Antifouling coating composition

Abstract

Provided is an antifouling coating composition capable of forming an antifouling coating film having good antifouling performance and an improved duration of a good state of the coating film surface. According to the present invention, there is provided an antifouling coating composition containing copolymer A, copolymer B, and an antifouling agent, wherein copolymer A is a copolymer of a monomer represented by the following general formula (1) and monomer (c), copolymer B is a copolymer of monomer (b) represented by the following general formula (2) and monomer (c), and monomer (c) is an ethylenically unsaturated monomer other than monomer (a) and monomer (b).

Description

Technical Field

[0001] The present invention relates to an antifouling coating composition. Background Art

[0002] Aquatic fouling organisms such as barnacles, serrated algae, mussels, bryophytes, ascidians, green laver, sea lettuce, slime, etc. adhere to ships (especially the bottom of ships), fishing gear such as fishing nets and fishing net accessories, and water structures such as power plant water pipes, resulting in problems such as impaired function and deteriorated appearance of ships.

[0003] To prevent such problems, it is known to apply an antifouling coating composition to ships, etc. to form an antifouling coating film, and an antifouling agent is slowly released from the antifouling coating film to provide long-term antifouling performance (Patent Documents 1 to 4).

[0004] However, the coating film solubility of the antifouling coating film composed of a polymer containing an alkoxycarbonylmethyl (meth)acrylate group described in Patent Documents 1 to 4 is very low, so it is difficult to exhibit antifouling properties for a long time.

[0005] To solve these problems, a technique capable of dissolving the coating film for a long time and exhibiting antifouling performance has been proposed (Patent Document 5).

[0006] Prior Art Documents

[0007] Patent Documents

[0008] Patent Document 1: Japanese Patent Laid-Open No. 63-61989

[0009] Patent Document 2: Japanese Patent Laid-Open No. 2003-119420

[0010] Patent Document 3: Japanese Patent Laid-Open No. 2003-119419

[0011] Patent Document 4: Japanese Patent Laid-Open No. 2002-3776

[0012] Patent Document 5: WO2020 / 045211 Summary of the Invention

[0013] Technical Problem to be Solved by the Invention

[0014] Patent Document 5 evaluated the coating film physical properties and antifouling performance for up to 24 months. The present inventors further evaluated the antifouling coating composition described in Patent Document 5 for a long time, and found problems such as a decrease in antifouling performance and abnormal coating film such as cracks. Therefore, there is a need for an antifouling coating composition capable of forming an antifouling coating film that maintains good antifouling performance and good coating film surface state for a longer time than the antifouling coating composition of Patent Document 5.

[0015] The present invention has been completed in view of such circumstances, and an object thereof is to provide an antifouling coating composition capable of forming an antifouling coating film with excellent antifouling performance and an extended duration of a good coating film surface state.

[0016] Means for Solving the Problem

[0017] The present invention provides an antifouling coating composition, the copolymer A contains a copolymer A, a copolymer B, and an antifouling agent, the copolymer A is a copolymer of a monomer (a) represented by the following general formula (1) and a monomer (c), the copolymer B is a copolymer of a monomer (b) represented by the following general formula (2) and the monomer (c), and the monomer (c) is an ethylenically unsaturated monomer other than the monomers (a) and (b).

[0018] The inventors of the present invention conducted in-depth research to solve the above problems and found that a composition containing a copolymer A, a copolymer B, and an antifouling agent can solve the above problems, thereby completing the present invention. Detailed Description of the Invention

[0019] The present invention will be described in detail below.

[0020] 1. Antifouling Coating Composition

[0021] The antifouling coating composition of the present invention contains a copolymer A, a copolymer B, and an antifouling agent.

[0022] 1-1. Copolymer A and Copolymer B

[0023] The copolymer A is a copolymer of the monomer (a) and the monomer (c). The copolymer B is a copolymer of the monomer (b) and the monomer (c).

[0024] In the copolymer A, the content of the monomer (a) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, relative to the total amount of the monomers (a) and (c). Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and it can also be within the range between any two values exemplified herein. In this case, the coating film solubility is particularly good.

[0025] In the copolymer B, the content of the monomer (b) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, relative to the total amount of the monomers (b) and (c). Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and it can also be within the range between any two values exemplified herein. In this case, the coating film solubility is particularly good.

[0026] 1-1-1. Monomer (a)

[0027] The monomer (a) is represented by the general formula (1).

[0028] [Chemical formula 1]

[0029]

[0030] In the formula, R 1 represents hydrogen, methyl or phenyl, and R 2 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group which may be substituted by an alkoxy group or a phenyl group having 1 to 8 carbon atoms, and n is an integer of 1 to 10.

[0031] R 1 is preferably hydrogen or methyl.

[0032] R 2 The number of carbon atoms of the alkoxy group or the alkyl group of is, for example, 1, 2, 3, 4, 5, 6, 7, 8, and may also be within the range between any two of the values exemplified herein. R 2 is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl, benzyl, phenyl, 2-methoxyethyl, 4-methoxybutyl, vinyl or allyl, and preferably methyl, ethyl, isopropyl or n-butyl.

[0033] n represents an integer of 1 to 10. n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and may also be within the range between any two of the values exemplified herein.

[0034] The monomer (a) preferably contains a compound in which n in the general formula (1) is 2 or more. By containing a compound in which n is 2 or more as the monomer (a), the coating film solubility is improved. The monomer (a) may be composed only of a compound in which n is 2 or more, or may be a mixture of a compound in which n is 1 and a compound in which n is 2 or more.

[0035] The monomer (a) is preferably composed of the monomer (a1) and the monomer (a2). The content of the monomer (a1) in the monomer (a) is preferably 20 to 100% by mass, more preferably 30 to 75% by mass, and particularly preferably 35 to 60% by mass. Specifically, the ratio is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and may also be within the range between any two of the values exemplified herein. Compared with the monomer (a2), the monomer (a1) has the properties of improving the coating film strength and reducing the coating film solubility. Therefore, if the content of the monomer (a1) is too small, the strength of the coating film tends to decrease, and the surface state of the coating film tends to deteriorate easily after a long period.

[0036] <Monomer (a1)>

[0037] The monomer (a1) is a compound in which n is 1 in the general formula (1).

[0038] Examples of the monomer (a1) include methoxycarbonylmethyl methacrylate, ethoxycarbonylmethyl methacrylate, isopropoxycarbonylmethyl methacrylate, n-propoxycarbonylmethyl methacrylate, n-butoxycarbonylmethyl methacrylate, tert-butoxycarbonylmethyl methacrylate, 2-ethylhexoxycarbonylmethyl methacrylate, cyclohexyloxycarbonylmethyl methacrylate, benzyloxycarbonylmethyl methacrylate, phenoxycarbonylmethyl methacrylate, 2-methoxyethoxycarbonylmethyl methacrylate, 4-methoxybutoxycarbonylmethyl methacrylate, allyl methacrylate, vinyloxycarbonylmethyl methacrylate, 1-(methoxycarbonyl)ethyl methacrylate, 1-(ethoxycarbonyl)ethyl methacrylate, 1-(n-propoxycarbonyl)ethyl methacrylate, 1-(isopropoxycarbonyl)ethyl methacrylate, 1-(n-butoxycarbonyl)ethyl methacrylate, 1-(tert-butoxycarbonyl)ethyl methacrylate, α-(methoxycarbonyl)benzyl methacrylate, α-(ethoxycarbonyl)benzyl methacrylate. Preferred examples include methoxycarbonylmethyl methacrylate, ethoxycarbonylmethyl methacrylate, isopropoxycarbonylmethyl methacrylate, n-propoxycarbonylmethyl methacrylate, n-butoxycarbonylmethyl methacrylate, 1-(methoxycarbonyl)ethyl methacrylate, 1-(ethoxycarbonyl)ethyl methacrylate.

[0039] <Monomer (a2)>

[0040] The monomer (a2) is a compound of the general formula (1) in which n is 2 or more. From the viewpoint of long-term antifouling properties, n in the general formula (1) is preferably 2 to 6.

[0041] As the monomer (a2), it is preferable to contain both a compound in which n is 2 and a compound in which n is 3 or more. Specifically, for example, in terms of solid content conversion, the mass ratio (n(2) / n(2-10)) is preferably 0.2 to 0.8, more preferably 0.3 to 0.7. In this case, there is a tendency for a stable coating film to dissolve continuously. Specifically, this value is, for example, 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, and it can also be within the range between any two of the values exemplified herein.

[0042] As the monomer (a2), for example, methyl methacrylate bis(oxycarbonylmethyl), ethyl methacrylate bis(oxycarbonylmethyl), isopropyl methacrylate bis(oxycarbonylmethyl), n-propyl methacrylate bis(oxycarbonylmethyl), n-butyl methacrylate bis(oxycarbonylmethyl), tert-butyl methacrylate bis(oxycarbonylmethyl), 2-ethylhexyl methacrylate bis(oxycarbonylmethyl), cyclohexyl methacrylate bis(oxycarbonylmethyl), benzyl methacrylate bis(oxycarbonylmethyl), phenyl methacrylate bis(oxycarbonylmethyl), 2-methoxyethyl methacrylate bis(oxycarbonylmethyl), 4-methoxybutyl methacrylate bis(oxycarbonylmethyl), allyl methacrylate bis(oxycarbonylmethyl), vinyl methacrylate bis(oxycarbonylmethyl), methyl methacrylate bis[1-(oxypolycarbonyl)ethyl], ethyl methacrylate bis[1-(oxypolycarbonyl)ethyl], n-propyl methacrylate bis[1-(oxypolycarbonyl)ethyl], isopropyl methacrylate bis[1-(oxypolycarbonyl)ethyl], n-butyl methacrylate bis[1-(oxypolycarbonyl)ethyl], tert-butyl methacrylate bis[1-(oxypolycarbonyl)ethyl], methyl methacrylate bis[α-(oxycarbonyl)benzyl], ethyl methacrylate bis[α-(oxycarbonyl)benzyl] can be cited. Preferably, methyl methacrylate bis(oxycarbonylmethyl), ethyl methacrylate bis(oxycarbonylmethyl), isopropyl methacrylate bis(oxycarbonylmethyl), n-propyl methacrylate bis(oxycarbonylmethyl), n-butyl methacrylate bis(oxycarbonylmethyl), methyl methacrylate bis[1-(oxypolycarbonylethyl)], ethyl methacrylate bis[1-(oxypolycarbonylethyl)], methyl methacrylate poly(oxycarbonylmethyl), ethyl methacrylate poly(oxycarbonylmethyl), isopropyl methacrylate poly(oxycarbonylmethyl), n-propyl methacrylate poly(oxycarbonylmethyl), n-butyl methacrylate poly(oxycarbonylmethyl), tert-butyl methacrylate poly(oxycarbonylmethyl), 2-ethylhexyl methacrylate poly(oxycarbonylmethyl), cyclohexyl methacrylate poly(oxycarbonylmethyl), benzyl methacrylate poly(oxycarbonylmethyl), phenyl methacrylate poly(oxycarbonylmethyl), 2-methoxyethyl methacrylate poly(oxycarbonylmethyl), 4-methoxybutyl methacrylate poly(oxycarbonylmethyl), allyl methacrylate poly(oxycarbonylmethyl), vinyl methacrylate poly(oxycarbonylmethyl), methyl methacrylate poly[1-(oxypolycarbonyl)ethyl], ethyl methacrylate poly[1-(oxypolycarbonyl)ethyl], n-propyl methacrylate poly[1-(oxypolycarbonyl)ethyl], isopropyl methacrylate poly[1-(oxypolycarbonyl)ethyl], n-butyl methacrylate poly[1-(oxypolycarbonyl)ethyl], tert-butyl methacrylate poly[1-(oxypolycarbonyl)ethyl], methyl methacrylate poly[α-(oxycarbonyl)benzyl], ethyl methacrylate poly[α-(oxycarbonyl)benzyl].Preferred examples include poly(oxycarbonylmethyl) methyl methacrylate, poly(oxycarbonylmethyl) ethyl methacrylate, poly(oxycarbonylmethyl) isopropyl methacrylate, poly(oxycarbonylmethyl) n-propyl methacrylate, poly(oxycarbonylmethyl) n-butyl methacrylate, poly[1-(oxycarbonylethyl)] methyl methacrylate, poly[1-(oxycarbonylethyl)] ethyl methacrylate, etc.

[0043] 1-1-2. Monomer (b)

[0044] Monomer (b) is represented by the general formula (2).

[0045] [Chemical formula 2]

[0046]

[0047] In the formula, R 3 represents hydrogen, methyl, or phenyl, and R 4 represents an alkyl group having 1 to 8 carbon atoms or phenyl which may be substituted by an alkoxy group having 1 to 8 carbon atoms or phenyl, and n represents an integer of 1 to 10.

[0048] R 3 and R 4 are the same as the descriptions of R 1 and R 2 in the general formula (1). The description of n is the same as the description of n in the general formula (1).

[0049] Monomer (b) preferably contains a compound in which n in the general formula (2) is 2 or more. When a compound in which n is 2 or more is contained as monomer (b), the solubility of the coating film is improved. Monomer (b) may consist only of a compound in which n is 2 or more, or may be a mixture of a compound in which n is 1 and a compound in which n is 2 or more.

[0050] Monomer (b) is preferably composed of monomer (b1) and monomer (b2). The content of monomer (b1) in monomer (b) is preferably 20 to 100% by mass, more preferably 30 to 75% by mass, and particularly preferably 35 to 60% by mass. Specifically, the ratio is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100% by mass, and may also be within the range between any two of the values exemplified herein. Monomer (b1) has the property of improving the strength of the coating film and reducing the solubility of the coating film as compared with monomer (b2). Therefore, if the content of monomer (b1) is too small, the strength of the coating film is likely to decrease, and the surface state of the coating film is likely to deteriorate after a long period.

[0051] <Monomer (b1)>

[0052] The monomer (b1) is a compound in which n is 1 in the general formula (2).

[0053] Examples of the monomer (b1) include the acrylate monomers listed in the above monomer (a1).

[0054] <Monomer (b2)>

[0055] The monomer (b2) is a compound represented by the general formula (2), where n is 2 or more. From the viewpoint of long-term antifouling properties, n in the general formula (2) is preferably 2 to 6.

[0056] The monomer (b2) preferably contains a compound with n = 2 and a compound with n ≥ 3. Specifically, for example, the mass ratio of the solid content (n(2) / n(2 - 10)) is preferably 0.2 to 0.8, more preferably 0.3 to 0.7. In this case, there is a tendency for the stable coating film dissolution to continue. Specifically, this value is, for example, 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, and can also be within the range between any two of the values exemplified herein.

[0057] Examples of the monomer (b2) include the acrylate monomers listed in the above monomer (a2).

[0058] 1 - 1 - 3. Monomer (c)

[0059] The monomer (c) is an ethylenically unsaturated monomer other than the monomer (a) and the monomer (b).

[0060] Examples of the monomer (c) include (meth)acrylates not represented by the general formulas (1) and (2), vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, etc. In addition, in this specification, (meth)acrylate means acrylate or methacrylate.

[0061] Examples of the (meth)acrylate not represented by the general formula (1) to (2) include (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid tert-butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, propylene glycol monomethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl methacrylate, mono(2-(meth)acryloyloxyethyl) succinate, N-(3-dimethylaminopropyl)(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, N,N'-dimethyl(meth)acrylamide and other (meth)acrylate compounds;

[0062] (Meth)acrylate silyl ester compounds such as triisopropylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, etc.

[0063] Examples of the vinyl compound include 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.

[0064] Examples of the aromatic compound include styrene, vinyltoluene, α-methylstyrene, etc.

[0065] Examples of the dialkyl ester compound of the dibasic acid include dimethyl maleate, dibutyl maleate, dimethyl fumarate, etc.

[0066] In copolymer A and copolymer B, these monomers (c) can be used alone or in combination of two or more. From the viewpoints of film solubility and film physical properties, monomer (c) preferably contains (meth)acrylate. From the viewpoint of crack resistance, monomer (c) preferably contains (meth)acrylate, such as methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, triisopropylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, etc.

[0067] 1-1-4. Physical Properties and Manufacturing Methods of Copolymer A and Copolymer B

[0068] The weight average molecular weight (Mw) of copolymer A and copolymer B is preferably 5,000 to 300,000. If the molecular weight is lower than 5,000, the film of the antifouling coating becomes brittle and is liable to peel or crack, or if it exceeds 300,000, the viscosity of the polymer increases and it becomes difficult to handle. Specifically, the Mw is, for example, 5000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000, 300,000, and can also be within the range between any two of the values exemplified herein.

[0069] As a method for measuring Mw, gel permeation chromatography (GPC method) can be cited.

[0070] Copolymer A can be any copolymer of monomer (a) and monomer (c), such as a random copolymer, an alternating copolymer, a periodic copolymer or a block copolymer. Copolymer B can similarly be a random copolymer, an alternating copolymer, a periodic copolymer or a block copolymer of monomer (b) and monomer (c).

[0071] Copolymer A and copolymer B can be prepared, for example, by polymerizing a monomer mixture selected from monomer (a), monomer (b) and monomer (c) in the presence of a polymerization initiator.

[0072] 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, 2,2'-azobis(N-butyl-2-methylpropionamide); peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl isopropyl percarbonate, tert-butyl 2-ethylhexanoate, tert-hexyl 2-ethylhexanoate, di-tert-hexyl peroxide, tert-butyl 2-ethylhexyl monocarbonate, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, tert-amyl peroxyneodecanoate, tert-hexyl peroxypivalate, tert-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl 2-ethylhexanoate. These polymerization initiators can be used alone or in combination of two or more. Particularly preferred as the aforementioned polymerization initiators are 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and 1,1,3,3-tetramethylbutyl 2-ethylhexanoate peroxide. By appropriately setting the amount of the polymerization initiator, the molecular weight of the resulting polymer A can be adjusted. In addition, to adjust the molecular weight of the obtained polymer, a chain transfer agent can be used. Examples of the chain transfer agent include thiols such as n-dodecyl mercaptan; thioethanolates such as octyl thioglycolate; α-methylstyrene dimer and terpinolene.

[0073] Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. Among them, from the viewpoints of simplicity and accuracy in obtaining copolymer A or copolymer B, solution polymerization or non-aqueous dispersion polymerization is particularly preferred.

[0074] In the polymerization reaction, an organic solvent can be used as needed. The organic solvent is not particularly limited, for example, aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, and propylene glycol 1-monomethyl ether 2-acetate; alcohol solvents such as isopropanol, butanol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

[0075] Among them, butyl acetate, isobutyl acetate, butanol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene are preferred. These solvents can be used alone or in combination of two or more.

[0076] The reaction temperature in the polymerization reaction can be appropriately set according to the type of the polymerization initiator, etc., and is usually 50 to 160 °C, preferably 60 to 150 °C.

[0077] The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.

[0078] There is no particular limitation on the total content of copolymer A and copolymer B in the composition of the present invention, but it is usually 5 to 50% by mass in terms of solid content. Specifically, for example, it is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50% by mass, and it can also be within the range between any two of the values exemplified herein.

[0079] The content of copolymer A is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, relative to the total of copolymer A and copolymer B. Specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and it can also be within the range between any two of the values exemplified herein. In this case, the coating film solubility and coating film physical properties are particularly good.

[0080] 1-2. Antifouling agent

[0081] As the antifouling agent, for example, inorganic reagents and organic reagents can be cited.

[0082] As the inorganic reagent, for example, cuprous oxide, copper thiocyanate (common name: endosulfan copper), copper powder, etc. can be cited. Among them, cuprous oxide and endosulfan copper are particularly preferred, and from the viewpoint of long-term storage stability, cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, lecithin, mineral oil, etc. is more preferred.

[0083] As the organic reagent, for example, copper 2-mercaptopyridine-N-oxide (common name: copper pyrithione), zinc 2-mercaptopyridine-N-oxide (common name: zinc pyrithione), zinc ethylene bisdithiocarbamate (common name: Zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (common name: SeaNine211), 3,4-dichlorophenyl-N-N-dimethylurea (common name: tricresyl phosphate), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (common name: Irgalol1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: Econea28), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: medetomidine), etc. can be cited.

[0084] These antifouling agents can be used alone or in combination of two or more.

[0085] The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60.0% by mass in terms of solid content. The content of the antifouling agent is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and can also be within the range between any two of the values exemplified herein.

[0086] 1 - 3. Other additives

[0087] In addition, the resin for the antifouling coating of the present invention may contain, as needed, resin components other than copolymer A and copolymer B, dissolution regulators, plasticizers, pigments, dyes, defoamers, dehydrating agents, stirring agents, modifiers, organic solvents, etc.

[0088] Examples of other resin components may include the following polymer P, etc.

[0089] Polymer P is a polymer obtained by polymerizing monomer (c).

[0090] In the present invention, monomer (c) can be used alone or in combination of two or more. In particular, from the viewpoint of compatibility with copolymer A, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, etc. are preferred.

[0091] The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc. can be applied to the methods described for copolymer A.

[0092] The content of polymer P in the composition of the present invention is not particularly limited, but in terms of solid content, the content ratio of copolymer A and copolymer B is a mass ratio (polymer P / copolymer A and copolymer B). It is usually 0.1 to 0.5, preferably 0.1 to 0.3. This mass ratio can be 0.1, 0.2, 0.3, 0.4, 0.5, and can also be within the range between any two of the values exemplified herein.

[0093] As dissolution regulators, for example, monocarboxylic acids and their salts such as rosin, rosin derivatives, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, tertiary carboxylic acid, trimethylisobutenylcyclohexene carboxylic acid and its metal salts, etc., or the above-mentioned alicyclic hydrocarbon resins can be cited. These can be used alone or in combination of two or more.

[0094] Examples of rosin derivatives include hydrogenated rosin, disproportionated rosin, maleic rosin, formylated rosin, polymerized rosin, etc.

[0095] Examples of alicyclic hydrocarbon resins include commercially available products such as Quinton1500, 1525L, 1700 (trade name, manufactured by Zeon Corporation of Japan), etc.

[0096] Among them, rosin, rosin derivatives, naphthenic acid, tertiary carboxylic acid, trimethylisobutenylcyclohexene formic acid, or metal salts thereof are preferred.

[0097] As plasticizers, for example, phosphate esters, phthalate esters, adipate esters, sebacate esters, polyester epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tertiary nonyl pentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, etc. can be cited. These can be used alone or in combination of two or more.

[0098] As the aforementioned dehydrating agents, for example, calcium sulfate, synthetic zeolite adsorbents, orthoester, silicate such as tetramethoxysilane, tetraethoxysilane, etc., or isocyanates, carbodiimides, carbodimidazoles, etc. can be cited. These can be used alone or in combination of two or more.

[0099] 2. Method for manufacturing antifouling coating composition

[0100] The antifouling coating composition of the present invention can be manufactured, for example, by mixing and dispersing a mixed liquid containing a copolymer, an antifouling agent, other additives, etc. using a disperser.

[0101] As the mixed liquid, it is preferably prepared by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.

[0102] As the disperser, for example, a disperser that can be used as a micro grinder can be appropriately used. For example, commercially available homogenizers, sand mills, bead mills, dispersers, etc. can be used. Or a glass bead for mixing and dispersing added to a container equipped with a stirrer can also be used to mix and disperse the mixed liquid.

[0103] 3. Antifouling treatment method, antifouling coating film and coated object

[0104] In the antifouling treatment method of the present invention, an antifouling coating composition is used to form an antifouling coating film on the surface of the object to be coated. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface, and the surface of the coating film is continuously renewed, thereby preventing the attachment of aquatic fouling organisms.

[0105] Examples of the object to be coated include ships (especially the bottom of the ship), fishing gear, underwater structures, etc.

[0106] The thickness of the antifouling coating film can be appropriately set according to the type of the object to be coated, the sailing speed of the ship, the seawater temperature, etc. For example, when the object to be coated is the bottom of the ship, the thickness of the antifouling coating is usually 50 to 700 μm, preferably 100 to 600 μm.

[0107] [Examples]

[0108] The features of the present invention will be further clarified by the following shown examples, etc. However, the present invention is not limited to the examples, etc.

[0109] In each production example, example and comparative example, % represents mass %. The weight average molecular weight (Mw) is the value measured by GPC (polystyrene conversion value). The conditions of GPC are as follows.

[0110] Apparatus: HLC-8220GPC manufactured by Tosoh Corporation

[0111] Column: 2 pieces of TSKgel SuperHZM-M

[0112] Flow rate: 0.35 mL / min

[0113] Detector: RI

[0114] Column thermostat temperature: 40 °C

[0115] Eluent: THF

[0116] The heat-residual component is the value measured according to JIS K 5601-1-2:1999 (ISO 3251:1993) "Test Methods for Coating Components - Heat-Residual Components".

[0117] 1. Production example

[0118] 1-1. Production example of monomer (a1)

[0119] <Production Example 1 (Production of monomer a1-1)>

[0120] In a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, add methyl chloroacetate: 109 g (1.00 mol), methacrylic acid: 86 g (1.00 mol), 4-methoxyphenol: 0.1 g, ethyl acetate: 500 g, and while stirring, keep the temperature below 40 °C and dropwise add triethylamine: 101 g (1.00 mol). After the dropping is completed, stir at 70 - 80 °C for 6 hours. After the reaction is completed, wash the organic layer successively with tap water, hydrochloric acid water and sodium bicarbonate water, and then concentrate under reduced pressure to remove the solvent to obtain monomer a1-1: 142.3 g.

[0121] <Manufacturing Examples 2 - 7 (Manufacture of Monomers a1-2 and b1-1 to b1-5)>

[0122] Using the raw materials shown in Table 1, monomers a1-2 and b1-1 to b1-5 are obtained by reacting in the same manner as in Manufacturing Example 1. The reaction conditions and yields of Manufacturing Examples 1 - 7 are shown in Table 1.

[0123] [Table 1]

[0124]

[0125] 1-2. Manufacturing Examples of Monomer (a2)

[0126] <Manufacturing Example 8 (Manufacture of Monomer a2-1)>

[0127] (First Reaction)

[0128] Add sodium chloroacetate: 215 g (1.85 mol), methyl chloroacetate: 201 g (1.85 mol) and N-methyl-2-pyrrolidone: 300 g to a four-necked flask equipped with a thermometer, a condenser and a stirrer, and stir at 70 - 80 °C for 6 hours. After the reaction is completed, add toluene: 500 ml to the reaction solution, and then wash the organic layer successively with tap water, hydrochloric acid water and sodium bicarbonate water, and then concentrate under reduced pressure to distill off the solvent to obtain methoxycarbonylmethyl chloroacetate: 262 g.

[0129] (Second Reaction)

[0130] Then, in a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, add methoxycarbonylmethyl chloroacetate: 200 g (1.20 mol), which is the product (intermediate) of the first reaction, methacrylic acid: 103 g (1.20 mol), 4-methoxyphenol: 0.1 g, and ethyl acetate: 500 g. While stirring, maintain the temperature below 40 °C and dropwise add triethylamine: 122 g (1.20 mol). After the addition is complete, stir at 70 - 80 °C for 6 hours. After the reaction is completed, wash the organic layer successively with tap water, hydrochloric acid solution, and sodium bicarbonate solution, and then concentrate under reduced pressure to distill off the solvent to obtain monomer a2-1: 230.6 g.

[0131] <Manufacturing Example 9 - 42 (Production of Monomers a2-2 to a2-10 and b2-1 to b2-25)>

[0132] Using the raw materials shown in Tables 2 - 4, perform the same reaction as in Manufacturing Example 8 to obtain monomers a2-2 to a2-10 and b2-1 to b2-25 shown in Table 2. The reaction conditions and yields of Manufacturing Examples 8 - 42 are shown in Tables 2 - 4.

[0133] [Table 2]

[0134]

[0135] [Table 3]

[0136]

[0137] [Table 4]

[0138]

[0139] The raw materials in Tables 1 - 4 are as follows in detail.

[0140] AA: Acrylic acid

[0141] MAA: Methacrylic acid

[0142] NMP: N-Methyl-2-pyrrolidone

[0143] CANa: Sodium monochloroacetate

[0144] CPANa: Sodium 2-chloropropionate

[0145] CAMe: Methyl chloroacetate

[0146] CAEt: Ethyl chloroacetate

[0147] CAiPr: Isopropyl chloroacetate

[0148] CANBu: n-Butyl chloroacetate

[0149] CPAMe: Methyl 2-chloropropionate

[0150] MEHQ: 4-Methoxyphenol

[0151] TEA: Triethylamine

[0152] 1-3. Preparation Examples of Copolymer Solutions

[0153] <Preparation Example P1 (Preparation of Copolymer Solution A-1)>

[0154] In a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, 50 g of xylene and 50 g of butyl acetate were added as solvents, nitrogen was introduced, and the temperature was maintained at 88 °C with stirring. Herein, a mixed solution of the monomers in the amounts (g) shown in Table 5 and 2.0 g of 1,1,3,3-tetramethylbutyl peroxydi(2-ethylhexanoate) as a polymerization initiator (initial addition) was dropped over 3 hours while maintaining the temperature at 88 °C. Then, after stirring at 88 °C for 1 hour, 0.1 g of 1,1,3,3-tetramethylbutyl peroxydi(2-ethylhexanoate) was added 3 times every 1 hour, and after stirring at the same temperature for 2 hours, it was cooled to room temperature to obtain copolymer solution A-1. The heating residue and Mw of A-1 are shown in Table 5.

[0155] <Preparation Examples P2 - P16 (Preparation of Copolymer Solutions A-2 - A-8, B-1 - B-8)>

[0156] Copolymer solutions A-2 - A-8, B-1 - B-8 were obtained. The heating residues and Mw of each polymer are shown in Tables 5 - 6. The numerical unit of the amounts of raw materials in the tables is g.

[0157] [Table 5]

[0158]

[0159] [Table 6]

[0160]

[0161] 1-4. Other Preparation Examples

[0162] <Preparation Example D1 (Preparation of Rosin Solution)>

[0163] 300 g of Chinese gum rosin (WW) and 310 g of xylene were added to a flask equipped with a thermometer, a reflux condenser, and a stirrer, and dehydrated by reduced pressure reflux at 70 - 80 °C for 1 hour to obtain a rosin xylene solution (brown transparent liquid, 50% solid content). The heating residue of the obtained solution was 50.3%.

[0164] <Preparation Example D2 (Preparation of Hydrogenated Rosin Solution)>

[0165] A xylene solution of hydrogenated rosin (brown transparent liquid, solid content 50%) was obtained in the same manner as in Production Example D1, except that the Chinese gum rosin (WW) in Production Example D1 was changed to hydrogenated rosin. The heat residue of the obtained solution was 50.1%.

[0166] <Production Example D3 (Production of zinc salt solution of gum rosin)>

[0167] In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene were added, and 120 g of zinc oxide was added to form zinc salts of all the resin acids in the aforementioned rosin. Then, the mixture was refluxed under reduced pressure at 70 to 80 °C for 3 hours for dehydration. Then, by cooling and filtering, a xylene solution of zinc salt of rosin (dark brown transparent liquid, solid content 50%) was obtained. The heat residue of the obtained solution was 50.2%.

[0168] <Production Example D4 (Production of zinc salt solution of hydrogenated rosin)>

[0169] A xylene solution of zinc salt of hydrogenated rosin (dark brown transparent liquid, solid content 50%) was obtained in the same manner as in Production Example D3, except that the Chinese gum rosin (WW) in Production Example D3 was changed to hydrogenated rosin. The residue when the obtained solution was heated was 50.5%.

[0170] 2. Examples 1 to 28 and Comparative Examples 1 to 4 (Production of coating compositions)

[0171] The coating composition was prepared by blending the components shown in Tables 7 to 10 at the ratios (mass%) shown in the same tables and mixing and dispersing the mixture with glass beads having a diameter of 1.5 to 2.5 mm.

[0172] [Table 7]

[0173]

[0174] [Table 8]

[0175]

[0176] [Table 9]

[0177]

[0178] [Table 10]

[0179]

[0180] Details of each component in the table are as follows.

[0181] <Dissolution regulator>

[0182] Zinc hydrogenated rosin solution: Use the solution obtained in Production Example D4

[0183] Zinc gum rosin salt solution: Use the solution obtained in Production Example D3

[0184] Gum rosin solution: Use the solution obtained in Production Example D1

[0185] Hydrogenated rosin solution: Use the solution obtained in Production Example D2

[0186] <Antifouling agent>

[0187] Cuprous oxide: Trade name "NC-301" (manufactured by Nisshin Chemco Co., Ltd.)

[0188] Copper pyrithione: Trade name "Copper Omagin" (manufactured by LONZA)

[0189] SeaNine: Trade name "SeaNine 211", 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (manufactured by R&H), 30% active ingredient xylene solution

[0190] Zineb: Zinc [ethylenebis(dithiocarbamate)] (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

[0191] Zinc pyrithione: (manufactured by LONZA)

[0192] Econea 028: Trade name "Econea 028", 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

[0193] Medetomidine: (±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (manufactured by Wako Pure Chemical Industries, Ltd.)

[0194] <Pigment>

[0195] Red iron oxide: Trade name "Bengara Kingyoku" (manufactured by Morishita Bengara Co., Ltd.)

[0196] Talc: Trade name "Talc MS" (manufactured by Nippon Talc Co., Ltd.)

[0197] Zinc oxide: Trade name "Zinc Oxide 2 types" (manufactured by Shodo Chemical Industry Co., Ltd.)

[0198] Titanium oxide: Trade name "FR-41" (manufactured by Furukawa Machinery Metal Co., Ltd.)

[0199] <Other additives>

[0200] Disparlon A603-20X: An amide-based thixotropic agent, trade name "Disparlon A603-20X" (manufactured by Nanben Kasei Co., Ltd.)

[0201] Tetraethoxysilane: Trade name "ethylsilicate 28" (manufactured by Colcoat Co., Ltd.)

[0202] Tricresyl phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)

[0203] Chlorinated paraffin: Trade name "Paraffin Chlorlated (Cl: 40%)" (manufactured by Wako Pure Chemical Industries, Ltd.)

[0204] 3. Tests

[0205] The following tests were conducted on the coating compositions of the examples and comparative examples. The evaluation results are shown in Tables 7 to 10.

[0206] In all comparative examples, the results in the rotation test and the antifouling test were not good compared to the examples.

[0207] <Test Example 1 (Rotation Test)>

[0208] A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank and rotated by an electric motor. In addition, a cooling device for maintaining a constant seawater temperature and a pH automatic controller for maintaining a constant seawater pH were installed.

[0209] Test plates were prepared according to the following method.

[0210] First, an anti-rust coating (epoxy vinyl-based A / C) was applied to a titanium plate (71×100×0.5 mm) to a dried thickness of about 100 μm, and an anti-rust coating film was formed after drying. Then, the coating compositions obtained in the examples and comparative examples were applied so that the dry film thickness was about 300 μm, and dried at 40 °C for 3 days to prepare test plates.

[0211] The prepared test plates were fixed to the rotating drum of the rotating device of the above device to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this period, the seawater temperature was maintained at 25 °C, the pH value was maintained at 8.0 - 8.2, and the seawater was changed every two weeks.

[0212] The remaining film thickness of each test panel at the initial stage and every six months after the start of the test was measured using a shape measurement laser microscope VK-X100 manufactured by Keyence Corporation, and the dissolved coating film thickness was calculated from the difference to obtain the coating film dissolution amount (μm / month) in one month. In addition, when measuring the remaining film thickness after 36 months of the rotation test, the surface state of each coating film was evaluated by observing the surface of each coating film with the naked eye and a microscope.

[0213] The surface state of the coating film was evaluated according to the following criteria.

[0214] ◎: When there is no abnormality at all

[0215] ○: Hairy cracks are visible on less than 10% of the total surface area of the coating film

[0216] △: Hairy cracks are visible on 10 - 30% of the total surface area of the coating film

[0217] ×: Hairy cracks are visible on more than 30% of the total surface area of the coating film

[0218] ××: Abnormalities in the coating film are visible, such as large cracks, blisters or peeling (only peeling on the surface or part of the edge of the coating film), delamination (the entire coating film peels off and no test coating film remains), etc.

[0219] <Test Example 2 (Antifouling Test)>

[0220] The coating compositions obtained in the examples and comparative examples were applied to both sides of a rigid polyvinyl chloride plate (hard PVC plate) (100×200×2 mm) so that the thickness of the dry coating film was about 300 μm. The test panel with a dry coating film thickness of about 300 μm was prepared by drying the obtained coated material at room temperature (25°C) for 3 days. The test panel was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and the fouling of the test panel caused by attached substances was observed after 12 months, 24 months, and 36 months, respectively.

[0221] The evaluation was carried out by visually observing the state of the coating film surface, and the judgment was made according to the following criteria.

[0222] ◎: No fouling organisms such as shellfish and algae are attached, and there is almost no slime.

[0223] ○: No fouling organisms such as shellfish and algae are attached, and there is a thin layer of slime attached (to the extent visible on the coating film surface), but it can be removed by gently wiping with a brush.

[0224] △: Although no fouling organisms such as shellfish or algae are attached, the slime is attached very thickly so that the coating film surface cannot be seen, and it cannot be removed even by wiping hard with a brush.

[0225] ×: The level of attachment of fouling organisms such as shellfish and algae.

Claims

1. An antifouling coating composition containing copolymer A, copolymer B and an antifouling reagent, characterized in that, The copolymer A is a copolymer of monomer (a) represented by the following general formula (1) and monomer (c); The copolymer B is a copolymer of monomer (b) represented by the following general formula (2) and the monomer (c); The monomer (c) is an ethylenically unsaturated monomer other than the monomers (a) and (b); [Chemical formula 1] wherein, R 1 represents hydrogen, methyl, or phenyl, and R 2 represents an alkyl group having 1 to 8 carbon atoms or a phenyl group which may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group, and n represents an integer of 1 to 10. [Chemical formula 2] In the formula, R 3 represents hydrogen, methyl, or phenyl, and R 4 represents an alkyl group or phenyl group having 1 to 8 carbon atoms that may be substituted with an alkoxy group or phenyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10.

2. The antifouling coating composition according to claim 1, characterized in that, It further contains a dissolution regulator.

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