Antifouling paint and antifouling coating

Abstract

The invention belongs to the technical field of coatings, and particularly discloses an antifouling coating which is prepared from the following components in parts by weight: 40 to 50 parts of waterborne epoxy emulsion, 10 to 20 parts of polycaprolactone polyol, 10 to 20 parts of fluorosilicone modified acrylate, 8 to 15 parts of modified zinc oxide, 0.2 to 0.6 part of dispersing agent, 0.2 to 0.6 part of defoaming agent, 0.2 to 0.6 part of flatting agent, 2 to 5 parts of coalescing agent and 5 to 15 parts of water. The coating disclosed by the invention has an excellent antifouling effect.

Description

Technical Field

[0001] The invention relates to the technical field of coatings, and in particular to an antifouling coating and an antifouling coating. Background Art

[0002] Antifouling coatings are widely needed in daily life and industrial applications, such as for building exterior walls, vehicle surfaces, marine facilities, etc., to prevent the adhesion of dust, stains, etc.

[0003] With the acceleration of industrialization, the accumulation of pollutants has caused serious impacts on the surface of buildings, vehicles and various equipment. However, existing antifouling coatings have problems such as poor antifouling effect.

[0004] In view of this, this application is filed. Summary of the invention

[0005] The invention provides an antifouling paint and an antifouling coating. The paint of the invention has excellent antifouling performance.

[0006] The present invention solves the technical problem by adopting the following technical solutions: An antifouling coating comprises the following components in parts by weight: 40-50 parts of waterborne epoxy emulsion, 10-20 parts of polycaprolactone polyol, 10-20 parts of fluorosilicone modified acrylate, 8-15 parts of modified zinc oxide, 0.2-0.6 parts of dispersant, 0.2-0.6 parts of defoamer, 0.2-0.6 parts of leveling agent, 2-5 parts of film-forming aid, and 5-15 parts of water; The preparation method of the modified zinc oxide comprises the following steps: adding zinc oxide and hexadecyltrimethylammonium bromide to a nitric acid solution, stirring evenly, and obtaining a zinc oxide dispersion; adding heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile to the zinc oxide dispersion, stirring at 65-85° C. for 2-5 hours, filtering, and drying, and obtaining the modified zinc oxide.

[0007] The present invention creatively combines the above-mentioned raw materials to obtain a coating with excellent anti-fouling effect, wherein the present invention uses water-based epoxy emulsion as a matrix, the water-based epoxy emulsion can form a solid coating, improve the oxidation resistance and corrosion resistance of the coating, effectively isolate external pollutants, and reduce the contact and adhesion of pollutants to the surface, wherein the polycaprolactone polyol can improve the stability of the coating, improve the waterproof and anti-pollution effects of the coating, and prevent moisture and stains from penetrating into the surface, wherein the fluorosilicone-modified acrylate contains fluorosilicone groups, which can significantly improve the hydrophobicity and anti-fouling performance of the coating, making it difficult for water droplets, oil stains, dust, etc. to adhere to the surface, and at the same time make the coating have certain self-cleaning properties, effectively improving the anti-fouling effect of the coating.

[0008] The present invention creatively modifies zinc oxide, and the modified zinc oxide can effectively prevent the growth of bacteria and avoid the generation of stains or dirt due to bacterial reproduction. At the same time, it has a certain photocatalytic effect and can decompose organic pollutants. At the same time, the dispersion effect of the modified zinc oxide in the coating is significantly improved to avoid its agglomeration phenomenon. It can significantly increase the surface energy of the coating and effectively improve the hydrophobic effect and stain resistance of the coating.

[0009] As a preferred embodiment of the present invention, the following components are included in parts by weight: 45 parts of aqueous epoxy emulsion, 15.5 parts of polycaprolactone polyol, 14 parts of fluorosilicone modified acrylate, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of defoamer, 0.5 parts of leveling agent, 4 parts of film-forming aid, and 8 parts of water.

[0010] As a preferred embodiment of the present invention, the molecular weight of the polycaprolactone polyol is 830-1000, the hydroxyl value is 119-140 KOHmg / g, and the viscosity at 75° C. is 90-130 mPa·s.

[0011] As a preferred embodiment of the present invention, the viscosity of the fluorosilicone modified acrylate at 25° C. is 2000-2300 mPa·s.

[0012] As a preferred embodiment of the present invention, the epoxy equivalent of the aqueous epoxy emulsion is 730~1050g / eq.

[0013] As a preferred embodiment of the present invention, the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide and nitric acid solution is 1:(0.05-0.2):(2-5); the molar concentration of the nitric acid solution is 0.1-2 mol / L.

[0014] As a preferred embodiment of the present invention, the weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is (0.05~0.12):(0.05~0.12):(0.05~0.12):(0.01~0.05):1.

[0015] As a preferred embodiment of the present invention, the film-forming aid includes at least one of lauryl alcohol ester, dipropylene glycol butyl ether, diethylene glycol butyl ether, and propylene glycol diacetate; The defoaming agent includes at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate, and silicone resin.

[0016] The leveling agent includes at least one of acrylated polysiloxane, polyether-modified polysiloxane, polysiloxane-polyether copolymer, and polysiloxane; The dispersant includes at least one of anionic carboxylate dispersants and cationic quaternary ammonium salt dispersants.

[0017] The present invention also provides a method for preparing an antifouling coating, comprising the following steps: The water, dispersant, defoamer and leveling agent are mixed evenly, and then water-based epoxy emulsion, polycaprolactone polyol, fluorosilicone modified acrylate, modified zinc oxide and film-forming aid are added, and stirred evenly to obtain the antifouling coating.

[0018] The present invention also provides an antifouling coating, which is prepared by using the antifouling coating described above.

[0019] Beneficial effects of the present invention: The present invention uses water-based epoxy emulsion as a matrix, and the water-based epoxy emulsion can form a solid coating, improve the coating's antioxidant and corrosion resistance, effectively isolate external pollutants, and reduce the contact and adhesion of pollutants to the surface. Among them, the polycaprolactone polyol can improve the stability of the coating, improve the coating's waterproof and anti-pollution effects, and prevent moisture and stains from penetrating into the surface. Among them, the fluorosilicone-modified acrylate contains fluorosilicone groups, which can significantly improve the coating's hydrophobicity and anti-fouling properties, making it difficult for water droplets, oil stains, dust, etc. to adhere to the surface. At the same time, the coating has certain self-cleaning properties, effectively improving the coating's anti-fouling effect. DETAILED DESCRIPTION

[0020] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0021] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0022] In the present invention, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0023] In the present invention, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0024] The reagents or instruments used in the present invention without indicating the manufacturer are all conventional products that can be obtained commercially. The raw materials used in the comparative examples and the raw materials used in the parallel experiments of the embodiments are the same commercially available products unless otherwise specified.

[0025] The sources of raw materials for the examples and comparative examples of the present invention are as follows: Water-based epoxy emulsion-1: Epoxy equivalent weight is 730~800 g / eq, source: Guangdong Huaguoshan Environmental Protection Co., Ltd., brand name Houxian® EP384.

[0026] Water-based epoxy emulsion-2: Epoxy equivalent is 950~1050 g / eq, source: Guangdong Huaguoshan Environmental Protection Co., Ltd., brand name Houxian® EP364.

[0027] Polycaprolactone polyol-1: molecular weight is 830, hydroxyl value is 130~140KOHmg / g, viscosity at 75°C is 90~110mPa·s, from Haoyi New Materials, brand PCL208.

[0028] Polycaprolactone polyol-2: molecular weight is 1000, hydroxyl value is 109~119KOHmg / g, viscosity is 110~130mPa·s at 75°C, it comes from Haoyi New Materials, brand PCL210.

[0029] Polycaprolactone polyol-3: molecular weight is 2000, hydroxyl value is 53~59KOHmg / g, viscosity is 210~270mPa·s at 75°C, it comes from Haoyi New Materials, brand PCL220N.

[0030] Polycaprolactone polyol-4: molecular weight is 530, hydroxyl value is 207~217KOHmg / g, viscosity is 30~50mPa·s at 75°C, it comes from Haoyi New Materials, brand PCL205.

[0031] Fluorosilicone modified acrylate-1: The viscosity at 25°C is 2300mPa·s, sourced from Guangzhou Runao Chemical, brand LuCure® 8658.

[0032] Fluorosilicone modified acrylate-2: The viscosity at 25°C is 2000mPa·s. It comes from Guangzhou Runao Chemical, brand LuCure® 8668.

[0033] Fluorosilicone modified acrylate-3: The viscosity at 25°C is 700mPa·s. It comes from Guangzhou Runao Chemical, brand LuCure® 8638.

[0034] Example 1

[0035] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-1, 14 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0036] The dispersant is Dow OROTAN 731A.

[0037] The leveling agent is TEGO2100.

[0038] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0039] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-1, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0040] Example 2

[0041] An antifouling coating comprises the following components in parts by weight: 40 parts of waterborne epoxy emulsion-1, 20 parts of polycaprolactone polyol-1, 10 parts of fluorosilicone modified acrylate-1, 15 parts of modified zinc oxide, 0.2 parts of dispersant, 0.6 parts of trimethylsiloxane, 0.2 parts of leveling agent, 5 parts of dodecyl alcohol ester and 5 parts of water.

[0042] The dispersant is Dow OROTAN 731A.

[0043] The leveling agent is TEGO2100.

[0044] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0045] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-1, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0046] Example 3

[0047] An antifouling coating comprises the following components in parts by weight: 50 parts of waterborne epoxy emulsion-1, 10 parts of polycaprolactone polyol, 20 parts of fluorosilicone modified acrylate, 8 parts of modified zinc oxide, 0.6 parts of dispersant, 0.2 parts of trimethylsiloxane, 0.6 parts of leveling agent, 2 parts of dodecyl alcohol ester and 15 parts of water.

[0048] The dispersant is Dow OROTAN 731A.

[0049] The leveling agent is TEGO2100.

[0050] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0051] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-1, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0052] Example 4

[0053] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-2, 15.5 parts of polycaprolactone polyol-1, 14 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0054] The dispersant is Dow OROTAN 731A.

[0055] The leveling agent is TEGO2100.

[0056] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0057] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-2, polycaprolactone polyol-1, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0058] Example 5

[0059] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-2, 14 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0060] The dispersant is Dow OROTAN 731A.

[0061] The leveling agent is TEGO2100.

[0062] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0063] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-2, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0064] Example 6

[0065] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-3, 14 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0066] The dispersant is Dow OROTAN 731A.

[0067] The leveling agent is TEGO2100.

[0068] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0069] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-3, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0070] Example 7

[0071] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-4, 14 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0072] The dispersant is Dow OROTAN 731A.

[0073] The leveling agent is TEGO2100.

[0074] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0075] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-4, fluorosilicone modified acrylate-1, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0076] Example 8

[0077] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-1, 14 parts of fluorosilicone modified acrylate-2, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0078] The dispersant is Dow OROTAN 731A.

[0079] The leveling agent is TEGO2100.

[0080] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0081] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-1, fluorosilicone modified acrylate-2, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0082] Example 9

[0083] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-1, 14 parts of fluorosilicone modified acrylate-3, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0084] The dispersant is Dow OROTAN 731A.

[0085] The leveling agent is TEGO2100.

[0086] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile are added to a zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is 0.1:0.1:0.1:0.04:1.

[0087] The method for preparing the antifouling coating comprises the following steps: The water, dispersant, trimethylsiloxane and leveling agent are mixed evenly, and then water-based epoxy emulsion-1, polycaprolactone polyol-1, fluorosilicone modified acrylate-3, modified zinc oxide and dodecyl alcohol ester are added, and stirred evenly to obtain an antifouling coating.

[0088] Comparative Example 1

[0089] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 uses an equal amount of zinc oxide to replace the modified zinc oxide, and the other contents are the same.

[0090] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-1, 14 parts of fluorosilicone modified acrylate-1, 12 parts of zinc oxide with an average particle size of 1 μm, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester, and 8 parts of water.

[0091] Comparative Example 2

[0092] The difference between Comparative Example 2 and Example 1 is that the preparation method of the modified zinc oxide in Comparative Example 2 is different from that in Example 1, and the other aspects are the same.

[0093] The preparation method of the modified zinc oxide is: Zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide are added to a 0.5 mol / L nitric acid solution, stirred at 200 rpm for 60 min to obtain a zinc oxide dispersion, filtered, and dried to obtain modified zinc oxide; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4.

[0094] Comparative Example 3

[0095] The difference between Comparative Example 3 and Example 1 is that the preparation method of the modified zinc oxide in Comparative Example 3 is different from that in Example 1, and the other aspects are the same.

[0096] The preparation method of the modified zinc oxide is: Add zinc oxide with an average particle size of 1 μm and hexadecyltrimethylammonium bromide into a 0.5 mol / L nitric acid solution, and stir at 200 rpm for 60 min to obtain a zinc oxide dispersion; the weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide, and the nitric acid solution is 1:0.1:4; Heptadecafluorodecyltrimethoxysilane was added to the zinc oxide dispersion, stirred at 80° C. and 200 rpm for 4 hours, filtered, and dried to obtain modified zinc oxide. The weight ratio of the heptadecafluorodecyltrimethoxysilane to the zinc oxide dispersion was 0.1:1.

[0097] Comparative Example 4

[0098] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 does not contain fluorosilicone-modified acrylate (replaced by an equal amount of water-based epoxy emulsion), and the rest are the same.

[0099] An antifouling coating comprises the following components in parts by weight: 59 parts of waterborne epoxy emulsion-1, 15.5 parts of polycaprolactone polyol-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0100] Comparative Example 5

[0101] The difference between Comparative Example 5 and Example 1 is that the amounts of polycaprolactone polyol and fluorosilicone modified acrylate are different, and the other aspects are the same.

[0102] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 24.5 parts of polycaprolactone polyol-1, 5 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0103] Comparative Example 6

[0104] The difference between Comparative Example 6 and Example 1 is that the amounts of polycaprolactone polyol and fluorosilicone modified acrylate are different, and the other aspects are the same.

[0105] An antifouling coating comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion-1, 5 parts of polycaprolactone polyol-1, 24.5 parts of fluorosilicone modified acrylate-1, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of trimethylsiloxane, 0.5 parts of leveling agent, 4 parts of dodecyl alcohol ester and 8 parts of water.

[0106] Test Case

[0107] The antifouling performance and water resistance of the paint film were tested in accordance with GB / T 5370-2007 "Shallow Sea Immersion Test Method for Antifouling Paint Samples". The test period is 12 months.

[0108] Table 1

[0109] It can be seen from Table 1 that the coating of the present invention has excellent antifouling performance.

[0110] Comparison of Examples 1 and 5 to 7 shows that the antifouling performance can be further improved by controlling the molecular weight of the polycaprolactone polyol to 830 to 1000, the hydroxyl value to 119 to 140 KOHmg / g, and the viscosity at 75° C. to 90 to 130 mPa·s.

[0111] By comparing Examples 1, 8 and 9, it can be seen that the antifouling performance can be further improved by controlling the viscosity of the fluorosilicone-modified acrylate at 25° C. to 2000-2300 mPa·s.

[0112] By comparing Example 1 with Comparative Examples 1 to 3, it can be seen that the modified zinc oxide described in the present invention can significantly improve the antifouling performance, and the modified zinc oxide prepared by different methods has different improvements in the antifouling performance. The modified zinc oxide prepared by the method of the present invention can more significantly improve the antifouling performance than the modified zinc oxide prepared by other methods.

[0113] By comparing Example 1 with Comparative Examples 4 to 6, it can be seen that the antifouling performance can be significantly improved by adding fluorosilicone-modified acrylate, and the antifouling performance can be more significantly improved by controlling the amount of fluorosilicone-modified acrylate and polycaprolactone polyol within the scope of the present invention.

[0114] Finally, it should be noted that the above embodiments are intended to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. An antifouling coating, characterized in that: The invention comprises the following components in parts by weight: 40-50 parts of waterborne epoxy emulsion, 10-20 parts of polycaprolactone polyol, 10-20 parts of fluorosilicone modified acrylate, 8-15 parts of modified zinc oxide, 0.2-0.6 parts of dispersant, 0.2-0.6 parts of defoamer, 0.2-0.6 parts of leveling agent, 2-5 parts of film-forming aid, and 5-15 parts of water; The preparation method of the modified zinc oxide comprises the following steps: adding zinc oxide and hexadecyltrimethylammonium bromide to a nitric acid solution, stirring evenly, and obtaining a zinc oxide dispersion; adding heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, and azobisisobutyronitrile to the zinc oxide dispersion, stirring at 65-85° C. for 2-5 hours, filtering, and drying, and obtaining the modified zinc oxide.

2. The antifouling coating according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 45 parts of waterborne epoxy emulsion, 15.5 parts of polycaprolactone polyol, 14 parts of fluorosilicone modified acrylate, 12 parts of modified zinc oxide, 0.5 parts of dispersant, 0.5 parts of defoamer, 0.5 parts of leveling agent, 4 parts of film-forming aid and 8 parts of water.

3. The antifouling coating according to claim 1, characterized in that: The polycaprolactone polyol has a molecular weight of 830-1000, a hydroxyl value of 119-140 KOHmg / g, and a viscosity of 90-130 mPa·s at 75°C.

4. The antifouling coating according to claim 1, characterized in that: The viscosity of the fluorosilicone modified acrylate at 25° C. is 2000-2300 mPa·s.

5. The antifouling coating according to claim 1, characterized in that: The epoxy equivalent of the aqueous epoxy emulsion is 730-1050 g / eq.

6. The antifouling coating according to claim 1, characterized in that: The weight ratio of the zinc oxide, hexadecyltrimethylammonium bromide and nitric acid solution is 1:(0.05-0.2):(2-5); the molar concentration of the nitric acid solution is 0.1-2 mol / L.

7. The antifouling coating according to claim 1, characterized in that: The weight ratio of the heptadecafluorodecyltrimethoxysilane, dodecafluoroheptyl acrylate, 2-bromoisobutyryl bromide, azobisisobutyronitrile, and zinc oxide dispersion is (0.05-0.12): (0.05-0.12): (0.05-0.12): (0.01-0.05):

1.

8. The antifouling coating according to any one of claims 1 to 7, characterized in that: The film-forming aid includes at least one of lauryl alcohol ester, dipropylene glycol butyl ether, diethylene glycol butyl ether, and propylene glycol diacetate; The defoaming agent includes at least one of tributyl phosphate, trimethylsiloxane, polyether, polyacrylate, and silicone resin; The leveling agent includes at least one of acrylated polysiloxane, polyether-modified polysiloxane, polysiloxane-polyether copolymer, and polysiloxane; The dispersant includes at least one of anionic carboxylate dispersants and cationic quaternary ammonium salt dispersants.

9. An antifouling coating, characterized in that: The antifouling coating is prepared by using the antifouling coating described in any one of claims 1 to 8.

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