Antifouling paint composition

Abstract

[Problem] To provide an antifouling paint composition whereby an antifouling coating film having excellent adhesion and antifouling properties can be formed. [Solution] The present invention provides an antifouling paint composition containing a copolymer (A), wherein the copolymer (A) has alkoxysilyl groups and ethylenically unsaturated monomer units, the ethylenically unsaturated monomer units having C6-24 straight or branched alkyl groups.

Description

[Technical Field]

[0001] The present invention relates to an antifouling coating composition for preventing, for a long period of time, the attachment and growth of aquatic fouling organisms on objects that are used or exist in water. [Background technology]

[0002] BACKGROUND ART Numerous aquatic fouling organisms such as barnacles, sea squirts, serpula, mussels, mussels, bryozoans, green laver, and sea lettuce live in the waters of the sea, rivers, lakes, and marshes. There has long been a problem of aquatic fouling organisms attaching to objects used or present underwater, such as ships; fishing gear such as fishing nets (aquaculture nets, fixed nets, etc.) and fishing net accessories; and underwater structures such as jetties, tetrapods, port facilities, buoys, pipelines, bridges, power plant water pipes, submarine bases, and submarine oil field drilling equipment. Specifically, it is known that when ships and the like are immersed in water for long periods of time, the aquatic fouling organisms attach to and grow on the parts that come into contact with water, causing a decrease in ship speed, a decrease in water flow, and the like, resulting in significant economic and resource losses. Therefore, in order to prevent the attachment of aquatic fouling organisms, studies have been conducted to solve the problem by applying antifouling paints.

[0003] For example, silicone rubber-based antifouling paints that form a coating film of a mixture of silicone rubber and silicone oil have been proposed (Patent Documents 1 to 4). The coating film formed prevents the adhesion of organisms such as barnacles due to properties such as low surface free energy and low elastic modulus. Furthermore, methods of incorporating antifouling agents such as copper pyrithione have also been investigated (Patent Document 5). On the other hand, when spraying silicone rubber-based antifouling paints, extensive curing is required around the painted area to prevent dust from adhering, which makes application very difficult.Furthermore, due to poor adhesion, there is also the problem of easy peeling at the interface with the base paint. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 51-96830 [Patent Document 2] Special Publication No. 56-26272 [Patent Document 3] Japanese Patent Application Publication No. 63-43973 [Patent Document 4] Japanese Patent Application Publication No. 3-255169 [Patent Document 5] Special Publication No. 2013-515122 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an antifouling coating composition capable of forming an antifouling coating film having excellent adhesion and antifouling properties. [Means for solving the problem]

[0006] According to the present invention, there is provided an antifouling coating composition containing a copolymer (A), wherein the copolymer (A) has an alkoxysilyl group and an ethylenically unsaturated monomer unit, and the ethylenically unsaturated monomer unit has a linear or branched alkyl group having 6 to 24 carbon atoms.

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that the above problems can be solved, leading to the completion of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described in detail below.

[0009] 1. Antifouling paint composition The antifouling coating composition of the present invention contains copolymer (A). The composition of the present invention can also be used as a one-component antifouling coating, and is excellent in workability. 1-1. Copolymer (A) The copolymer (A) has an alkoxysilyl group and an ethylenically unsaturated monomer unit, and the ethylenically unsaturated monomer unit has a linear or branched alkyl group having a carbon number of 6 to 24. The ethylenically unsaturated monomer is a monomer having an ethylenically unsaturated double bond, such as the monomer (a) described below.

[0010] The alkoxysilyl group may be provided on a side chain of the copolymer (A), may be provided at a terminal, or may be provided on both a side chain and a terminal.

[0011] The copolymer (A) having an alkoxysilyl group in the side chain can be obtained, for example, by polymerizing a mixture containing a monomer containing an alkoxysilyl group. Examples of the monomer containing an alkoxysilyl group include 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(trimethoxysilyl)octyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(methyldimethoxysilyl)propyl (meth)acrylate, 3-(methyldiethoxysilyl)propyl (meth)acrylate, vinyltrimethoxysilane, vinyltriethoxysilane, octenyltrimethoxysilane, and p-styryltrimethoxysilane.

[0012] Copolymer (A) having alkoxysilyl groups in its side chains can also be prepared using a monomer containing a first functional group and an alkoxysilyl compound having a second functional group and an alkoxysilyl group. Specifically, a mixture containing a monomer containing the first functional group is polymerized to prepare a copolymer having the first functional group in its side chain. Then, the first functional group of the copolymer reacts with the second functional group of the alkoxysilyl compound to form a chemical bond, thereby providing the alkoxysilyl group of the alkoxysilyl compound in the side chain of copolymer (A). Examples of chemical bonds include urethane bonds, urea bonds, ether bonds, and ester bonds. The first and second functional groups are a pair capable of forming such a chemical bond. For example, in the case of a urethane bond, the first functional group is a hydroxyl group and the second functional group is an isocyanate group.

[0013] When the second functional group is an isocyanate group, the alkoxysilyl compound can be an alkoxysilyl compound having an alkoxysilyl group and an isocyanate group in the molecule. Examples of such compounds include 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane.

[0014] The copolymer (A) having an alkoxysilyl group at its terminal can be obtained, for example, by polymerizing a mixture containing a monomer and a chain transfer agent containing an alkoxysilyl group. The alkoxysilyl group of the chain transfer agent is provided at the terminal of the copolymer (A). Examples of the chain transfer agent having an alkoxysilyl group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-mercaptopropyltriethoxysilane.

[0015] Alternatively, copolymer (A) having an alkoxysilyl group at its terminal can be prepared using a monomer, a chain transfer agent containing a first functional group, and an alkoxysilyl compound having a second functional group and an alkoxysilyl group. Specifically, a mixture containing a monomer and a chain transfer agent containing a first functional group is polymerized to prepare a copolymer having the first functional group at its terminal. Next, the first functional group of the copolymer reacts with the second functional group of the alkoxysilyl compound to form a chemical bond, thereby providing the alkoxysilyl group of the alkoxysilyl compound at the terminal of copolymer (A). The alkoxysilyl compound and the chemical bond are described above.

[0016] The content of the alkoxysilane group is 0.5 to 90 mol %, preferably 0.5 to 15 mol %, and particularly preferably 1 to 10 mol %, based on the total mass of the monomers (a) and (b), from the viewpoints of long-term antifouling performance after standing and preventing abnormalities in the coating film.

[0017] Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, and 2,2'-azobis(N-butyl-2-methylpropionamide); benzoyl peroxide, di-tert-butyl peroxide, te Examples of peroxides include rt-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, t-amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 1,1-bis(1,1-dimethylethylperoxy)cyclohexane, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane. These polymerization initiators can be used alone or in combination of two or more. The polymerization initiators are particularly preferably 2 ,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1-bis(1,1-dimethylethylperoxy)cyclohexane, and 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane are preferred.

[0018] The molecular weight of the copolymer (A) can be adjusted by appropriately setting the amount of the polymerization initiator used or by using a chain transfer agent, such as 3-mercapto-1-propanol, 2,4-diphenyl-4-methyl-1-pentene, or 2-ethylhexyl 3-mercaptopropionate.

[0019] The weight-average molecular weight (Mw) of the copolymer (A) is preferably 3,000 to 300,000. If the molecular weight is less than 3,000, the coating film of the antifouling coating becomes brittle and prone to peeling and cracking, while if it exceeds 300,000, the viscosity of the copolymer solution increases, making it difficult to handle. Specific examples of Mw include 3,000, 5,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000, and 300,000, and may be within a range between any two of the values ​​exemplified here.

[0020] Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization, etc. Among these, solution polymerization and non-aqueous dispersion polymerization are particularly preferred because they allow the copolymer to be obtained simply and accurately.

[0021] In the polymerization reaction, an organic solvent may be used as needed. Examples of organic solvents include aromatic hydrocarbon solvents such as xylene, ethylbenzene, and toluene; aliphatic hydrocarbon solvents such as hexane, heptane, and mineral spirits; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, and 2-methoxy-1-methylethyl acetate; alcohol solvents such as ethanol, isopropyl alcohol, butyl alcohol, and 1-methoxy-2-propanol; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Among these, aromatic hydrocarbon solvents are particularly preferred, and xylene is more preferred. These solvents can be used alone or in combination of two or more.

[0022] The reaction temperature in the polymerization reaction may be set appropriately depending on the type of polymerization initiator, etc., and is usually 50 to 170° C., and preferably 60 to 150° C. The reaction time in the polymerization reaction may be set appropriately depending on the reaction temperature, etc., and is usually about 4 to 10 hours.

[0023] The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[0024] The copolymer (A) is preferably a copolymer of a monomer (a) and a monomer (b) other than the monomer (a), and can be obtained by copolymerizing a mixture containing the monomers (a) and (b). The copolymerization is carried out, for example, in the presence of a polymerization initiator. The copolymer (A) may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer of the monomers (a) and (b).

[0025] The monomer containing an alkoxysilyl group or a first functional group may be contained in either the monomer (a) or (b).

[0026] <Monomer (a)> Monomer (a) is an ethylenically unsaturated monomer having a linear or branched alkyl group having 6 to 24 carbon atoms.

[0027] The alkyl group preferably has 6 to 20 carbon atoms, specifically, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, and may be within a range between any two of the values ​​exemplified here. The alkyl group is preferably a branched alkyl group having 6 to 20 carbon atoms.

[0028] Examples of the alkyl group include 2-ethylhexyl, n-octyl, isononyl, isodecyl, 2-propylheptyl, lauryl, tridecyl, stearyl, isostearyl, and neodecane.

[0029] Examples of the monomer (a) include (meth)acrylic acid alkyl esters such as 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, 2-propylheptyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, octoxypolyethylene glycol polypropylene glycol methacrylate, and nonylphenoxypolyethylene glycol polypropylene glycol acrylate; vinyl esters such as 2-ethylhexyl acid vinyl ester, versatic acid vinyl ester, and neodecanoic acid vinyl ester; These monomers may be used singly or in combination of two or more.

[0030] From the viewpoints of long-term static antifouling performance and preventing coating film abnormalities, the content of monomer (a) is 1 to 90 mol%, preferably 2 to 30 mol%, and particularly preferably 3 to 10 mol%, based on the total moles of monomers (a) and (b). A branched alkyl group is also preferred. Specific examples of the content of monomer (a) are 1, 2, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90 mol%, and may be within a range between any two of the values ​​exemplified here.

[0031] <Monomer (b)> The monomer (b) is a monomer other than the monomer (a), and is preferably an ethylenically unsaturated monomer.

[0032] Examples of the monomer (b) include: (Meth)acrylic acid silyl esters such as triisopropylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, diisopropylphenylsilyl (meth)acrylate, and diisopropylcyclohexylsilyl (meth)acrylate

[0033] Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, allyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, 4-hydroxybutyl acrylate glycidyl ether, N-isopropylacrylamide, 2-(dimethylamino)ethyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, (meth)acrylic acid, 4-hydroxybutyl (meth)acrylate, polypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, methoxypolyethylene (meth)acrylate Licor, 2-(2-ethoxyethoxy)ethyl (meth)acrylate, 2-[2-(2-ethoxyethoxy)ethoxy]ethyl (meth)acrylate, N,N'-diethylacrylamide, 3-methoxybutyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, mono(2-(meth)acryloyloxyethyl) succinate, N-(3-dimethylaminopropyl)(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2-[2-(2-methyl) (meth)acrylate (meth)acrylic esters such as 2-(2-methoxyethoxy)ethoxyethyl, N,N'-dimethyl(meth)acrylamide, 2-(2-methoxyethoxy)ethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-(acetoacetyloxy)ethyl (meth)acrylate, 2-(2-hydroxyethoxy)ethyl (meth)acrylate, glycidyl (meth)acrylate, N-vinyl-2-pyrrolidone, silicone-modified (meth)acrylate, and glycerin monomethacrylate; vinyl compounds having functional groups such as acrylonitrile, vinyl propionate, and vinyl acetate;

[0034] Dicarboxylic acid esters such as itaconic acid, maleic acid, and succinic acid, styrenes such as styrene and α-methylstyrene; These monomers may be used singly or in combination of two or more.

[0035] 1-2. Other additives The antifouling coating composition of the present invention may contain, as necessary, bleed oil, curing catalyst, filler, antifouling agent, organic solvent, coating film-forming components other than copolymer (A), plasticizer, elution modifier, pigments such as coloring pigments, extender pigments and anti-rust pigments, dehydrating agent, anti-sagging agent, silane coupling agent, reactive oil, antifoaming agent, etc.

[0036] <Bleed Oil (B)> The bleed oil (B) is a component that floats to the surface of the coating film formed from the composition of the present invention to impart antifouling properties. Specific examples of the bleed oil (B) include silicone oil, a graft copolymer of an acrylic polymer and dimethylpolysiloxane, perfluoropolyether oil, polyglyceryl-10 pentaoleate, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, glyceryl undecylenate, etc. These compounds can be used alone or in combination of two or more.

[0037] As the silicone oil, any silicone oil that has been conventionally used in silicone rubber-based antifouling paints can be used. The viscosity of the silicone oil is 20 to 100,000 mm 2 ·s is preferred, 50 to 10,000 mm 2 ·s is more preferable.

[0038] Silicone oils are divided into straight silicone oils and modified silicone oils, but either type can be used in the composition of the present invention. Examples of straight silicone oils include dimethyl silicone oil, methyl phenyl silicone oil, diphenyl silicone oil, methyl hydrogen silicone oil, etc. Although any of these straight silicone oils can be used, methyl phenyl silicone oil, etc. are particularly preferred. Commercially available straight silicone oils include KF-99, KF-9901, KF-50, KF-53, KF-54, KF-56, HIVAC-F-5, X-21-3265, and KF-96 (all manufactured by Shin-Etsu Chemical Co., Ltd.), DOWSIL 200 Fluid, DOWSIL 510 Fluid, DOWSIL SH510 Fluid, DOWSIL SH550 Fluid, DOWSIL 550 Fluid, and DOWSIL SH710 Fluid (all manufactured by Dow Corning Silicones), Bluesil FLD47V100, Bluesil FLD47V500, Bluesil FLD47V1000, and Bluesil Examples include FLD550 (all Blue Star Silicones products), TSF451, TSF4300, TSF437, TSF400, TSF401, TSF484, TSF433, and TSF431 (all Momentive Performance Materials products).

[0039] Depending on the type of modification, modified silicone oils may be classified into alkyl-aralkyl-modified, amino-modified, carboxyl-modified, epoxy-modified, polyether-modified, alkyl-aralkyl-polyether-modified, polyglycoside-modified, polyglycerin-modified, polyglycerin-alkyl-modified, carbinol-modified, methylstyryl-modified, alkyl-modified, higher fatty acid ester-modified, higher fatty acid amide-modified, special hydrophilic modified, higher alkoxy-modified, higher fatty acid-containing modified, fluorine-modified, etc. Any of these modified silicone oils can be used, but amino-modified, alkyl-aralkyl-modified, epoxy-modified, polyether-modified, or alkyl-aralkyl-polyether-modified silicone oils are particularly preferred.

[0040] Commercially available alkyl-aralkyl modified silicone oils include KF-410, KF-412, KF-414, KF-7235B, X-22-7322, and X-22-1877 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF4421, XF42-334, and XF42-B3629 (all manufactured by Momentive Performance Materials). Commercially available amino-modified silicone oils include DOWSIL BY 16-849 Fluid and DOWSIL 16-853 U Fluid (manufactured by Dow Chemical Company), FZ3712, AFL-40 (manufactured by Nippon Unicar Co., Ltd.), KF-859, KF-861, KF-865, X-22-161, KF-8008, X-22-9409, KF-8001 (all manufactured by Shin-Etsu Chemical Co., Ltd.), TSF4700, TSF4701 (all manufactured by Momentive Performance Materials, Inc.), etc.

[0041] Commercially available carboxyl-modified silicone oils include DOWSIL BY 16-750 Fluid (a product of The Dow Chemical Company), FXZ3707 (a product of Nippon Unicar Co., Ltd.), X-22-3701E, X-22-3710, and X-22-162C (manufactured by Shin-Etsu Chemical Co., Ltd.), etc.

[0042] Commercially available epoxy-modified silicone oils include DOWSIL BY 16-870 Fluid and DOWSIL BY 16-839 Fluid (Dow Chemical Company products), L-9300, T-29 (Nippon Unicar Company products), KF-101, KF-102, KF-105 (Shin-Etsu Chemical Company products), TSF4730, YF3965 (Momentive Performance Materials Company products), etc.

[0043] Commercially available polyether-modified silicone fluids include DOWSIL SH28 Paint Additive, DOWSIL SF8428 Fluid, DOWSIL SF8427 Fluid, DOWSIL FZ-2104, DOWSIL FZ-2164, DOWSIL FZ-2191, DOWSIL FZ-2101, and DOWSIL BY 16-036 (Dow Chemical Company products), KF-945, KF-6015, KF-6017, KF-6020, KF-6123, X-22-4515, and X-22-4272 (Shin-Etsu Silicones Co., Ltd. products), TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, and TSF4460 (Momentive Performance Materials Co., Ltd. products), and BELSIL OW 1500, BELSIL DMC 6038, BELSIL DMC 6031 (all manufactured by Wacker Chemie), etc.

[0044] Commercially available alkyl-aralkyl-polyether modified silicone oils include DOWSIL SF8416 Fluid (Dow Chemical Company), X-22-2516, X-22-6548 (Shin-Etsu Silicones), and TSF4450 (Momentive Performance Materials).

[0045] Commercially available polyglycoside-modified silicone oils include BELSIL SPG 128 VP (manufactured by Wacker Chemie).

[0046] A commercially available polyglycoside-alkyl-modified silicone oil is BELSIL WO 5000 (manufactured by Wacker Chemie).

[0047] Commercially available polyglycerin-modified silicone oils include KF-6100, KF-6104, and KF-6106 (all manufactured by Shin-Etsu Silicone Co., Ltd.).

[0048] Commercially available polyglycerin alkyl-modified silicone oils include KF-6105 (a product of Shin-Etsu Silicone Co., Ltd.).

[0049] Commercially available carbinol-modified silicone oils include X-22-4015, X-22-160AS, KF-6001, KF-6002, KF-6003, X-22-170DX, and X-22-176 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0050] Commercially available higher fatty acid ester-modified silicone oils include X-22-715 (Shin-Etsu Silicones), TSF410, and TSF411 (all Momentive Performance Materials), while a commercially available higher fatty acid amide-modified silicone oil is KF-3935 (Shin-Etsu Silicones).

[0051] Commercially available graft copolymers consisting of acrylic polymer and dimethylpolysiloxane include KP-578, KP-541, KP-543, KP-545, KP-550, and KP-545L (all manufactured by Shin-Etsu Silicones Co., Ltd.).

[0052] Commercially available fluorine-modified silicone oils include FL-5, X-22-821, and FL-100 (manufactured by Shin-Etsu Silicone Co., Ltd.).

[0053] Commercially available perfluoropolyether oils include FLUOROLINK E10-H, FLUOROLINK 5147X, FLUOROLINK S10, FLUOROLINK MD700, FLUOROLINK AD1700, FLUOROLINK P54, FLUOROLINK TLS 5018, FLUOROLINK F10, FLUOROLINK P56, FLUOROLINK A10P, FLUOROLINK PA100E, FOMBLIN HC / 04, FOMBLIN HC / 25, FOMBLIN HC / R, FOMBLIN HC / OH-1000, and FOMBLIN HC / SA-18 (all products of Solvay).

[0054] Commercially available polyoxyethylene fatty acid esters include polyoxyethylene oleate (trade name: NIKKOL MYO-6V, manufactured by Nikko Chemicals), polyoxyethylene laurate (trade name: NIKKOL MYL-10, manufactured by Nikko Chemicals), PEG-2 dioleate (trade name: EMALEX DEG-di-O, manufactured by Nippon Emulsion), PEG-6 dioleate (trade name: EMALEX 300di-O, manufactured by Nippon Emulsion), polyoxyethylene (30) lanolin (trade name: Aqualose L30, manufactured by Croda), polyoxyethylene (75) lanolin (trade name: PEG-75 Flake, manufactured by NK Chemicals), polyoxyethylene (40) castor oil (trade name: NIKKOL CO-40, manufactured by Nikko Chemicals), and polyoxyethylene (50) hydrogenated castor oil (trade name: NIKKOL HCO-50, manufactured by Nikko Chemicals Co., Ltd.), etc.

[0055] The content of the bleed oil (B) in the composition of the present invention is not limited, but is preferably 2 to 200 parts by weight, more preferably 3 to 150 parts by weight, per 100 parts by weight of the copolymer (A). If the content of the bleed oil (B) is less than 2 parts by weight, the antifouling effect may not be exerted for a long period of time. If the content of the bleed oil (B) is more than 200 parts by weight, the strength of the resulting coating film may decrease, and the antifouling effect may not be sustained.

[0056] <Curing catalyst> Examples of the curing catalyst include organic tin compounds such as dibutyltin dilaurate and dibutyltin bis(acetylacetonate); Organic titanate esters such as tetrabutyl titanate and tetraisopropyl titanate; organic titanium chelate compounds such as diisopropoxybis(acetylacetonato)titanium and diisopropoxybis(ethylacetoacetate)titanium Organoaluminum compounds such as aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate) Metal curing catalysts such as organozirconium compounds such as zirconium tetra(acetylacetonate) and zirconium tetrabutylate; Amine compounds such as 1-amino-2-ethylhexane, 3-(trimethoxysilyl)propylamine, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N,N,N',N'-tetramethyl-N''-[3-(trimethoxysilyl)propyl]guanidine, and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine These may be used alone or in combination of two or more.

[0057] <Filler> The composition of the present invention may further contain an inorganic filler and / or an organic filler for the purpose of controlling the fluidity and thixotropy or for the purpose of improving the mechanical strength of the coating film.

[0058] The content of the inorganic filler in the composition of the present invention is usually 1 to 100 parts by weight, preferably 2 to 60 parts by weight, per 100 parts by weight of the copolymer (A). Specific examples of this content include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100, and may be within a range between any two of the values ​​exemplified here.

[0059] <Anti-fouling agent> The compositions of the present invention may further comprise an antifouling agent. Antifouling agents include, for example, inorganic agents and organic agents. Examples of inorganic agents include cuprous oxide, copper thiocyanate (common name: copper rhodanate), copper powder, copper carbonate, copper chloride, copper-nickel alloy, brass, silver chloride, silver nitrate, etc. Among these, cuprous oxide and copper rhodanate are particularly preferred, and cuprous oxide that has been surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc. is more preferred in terms of long-term storage stability.

[0060] Examples of organic chemicals include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate (generic name: zineb), zinc dimethyldithiocarbamate (generic name: ziram), a complex compound of N,N'-ethylenebis(dithiocarbamate) manganese and N,N'-ethylenebis(dithiocarbamate) zinc (generic name: mancozeb), pyridinetriphenylborane, 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: She-Nine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 4-bromo-2-(4 -chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (generic name: tralopyril), (±)4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (generic name: medetomidine), N-{[dichloro(fluoro)methyl]sulfanyl}-N',N'-dimethyl-Np-tolylsulfamide (generic name: tolylfluanid), N-(dichlorofluoro) Examples of antifouling agents include (methylthio)-N-(dimethylaminosulfonyl)aniline (generic name: dichlofluanid), N-[(4-hydroxy-3-methoxyphenyl)methyl]-8-methyl-6-nonenamide (generic name: capsaicin), 5,10-dihydro-5,10-dioxonaphtho[2,3-b]-1,4-dithi-yne-2,3-dicarbonitrile (generic name: dithianon), avermectin Bla, and avermectin Blb. These antifouling agents can be used alone or in combination of two or more.

[0061] <Solvent> The composition of the present invention is usually dissolved or dispersed in an organic solvent, so that it can be suitably used as a coating material. Examples of organic solvents include xylene, toluene, hexane, heptane, octane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, 2-ethoxyethyl acetate, propanol, isoamyl alcohol, n-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol tertiary butyl ether, ethylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monopropyl ether, ethylene glycol phenyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, ethylene glycol, diethylene glycol, propylene glycol, decamethylcyclopentasiloxane, octamethyltrisiloxane, aromatic hydrocarbons, aliphatic hydrocarbons, white spirit, alicyclic hydrocarbon solvents, naphthenic hydrocarbons, mineral spirits, aliphatic solvent naphtha, isoparaffin, normal paraffin, glycol esters, etc. These organic solvents can be used alone or in combination.

[0062] <Film-forming components other than copolymer (A)> Examples of coating film-forming components other than the copolymer (A) include organopolysiloxane, silicone-modified epoxy resin, acrylic resin, trialkylsilyl (meth)acrylate copolymer resin, polyester resin, polyester polyol resin, biodegradable biopolyester resin, epoxy resin, maleic acid-based copolymer resin, silicone-modified acrylic resin, fluororesin, polybutene resin, urethane resin, urethane rubber, polyester-modified silicone, silicone rubber, nitrile rubber, isoprene rubber, natural rubber, polyamide resin, polybutadiene resin, polybutadiene with hydroxyl groups at both ends, styrene-butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, petroleum-based resin, alkyd resin, vinyl ether-vinyl chloride copolymer resin, vinyl chloride resin, chlorinated rubber, chlorinated polyolefin resin, etc. These can be used alone or in combination of two or more.

[0063] <Plasticizer> Examples of the plasticizer include phosphate esters, phthalate esters, adipate esters, sebacate esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, and paraffin. These can be used alone or in combination of two or more. The content of the plasticizer is usually about 20 parts by weight or less, preferably 1 to 10 parts by weight, per 100 parts by weight of the copolymer (A).

[0064] <Dissolution modifier> Examples of the elution modifier include monocarboxylic acids and their salts, such as rosin, rosin derivatives, naphthenic acid, neodecanoic acid, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof, as well as the alicyclic hydrocarbon resins and coumarone resins. These can be used alone or in combination of two or more. Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, polymerized rosin, rosin ester, and hydrogenated rosin ester. Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferred.

[0065] <Dehydrating agent> Examples of the dehydrating agent include zeolite, anhydrous gypsum, hemihydrate gypsum, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriisopropenoxysilane, ethyltriisopropenoxysilane, vinyltriisopropenoxysilane, etc. These can be used alone or in combination of two or more.

[0066] <Anti-sagging agent> Examples of the anti-sagging agent include fatty acid amides, polyethylene oxide, silica, fumed silica, etc. These may be used alone or in combination of two or more.

[0067] 2. Method for producing antifouling coating composition The antifouling coating composition of the present invention can be prepared by mixing and dispersing the above-mentioned copolymer (A), and if necessary, bleed oil (B), a curing catalyst, an inorganic filler, an antifouling agent, an organic solvent, a plasticizer, a dehydrating agent, and the like, using a high-speed disperser such as a paint shaker, a mixer, or a dissolver, an ultrasonic homogenizer, a ball mill, a planetary ball mill, a pearl mill, a wet jet mill, a grinder, or the like.

[0068] The antifouling coating composition of the present invention may be provided as a one-component paint or a multi-component paint consisting of two or more components. In the case of a multi-component paint consisting of two or more components, each mixture contains one or more components and is packaged and stored in a separate container such as a can. For example, if a mixture containing one or more copolymers (A) as the main component is designated as component a and a mixture containing one or more crosslinking agents as the main component is designated as component b, the antifouling coating composition of the present invention is prepared by mixing components a and b.

[0069] 3. Antifouling treatment method The antifouling treatment method of the present invention is characterized in that an antifouling coating film is formed on the surface of an object to be coated using the above antifouling coating composition. The coating composition of the present invention absorbs moisture in the air and cures gradually, so it is preferable to prepare it just before use and apply it as soon as possible after preparation. Examples of objects to be coated include ships; fishing equipment such as fishing nets (aquaculture nets, fixed nets, etc.) and fishing net accessories; and underwater structures such as jetties, tetrapods, port facilities, buoys, pipelines, bridges, power plant water pipes, undersea bases, and undersea oil field drilling equipment. The antifouling coating film of the present invention can be formed by applying the above antifouling coating composition to the surface (all or part) of an article to be coated. The antifouling coating composition can be applied by a method known per se, either in a single application or by multiple reapplications. Examples of the application method include brush coating, spraying, dipping, flow coating, spin coating, etc. These methods may be used alone or in combination of two or more. After application, the coating absorbs moisture (e.g., moisture in the air) and hardens to form the antifouling coating film of the present invention. Hardening proceeds even at room temperature (25°C), but can be accelerated by heating to a temperature of, for example, about 80°C.

[0070] 4. Antifouling coatings and painted objects The antifouling coating film of the present invention can be formed using the above-described composition of the present invention. The thickness of the antifouling coating film of the present invention may be appropriately set depending on the type of substrate, etc. Usually, it is 30 to 400 μm per coating, preferably 30 to 200 μm per coating, and after multiple coatings, the film thickness after curing is 100 to 1000 μm. The coated article of the present invention has the antifouling coating film on its surface. The coated article of the present invention may have the antifouling coating film on the entire surface or on only a part of the surface. The coated article of the present invention can continuously exhibit antifouling effects and is therefore suitable for use in the above-mentioned ships (particularly ship bottoms), fishing equipment, underwater structures, and the like. [Example]

[0071] The following examples will be given to further clarify the features of the present invention, but the present invention is not limited to these examples.

[0072] 1. Copolymer production example <Production Example 1 (Production of Copolymer A1)> A four-neck flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was charged with 260 g of xylene (containing ethylbenzene) (initial solvent), and nitrogen gas was introduced while stirring and maintaining the temperature at 100°C. A mixture of 105 g of 3-methacryloxypropyltrimethoxysilane, 119 g of lauryl methacrylate, 308 g of n-butyl acrylate, 161 g of methyl methacrylate, 7 g of 3-mercaptopropyltrimethoxysilane, 5.1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (initial addition), and 30 g of xylene (containing ethylbenzene) was added dropwise over 3 hours while maintaining the temperature at 100°C. After stirring at 100°C for 1 hour, 0.3 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (post-added) was added three times every hour, and the mixture was stirred at the same temperature for another 2 hours. Then, 10 g of xylene (containing ethylbenzene) (dilution solvent) was added and the mixture was cooled to room temperature to obtain copolymer solution A1. The heating residue and Mw of A1 are shown in Table 1.

[0073] <Manufacturing Examples 2-47, 54-66> Copolymer solutions A2 to A47 were obtained by carrying out a polymerization reaction using the monomers, polymerization initiators, and solvents shown in Tables 1 to 8 and Tables 10 to 13 under the respective reaction temperature conditions in the same manner as in Production Example 1. The heating residues and Mw of A2 to A47 and A54 to A66 are shown in Tables 1 to 8 and Tables 10 to 13. The values ​​in the tables are in mass%.

[0074] <Production Example 48 (Production of Copolymer A48)> A four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was charged with 260 g of xylene (containing ethylbenzene) (initial solvent), and nitrogen gas was introduced. The mixture was stirred and maintained at 88°C. 70 g of isononyl acrylate, 21 g of n-butyl acrylate, 7 g of methyl methacrylate, 7 g of styrene, 7 g of tetrahydrofurfuryl acrylate, 147 g of 2-methoxyethyl acrylate, 21 g of 2-methoxyethyl methacrylate, and methoxypolyethylene glycol methacrylate (Mn A mixture of 14 g of methyl acrylate (approximately 500), 21 g of 2-(2-ethoxyethoxy)ethyl acrylate, 14 g of 4-hydroxybutyl acrylate, 14 g of polypropylene glycol methacrylate, 308 g of triisopropylsilyl methacrylate, 14 g of triisopropylsilyl acrylate, 21 g of silicone-modified acrylate (Mn=1000), 7 g of silicone-modified acrylate (Mn=10000), 7 g of 3-mercapto-1-propanol, 2.2 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (initial addition), and 30 g of xylene (containing ethylbenzene) was added dropwise over 3 hours while maintaining the temperature at 88°C. After stirring for 1 hour at 88°C, 0.3 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (post-added) was added three times every hour. After stirring for another 2 hours at the same temperature, 10 g of xylene (containing ethylbenzene) (dilution solvent) was added. 45 g of 3-isocyanatopropyltrimethoxysilane was added and stirred for 1 hour at the same temperature. After confirming the disappearance of the isocyanate peak derived from 3-isocyanatopropyltrimethoxysilane by IR, the mixture was cooled to room temperature to obtain copolymer solution A48. The heating residue and Mw of A48 are shown in Table 9.

[0075] <Production Examples 49-53> Copolymer solutions A49 to A53 were obtained by carrying out a polymerization reaction in the same manner as in Production Example 48 under various reaction temperature conditions using the monomers, polymerization initiators, and solvents shown in Table 9. The heating residues and Mw of A49 to A53 are shown in Table 9. The values ​​in the table are in mass%.

[0076] [Table 1]

[0077] Table 2

[0078] Table 3

[0079] Table 4

[0080] Table 5

[0081] Table 6

[0082] Table 7

[0083] Table 8

[0084] Table 9

[0085] Table 10

[0086] Table 11

[0087] [Table 12]

[0088] [Table 13]

[0089] Details of the various components in the above production examples are as follows: Xylene (contains ethylbenzene): Reagent, contains 5-70% ethylbenzene by weight, manufactured by Tokyo Chemical Industry Co., Ltd. Methoxypolyethylene glycol methacrylate: Reagent, Sigma-Aldrich, Mn = approx. 500 Silicone-modified acrylate (Mn=1000): Product name "Silaplane FM-0711", manufactured by JNC Corporation Silicone-modified acrylate (Mn=10000): Product name "Silaplane FM-0725", manufactured by JNC Corporation Polypropylene glycol methacrylate: Product name "Blenmar PP-1000", manufactured by NOF Corporation 2-Ethylhexyl vinyl ester: Trade name "VeoVa EH", manufactured by Hexion Versatic 9-vinyl ester: Trade name "VeoVa 9", manufactured by Hexion Neodecanoic acid vinyl ester: Product name "VeoVa 10", manufactured by Hexion Methoxypolyethylene glycol methacrylate (n=2): product name "Blenmar PME-100", manufactured by NOF Corporation Methoxypolyethylene glycol acrylate (n≒9): Product name "Blenmer AME-400", manufactured by NOF Corporation Methoxypolyethylene glycol methacrylate (n≒23): Product name "Blenmar PME-1000", manufactured by NOF Corporation Silicone-modified acrylate (Mn=5000): Product name "Silaplane FM-0721", manufactured by JNC Corporation Octoxy polyethylene glycol polypropylene glycol methacrylate: Product name "Blenmar 50POEP-800B" manufactured by NOF Corporation Nonylphenoxy polyethylene glycol polypropylene glycol acrylate: product name "Blenmar 75ANEP-600", manufactured by NOF Corporation Glycerin monomethacrylate: Product name "Blenmar GLM", manufactured by NOF Corporation

[0090] 2. Examples and Comparative Examples The antifouling coating compositions of Examples and Comparative Examples were prepared according to the formulations shown in Tables 14 to 28.

[0091] [Table 14]

[0092] [Table 15]

[0093] [Table 16]

[0094] [Table 17]

[0095] [Table 18]

[0096] [Table 19]

[0097] [Table 20]

[0098] [Table 21]

[0099] [Table 22]

[0100] [Table 23]

[0101] [Table 24]

[0102] [Table 25]

[0103] [Table 26]

[0104] [Table 27]

[0105] [Table 28]

[0106] Details of the antifouling agents and other additives in the above table are as follows:

[0107] <Anti-sagging agent> Polyamide wax: Product name "Disparlon A603-20X" (Kusumoto Chemicals Co., Ltd.) Oxidized polyethylene: Product name "Disparlon 4200-20" (manufactured by Kusumoto Chemicals Co., Ltd.)

[0108] <Pigments> Red iron oxide: Bengara: Product name: Bengara Kingyoku A brand (manufactured by Morishita Bengara Kogyo Co., Ltd.) Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.) Calcined kaolin: Product name "Kaolin 90" (manufactured by Toyo Kasei Co., Ltd.) Silica: Product name "AEROSIL R972" hydrophobic fumed silica (manufactured by Evonik) Hydrophilic silica 1: Product name "AEROSIL 200" hydrophilic fumed silica (manufactured by Evonik) Hydrophilic silica 2: Product name "VP-4200" hydrophilic fumed silica (manufactured by Evonik)

[0109] <Drugs> Copper pyrithione: Trade name "Copper Omadine" (manufactured by LONZA) Zinc pyrithione: Trade name "Zinc Omadin" (manufactured by LONZA) Cuprous oxide: Product name "NC-301" (manufactured by Nisshin Chemco Co., Ltd.) Tralopyril: Trade name "Econea" 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (manufactured by Janssen PMP) DCOIT (30% solution): Trade name "SEA-NINE 211N" 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by The Dow Chemical Company) Medetomidine: "Selektope" "(+)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (I-tech) Copper thiocyanate: Trade name "Copper(I) Thiocyanate" (Fujifilm Wako Pure Chemical Industries, Ltd.) Tolylfluanid: Trade name "Preventol A 5-S" N-{[dichloro(fluoro)methyl]sulfanyl}-N',N'-dimethyl-Np-tolylsulfamide (manufactured by Lanxess) Zineb: Product name "Zineb" (manufactured by SIGMA-ALDRICH) Diuron: Product name "Diuron" (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0110] <Bleed Oil> Polyglycoside-alkyl-modified silicone oil: Product name "BELSIL WO 5000" A polydimethylsiloxane dilution of side-chain alkyl- and polyglucoside-modified polysiloxane (manufactured by Wacker Chemie) Polyglycerin-alkyl-modified silicone oil: Product name "KF-6106" Side-chain polyglycerin, alkyl- and silicone-modified polysiloxane (Shin-Etsu Chemical Co., Ltd.) Both-end polyglycerol-modified silicone oil: Product name "SOFCARE GS-G" (Kao Corporation) Polyether-modified polysiloxane 1: Trade name "KF-6020" side-chain polyethylene oxide and polypropylene oxide-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) Polyether-modified polysiloxane 2: Trade name "X-22-2516" Side-chain polyethylene oxide, polypropylene oxide, long-chain alkyl, aralkyl-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) Polyether-modified polysiloxane 3: Product name "TSF4460" side-chain polypropylene oxide-modified silicone oil (manufactured by Momentive) Both-end polyether-modified polysiloxane: Trade name "KF-6123" Both-end polyethylene oxide and polypropylene oxide-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) Alkyl-modified silicone oil: Product name "TSF4421" side chain alkyl-modified silicone oil (manufactured by Momentive) Polyoxyethylene (30) lanolin: Trade name "NIKKOL TW-30" (manufactured by Nikko Chemicals Co., Ltd.) Polyoxyethylene (40) castor oil: trade name "NIKKOL CO-40" (manufactured by Nikko Chemicals Co., Ltd.) Modified perfluoropolyether oil: Product name "Fluorolink E10-H" double-terminated polyoxyethylene modified perfluoropolyether oil (manufactured by Solvay) Glyceryl undecylenate: Trade name "NIKKOL MGU" (manufactured by Nikko Chemicals Co., Ltd.) Polyglyceryl-10 pentaoleate: Trade name "NIKKOL Decaglyn 5-OV" (manufactured by Nikko Chemicals Co., Ltd.)

[0111] <Solvent> Xylene (containing ethylbenzene): Contains 5 to 70% by weight of ethylbenzene (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) Low-boiling aromatic naphtha: Product name "Shellsol A100" (manufactured by Shell Chemical Co.) White spirits: Product name "Tesol 3040" (manufactured by JXTG Energy Corporation) Naphthenic hydrocarbons: Exxor DSP145 / 160 (manufactured by ExxonMobil) Paraffin hydrocarbon: Shellsol S (manufactured by Shell Chemical Co.) Acetylacetone: (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) Dipropylene glycol: (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) Diethylene glycol monobutyl ether (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.) n-Butanol (reagent, manufactured by Tokyo Chemical Industry Co., Ltd.)

[0112] <Curing catalyst> 1-Amino-2-ethylhexane: Trade name "1-amino-2-ethylhexane" (HighChem Co., Ltd.) 3-(Trimethoxysilyl)propylamine: Trade name "KBM-903" (Shin-Etsu Chemical Co., Ltd.) N-2-aminoethyl-3-aminopropyltrimethoxysilane: trade name "GENIOSIL GF9" (manufactured by Wacker) N,N,N',N'-Tetramethyl-N''-[3-(trimethoxysilyl)propyl]guanidine: (Constru Chemical Co.) 3-Triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine: Trade name "KBE-9103P" (Shin-Etsu Chemical Co., Ltd.) Neodecanoic acid: (Marubeni Chemix Corporation) Di-n-butyltin dilaurate: Trade name "Neostan U-100" (manufactured by Nitto Kasei) Dibutylbis(2,4-pentanedionato)tin(IV): Trade name "Neostan U-220H" (manufactured by Nitto Kasei) Titanium diisopropoxybis(ethyl acetoacetate): Trade name "T-100" (Matsumoto Fine Chemical Co., Ltd.)

[0113] <Plasticizer> Paraffin mineral oil: Product name "Pure Safety 22" (Cosmo Oil Lubricants Co., Ltd.) Polybutene: Product name "Nippon Oil Polybutene LV-50" (manufactured by JXTG Nippon Oil & Energy Corporation) Chlorinated paraffin: trade name "Toyoparax A40S" (manufactured by Tosoh Corporation) Methylphenylpolysiloxane: Trade name "KF-50" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0114] <Other resins> Polyorganosiloxane having silanol groups at the ends: Trade name "DMS-S35" Mw 49000 (manufactured by Gelest) γ-trimethoxy-terminated modified polyether: trade name "SPUR+1015LM" (manufactured by MOMENTIVE) α-Dimethoxy-terminated polypropylene glycol 1: Trade name "GENIOSIL STD-10" (manufactured by Wacker Chemie) α-Dimethoxy-terminated polypropylene glycol 2: Trade name "GENIOSIL XT50" (manufactured by Wacker Chemie) Highly modified α-dimethoxy-terminated polypropylene glycol: Trade name "GENIOSIL XB502" (manufactured by Wacker Chemie) Dimethoxy-terminated branched polypropylene glycol: trade name "MS Polymer S303" (manufactured by Kaneka Corporation) Polypropylene glycol: Product name: "Polypropylene glycol, diol type, 2,000" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Polyester polyol: Product name "Nipporun 141" (manufactured by Tosoh Corporation) Chlorinated polyolefin, chlorine content 41% (60% toluene solution): Product name "814HS" (Nippon Paper Industries Co., Ltd.) Chlorinated ethylene vinyl acetate copolymer, chlorine content 18% (20% toluene solution): Product name "Superchlor BX" (Nippon Paper Industries Co., Ltd.) Bisphenol A epoxy resin: Product name "Epicoat 828" (manufactured by Mitsubishi Chemical Corporation) <Dehydrating agent> Vinyltrimethoxysilane (Tokyo Chemical Industry Co., Ltd.) Tris(isopropenyloxy)vinylsilane: Trade name "LS-3975" (Shin-Etsu Chemical Co., Ltd.) Zeolite: Product name "Molecular Sieve 4A" (manufactured by Union Showa Co., Ltd.) Anhydrous gypsum: Product name "D-1N" (manufactured by Noritake Company Limited)

[0115] <Crosslinking agent> Partial hydrolysis condensate of tetraethoxysilane: trade name "TES40 WN" (manufactured by Wacker Chemie)

[0116] <Reactive oil> Polyether-modified alkoxysilane: Trade name "Dynasylan 4150" methoxy PEG-10 propyl trimethoxysilane (manufactured by Evonik)

[0117] <Antifoaming agent> Dimethylpolysiloxane: Product name "KF-96-100" (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0118] 3. Evaluation Adhesion tests and antifouling tests were carried out on the antifouling coating compositions of the Examples and Comparative Examples according to the methods described below. Two-component antifouling coating compositions were mixed immediately before the tests. The test results are shown in Tables 14 to 28.

[0119] As shown in the above table, the coating films formed using the antifouling coating compositions of all Examples were excellent in adhesion and antifouling properties, whereas the coating films formed using the antifouling coating compositions of Comparative Examples were poor in adhesion.

[0120] <Adhesion test> The antifouling coating compositions obtained in the Examples and Comparative Examples were applied to rigid PVC panels (110 x 60 x 2 mm) coated with an epoxy primer, HEMPADUR QUATTRO XO 17870 (manufactured by HEMPEL), to a dry film thickness of approximately 100 μm. The panels were then cured at room temperature for 48 hours to prepare test panels. An X-shaped cut was made in the panel using a cutter, reaching down to the anticorrosion coating, and the coating adhesion was evaluated by rubbing the panel firmly with a finger perpendicular to the cut. ○: The coating does not peel off △: Part of the area around the cut peeled off ×: The coating peeled off easily

[0121] <Anti-fouling test> The antifouling coating compositions obtained in the Examples and Comparative Examples were applied to rigid PVC panels (110 x 60 x 2 mm) to a dry film thickness of approximately 200 μm, each coated with an epoxy primer, HEMPADUR QUATTRO XO 17870 (manufactured by Hempel) to a thickness of approximately 100 μm (for the Comparative Examples, a silicone tie coat, HEMPASIL NEXUS X-TEND 27500 (manufactured by Hempel), was further applied to a dry film thickness of approximately 100 μm). The test panels were cured at room temperature for 7 days and then immersed in Owase Bay at 2.0 m below sea level for 12 months. The test panels were then observed for fouling by attached organisms after 3, 6, and 12 months. The condition of the coating surface was visually observed and judged according to the following criteria. ◎: No adhesion of fouling organisms such as shellfish or algae, and no adhesion of slime. 〇: No shellfish, algae or other fouling organisms attached, but only slime attached. △: Partial adhesion of fouling organisms such as shellfish and algae. ×: The level where fouling organisms such as shellfish and algae are attached to the entire surface.

Claims

1. An antifouling coating composition containing a copolymer (A) and an antifouling agent, The copolymer (A) has an alkoxysilyl group provided at each of a side chain and an end of the copolymer (A), and an ethylenically unsaturated monomer unit, The ethylenically unsaturated monomer unit has a branched alkyl group having 6 to 24 carbon atoms, The copolymer (A) is obtained by polymerizing a mixture containing a monomer having an alkoxysilyl group, The antifouling coating composition, wherein the alkoxysilyl group-containing monomer is 3-(trimethoxysilyl)propyl (meth)acrylate, 3-(triethoxysilyl)propyl (meth)acrylate, 3-(methyldimethoxysilyl)propyl (meth)acrylate, or 3-(methyldiethoxysilyl)propyl (meth)acrylate.

2. The antifouling coating composition according to claim 1, The antifouling coating composition further contains a bleed oil.

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