Antifouling coating composition

Abstract

The present invention addresses the problem of providing an antifouling coating composition with which it is possible to form an antifouling coating film having low coating film water absorbency and excellent adhesion and antifouling properties.　The present invention provides an antifouling coating composition containing a copolymer A, a copolymer B, and a curing agent C, wherein: the copolymer A is a copolymer that is liquid at 25°C and 1 atm and does not have a functional group capable of reacting with the curing agent C; the copolymer A is composed of a monomer (a1), a monomer (a2), and a monomer (a3) other than the monomers (a1) and (a2); the monomer (a1) is represented by general formula (1); in the monomer (a2), the common logarithm value logP of the 1-octanol / water partition coefficient is 0.97 or less; the copolymer B is composed of a monomer (b1), a monomer (b2), and a monomer (b3) other than the monomers (b1) and (b2); the monomer (b1) is represented by general formula (2); and the monomer (b2) has a functional group capable of reacting with the curing agent C.

Description

Antifouling paint composition

[0001] The present invention relates to an antifouling coating composition for preventing aquatic fouling organisms from attaching to and growing on objects used or present in water over a long period of time.

[0002] Numerous aquatic fouling organisms such as barnacles, sea squirts, cephalopods, mussels, freshwater mussels, bryozoans, green laver, and sea lettuce inhabit the waters of the sea, rivers, and lakes. There has long been a problem with these organisms attaching to objects used or existing underwater, such as ships, fishing nets (aquaculture nets, fixed nets, etc.), fishing net accessories, and underwater structures like jetties, tetrapods, port facilities, buoys, pipelines, bridges, power plant water conduits, underwater bases, and offshore oil drilling equipment. Specifically, it is known that when ships and other objects are submerged in water for extended periods, these organisms attach and grow on the parts in contact with the water, causing a decrease in ship speed and water flow, resulting in significant economic and resource losses. Therefore, studies have been conducted to address this problem by applying antifouling paint to prevent the attachment of aquatic fouling organisms.

[0003] For example, silicone rubber-based antifouling coatings that form a coating film of a mixture of silicone rubber and silicone oil have been proposed (Patent Documents 1-4). The formed coating film prevents the adhesion of organisms such as barnacles due to its properties such as low surface free energy and low elastic modulus. Furthermore, methods of incorporating antifouling agents such as copper pyrithione are also being considered (Patent Document 5).

[0004] On the other hand, when spray-applying silicone rubber-based antifouling paint, it was necessary to mask off a wide area around the painted surface to prevent dust adhesion, resulting in very poor workability. Also, when navigating in freshwater, the paint film's high water absorption caused it to blister, leading to problems such as cold flow. Furthermore, poor adhesion, including adhesion during recoating, meant that it easily peeled off at the interface with the base coat.

[0005] JP-A-51-96830, JP-A-56-26272, JP-A-63-43973, JP-A-3-255169, Special Publication No. 2013-515122

[0006] The object of this invention is to provide an antifouling coating composition that can form an antifouling coating film with low water absorption, excellent adhesion, and superior antifouling properties.

[0007] According to the present invention, an antifouling paint composition is provided, comprising copolymer A, copolymer B, and curing agent C, wherein copolymer A is a copolymer that is liquid at 25°C and 1 atm, and does not have functional groups that can react with curing agent C, copolymer A is composed of monomer (a1), monomer (a2), and monomer (a3) ​​other than monomer (a1) and (a2), monomer (a1) is represented by general formula (1), monomer (a2) has a common logarithm logP of the partition coefficient between 1-octanol and water of 0.97 or less, and copolymer B is composed of monomer (b1), monomer (b2), and monomer (b3) other than monomer (b1) and (b2), monomer (b1) is represented by general formula (2), and monomer (b2) has functional groups that can react with curing agent C.

[0008] The inventors of the present invention conducted extensive research to solve the above problems and, as a result, discovered that the above-mentioned antifouling coating composition can solve the above problems, thus completing the present invention.

[0009] The present invention will be described in detail below. Unless otherwise stated, the various physical properties described below can be obtained according to the methods shown in the examples.

[0010] 1. Antifouling paint composition The antifouling paint composition of the present invention contains copolymer A, copolymer B, and curing agent C.

[0011] 1-1. Copolymer A Copolymer A is a copolymer that is liquid at 25°C and 1 atm and does not have functional groups that can react with curing agent C. Therefore, copolymer A remains liquid even within the antifouling coating and functions as a bleed oil. Preferably, curing agent C is an isocyanate compound having an isocyanate group, and functional groups that can react with curing agent C include hydroxyl groups and amino groups. Copolymer A does not have either a hydroxyl group or an amino group. Urethane bonds are formed by the reaction between the isocyanate group and the hydroxyl group. Urea bonds are formed by the reaction between the isocyanate group and the amino group.

[0012] Copolymer A is composed of monomer (a1), monomer (a2), and monomer (a3) ​​other than monomers (a1) and (a2). Monomer (a1), monomer (a2), and monomer (a3) ​​do not have functional groups that can react with curing agent C.

[0013] <Monomer (a1)> Monomer (a1) is represented by general formula (1). General formula (1): (In the formula, R １ R is a hydrogen or methyl group. ２ (This indicates a hydrocarbon group with 6 to 18 carbon atoms.)

[0014] R ２ The number of carbon atoms is 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18, and may be within the range of any two of the values ​​exemplified here.

[0015] R ２ The hydrocarbon group is, for example, a phenyl group, a hexyl group, an isohexyl group, a benzyl group, a tolyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a 2-octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a naphthyl group, a 2-propylheptyl group, a biphenyl group, a dodecyl group, a tridecyl group, a 2-hexyldecyl group, a cetyl group, a stearyl group, or an isostearyl group. Preferably, it is a hexyl group, an isohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a 2-octyl group, an isooctyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a 2-propylheptyl group, a dodecyl group, a tridecyl group, a 2-hexyldecyl group, a stearyl group, or an isostearyl group.

[0016] From the viewpoint of long-term antifouling properties, the content of monomer (a1) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of monomer (a1), monomer (a2), and monomer (a3). Specifically, the content of monomer (a1) may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by mass, and may be within the range of any two of the values ​​exemplified here.

[0017] Monomer (a1) is R of general formula (1) from the viewpoint of long-term antifouling properties. ２ It is preferable to include long-chain monomers having 8 to 18 carbon atoms (preferably 9 to 18). The content of these long-chain monomers is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass, relative to the total mass of monomers (a1), monomer (a2), and monomer (a3). Specifically, this content may be, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by mass, and may be within the range of any two of the values ​​exemplified here.

[0018] <Monomer (a2)> Monomer (a2) has a common logarithm of the partition coefficient P between 1-octanol and water, logP, of 0.97 or less. Since the logP values ​​of ethyl acrylate and methyl methacrylate are 0.98 and 0.99, respectively, monomer (a2) is more hydrophilic than either ethyl acrylate or methyl methacrylate. By incorporating such monomer (a2), the hydrophilicity of copolymer A is increased, making copolymer A more suitable to function as a bleed oil.

[0019] The partition coefficient P is the ratio of the partition concentrations of a substance into each phase of a two-phase solvent system consisting of n-octanol and water, and logP is the common logarithm of the partition coefficient P. A larger value of logP indicates higher lipophilicity (lower hydrophilicity). In this specification, logP refers to the value calculated based on Crippen's fragmentation method (J. Chem. Inf. Comput. Sci., 27, 21 (1987)). logP calculated using this method can be calculated, for example, using the ChemDraw Professional 17 Suite program from PerkinElmer.

[0020] The logP value is preferably 0.80 or less, and more preferably 0.60 or less. Furthermore, from the viewpoint of the water resistance of the coating film, it is preferable that it be -0.80 or higher. logP is, for example, between -0.80 and 0.97, specifically, for example, -0.80, -0.75, -0.70, -0.65, -0.60, -0.55, -0.50, -0.45, -0.40, -0.35, -0.30, -0.25, -0.20, -0.15, -0.10, -0.05, 0.00, 0.05, 0.10, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85, 0.90, 0.95, 0.97, and may be within the range between any two of the values ​​exemplified here, or less than or equal to any two of them.

[0021] Examples of monomers (a2) include N-isopropylmethacrylamide (logP: 0.62), NN-diethylacrylamide (logP: 0.87), 2-methoxyethyl methacrylate (logP: 0.83), 2-methoxyethyl acrylate (logP: 0.48), tetrahydrofurfuryl acrylate (logP: 0.78), methyl acrylate (logP: 0.64), 2-(2-ethoxyethoxy)ethyl acrylate (logP: 0.67), glycidyl methacrylate (logP: 0.57), glycidyl acrylate (logP: 0.22), and methacrylic acid. Examples include (meth)acrylic acid esters such as 2-(acetoacetyloxy)ethyl (logP: 0.27), γ-butyrolactone methacrylate (logP: 0.53), γ-butyrolactone acrylate (logP: 0.19), polyethylene glycol monomethyl ether methacrylate (n=approx. 9) (logP: -0.41), polyethylene glycol monomethyl ether acrylate (n=approx. 9) (logP: -0.76); and vinyl compounds having functional groups such as N-vinyl-2-pyrrolidone (logP: 0.24) and vinyl acetate (logP: 0.54).

[0022] From the viewpoint of long-term stain resistance, the content of monomer (a2) is preferably 1 to 60% by mass, more preferably 15 to 50% by mass, and particularly preferably 20 to 40% by mass, relative to the total mass of monomer (a1), monomer (a2), and monomer (a3). Specifically, the content of monomer (a2) may be, for example, 1, 3, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, or 60% by mass, and may be within the range of any two of the values ​​exemplified here.

[0023] <Monomer (a3)> Monomer (a3) ​​is a monomer other than monomer (a1) and monomer (a2), and is preferably an ethylenically unsaturated monomer.

[0024] Examples of monomers (a3) ​​include methyl methacrylate (logP: 0.99), ethyl methacrylate (logP: 1.33), ethyl acrylate (logP: 0.98), butyl methacrylate (logP: 2.23), butyl acrylate (logP: 1.88), isobutyl methacrylate (logP: 2.21), isobutyl acrylate (logP: 1.86), t-butyl methacrylate (logP: 1.86), and t-butyl acrylate (logP: 1.86). Examples include (meth)acrylic acid esters such as 51); vinyl compounds having functional groups such as vinyl chloride (logP: 1.51), vinylidene chloride (logP: 1.79), vinyl butyrate (logP: 1.61), butyl vinyl ether (logP: 1.91), and lauryl vinyl ether (logP: 5.25); and aromatic compounds such as styrene (logP: 2.67), vinyltoluene (logP: 3.16), and α-methylstyrene (logP: 2.84).

[0025] <Physical Properties and Synthesis of Copolymer A> The weight-average molecular weight of copolymer A is preferably 2,500 to 25,000, more preferably 2,500 to 20,000, even more preferably 2,500 to 15,000, and particularly preferably 4,000 to 15,000. If the molecular weight is too small, bleeding will be too fast, and if the molecular weight is too large, bleeding will be too slow, and in either case, it will be difficult to maintain long-term antifouling properties. Specifically, these weight-average molecular weights are, for example, 2500, 3000, 3500, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, and 25000, and may be within a range of any two of the values ​​exemplified here.

[0026] The number-average molecular weight of copolymer A is preferably 1,000 to 15,000, more preferably 1,500 to 10,000, even more preferably 1,500 to 7,000, and even more preferably 2,500 to 7,000. In this case, the bleeding rate becomes particularly appropriate, making it easier to maintain long-term antifouling properties. Specifically, this number-average molecular weight is, for example, 1,000, 1,500, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 12,000, 13,000, 14,000, and 15,000, and may also be in the range between any two of the values ​​exemplified here.

[0027] The glass transition temperature (Tg) of copolymer A is, for example, -70 to 0°C, preferably -60 to -5°C, more preferably -55 to -10°C, and even more preferably -50 to -20°C. In this case, the bleeding rate becomes particularly appropriate, making it easier to maintain long-term antifouling properties. Specifically, this Tg is, for example, -70, -65, -60, -55, -50, -45, -40, -35, -30, -25, -20, -15, -10, -5, and 0°C, and may be in the range between any two of the values ​​exemplified here.

[0028] Copolymer A can be obtained by copolymerizing monomer (a1), monomer (a2), and monomer (a3). The copolymerization is carried out, for example, in the presence of a polymerization initiator.

[0029] Examples of polymerization initiators used in the polymerization reaction include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate, and polydimethylsiloxane unit-containing polymer azo polymerization initiator (Fujifilm Wako Pure Chemical Industries, Ltd.; VPS-1001N), and peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroctoate, tert-butyl peroxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, and 1,1,3,3-tetramethylbutyl peroxyneodecanoate. These polymerization initiators can be used individually or in combination of two or more. Particularly preferred polymerization initiators are 2,2'-azobis-2-methylbutyronitrile, tert-butyl peroctoate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. The molecular weight of the copolymer can be adjusted by appropriately setting the amount of polymerization initiator used.

[0030] Polymerization methods include, for example, solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Among these, solution polymerization is particularly preferred because it allows for the simple and accurate acquisition of copolymer A.

[0031] In the polymerization reaction described above, organic solvents may be used as needed. Examples of organic solvents include aromatic hydrocarbon solvents such as xylene, toluene, and ethylbenzene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, ester solvents and aromatic hydrocarbon solvents are particularly preferred, and butyl acetate, isobutyl acetate, xylene, and ethylbenzene are more preferred. These solvents can be used individually or in combination of two or more.

[0032] The reaction temperature in the polymerization reaction can be set appropriately according to the type of polymerization initiator, etc., and is usually 70 to 1600°C, preferably 80 to 150°C. The reaction time in the polymerization reaction can be set appropriately according to the reaction temperature, etc., and is usually about 4 to 8 hours. The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen gas or argon gas.

[0033] Copolymer A preferably contains sulfur atoms in its composition. This is because the inclusion of sulfur atoms can slow down the reaction between copolymer B and curing agent C, thereby extending the pot life in painting operations. Methods for incorporating sulfur atoms into copolymer A include, for example, using a mercaptan-based chain transfer agent, a sulfur atom-containing monomer, or a RAFT agent during the polymerization reaction. The sulfur atom content in copolymer A is preferably, for example, 0.1 to 20% by mass, more preferably 0.2 to 16% by mass, and more preferably 0.4 to 10% by mass, in order to obtain an appropriate pot life. Specifically, these values ​​are, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20% by mass, and may also be within a range between any two of the values ​​exemplified here.

[0034] Examples of mercaptan-based chain transfer agents include n-butyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecanethiol, n-dodecyl mercaptan, t-dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, 2-ethylhexyl-β-mercaptopropionic acid, 2-ethylhexyl thioglycolate, n-octyl thioglycolate, and methoxybutyl-β-mercaptopropionic acid. Examples of monofunctional thiol compounds include captopropionates, as well as difunctional thiol compounds such as tetraethylene glycol bis(3-mercaptopropionate), polysiloxanes with mercapto-modified ends (manufactured by Shin-Etsu Chemical Co., Ltd.; X-22-167B), 3-mercaptopropionic acid ester of pentaerythritol, and polyfunctional polysiloxanes with mercapto-modified side chains (Shin-Etsu Chemical Co., Ltd.; KF-2001, KF-2004). Examples of RAFT agents include 2-cyano-2-[(dodecylsulfanylthiocarbonyl)sulfanil]propane, 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanil]methyl pentanoate, 2-cyanopropan-2-yl benzodithioate, and cyanomethyl 3,5-dimethylpyrazole-1-carbodichithioate.

[0035] The content of copolymer A in the composition of the present invention is, for example, 10 to 100 parts by mass, preferably 20 to 80 parts by mass, per 100 parts by mass of copolymer B. Specifically, the content of copolymer A per 100 parts by mass of copolymer B is, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100 parts by mass, and may be in the range between any two of the values ​​exemplified herein.

[0036] 1-2. Copolymer B Copolymer B is composed of monomer (b1), monomer (b2), and monomer (b3) other than monomers (b1) and (b2).

[0037] <Monomer (b1)> The monomer (b1) is represented by general formula (2). General formula (2): (In the formula, R ３is hydrogen or a methyl group, R ４ represents a hydrocarbon group having 6 to 18 carbon atoms.)

[0038] R in the general formula (2) ３ and R ４ are each the same as the description of R １ and R ２ in the general formula (1).

[0039] From the viewpoint of long-term antifouling property, the content of the monomer (b1) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass based on the total mass of the monomer (b1), the monomer (b2), and the monomer (b3). Specifically, the content of the monomer (b1) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80% by mass, and may be within the range between any two of the exemplified values.

[0040] From the viewpoint of long-term antifouling property, the monomer (b1) preferably contains a long-chain monomer in which the carbon number of R ４ in the general formula (2) is 8 to 18 (preferably 9 to 18). The content of this long-chain monomer is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 15 to 60% by mass based on the total mass of the monomer (b1), the monomer (b2), and the monomer (b3). Specifically, this content is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80% by mass, and may be within the range between any two of the exemplified values.

[0041] <Monomer (b2)> Monomer (b2) has a functional group that can react with the curing agent C. Examples of functional groups that can react with the curing agent C include hydroxyl groups and amino groups. It is preferable that monomer (b2) is a hydroxyl group-containing monomer. Examples of monomer (b2) include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol monoacrylate (Mitsubishi Chemical Corporation; CHDMMA), N-(3,4-dihydroxyphenethyl)acrylamide, caprolactone-modified hydroxy(meth)acrylate (Daicel Chemical Industries, Ltd.; Praxel FM), and one or more of these can be used.

[0042] The content of monomer (b2) is, for example, 1 to 30% by mass, preferably 3 to 25% by mass, and more preferably 4 to 20% by mass, relative to the total mass of monomers (b1), monomer (b2), and monomer (b3), from the viewpoint of long-term antifouling properties, coating film hardening, and adhesion. Specifically, this content is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, and 30% by mass, and may be in the range between any two of the values ​​exemplified here. Furthermore, it is preferable that the content of monomer (b2) be such that the hydroxyl value of copolymer B is the value described later.

[0043] <Monomer (b3)> Monomer (b3) is a monomer other than monomer (b1) and monomer (b2), and is preferably an ethylenically unsaturated monomer.

[0044] Examples of monomers (b3) include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, and t-butyl (meth)acrylate; vinyl compounds having functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone; and aromatic compounds such as styrene, vinyltoluene, and α-methylstyrene.

[0045] <Physical Properties and Synthesis of Copolymer B> The weight-average molecular weight of copolymer B is preferably 5,000 to 40,000, preferably 8,000 to 30,000, and more preferably 11,000 to 27,000. If the molecular weight is too low, the coating film of the antifouling paint becomes fragile and prone to peeling, and if the molecular weight is too high, the viscosity of the copolymer solution increases, which may make it difficult to handle. The weight-average molecular weight of copolymer B is specifically, for example, 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, and 40000, and may be within a range between any two of the values ​​exemplified here.

[0046] The number-average molecular weight of copolymer B is preferably 3,000 to 15,000, and more preferably 5,000 to 10,000. In this case, the copolymer solution is easy to handle and the coating film is less likely to peel off. Specifically, this number-average molecular weight is, for example, 3,000, 4,000, 5,000, 5,500, 6,000, 7,000, 8,000, 9,000, 9,500, 10,000, 11,000, 12,000, 13,000, 14,000, and 15,000, and may also be in the range between any two of the values ​​exemplified here.

[0047] The glass transition temperature (Tg) of copolymer B is, for example, -60 to -5°C, preferably -55 to -10°C, and more preferably -50 to -15°C. In this case, the copolymer solution is easy to handle and the coating film is less likely to peel off. Specifically, this Tg is, for example, -60, -55, -50, -45, -40, -35, -30, -25, -20, -15, -10, and -5°C, and may be in the range between any two of the values ​​exemplified here.

[0048] The hydroxyl value of copolymer B is, for example, 10 to 160 mg / g of KOH / g, preferably 12 to 160 mg / g of KOH / g, preferably 13 to 90 mg / g of KOH / g, more preferably 17 to 90 mg / g of KOH / g, even more preferably 17 to 80 mg / g of KOH / g, and even more preferably 23 to 50 mg / g of KOH / g. Specifically, the hydroxyl value of copolymer B is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 50, 60, 70, 80, 90, and 160 mg / g of KOH / g, and may be within the range of any two of the values ​​exemplified here. The hydroxyl value is expressed as the number of milligrams (mg) of potassium hydroxide equivalent to the number of hydroxyl groups in 1 g of copolymer B.

[0049] Copolymer B can be obtained by copolymerizing monomer (b1), monomer (b2), and monomer (b3). This copolymerization is carried out, for example, in the presence of a polymerization initiator. The polymerization method, initiator, solvent, temperature, and other conditions can be the same as those described for copolymer A.

[0050] Copolymer B preferably contains sulfur atoms in its composition. This is because the inclusion of sulfur atoms can slow down the reaction between copolymer B and curing agent C, thereby extending the pot life in painting operations. Methods for incorporating sulfur atoms into copolymer B include, for example, using a mercaptan-based chain transfer agent, a sulfur atom-containing monomer, or a RAFT agent during the polymerization reaction. The sulfur atom content in copolymer B is preferably 0.6 to 4.0% by weight, and more preferably 0.8 to 2.0% by weight, to obtain an appropriate pot life. Specifically, these values ​​are, for example, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, and 4.0 mass%, and may also be within a range between any two of the values ​​exemplified here.

[0051] As a mercaptan-based chain transfer agent, the previously described copolymer A can be used. As a RAFT agent, the previously described copolymer A can be used.

[0052] 1-3. Curing Agent C Curing agent C is an isocyanate compound having an isocyanate group. The isocyanate compound is preferably a polyisocyanate containing multiple isocyanate groups. The number of isocyanate groups contained in the polyisocyanate is preferably two or three.

[0053] The isocyanate compounds include alkyl diisocyanates such as trimethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; cycloalkylene diisocyanates such as bis(isocyanate-methyl)cyclohexane, cyclopentane diisocyanate, cyclohexane diisocyanate, and isophorone diisocyanate; aromatic diisocyanates such as tolylene diisocyanate, phenylene diisocyanate, diphenylmethane diisocyanate, and diphenyl ether diisocyanate; and xylylene diisocyanates. Examples include aromatic aliphatic diisocyanates such as diisocyanate and diisocyanate diethylbenzene; triisocyanates such as triphenylmethane triisocyanate, triisocyanate benzene, and triisocyanate toluene; tetraisocyanates such as diphenyldimethylmethane tetraisocyanate; and polyisocyanates such as dimers and trimers of diisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, and isophorone diisocyanate, including uretdione, allophanate, trimethylolpropane adduct, isocyanurate, and biuret compounds. These isocyanate compounds can be used individually or in combination of two or more.

[0054] The content of curing agent C in the composition of the present invention is, for example, 1 to 50 parts by mass, preferably 5 to 40 parts by mass, and more preferably 8 to 30 parts by mass, per 100 parts by mass of copolymer B. Specifically, the content of curing agent C per 100 parts by mass of copolymer B is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 30, 40, or 50 parts by mass, and may be in the range between any two of the values ​​exemplified here.

[0055] The ratio of moles of hydroxyl groups in copolymer B to moles of isocyanate groups in curing agent C (hereinafter referred to as the "OH / NCO ratio") is, from the viewpoint of adhesion and the like, for example, 0.10 to 6.00, preferably 0.50 to 3.00, more preferably 1.00 to 2.00, even more preferably 1.05 to 1.30, and even more preferably 1.10 to 1.20. Specifically, these ratios are, for example, 0.10, 0.20, 0.30, 0.40, 0.50, 0.60, 0.70, 0.80, 0.85, 0.90, 0.95, 1.00, 1.05, 1.10, 1.15, 1.20, 1.25, 1.30, 1.35, 1.40, 1.45, 1.50, 2.00, 3.00, 4.00, 5.00, and 6.00, and may also be within a range between any two of the values ​​exemplified here.

[0056] 1-4. Other Additives, etc. The antifouling coating composition of the present invention may optionally contain a curing catalyst, sulfur compounds, antifouling agents, organic solvents, fillers, plasticizers, elution modifiers, bleed oils of a composition other than copolymer A, other hydroxyl group-containing resins other than copolymer B, pigments such as coloring pigments, extender pigments, rust-preventive pigments, dehydrating agents, anti-sagging agents, defoaming agents, light stabilizers, ultraviolet absorbers, etc.

[0057] <Curing Catalyst> Examples of the curing catalyst include: bismuth compounds such as bismuth(III) trisneodecanate and bismuth(III) tris(2-ethylhexanate); organotin compounds such as dibutyltin dilaurate and dibutyltinbis(acetylacetonate); organotitanium esters such as tetrabutyl titanate and tetraisopropyl titanate; organotitanium chelate compounds such as diisopropoxybis(acetylacetonate)titanium and diisopropoxybis(ethylacetoacetate)titanium; organoaluminum compounds such as aluminum tris(acetylacetonate) and aluminum tris(ethylacetoacetate); organozirconium compounds such as zirconium tetra(acetylacetonate) and zirconium tetrabutyrate; metal curing catalysts such as 1-amino-2-ethylhexane, 3-(trimethoxysilyl)propylamine, N-2-aminoethyl-3-aminopropyltrimethoxysilane, N, N, N', Examples include amine compounds such as N'-tetramethyl-N''-[3-(trimethoxysilyl)propyl]guanidine and 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine; bismuth compounds such as bismuth(III) trisneodecanate and bismuth(III) tris(2-ethylhexanate) are particularly preferred. These can be used individually or in combination of two or more.

[0058] <Sulfur Compounds> Sulfur compounds are compounds that contain a sulfur atom, and examples include sulfides and thiols. Examples of sulfides include hexadecyl sulfide, tetradecyl sulfide, and di-tert-dodecyl disulfide. Examples of thiols include monofunctional thiol compounds such as n-butyl mercaptan, n-octyl mercaptan, t-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, tridecyl mercaptan, tetradecyl mercaptan, hexadecyl mercaptan, β-mercaptopropionic acid, and 2-ethylhexyl thioglycolate, as well as difunctional thiol compounds such as polysiloxanes with mercapto-modified ends (Shin-Etsu Chemical Co., Ltd.; X-22-167B), and polyfunctional polysiloxanes with mercapto-modified side chains (Shin-Etsu Chemical Co., Ltd.; KF-2001, KF-2004).

[0059] <Anti-fouling agents> The composition of the present invention may further contain anti-fouling agents. Anti-fouling agents are agents that can suppress the attachment of aquatic fouling organisms. Examples of anti-fouling agents include inorganic agents and organic agents. Examples of inorganic agents include cuprous oxide, copper thiocyanate (common name: copper rhodane), copper powder, copper carbonate, copper chloride, copper-nickel alloy, brass, silver chloride, silver nitrate, etc. Among these, cuprous oxide and copper rhodane are particularly preferred, and cuprous oxide that has been surface-treated with glycerin, sucrose, stearic acid, lauric acid, lycithin, mineral oil, etc. is more preferred in terms of long-term stability during storage.

[0060] Examples of organic agents include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebis(dithiocarbamate) (generic name: zineb), zinc dimethyldithiocarbamate (generic name: ziram), 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-isothiazolon (generic name: C9 211), 3,4-dichlorophenyl-N-N-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-N-p-tolylsulfamide (generic name: tolylfluanide), N-(dichlorofluoromethylthio)-N-(dimethylaminosulfonyl)aniline (generic name: diclofluanide), 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-in-2,3-dicarbonitrile (generic name: dithianone), avermectin Bla, avermectin Examples include Blb, etc. These antifouling agents can be used individually or in combination of two or more.

[0061] In the present invention, 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), zinc ethylene bisdithiocarbamate (generic name: zineb), 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), and 4,5-dichloro-2-n-octyl-3-isothiazolon (generic name: C9 211) are particularly preferred.

[0062] <Organic Solvents> The compositions of the present invention are usually dissolved and dispersed in an organic solvent. This makes them suitable for use as paints. 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, decamethylcyclopentasiloxane, octamethyltrisiloxane, aromatic hydrocarbons, aliphatic hydrocarbons, white spirits, alicyclic hydrocarbon solvents, naphthenic hydrocarbons, mineral spirits, aliphatic solvent naphtha, isoparaffins, normal paraffins, glycol esters, and the like. These organic solvents can be used individually or in combination of two or more.

[0063] <Fillers> The composition of the present invention may further contain inorganic fillers and / or organic fillers for the purpose of controlling fluidity and thixotropy, or for the purpose of improving the mechanical strength of the coating film.

[0064] <Plasticizer> Examples of the plasticizer include phosphate esters, phthalate esters, adipic esters, sebacate esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonylpentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, paraffin, etc. These can be used individually 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).

[0065] <Dissolution modifier> Examples of the dissolution modifier include monocarboxylic acids and their salts, such as rosin, rosin derivatives, naphthenic acid, neodecanoic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof, or the alicyclic hydrocarbon resin and coumarone resin. These can be used individually or in combination of two or more. Examples of the rosin derivative 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.

[0066] <Bleed oils with compositions other than copolymer A> Examples of bleed oils with compositions other than copolymer A include silicone oil, graft copolymers consisting of acrylic polymer and dimethylpolysiloxane, perfluoropolyether oil, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, lanolin, orange peel wax, and cupuacu butter. These compounds can be used individually or in combination of two or more.

[0067] <Other hydroxyl group-containing resins other than copolymer B> Other hydroxyl group-containing resins other than copolymer B include, specifically, polyorganosiloxanes having hydroxyl groups at their ends, polypropylene glycol (diol type, triol type), polyethylene glycol monomethyl ether, etc.

[0068] <Dehydrating Agents> Examples of the dehydrating agents include zeolite, anhydrous gypsum, hemihydrate gypsum, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, methyltriisopropenoxysilane, ethyltriisopropenoxysilane, vinyltriisopropenoxysilane, etc. These can be used individually or in combination of two or more.

[0069] <Anti-dripping agent> Examples of the anti-dripping agent include polyamide, oxidized polyolefin, silica, fumed silica, etc. These can be used individually or in combination of two or more.

[0070] <Antifoaming agents> Examples of antifoaming agents include silicone polymers, fluorine-modified silicone polymers, alkyl vinyl ether polymers, butadiene copolymers, acrylic polymers, olefin polymers, and the like. These can be used individually or in combination of two or more. In particular, in the present invention, it is preferable to use olefin polymers and silicone polymers as antifoaming agents.

[0071] <UV absorbers and light stabilizers> Examples of UV absorbers include benzotriazole compounds, salicylate compounds, cyanoacrylate compounds, and triazine compounds. These can be used individually or in combination of two or more. In particular, in the present invention, it is preferable to use benzotriazole compounds. Examples of light stabilizers include hindered amine compounds. These can be used individually or in combination of two or more.

[0072] 2. Method for producing the antifouling paint composition The antifouling paint composition of the present invention can be prepared by mixing and dispersing the above components A to C, and optionally the above-mentioned additives, using a high-speed disperser such as a paint shaker, mixer, or disperser, an ultrasonic homogenizer, a ball mill, a planetary ball mill, a pearl mill, a wet jet mill, or a grinder.

[0073] The antifouling coating composition of the present invention may be provided as a one-component coating or as a multi-component coating of two or more components. In the case of a multi-component coating of two or more components, each mixture contains one or more components and is packaged in separate containers such as cans for storage. For example, if a mixture mainly composed of one or more copolymers B is called liquid a, and a mixture mainly composed of one or more crosslinking agents C is called liquid b, the antifouling coating composition of the present invention is prepared by mixing liquid a and liquid b. In this case, copolymer A may be contained in either liquid a or liquid b.

[0074] 3. Antifouling Treatment Method The antifouling treatment method of the present invention is characterized by forming an antifouling coating on the surface of an object to be coated using the above-described antifouling coating composition. The coating composition of the present invention gradually hardens by absorbing moisture from the air, so it is preferable to prepare it immediately before use and to apply it as soon as possible after preparation. Examples of objects to be coated include ships; fishing gear such as fishing nets (aquaculture nets, fixed nets, etc.) and fishing net accessories; underwater structures such as breakwaters, tetrapods, port facilities, buoys, pipelines, bridges, water conduits for power plants, submarine bases, and offshore oil drilling equipment. The antifouling coating of the present invention can be formed by applying the above-described antifouling coating composition to the surface (all or part) of the object to be coated. The application of the antifouling coating composition can be carried out by known means, either in a single application or by applying multiple coats. Examples of application methods include brush application, spray application, dipping, flow coating, and spin coating. These may be used individually or in combination of two or more methods. After application, hardening progresses, forming the antifouling coating film of the present invention.

[0075] 4. Antifouling coating and coated object The antifouling coating of the present invention can be formed using the composition of the present invention described above. The thickness of the antifouling coating of the present invention can be appropriately set depending on the type of object to be coated. Typically, it is appropriate to apply multiple coats of 30 to 400 μm, preferably 30 to 200 μm each, and then cure the coating to a thickness of 100 to 1000 μm. The coated object of the present invention has the antifouling coating on its surface. The coated object of the present invention may have the antifouling coating on the entire surface or on only a part of it. Since the coated object of the present invention can continuously exhibit an antifouling effect, it can be suitably used on the above-mentioned ships (especially the bottom of the hull), fishing gear, underwater structures, etc.

[0076] The following examples illustrate the features of the present invention. However, the present invention is not limited to these examples.

[0077] Unless otherwise specified, the units of the numerical values ​​in each manufacturing example, comparative manufacturing example, example, and comparative example are in mass percent.

[0078] The heat residue was determined by heating at 125°C for 1 hour, in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Test method for paint components - Heat residue". Viscosity was measured at 25°C using a Type B viscometer, in accordance with JIS 7117-1.

[0079] The weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​obtained by gel permeation chromatography (GPC) (polystyrene equivalent). The GPC conditions are as follows: Apparatus: Tosoh Corporation HLC-8320GPC Column: TSKgel SuperHZM-M 4.6 mm I.D. 15 cm x 2 Flow rate: 0.35 mL / min Detector: Differential refractive index detector (RI) Column bath temperature: 40°C Eluent: THF

[0080] The glass transition temperature (Tg) of the copolymer was determined by calculating the apparent glass transition temperature using the following Fox equation, and this was taken as the polymer's Tg: 1 / Tg = W1 / Tg1 + W2 / Tg2 + W3 / Tg3 + ...Wi / Tgi (Fox equation) Here, the subscripts 1, 2, 3, ...i represent the constituent monomer components, Wi is the weight fraction of constituent monomer component i, and Tgi represents the Tg of the homopolymer of constituent monomer component i. The unit is Kelvin. The Tg of each monomer homopolymer is listed, for example, in the Polymer Handbook Fourth Edition (J. BRANDRUP, EH IMMERGUT, and EA GRULKE), and the Tg of the monomer homopolymers used in the copolymerization of copolymer A or B is shown in Table 7.

[0081] The hydroxyl value refers to the number of mg of potassium hydroxide equivalent to the hydroxyl groups in 1 g of copolymer B. It was calculated by converting the hydroxyl group content in grams of copolymer B to the number of mg of potassium hydroxide. The hydroxyl group content in copolymer B was calculated from the monomer formulations listed in Tables 4 to 6.

[0082] 1. Examples of Copolymer Production <Production Example A1 (Production of Copolymer A1)> In a four-necked flask equipped with a thermometer, condenser, stirrer, and quantitative liquid delivery pump, 220 g of xylene (initial solvent) was charged, nitrogen gas was introduced, and the temperature was maintained at 100°C while stirring. A mixture of 375 g of isononyl acrylate, 150 g of mPEG acrylate, 210 g of methyl methacrylate, 15 g of n-butyl acrylate, 50 g of n-dodecyl mercaptan, polymerization initiator 1:10.5 g (initial addition), and xylene 5.0 g was added dropwise over 2 hours while maintaining the temperature at 100°C. After stirring at 100°C for 10 minutes, a mixture of polymerization initiator 1:0.4 g (later addition) and xylene 8.3 g was added dropwise over 30 minutes while maintaining the temperature at 100°C, and after stirring at the same temperature for another 30 minutes, the mixture was cooled to room temperature to obtain copolymer solution A1. Table 1 shows the heating residue, viscosity, Mw, Mn, and Tg of copolymer solution A1. After measuring the heating residue of copolymer solution A1, the copolymer was liquid at 25°C and 1 atm.

[0083] <Production Examples A2-A22, Production Comparative Example 1> Copolymer solutions A2-A22 and H1 were obtained by performing polymerization reactions in the same manner as in Production Example A1 under the monomers, polymerization initiators, and solvents shown in Tables 1-3, under the respective reaction temperature conditions. The heating residue, viscosity, Mw, Mn, and Tg are shown in Tables 1-3. The copolymers of copolymer solutions A2-A22 and H1 were liquid at 25°C and 1 atm after measurement of the heating residue.

[0084] <Production Example B1 (Production of Copolymer B1)> In a four-necked flask equipped with a thermometer, condenser, stirrer, and quantitative liquid delivery pump, 220 g of xylene (initial solvent) was charged, nitrogen gas was introduced, and the temperature was maintained at 100°C while stirring. A mixture of 225 g of isononyl acrylate, 30 g of 4-hydroxybutyl acrylate, 37.5 g of 2-methoxyethyl acrylate, 112.5 g of methyl methacrylate, 345 g of n-butyl acrylate, 15 g of n-dodecyl mercaptan, polymerization initiator 1:8.0 g (initial addition), and xylene solvent 5.0 g was added dropwise over 2 hours while maintaining the temperature at 100°C. Subsequently, the mixture was stirred at 100°C for 10 minutes. Then, a mixture of polymerization initiator 1:2.5 g (added later) and xylene 15 g was added dropwise over 30 minutes while maintaining the temperature at 100°C. After stirring at the same temperature for another 30 minutes, 10 g of xylene (diluting solvent) was added, and the mixture was cooled to room temperature to obtain copolymer solution B1. The heating residue, viscosity, Mw, Mn, Tg, and hydroxyl value of copolymer solution B1 are shown in Table 4.

[0085] <Production Examples B2-B25> Copolymer solutions B2-B25 were obtained by carrying out polymerization reactions using the monomers, polymerization initiators, and solvents shown in Tables 4-6, under the same reaction temperature conditions as in Production Example B1. The heating residue, viscosity, Mw, Mn, Tg, and hydroxyl value are shown in Tables 4-6.

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093] Details of the abbreviations in Tables 1 to 7 are as follows: Polymerization initiator 1: 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate Polymerization initiator 2: 2,2'-azobis(2-methylbutyronitrile) mPEG methacrylate: polyethylene glycol monomethyl ether methacrylate (n=approx. 9), manufactured by Tokyo Chemical Industry Co., Ltd. mPEG acrylate: polyethylene glycol monomethyl ether acrylate (n=approx. 9), manufactured by Tokyo Chemical Industry Co., Ltd.

[0094] 2. Examples and Comparative Examples The antifouling coating compositions of the examples and comparative examples were prepared according to the formulations shown in Tables 8 to 17. The OH / NCO ratio was 1.1 in Examples 1 to 6, 1.0 in Example 43, and 1.2 in the other examples. The main difference between Examples 1 to 6 is the difference in the hydroxyl value of copolymer B. The main difference between Examples 7 to 10 and 19 to 21 is the difference in the formulation of the long-chain monomers among the monomers used in the copolymerization of copolymer B. The main difference between Examples 11 to 14 is the difference in the molecular weight of copolymer B. The main difference between Examples 15 to 18 is the difference in the manner of sulfur atom addition. The main difference between Examples 22 to 25 is the difference in the Tg of copolymer B. Examples 28 to 29 and 44 are examples of blending with other hydroxyl group-containing resins. The main difference between Examples 30 to 33 is the difference in the molecular weight of copolymer A. Examples 34 to 37 differ mainly in the proportion of monomer (a2) among the monomers used in the copolymerization of copolymer A. Examples 38 to 42 differ mainly in the proportion of long-chain monomers among the monomers used in the copolymerization of copolymer A. Examples 4 and 43 differ mainly in the OH / NCO ratio.

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105] Details of the antifouling agents and other additives in Tables 8 to 17 are as follows:

[0106] <Other hydroxyl group-containing resins> Polyorganosiloxane with hydroxyl groups at the ends: Product name "X-22-170DX", one-terminated carbinol-modified polyorganosiloxane, viscosity 65 mm ２ / s (25℃), hydroxyl value 12 mg KOH / g (manufactured by Shin-Etsu Chemical Co., Ltd.) Polypropylene glycol, triol type, 3,000: Reagent, LOT. TPE5400, viscosity 510 mPa·s, hydroxyl value 55 mg KOH / g (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Polypropylene glycol, diol type, 3,000: Reagent, LOT No. ACE6315, viscosity 570 mPa·s, hydroxyl value 37 mg KOH / g (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Polyethylene glycol monomethyl ether 400: Reagent, LOT. C37CG, hydroxyl value 141 mg KOH / g (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0107] <Anti-dripping agent> Polyamide: Product name "3900EF", 70% active ingredient, 68% bio-based by dry weight, solvent alkylcyclohexane / PMA amide thixotropic agent (manufactured by Kusumoto Chemical Co., Ltd.) Fumed Silica AEROSIL R974: Dichlorodimethylsilane-treated fumed silica, reagent, LOT. C7S4G-PD, specific surface area 173.0 m2 / g, pH 4.7 (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0108] <Resin Additives> Benzotriazole-based UV absorber: Product name "RIASORB UV-1130", main component: sesqui(benzotriazolyl T-butylhydroxyphenylpropionic acid) PEG-6, kinematic viscosity: 7200-7600 mPa·s (20°C), manufactured by Rianlon. Hindered amine-based light stabilizer: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, reagent (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0109] <Sulfur Compounds> n-Dodecyl mercaptan: Reagent (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0110] <Pigment> Ferric oxide: Product name "Bengara Kinugyoku A" (manufactured by Kanto Denka Finetech Co., Ltd.)

[0111] <Defoaming Agents> Defoaming agent 1: Product name "BYK-1790", 100% polyolefin defoaming agent (manufactured by BYK Co., Ltd.) Defoaming agent 2: Product name "BYK-1880", silicone-containing defoaming agent, manufactured by BYK Co., Ltd. Defoaming agent 3: Product name "BYK-1791", silicone-free, polymer-based, isoparaffin solvent, non-volatile content 40.5% (manufactured by BYK Co., Ltd.)

[0112] <Anti-fouling agents> Copper pyrithione: Trade name "Copper Omazine" (manufactured by LONZA) Zinc pyrithione: Trade name "Zinc Omazine" (manufactured by LONZA) Tralopiril: Trade name "Econea" 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitride (manufactured by Janssen PMP) Encapsulated Sea-Nine: Trade name "SEA-NINE CR2", active ingredient 4,5-dichloro-2-n-octyl-3-isothiazolon, yellow to yellowish-brown powder (manufactured by Dow Chemical) Medetomidine: Trade name "Selektope" "(+)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (manufactured by I-tech) Zineb: Trade name "Zineb" (manufactured by Sigma-Aldrich)

[0113] <Curing Catalysts> Bismuth neodecanoate (III): Manufactured by Nitto Chemical Co., Ltd. Bismuth 2-ethylhexanoate (III): Product name "Neostan U-600" (Manufactured by Nitto Chemical Co., Ltd.)

[0114] <Solvent> Xylene: Reagent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0115] <Hardening Agent C> Polyisocyanurate: Product name "Duranate TPA-100", hexamethylene diisocyanurate trimmer, solids content 100%, NCO 23.1 wt% (manufactured by Asahi Kasei Corporation)

[0116] <Bleeding Oil> Polyether-modified silicone oil: Product name "KF-6020", side-chain EO / PO-modified silicone oil, HLB 4 (manufactured by Shin-Etsu Chemical Co., Ltd.)

[0117] <Commercially available paints> Hempaguard X7: Silicone hydrogel antifouling paint (manufactured by Hempel) Hempasil X3+: Silicone-based antifouling paint (manufactured by Hempel)

[0118] 3. Evaluation Adhesion tests and antifouling tests were conducted on the antifouling coating compositions of the examples and comparative examples according to the method described below. The antifouling coating compositions were mixed immediately before the test. The test results are shown in Tables 8 to 17.

[0119] As shown in the table above, the coatings formed using the antifouling coating compositions of all examples had low water absorption rates and excellent adhesion and long-term antifouling properties. On the other hand, the coatings formed using the antifouling coating compositions of Comparative Examples 1, 3, and 4 did not have good adhesion, and the coating formed using the antifouling coating composition of Comparative Example 2 had insufficient long-term antifouling properties.

[0120] <Coating Hardness> Durometer hardness type A was measured in accordance with JIS K6253:2012. Using the antifouling coating compositions obtained in the examples and comparative examples, test specimens were prepared so that the dry film thickness was 6.0 mm or more, and measured at room temperature for 3 days using a digital durometer type A (GSD-719K, manufactured by Teclock Co., Ltd.). Five measurement points were taken, and the median value was taken as the durometer hardness.

[0121] <Pot Life> Pot life was defined as the time it took for the viscosity to double from the initial viscosity under conditions of 25°C. A Brookfield Viscometer Model Cap1000+ viscometer was used.

[0122] <Adhesion Test> A rigid PVC board (110 x 60 x 2 mm) coated with epoxy primer HEMPADUR QUATTRO XO 17870 (manufactured by HEMPEL) to a dry film thickness of approximately 100 μm was coated with the antifouling coating compositions obtained in the examples and comparative examples to a dry film thickness of approximately 150 μm. The board was cured at room temperature for 3 days to prepare a test board. After making X-shaped cuts with a cutter that reached the primer coating, the adhesion of the coating film was evaluated by rubbing it firmly with a finger perpendicular to the cuts. ○: Coating film did not peel off △: Partial peeling around the cuts ×: Coating film peeled off easily

[0123] <Adhesion Test During Recoating> A rigid PVC board (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 was coated. The antifouling coating compositions obtained in the examples and comparative examples were then applied to a dry film thickness of approximately 150 μm, and the board was cured at room temperature for 3 days to prepare a test board. The test board was immersed in the sea at 2.0 m below the surface of Owase Bay for 3 months. After rinsing the surface with water and drying, the same antifouling coating composition was applied to a dry film thickness of approximately 150 μm and cured at room temperature for 3 days. After making X-shaped cuts using a cutter that reached the primer coating, the test board was again immersed in the sea at 2.0 m below the surface of Owase Bay for 3 months, and the adhesion during recoating was evaluated. ○: The paint film did not peel off. △: Some peeling occurred around the cut. ×: The paint film peeled off completely.

[0124] <Water Absorption Rate> A rigid PVC board (110 x 60 x 2 mm) was coated with an epoxy primer, HEMPADUR QUATTRO XO 17870 (manufactured by HEMPEL), to a dry film thickness of approximately 100 μm (for Comparative Examples 3 and 4, a silicone-based tiecoat, HEMPASIL NEXUS X-TEND 27500 (manufactured by HEMPEL), was further coated to a dry film thickness of approximately 100 μm). The antifouling coating compositions obtained in the examples and comparative examples were then applied to a dry film thickness of approximately 150 μm. This test board was immersed in purified water (manufactured by Kishida Chemical Co., Ltd.) at 25°C for 42 days. The water absorption rate after 8, 14, and 42 days was determined by measuring the mass of the sample before and after water absorption, and calculating the ratio of the increase in weight to the original weight. The water absorption rate after 42 days is preferably 5.0% or less, more preferably 3.0% or less, and even more preferably 1.0% or less. This water absorption rate is, for example, 0.0 to 5.0%, specifically, for example, 0.0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, and 5.0%, and may be in the range between any two of the values ​​exemplified here, or less than or equal to either of them.

[0125] <Antifouling Test> A rigid PVC board (110 x 60 x 2 mm) was coated with an epoxy primer, HEMPADUR QUATTRO XO 17870 (manufactured by Hempel), to a dry film thickness of approximately 100 μm (for Comparative Examples 3 and 4, a silicone-based tie-coat, HEMPASIL NEXUS X-TEND 27500 (manufactured by Hempel), was further coated to a dry film thickness of approximately 100 μm). The antifouling coating compositions obtained in the examples and comparative examples were then applied to a dry film thickness of approximately 150 μm. After curing the test board at room temperature for 3 days, it was immersed in the sea at 2.0 m below the surface of Owase Bay for 24 months. The fouling of the test board by attached organisms was observed after 6 months, 12 months, 18 months, and 24 months. The evaluation was judged by visually observing the condition of the coating surface according to the following criteria. ◎: No fouling organisms such as shellfish and algae attached, and no slime attached. 〇: No fouling organisms such as shellfish and algae attached, but slime is attached. △: Some fouling organisms such as shellfish and algae attached. ×: Fouling organisms such as shellfish and algae attached to the entire surface.

Claims

1. An antifouling paint composition containing copolymer A, copolymer B, and curing agent C, wherein copolymer A is a copolymer that is liquid at 25°C and 1 atm, and does not have functional groups that can react with curing agent C, copolymer A is composed of monomer (a1), monomer (a2), and monomer (a3) ​​other than monomer (a1) and (a2), monomer (a1) is represented by general formula (1), general formula (1): (In the formula, R １ R is a hydrogen or methyl group. ２ (wherein represents a hydrocarbon group having 6 to 18 carbon atoms.) The monomer (a2) has a common logarithm of the partition coefficient between 1-octanol and water, logP, which is 0.97 or less. The copolymer B is composed of monomer (b1), monomer (b2), and monomer (b3) other than monomers (b1) and (b2). The monomer (b1) is represented by general formula (2), General formula (2): (In the formula, R ３ R is a hydrogen or methyl group. ４ (This represents a hydrocarbon group having 6 to 18 carbon atoms.) The monomer (b2) is an antifouling coating composition having a functional group that can react with the curing agent C.

2. The antifouling paint composition according to claim 1, wherein the copolymer B has a hydroxyl value of 12 to 160 mgKOH / g.

3. The antifouling paint composition according to claim 1, wherein the copolymer A contains sulfur atoms.

4. An antifouling paint composition according to claim 1, further comprising a sulfur compound.

5. An antifouling paint composition according to claim 1, further comprising an antifouling agent.

6. An antifouling paint composition according to any one of claims 1 to 5, further comprising a bismuth compound.

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