYK152 (BYK Chemical), and more preferably NUOSPERSE FX 365, BYK156 or BYK152. In the present invention, the aqueous wetting and dispersing agent can improve the interface effect between the antifouling agent, the pigment and the filler and the emulsion, which is beneficial to improve the dispersion stability of the antifouling agent and the pigment and filler in the coating.

[0075] The present invention has no particular limitation on the water used to prepare the aqueous antifouling slurry, and deionized water is preferably used.

[0076] In the present invention, the fineness of the aqueous antifouling slurry is preferably ≤40 μm, and specifically may be 20 μm, 30 μm or 40 μm.

[0077] In the present invention, the method for preparing the aqueous antifouling slurry preferably comprises the following steps:

[0078] The antifouling agent, pigment, filler, thickener, aqueous wetting dispersant and water are mixed and ball-milled to obtain aqueous antifouling slurry.

[0079] In the present invention, the mixing preferably includes: mixing the thickener, aqueous wetting dispersant and water, then adding the antifouling agent and pigment filler, and stirring and dispersing at 800-1000 r / min for 25-35 min.

[0080] The present invention has no special limitation on the ball milling, as long as the fineness of the final water-based antifouling slurry is ensured to be ≤40 μm.

[0081] Based on the mass fraction of the strippable acrylic film-forming emulsion, the environmentally friendly strippable coating composition with anti-marine biofouling function provided by the present invention includes 1 to 5 parts of an auxiliary agent, and in a specific embodiment, it can be 1 part, 2 parts, 3 parts, 4 parts or 5 parts. In the present invention, the auxiliary agent preferably includes an aqueous leveling agent, an aqueous defoaming agent and an antifreeze agent, and the mass ratio of the aqueous leveling agent, the aqueous defoaming agent and the antifreeze agent is preferably 1: (1 to 2): (2 to 4).

[0082] In the present invention, the water-based leveling agent preferably includes 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 occurrence of shrinkage craters in the paint film, which is beneficial to improving the leveling performance of the paint film.

[0083] In the present invention, the aqueous defoamer preferably includes at least one of aqueous defoamers DA PRO AP7010, BYK025 and DC65, and more preferably aqueous defoamers DAPROAP7010, BYK025 or DC65; the aqueous defoamer can eliminate bubbles in the coating, which is beneficial to improving the appearance of the paint film and improving the construction performance of the coating.

[0084] In the present invention, the antifreeze agent preferably includes ethylene glycol and / or propylene glycol; the antifreeze agent can lower the freezing point of the water-based paint, which is beneficial to improving the storage stability of the water-based paint in a low-temperature environment.

[0085] Based on the mass fraction of the strippable acrylic film-forming emulsion, the environmentally friendly strippable coating composition with anti-marine biofouling function provided by the present invention comprises 1 to 5 parts of water. In the present invention, the water in the coating is preferably deionized water.

[0086] In the present invention, the method for preparing the environmentally friendly peelable coating composition having anti-marine biofouling function preferably comprises the following steps:

[0087] The strippable acrylic film-forming emulsion, the rosin tackifying emulsion, the water-based antifouling slurry, the auxiliary agent and water are mixed and filtered to obtain an environmentally friendly strippable coating composition with the function of preventing marine biofouling.

[0088] In the present invention, the mixing is preferably stirring mixing; the present invention has no special requirements for the filtering method, and any filtering method known in the art can be used.

[0089] The present invention provides a coating obtained by forming a film of the above-mentioned environmentally friendly peelable coating composition with anti-marine biofouling function. In the present invention, the film-forming method preferably includes one or more of spraying, brushing and roller coating. In the present invention, the thickness of the coating is preferably 100μm to 150μm. The environmentally friendly peelable coating with anti-marine biofouling function provided by the present invention is mainly used for the surface of underwater navigation bodies, underwater precision instruments, and marine equipment. When the surface of underwater navigation bodies, underwater precision instruments, and marine equipment encounters failure of the anti-fouling coating or a large number of marine organisms are attached, the coating can be peeled off together with the marine organisms attached to the surface, which is convenient for subsequent re-spraying construction.

[0090] The environmentally friendly peelable coating composition and coating thereof with anti-marine biofouling function provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0091] Example 1

[0092] Preparation of water-based antifouling slurry:

[0093] 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 mancozeb and 9.5g of pigment filler (7g of polytetrafluoroethylene powder, 2.5g of organic bentonite), stir and disperse at 900r / min for 30min, and then use a QM-3SP2 planetary ball mill to ball mill the obtained mixture until the slurry fineness is less than 40μm to obtain an aqueous slurry.

[0094] Preparation of environmentally friendly peelable coatings with anti-marine biofouling function:

[0095] Weigh 30.0 g of strippable acrylic film-forming emulsion, 15.0 g of SNOWTACK 780G rosin tackifying emulsion, 45.0 g of 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 defoaming agent DA PRO AP7010 and 5.5 g of deionized water, stir and disperse at 300 r / min for 30 min, filter, and obtain an environmentally friendly strippable coating with anti-marine biofouling function.

[0096] The strippable acrylic film-forming emulsion is a mixture of silicone oil-modified acrylic emulsion and a wax additive; the mass ratio of the silicone oil-modified acrylic emulsion to the wax additive is 4.5:1; the wax additive is a mixture of white mineral oil and liquid paraffin, and the mass ratio of the white mineral oil to the liquid paraffin is 2:1.

[0097] The silicone oil modified acrylate emulsion comprises the following raw materials in percentage by weight:

[0098] Dodecafluoroheptyl methacrylate 6%;

[0099] Vinyl silicone oil monomer 3%;

[0100] Acrylate monomer 35%;

[0101] Acrylic acid 1%;

[0102] Emulsifier: sodium lauryl sulfate 1.5%;

[0103] Initiator ammonium persulfate 0.5%;

[0104] Sodium bicarbonate 0.1%;

[0105] pH adjuster: ammonia water 0.4%;

[0106] The balance is water.

[0107] The preparation method of the silicone oil modified acrylate emulsion is:

[0108] (1) 6% dodecafluoroheptyl methacrylate, 3% vinyl silicone oil (V401-2000), 35% acrylate monomer (methyl methacrylate: butyl acrylate = 2:1), 1% acrylic acid, 1.5% sodium dodecyl sulfate and 7% water were mixed and dispersed and emulsified at a speed of 200 r / min for 10 minutes to obtain a monomer emulsion;

[0109] (2) dissolving 0.5% ammonium persulfate in 5% water to obtain an initiator aqueous solution;

[0110] (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) were stirred (500 r / min) and mixed, and then heated to 80° C., and stirred for 60 minutes while maintaining the temperature to obtain a seed emulsion;

[0111] (4) At 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 to the seed emulsion within 1.5 to 2 hours. After the addition is completed, the temperature is kept for 60 minutes, the temperature is raised to 87° C. and kept for 55 minutes, and then the temperature is lowered to 55° C. 0.4% ammonia water is added to the obtained system to adjust the pH value to between 6 and 7 to obtain a silicone oil-modified acrylate emulsion.

[0112] (5) According to the mass ratio of silicone oil modified acrylate emulsion to wax additive (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 2:1) of 4.5:1, the wax additive is added to the silicone oil modified acrylate emulsion at 55°C, stirred and dispersed for 30 minutes, and then naturally cooled to room temperature, and then the strippable acrylate film-forming emulsion can be discharged, filtered and packaged to obtain the strippable acrylate film-forming emulsion.

[0113] Example 2

[0114] Prepare an aqueous antifouling slurry according to the method of Example 1;

[0115] Preparation of environmentally friendly peelable coatings with anti-marine biofouling function:

[0116] Weigh 31.0 g of strippable acrylic film-forming emulsion, 11.0 g of SNOWTACK 780G rosin tackifying emulsion, 50.0 g of 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 defoaming agent DA PRO AP7010 and 3 g of deionized water, stir and disperse at 300 r / min for 30 min, filter, and obtain an environmentally friendly strippable coating with anti-marine biofouling function.

[0117] The strippable acrylic film-forming emulsion is a mixture of silicone oil-modified acrylic emulsion and a wax additive; the mass ratio of the silicone oil-modified acrylic emulsion to the wax additive is 4:1; the wax additive is a mixture of white mineral oil and liquid paraffin, and the mass ratio of the white mineral oil to the liquid paraffin is 2:1;

[0118] The silicone oil modified acrylate emulsion comprises the following raw materials in percentage by weight:

[0119] Dodecafluoroheptyl methacrylate 8%;

[0120] Vinyl silicone oil monomer 5%;

[0121] Acrylate monomer 37%;

[0122] Acrylic acid 0.8%;

[0123] Emulsifier sodium stearate 1%;

[0124] Initiator ammonium persulfate 0.3%;

[0125] Sodium bicarbonate 0.1%;

[0126] pH adjuster: ammonia water 0.4%;

[0127] The balance is water.

[0128] The preparation method of the silicone oil modified acrylate emulsion is:

[0129] (1) 8% dodecafluoroheptyl methacrylate, 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 were mixed and dispersed and emulsified at a speed of 300 r / min for 10 minutes to obtain a monomer emulsion;

[0130] (2) dissolving 0.3% ammonium persulfate in 3% water to obtain an initiator aqueous solution;

[0131] (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) were stirred (500 r / min) and mixed, and then heated to 81° C., and stirred for 60 minutes while maintaining the temperature to obtain a seed emulsion;

[0132] (4) At 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 to the seed emulsion within 1.5 to 2 hours. After the addition is completed, the temperature is kept for 60 minutes, the temperature is raised to 88° C. and kept for 50 minutes, and then the temperature is lowered to 50° C. 0.4% ammonia water is added to the obtained system to adjust the pH value to between 6 and 7 to obtain a silicone oil-modified acrylate emulsion.

[0133] (5) According to the mass ratio of silicone oil modified acrylate emulsion to wax additive (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 2:1) of 4:1, the wax additive is added to the silicone oil modified acrylate emulsion at 50°C, stirred and dispersed for 30 minutes, and then naturally cooled to room temperature, and then the strippable acrylate film-forming emulsion can be discharged, filtered and packaged to obtain the strippable acrylate film-forming emulsion.

[0134] Example 3

[0135] Preparation of water-based antifouling slurry:

[0136] Weigh 40.5 g of deionized water, 0.6 g of thickener DeuRheo WT-105A, 0.02 g of hydroxyethyl cellulose and 0.9 g of aqueous wetting and dispersing agent BYK156, mix them in a dispersion tank, add 40 g of cuprous oxide, 7 g of copper pyridinethione, and 11 g of pigments and fillers (7 g of polytetrafluoroethylene powder, 2 g of zinc oxide, and 2 g of organic bentonite), stir and disperse at 900 r / min for 30 min, and then use a QM-3SP2 planetary ball mill to ball mill the obtained mixture until the slurry fineness is less than 40 μm to obtain an aqueous slurry.

[0137] Preparation of environmentally friendly peelable coatings with anti-marine biofouling function:

[0138] Weigh 35.0 g of strippable acrylic film-forming emulsion, 10.0 g of SNOWTACK 780G rosin tackifying emulsion, 47.0 g of water-based antifouling slurry, 2.0 g of propylene glycol, 0.6 g of water-based leveling agent WCT 2490, 0.9 g of water-based defoaming agent DA PRO AP7010 and 4.5 g of deionized water, stir and disperse at 300 r / min for 30 min, filter, and obtain an environmentally friendly strippable coating with anti-marine biofouling function.

[0139] The strippable acrylic film-forming emulsion is a mixture of silicone oil-modified acrylic emulsion and a wax additive; the mass ratio of the silicone oil-modified acrylic emulsion to the wax additive is 5:1; the wax additive is a mixture of white mineral oil and liquid paraffin, and the mass ratio of the white mineral oil to the liquid paraffin is 1:2;

[0140] The silicone oil modified acrylate emulsion comprises the following raw materials in percentage by weight:

[0141] Dodecafluoroheptyl methacrylate 9%;

[0142] Vinyl silicone oil monomer 6%;

[0143] Acrylate monomer 32%;

[0144] Acrylic acid 1.2%;

[0145] Emulsifier fatty alcohol polyoxyethylene ether 1.7%;

[0146] Initiator potassium persulfate 0.5%;

[0147] Sodium bicarbonate 0.1%;

[0148] pH adjuster: 0.5% ammonia water;

[0149] The balance is water.

[0150] The preparation method of the silicone oil modified acrylate emulsion is:

[0151] (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 minutes to obtain a monomer emulsion;

[0152] (2) dissolving 0.5% potassium persulfate in 5% water to obtain an initiator aqueous solution;

[0153] (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 stirred (500 r / min) and then heated to 80° C., and stirred for 70 min while maintaining the temperature to obtain a seed emulsion;

[0154] (4) At 81° C., the remaining monomer emulsion (65% of the total amount) and the remaining initiator aqueous solution (85% of the total amount) are added dropwise to the seed emulsion within 1.5 to 2 hours. After the addition is completed, the temperature is kept warm for 60 minutes, the temperature is raised to 87° C. and kept warm for 60 minutes, and then the temperature is lowered to 53° C., and 0.5% ammonia water is added to the obtained system to adjust the pH value to between 6 and 7 to obtain a silicone oil-modified acrylate emulsion.

[0155] (5) According to the mass ratio of silicone oil modified acrylate emulsion to wax additive (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 1:2) of 5:1, the wax additive is added to the silicone oil modified acrylate emulsion at 53°C, stirred and dispersed for 30 minutes, and then naturally cooled to room temperature, and then the strippable acrylate film-forming emulsion can be discharged, filtered and packaged to obtain.

[0156] Example 4

[0157] Prepare an aqueous antifouling slurry according to the method of Example 3;

[0158] Preparation of environmentally friendly peelable coatings with anti-marine biofouling function:

[0159] Weigh 25.0 g of strippable acrylic film-forming emulsion, 10.0 g of SNOWTACK 780G rosin tackifying emulsion, 55.0 g of 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 defoaming agent DA PRO AP7010 and 5.5 g of deionized water, stir and disperse at 300 r / min for 30 min, filter, and obtain an environmentally friendly strippable coating with anti-marine biofouling function.

[0160] The strippable acrylic film-forming emulsion is a mixture of silicone oil-modified acrylic emulsion and a wax additive; the mass ratio of the silicone oil-modified acrylic emulsion to the wax additive is 5:1; the wax additive 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;

[0161] The silicone oil modified acrylate emulsion comprises the following raw materials in percentage by weight:

[0162] Dodecafluoroheptyl methacrylate 5%;

[0163] Vinyl silicone oil monomer 7%;

[0164] Acrylate monomer 31%;

[0165] Acrylic acid 0.6%;

[0166] Emulsifier: dodecyl ammonium chloride 1.6%;

[0167] Initiator potassium persulfate 0.4%;

[0168] Sodium bicarbonate 0.075%;

[0169] pH adjuster: ammonia water 0.325%;

[0170] The balance is water.

[0171] The preparation method of the silicone oil modified acrylate emulsion is:

[0172] (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 were mixed and dispersed and emulsified at a speed of 400 r / min for 10 minutes to obtain a monomer emulsion;

[0173] (2) dissolving 0.4% potassium persulfate in 4% water to obtain an initiator aqueous solution;

[0174] (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) were stirred (600 r / min) and mixed, and then heated to 81° C., and stirred for 65 minutes while maintaining the temperature to obtain a seed emulsion;

[0175] (4) At 81° C., the remaining monomer emulsion (75% of the total amount) and the remaining initiator aqueous solution (88% of the total amount) are added dropwise to the seed emulsion within 1.5 to 2 hours. After the addition is completed, the temperature is kept warm for 60 minutes, the temperature is raised to 88° C. and kept warm for 60 minutes, and then the temperature is lowered to 55° C., and 0.325% ammonia water is added to the obtained system to adjust the pH value to between 6 and 7 to obtain a silicone oil-modified acrylate emulsion.

[0176] (5) According to the mass ratio of silicone oil modified acrylate emulsion to wax additive (VJ989 white mineral oil: YT-RH liquid paraffin emulsion = 3:1) of 5:1, the wax additive is added to the silicone oil modified acrylate emulsion at 55°C, stirred and dispersed for 30 minutes, and then naturally cooled to room temperature, and then the strippable acrylate film-forming emulsion can be discharged, filtered and packaged to obtain the strippable acrylate film-forming emulsion.

[0177] Comparative Example 1

[0178] The aqueous antifouling slurry was prepared according to Example 1.

[0179] When preparing an environmentally friendly peelable coating with anti-marine biofouling function, according to Example 1, a moderate amount of the peelable acrylic film-forming emulsion is replaced with an aqueous acrylic emulsion that is not modified with silicone oil and does not add wax additives. When other conditions are the same, the peelability of the coating is tested.

[0180] The aqueous acrylic emulsion comprises the following raw materials in percentage by weight:

[0181] Dodecafluoroheptyl methacrylate 10%;

[0182] Methyl methacrylate 14%;

[0183] Butyl acrylate 10%;

[0184] Isooctyl acrylate 8%;

[0185] Acrylic acid 0.6%;

[0186] Emulsifier: dodecyl ammonium chloride 1.6%;

[0187] Initiator potassium persulfate 0.4%;

[0188] Sodium bicarbonate 0.075%;

[0189] pH adjuster: ammonia water 0.325%;

[0190] The balance is water.

[0191] The preparation method of the aqueous acrylic emulsion is:

[0192] (1) 10% dodecafluoroheptyl methacrylate, 14% methyl methacrylate, 10% butyl acrylate, 8% isooctyl acrylate, 0.6% acrylic acid, 1.6% dodecyl ammonium chloride and 8% water were mixed, and the mixture was dispersed and emulsified at a speed of 400 r / min for 10 minutes to obtain a monomer emulsion;

[0193] (2) dissolving 0.4% potassium persulfate in 4% water to obtain an initiator aqueous solution;

[0194] (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 stirred (600 r / min) and then heated to 81° C., and stirred for 65 minutes while maintaining the temperature to obtain a seed emulsion;

[0195] (4) At 81°C, the remaining monomer emulsion (75% of the total amount) and the remaining initiator aqueous solution (88% of the total amount) are added dropwise to the seed emulsion within 1.5 to 2 hours. After the addition is completed, the temperature is kept for 60 minutes, the temperature is raised to 88°C and kept for 60 minutes, and then the temperature is lowered to 55°C. 0.325% ammonia water is added to the obtained system to adjust the pH value to between 6 and 7 to obtain an aqueous acrylic ester emulsion. After that, the system is naturally cooled to room temperature, and the aqueous acrylic ester film-forming emulsion can be discharged, filtered and packaged to obtain the aqueous acrylic ester film-forming emulsion.

[0196] Evaluation of physical and chemical properties, peeling properties and antifouling properties

[0197] (1) The VOC content of the environmentally friendly peelable coatings with anti-marine biofouling function prepared in Examples 1 to 5 was measured according to the method in GB18582-2008;

[0198] (2) The environmentally friendly peelable coating with anti-marine biofouling function prepared in Examples 1 to 5 was sprayed on the surface of the base plate to form a paint film, and the performance of the paint film was tested as follows:

[0199] The flexibility of the paint film was tested according to the GB / T 1731-2020 method;

[0200] The impact resistance of the paint film was tested according to the GB / T 1732-2020 method;

[0201] According to the GB / T 2792-2014 method, the peelable coating was cut and sampled, and a 180° peel strength test was performed.

[0202] (3) The environmentally friendly peelable coating with anti-marine biofouling function prepared in Examples 1 to 5 was sprayed on a low-carbon steel plate (200mm×300mm×2mm) with an epoxy anti-corrosion primer (80 to 100 microns) to make a sample. After fully curing at room temperature for 2 days, the sample was placed at a depth of 1 meter under seawater for a static real sea hanging test. The test period was 4 months, and the test site was: Shenzhen Nan'ao waters.

[0203] The coating obtained in Example 1 was sprayed on a steel plate with epoxy primer, and the surface was peeled off after 24 hours. Figure 1 As shown, the state after peeling is as follows Figure 2 As shown. Figure 1 and Figure 2 It can be seen that the coating can be easily peeled off as a whole, with no residue on the substrate and no damage to the paint film.

[0204] The physical and chemical properties and antifouling performance data of the environmentally friendly peelable coatings with anti-marine biofouling function in Examples 1 to 5 are shown in Table 1.

[0205] Table 1 Physical and chemical properties, peeling performance and antifouling performance evaluation test results

[0206]

[0207]

[0208] As can be seen from Table 1, the environmentally friendly peelable coating with anti-marine biofouling function provided by the present invention has good physical and chemical properties, stable peelability and excellent anti-marine biofouling performance; the VOC content in the coating is less than 70g / L, which is environmentally friendly.

[0209] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An environmentally friendly peelable coating composition with anti-marine biofouling function, characterized in that: In parts by mass, it includes the following components: The strippable acrylic film-forming emulsion is a mixture of silicone oil-modified acrylic emulsion and a wax auxiliary agent; the mass ratio of the silicone oil-modified acrylic emulsion to the wax auxiliary agent is 4 to 5:

1.

2. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that: The silicone oil modified acrylate emulsion comprises the following raw materials in percentage by weight:

3. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 2, characterized in that: The vinyl silicone oil monomer includes polydimethylsiloxane with a vinyl group at each end of the molecular chain; The acrylic acid ester monomer includes one or more of methyl methacrylate, butyl acrylate and isooctyl acrylate; The initiator includes a persulfate initiator; The emulsifier includes one or more of anionic emulsifiers, cationic emulsifiers and nonionic emulsifiers; The pH regulator includes ammonia water, and the mass concentration of the ammonia water is 25-28%.

4. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1 or 2, characterized in that: The wax additive is white mineral oil and / or liquid paraffin; The solid content of the strippable acrylic ester film-forming emulsion is 45-55%.

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

6. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that: The aqueous antifouling slurry comprises the following components in terms of mass percentage:

7. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 6, characterized in that: The antifouling agent includes a main antifouling agent and an auxiliary antifouling agent; The main antifouling agent includes cuprous oxide and / or copper; the auxiliary antifouling agent includes one or more of copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazoline-3-one, diuron and mancozeb; The mass ratio of the main antifouling agent to the auxiliary antifouling agent is 5 to 7:

1.

8. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 6, characterized in that: The pigment and filler include one or more of polytetrafluoroethylene powder, organic bentonite, red iron oxide, zinc oxide, calcium carbonate, barium sulfate, mica powder, quartz powder and talcum powder; The fineness of the aqueous antifouling slurry is ≤40 μm.

9. The environmentally friendly peelable coating composition with anti-marine biofouling function according to claim 1, characterized in that: The auxiliary agent comprises a water-based leveling agent, a water-based defoaming agent and an antifreeze agent, and the mass ratio of the water-based leveling agent, the water-based defoaming agent and the antifreeze agent is 1: (1-2): (2-4).

10. A coating obtained by forming a film of the environmentally friendly peelable coating composition having anti-marine biofouling function according to any one of claims 1 to 9.

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