Antifouling paint composition

Abstract

Provided is an antifouling coating composition which, in seawater over a long period, retains a stable coating-film dissolution rate, suffers no coating-film abnormalities, e.g., cracking, and can retain stable antifouling performance.　This antifouling coating composition comprises a carboxylic acid ester Q represented by general formula (1) and an antifouling chemical.

Description

[Technical Field]

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

[0002] Aquatic fouling organisms such as barnacles, serpula, mussels, bryozoans, sea squirts, green laver, sea lettuce, slime, etc. attach to ships (especially the bottom of ships), fishing equipment such as fishing nets and fishing net accessories, and underwater structures such as power plant water pipes, causing problems such as impairing the function of these ships and damaging their appearance. To prevent such problems, a technique is known in which an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is gradually released from the antifouling coating film, thereby providing antifouling performance over a long period of time (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-17203 Summary of the Invention [Problem to be solved by the invention]

[0004] However, even when the technology of Patent Document 1 is adopted, there are cases where the initial coating dissolution is excessively large or coating abnormalities such as cracks occur after a relatively short period of time, and further improvements are required.

[0005] The present invention has been made in view of the above circumstances, and provides an antifouling coating composition that can maintain a stable coating film dissolution rate in seawater over a long period of time, and can maintain stable antifouling performance without causing coating film abnormalities such as cracks. [Means for solving the problem]

[0006] According to the present invention, there is provided an antifouling coating composition containing a carboxylic acid ester Q represented by general formula (1) and an antifouling agent.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that a composition containing a carboxylic acid ester Q can solve the above problems, leading to the completion of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention will be described in detail below. 1. Antifouling paint composition The antifouling coating composition of the present invention contains a carboxylic acid ester Q and an antifouling agent, and preferably contains at least one of copolymer A, copolymer B, and copolymer C.

[0009] 1-1.Carboxylic acid ester Q

[0010] The carboxylic acid ester Q is represented by the general formula (1).

[0011] [ka] (In the formula, R 1 represents a carboxylic acid residue having 20 or less carbon atoms, and R 2 represents hydrogen, a methyl group, or a phenyl group, and R 3 represents an alkoxy group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms which may be substituted with a phenyl group, or represents a phenyl group, and n represents an integer of 1 to 10.

[0012] R 1 The number of carbon atoms in R is, for example, 1 to 20, preferably 5 to 20, and more preferably 8 to 20. Specific examples of the number of carbon atoms include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20, and may be within a range between any two of the numerical values ​​exemplified here. 1is preferably a gum rosin acid residue, a hydrogenated rosin acid residue, a disproportionated rosin acid residue, a versatic acid residue, or a naphthenic acid residue, and more preferably a gum rosin acid residue or a hydrogenated rosin acid residue.

[0013] R 3 The number of carbon atoms in the alkoxy group or alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and may be within a range between any two of the values ​​exemplified here. 3 is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, a cyclohexyl group, a benzyl group, a phenyl group, a 2-methoxyethyl group, a 4-methoxybutyl group, a vinyl group, or an allyl group, and is preferably a methyl group, an ethyl group, an isopropyl group, or an n-butyl group.

[0014] n represents an integer of 1 to 10, and from the viewpoint of long-term stain resistance, is preferably 2 to 6. n is, for example, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and may be within a range between any two of the numerical values ​​exemplified here.

[0015] The carboxylic acid ester Q preferably contains both a compound where n is 1 and a compound where n is 2 or greater. In this case, stable coating film dissolution and crack resistance tend to be maintained.

[0016] Examples of the carboxylic acid ester Q include methoxycarbonylmethyl ester, ethoxycarbonylmethyl ester, isopropoxycarbonylmethyl ester, n-propoxycarbonylmethyl ester, n-butoxycarbonylmethyl ester, t-butoxycarbonylmethyl ester, 2-ethylhexyloxycarbonylmethyl ester, cyclohexyloxycarbonylmethyl ester, benzyloxycarbonylmethyl ester, phenoxycarbonylmethyl ester, 2-methoxyethoxycarbonylmethyl ester, 4-methyl Di(oxycarbonylmethyl)ester, allyloxycarbonylmethyl ester, vinyloxycarbonylmethyl ester, 1-(methoxycarbonyl)ethyl ester, 1-(ethoxycarbonyl)ethyl ester, 1-(n-propoxycarbonyl)ethyl ester, 1-(isopropoxycarbonyl)ethyl ester, 1-(n-butoxycarbonyl)ethyl ester, 1-(t-butoxycarbonyl)ethyl ester, α-(methoxycarbonyl)benzyl ester, α-(ethoxycarbonyl)ester, methyldi(oxycarbonylmethyl)ester ter, ethyl di(oxycarbonylmethyl) ester, isopropyl di(oxycarbonylmethyl) ester, n-propyl di(oxycarbonylmethyl) ester, n-butyl di(oxycarbonylmethyl) ester, t-butyl di(oxycarbonylmethyl) ester, 2-ethylhexyl di(oxycarbonylmethyl) ester, cyclohexyl di(oxycarbonylmethyl) ester, benzyl di(oxycarbonylmethyl) ester, phenyl di(oxycarbonylmethyl) ester, 2-methoxyethyl di(oxycarbonylmethyl) ester , 4-methoxybutyl di(oxycarbonylmethyl) ester, allyl di(oxycarbonylmethyl) ester, vinyl di(oxycarbonylmethyl) ester, methyl di[1-(oxypolycarbonyl)ethyl] ester, ethyl di[1-(oxypolycarbonyl)ethyl] ester, n-propyl di[1-(oxypolycarbonyl)ethyl] ester, isopropyl di[1-(oxypolycarbonyl)ethyl] ester, n-butyl di[1-(oxypolycarbonyl)ethyl] ester, t-butyl di[1-(oxypolycarbonyl)ethyl] ester,Examples include methyl di[α-(oxycarbonyl)benzyl] ester and ethyl di[α-(oxycarbonyl)benzyl] ester.

[0017] The carboxylic acid ester Q is preferably a methyl di(oxycarbonylmethyl) ester, an ethyl di(oxycarbonylmethyl) ester, an isopropyl di(oxycarbonylmethyl) ester, an n-propyl di(oxycarbonylmethyl) ester, an n-butyl di(oxycarbonylmethyl) ester, a methyl di[1-(oxypolycarbonylethyl)] ester, an ethyl di[1-(oxypolycarbonylethyl)] ester, a methyl poly(oxycarbonylmethyl) ester, an ethyl poly(oxycarbonylmethyl) ester, an iso Propyl poly(oxycarbonylmethyl) ester, n-propyl poly(oxycarbonylmethyl) ester, n-butyl poly(oxycarbonylmethyl) ester, t-butyl poly(oxycarbonylmethyl) ester, 2-ethylhexyl poly(oxycarbonylmethyl) ester, cyclohexyl poly(oxycarbonylmethyl) ester, benzyl poly(oxycarbonylmethyl) ester, phenyl poly(oxycarbonylmethyl) ester, 2-methoxyethyl poly(oxycarbonylmethyl) ester, 4-methoxybutyl poly(oxycarbonylmethyl) ester nylmethyl) ester, allyl poly(oxycarbonylmethyl) ester, vinyl poly(oxycarbonylmethyl) ester, methyl poly[1-(oxypolycarbonyl)ethyl] ester, ethyl poly[1-(oxypolycarbonyl)ethyl] ester, n-propyl poly[1-(oxypolycarbonyl)ethyl] ester, isopropyl poly[1-(oxypolycarbonyl)ethyl] ester, n-butyl poly[1-(oxypolycarbonyl)ethyl] ester, t-butyl poly[1-(oxypolycarbonyl)ethyl] ester, methyl poly[α- [(oxycarbonyl)benzyl] ester, ethyl poly[α-(oxycarbonyl)benzyl] ester, and the like, and more preferred are methoxycarbonylmethyl ester, ethoxycarbonylmethyl ester, isopropoxycarbonylmethyl ester, n-propoxycarbonylmethyl ester, n-butoxycarbonylmethyl ester, 1-(methoxycarbonyl)ethyl ester, 1-(ethoxycarbonyl)ethyl ester, methyl poly(oxycarbonylmethyl) ester, ethyl poly(oxycarbonylmethyl) ester,Examples include isopropyl poly(oxycarbonylmethyl) ester, n-propyl poly(oxycarbonylmethyl) ester, n-butyl poly(oxycarbonylmethyl) ester, methyl poly[1-(oxypolycarbonylethyl)] ester, and ethyl poly[1-(oxypolycarbonylethyl)] ester.

[0018] 1-2.Copolymer A Copolymer A is a copolymer of monomer (a) and an ethylenically unsaturated monomer (b) other than monomer (a), and contains monomer units derived from monomer (a) and monomer (b). The content of monomer (a) relative to the total of monomer (a) and monomer (b) is preferably 10 to 90 mass%, more preferably 20 to 70 mass%. Specific examples include 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90 mass%, and may be within a range between any two of the values ​​exemplified here. In this case, coating film solubility is particularly good.

[0019] 1-2-1.Monomer (a) The monomer (a) is represented by the general formula (2).

[0020] [ka] (In the formula, R 4 represents hydrogen or a methyl group, and R 5 represents hydrogen, a methyl group, or a phenyl group, and R 6 represents an alkoxy group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms which may be substituted with a phenyl group, or represents a phenyl group, and n represents an integer of 1 to 10.

[0021] R 5 is preferably hydrogen or a methyl group. 6 For an explanation of 3 This is the same as the explanation above.

[0022] n represents an integer of 1 to 10, and n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and may be within a range between any two of the numerical values ​​exemplified here.

[0023] Monomer (a) includes a compound in which n is 2 or greater in general formula (2). When monomer (a) contains a compound in which n is 2 or greater, coating film solubility increases. Monomer (a) may be composed solely of a compound in which n is 2 or greater, or may be a mixture of a compound in which n is 1 and a compound in which n is 2 or greater.

[0024] The monomer (a) preferably comprises a monomer (a1) and a monomer (a2). The content of the monomer (a1) in the monomer (a) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and particularly preferably 60 to 70% by mass. The monomer (a1) has the property of increasing the coating film strength and decreasing the coating film solubility compared to the monomer (a2). Therefore, if the content of the monomer (a1) is too low, the coating film strength tends to decrease, and the coating film surface condition may be easily deteriorated after a long period of time. On the other hand, if the content of the monomer (a1) is too high, the coating film solubility may decrease, and the antifouling performance may be reduced. The content of the monomer (a1) may be, for example, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80% by mass, and may be within a range between any two of the values ​​exemplified here.

[0025] <Monomer (a1)> The monomer (a1) is a compound in which n is 1 in the general formula (2).

[0026] Examples of the monomer (a1) include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, t-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyloxycarbonylmethyl (meth)acrylate, phenoxycarbonylmethyl (meth)acrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, 4-methoxybutoxycarbonylmethyl (meth)acrylate, allyloxycarbonylmethyl (meth)acrylate, vinyloxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)(meth)acrylate,

[0044] Examples of the acrylate include 1-(ethoxycarbonyl)ethyl (meth)acrylate, 1-(n-propoxycarbonyl)ethyl (meth)acrylate, 1-(isopropoxycarbonyl)ethyl (meth)acrylate, 1-(n-butoxycarbonyl)ethyl (meth)acrylate, 1-(t-butoxycarbonyl)ethyl (meth)acrylate, α-(methoxycarbonyl)benzyl (meth)acrylate, and α-(ethoxycarbonyl)benzyl (meth)acrylate, and preferred examples include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, and 1-(ethoxycarbonyl)ethyl (meth)acrylate.

[0027] <Monomer (a2)> The monomer (a2) is a compound in which n in the general formula (2) is at least 2. n in the general formula (2) is preferably 2 to 6 from the viewpoint of long-term antifouling properties.

[0028] Monomer (a2) preferably contains both a compound in which n is 2 and a compound in which n is 3 or greater. Specifically, the mass ratio (n(2) / n(2-10)) is preferably 0.4 to 0.8, more preferably 0.5 to 0.7, calculated on a solid content basis. In this case, stable coating film dissolution tends to be sustained. Specific examples of this value are 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, and 0.80, and may be within a range between any two of the values ​​exemplified here.

[0029] Examples of the monomer (a2) include methyl di(oxycarbonylmethyl) (meth)acrylate, ethyl di(oxycarbonylmethyl) (meth)acrylate, isopropyl di(oxycarbonylmethyl) (meth)acrylate, n-propyl di(oxycarbonylmethyl) (meth)acrylate, n-butyl di(oxycarbonylmethyl) (meth)acrylate, t-butyl di(oxycarbonylmethyl) (meth)acrylate, 2-ethylhexyl di(oxycarbonylmethyl) (meth)acrylate, cyclohexyl di(oxycarbonylmethyl) (meth)acrylate, di(oxycarbonylmethyl), benzyl (meth)acrylate di(oxycarbonylmethyl), phenyl (meth)acrylate di(oxycarbonylmethyl), 2-methoxyethyl (meth)acrylate di(oxycarbonylmethyl), 4-methoxybutyl (meth)acrylate di(oxycarbonylmethyl), allyl (meth)acrylate di(oxycarbonylmethyl), vinyl (meth)acrylate di(oxycarbonylmethyl), methyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], ethyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl] )ethyl], n-propyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], isopropyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], n-butyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], t-butyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], methyl (meth)acrylate di[α-(oxycarbonyl)benzyl], ethyl (meth)acrylate di[α-(oxycarbonyl)benzyl], and preferably methyl (meth)acrylate di(oxycarbonyl) (oxycarbonylmethyl), ethyl (meth)acrylate di(oxycarbonylmethyl), isopropyl (meth)acrylate di(oxycarbonylmethyl), n-propyl (meth)acrylate di(oxycarbonylmethyl), n-butyl (meth)acrylate di(oxycarbonylmethyl), methyl (meth)acrylate di[1-(oxypolycarbonylethyl)], ethyl (meth)acrylate di[1-(oxypolycarbonylethyl)], methyl (meth)acrylate poly(oxycarbonylmethyl), ethyl (meth)acrylate poly(oxycarbonylmethyl),Isopropyl poly(oxycarbonylmethyl) (meth)acrylate, n-propyl poly(oxycarbonylmethyl) (meth)acrylate, n-butyl poly(oxycarbonylmethyl) (meth)acrylate, t-butyl poly(oxycarbonylmethyl) (meth)acrylate, 2-ethylhexyl poly(oxycarbonylmethyl) (meth)acrylate, cyclohexyl poly(oxycarbonylmethyl) (meth)acrylate, benzyl poly(oxycarbonylmethyl) (meth)acrylate, phenyl poly(oxycarbonylmethyl) (meth)acrylate, 2-methoxyethyl poly(oxycarbonylmethyl) (meth)acrylate, 4-methoxybutyl poly(oxycarbonylmethyl) (meth)acrylate, allyl poly(oxycarbonylmethyl) (meth)acrylate, vinyl poly(oxycarbonylmethyl) (meth)acrylate, methyl poly[1-(oxypolycarbonyl)ethyl] (meth)acrylate, ethyl poly[1-(oxypolycarbonyl)ethyl] (meth)acrylate, (meth) Examples thereof include n-propyl acrylate poly[1-(oxypolycarbonyl)ethyl], isopropyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], n-butyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], t-butyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], methyl (meth)acrylate poly[α-(oxycarbonyl)benzyl], and ethyl (meth)acrylate poly[α-(oxycarbonyl)benzyl], and preferably (methyl Examples of such poly(oxycarbonylmethyl) (meth)acrylate include methyl poly(oxycarbonylmethyl) (meth)acrylate, ethyl poly(oxycarbonylmethyl) (meth)acrylate, isopropyl poly(oxycarbonylmethyl) (meth)acrylate, n-propyl poly(oxycarbonylmethyl) (meth)acrylate, n-butyl poly(oxycarbonylmethyl) (meth)acrylate, methyl poly(1-(oxypolycarbonylethyl) (meth)acrylate, and ethyl poly(1-(oxypolycarbonylethyl) (meth)acrylate).

[0030] 1-2-2.Monomer (b) The monomer (b) is an ethylenically unsaturated monomer other than the monomer (a). The monomer (b) can be classified into a monomer (b1) and a monomer (b2). The monomer (b) used in the polymerization of the copolymer A includes one or both of the monomer (b1) and the monomer (b2).

[0031] <Monomer (b1)> The monomer (b1) is represented by the general formula (3). [ka] (In the formula, R 7 is hydrogen or a methyl group, R 8 ~R 10 are the same or different and each represents a branched alkyl group having 3 to 8 carbon atoms or a phenyl group.

[0032] The number of carbon atoms in the branched alkyl group is, for example, 3, 4, 5, 6, 7, or 8, and may be within a range between any two of the numbers exemplified here. Examples of branched alkyl groups include an isopropyl group, an isopropenyl group, an isobutyl group, an s-butyl group, a t-butyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 1-methylpentyl group, a 1,1-dimethylpropyl group, a 1,1-dimethylbutyl group, a thexyl group, a cyclohexyl group, a 1,1-dimethylpentyl group, a 1-methylhexyl group, a 1,1-dimethylhexyl group, a 1-methylheptyl group, a 2-methylbutyl group, a 2-ethylbutyl group, a 2,2-dimethylpropyl group, a cyclohexylmethyl group, a 2-ethylhexyl group, a 2-propylpentyl group, and a 3-methylpentyl group. R 8 ~R 10 are preferably the same or different and are an isopropyl group, an isopropenyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group, and particularly preferably are an isopropyl group and a 2-ethylhexyl group.

[0033] Examples of the monomer (b1) include triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, triphenylsilyl meth(meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyl-s-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, isopropyldiisobutylsilyl (meth)acrylate, isopropyldi-s-butylsilyl (meth)acrylate, t-butyldiisobutylsilyl (meth)acrylate, and (meth)acrylate. Examples of the monomer (c) include (meth)acrylic acid silyl esters such as t-butyldiisopentylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, diisopropylthexylsilyl (meth)acrylate, diisopropylcyclohexylsilyl (meth)acrylate, tricyclohexylsilyl (meth)acrylate, tri-1,1-dimethylpentylsilyl (meth)acrylate, tri-2,2-dimethylpropylsilyl (meth)acrylate, tricyclohexylmethylsilyl (meth)acrylate, diisopropylcyclohexylmethylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, and tri-2-propylpentylsilyl (meth)acrylate. These monomers (c) can be used alone or in combination of two or more.

[0034] <Monomer (b2)> Monomer (b2) is obtained by removing monomer (b1) from monomer (b). In other words, monomer (b2) is a monomer not represented by any of general formulas (2) to (3). Examples of monomer (b2) include (meth)acrylic acid esters not represented by general formulas (2) to (3), vinyl compounds, aromatic compounds, and dialkyl ester compounds of dibasic acids. In this specification, (meth)acrylic acid esters refer to acrylic acid esters or methacrylic acid esters.

[0035] Examples of (meth)acrylic acid esters not represented by the general formulas (2) and (3) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 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, and (meth)acrylic acid esters such as 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, and N,N'-dimethyl(meth)acrylamide.

[0036] Examples of vinyl compounds include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.

[0037] Examples of aromatic compounds include styrene, vinyltoluene, and α-methylstyrene.

[0038] Examples of dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

[0039] In copolymer A, these monomers (b) can be used alone or in combination of two or more. From the viewpoint of coating film solubility and coating film physical properties, it is preferable that monomer (b) contains a (meth)acrylic acid ester of monomer (b1) or monomer (b2). From the viewpoint of crack resistance, it is preferable that monomer (b) contains a (meth)acrylic acid ester of monomer (b2), and more preferably contains methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-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, or the like. From the viewpoint of coating film solubility, the monomer (b) preferably contains a monomer (b1), and more preferably contains triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, or the like.

[0040] 1-2-3. Properties and manufacturing method of copolymer A The weight-average molecular weight (Mw) of copolymer A is preferably 5,000 to 300,000. If the molecular weight is less than 5,000, the coating film of the antifouling coating becomes brittle and prone to peeling and cracking, while if it exceeds 300,000, the viscosity of the polymer solution increases, making it difficult to handle. Specific examples of Mw include 5,000, 10,000, 20,000, 25,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000, and 300,000, and may be within a range between any two of the values ​​exemplified here.

[0041] The Mw can be measured by, for example, gel permeation chromatography (GPC).

[0042] Copolymer A may be any of a random copolymer, an alternating copolymer, a periodic copolymer, and a block copolymer of monomer (a) and monomer (b).

[0043] Copolymer A can be obtained, for example, by polymerizing monomer (a) and monomer (b) in the presence of a polymerization initiator.

[0044] Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, and 2,2'-azobis(N-butyl-2-methylpropionamide); benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, and 1 Examples of suitable polymerization initiators include peroxides such as 1,3,3-tetramethylbutylperoxyneodecanoate, t-amylperoxyneodecanoate, t-hexylperoxypivalate, t-amylperoxypivalate, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate. These polymerization initiators can be used alone or in combination of two or more. Particularly preferred 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-tetramethylbutylperoxy-2-ethylhexanoate. The molecular weight of copolymer A can be adjusted by appropriately setting the amount of polymerization initiator used.

[0045] Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization, etc. Among these, solution polymerization or non-aqueous dispersion polymerization is particularly preferred because it allows copolymer A to be obtained easily and accurately.

[0046] In the polymerization reaction, an organic solvent may be used if necessary. The organic solvent is not particularly limited, but examples thereof include 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 isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, butyl acetate, isobutyl acetate, butyl alcohol, 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.

[0047] The reaction temperature in the polymerization reaction may be appropriately set depending on the type of polymerization initiator, etc., and is usually 50 to 160°C, and preferably 60 to 150°C.

[0048] The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.

[0049] The content of copolymer A in the composition of the present invention is not particularly limited, but the mass ratio (carboxylic acid ester Q / copolymer A) of the content relative to carboxylic acid ester Q, calculated as solid content, is usually 0.01 to 0.9, and preferably 0.05 to 0.4. This mass ratio may be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, and may be within a range between any two of the values ​​exemplified here.

[0050] 1-3.Copolymer B Copolymer B is a copolymer of monomer (b1) and monomer (b2) and contains monomer units derived from monomer (b1) and monomer (b2). The content of monomer (b1) relative to the total of monomer (b1) and monomer (b2) is preferably 10 to 90 mass%, more preferably 20 to 70 mass%. Specific examples include 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, and 90 mass%, and may be within a range between any two of the values ​​exemplified here. In this case, coating film solubility is particularly good.

[0051] The polymerization method, initiator, solvent, temperature, other conditions, and method for measuring Mw can be the same as those described for Copolymer A. The content of copolymer B in the composition of the present invention is not particularly limited, but the mass ratio (carboxylic acid ester Q / copolymer B) of the content relative to carboxylic acid ester Q, calculated as solid content, is usually 0.01 to 0.9, and preferably 0.05 to 0.4. This mass ratio may be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, and may be within a range between any two of the values ​​exemplified here.

[0052] 1-4.Copolymer C Copolymer C is a copolymer of monomer (b2). The polymerization method, initiator, solvent, temperature, other conditions, and method for measuring Mw can be the same as those described for Copolymer A. The content of copolymer C in the composition of the present invention is not particularly limited, but the mass ratio (carboxylic acid ester Q / copolymer C) of the content relative to carboxylic acid ester Q, calculated as solid content, is usually 0.01 to 0.9, and preferably 0.05 to 0.4. This mass ratio may be, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, or may be within a range between any two of the values ​​exemplified here.

[0053] 1-5. Antifouling agents Antifouling agents include, for example, inorganic agents and organic agents. Examples of inorganic agents include cuprous oxide, copper thiocyanate (common name: copper rhodanide), copper powder, etc. Among these, cuprous oxide and copper rhodanide are particularly preferred, and cuprous oxide that has been surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc. is more preferred in terms of long-term storage stability. Examples of organic agents include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylenebisdithiocarbamate (generic name: zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: She-Nine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea 28), and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (generic name: medetomidine). These antifouling agents can be used alone or in combination of two or more.

[0054] 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 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, or 60 mass %, and may be within a range between any two of the values ​​exemplified here.

[0055] 1-6. Other additives Furthermore, if necessary, other resin components than copolymers A, B, and C, elution regulators, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents, thixotropic agents, organic solvents, etc. can be added to the resin for antifouling coating materials of the present invention to form an antifouling coating material.

[0056] Examples of other resin components include polyester resins, vinyl resins, petroleum resins, metal-containing resins, zwitterionic compound-containing resins, silicone resins, and alicyclic hydrocarbon resins.

[0057] Examples of the elution modifier include rosin, hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, polymerized rosin, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof, monocarboxylic acid and its salts, or the alicyclic hydrocarbon resins. These can be used alone or in combination of two or more.

[0058] Examples of the plasticizer include phosphate esters, phthalate esters, adipate esters, sebacate esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, etc. These can be used alone or in combination of two or more.

[0059] Examples of the dehydrating agent include calcium sulfate, synthetic zeolite adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, carbodiimidazoles, etc. These can be used alone or in combination of two or more.

[0060] 2. Method for producing antifouling coating composition The antifouling coating composition of the present invention can be produced, for example, by mixing and dispersing a mixture containing carboxylic acid ester Q, an antifouling agent, and optionally at least one of copolymers A to C, and other additives, using a disperser.

[0061] As the dispersing machine, for example, a machine that can be used as a fine grinding machine can be suitably used. For example, a commercially available homomixer, sand mill, bead mill, disperser, etc. can be used. Alternatively, the mixed liquid may be mixed and dispersed using a container equipped with a stirrer and containing glass beads for mixing and dispersion.

[0062] 3. Antifouling treatment method, antifouling coating film, and coated object The antifouling treatment method of the present invention uses the above antifouling coating composition to form an antifouling coating film on the surface of an object to be coated. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface, allowing the coating surface to be constantly renewed, thereby preventing the adhesion of aquatic fouling organisms. Examples of objects on which a coating film is formed include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like. The thickness of the antifouling coating film may be appropriately set depending on the type of 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 a ship, the thickness of the antifouling coating film is usually 50 to 700 μm, and preferably 100 to 600 μm. [Example]

[0063] The following examples will be given to further clarify the features of the present invention, but the present invention is not limited to these examples. In each Production Example, Example, and Comparative Example, % represents % by mass. The weight average molecular weight (Mw) is a value determined by GPC (polystyrene equivalent value). The GPC conditions are as follows. Equipment: Tosoh Corporation HLC-8220GPC Columns: TSKgel SuperHZM-M (2 columns) Flow rate...0.35mL / min Detector: RI Column thermostatic bath temperature: 40°C Eluent...THF The heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Paint component testing method - heating residue."

[0064] 1. Manufacturing example 1-1. Example of producing carboxylic acid ester solution A carboxylic acid ester solution containing carboxylic acid ester Q was prepared according to the following method.

[0065] <Production Example 1 (Production of Carboxylic Acid Ester Solution q-1)> A four-neck flask equipped with a thermometer, condenser, stirrer, and dropping funnel was charged with 109 g (1.00 mol) of methyl chloroacetate, 335 g of Chinese gum rosin (WW), and 500 g of xylene, and 101 g (1.00 mol) of triethylamine was added dropwise while stirring, maintaining the temperature below 40°C. After the addition was complete, the mixture was stirred at 70-80°C for 6 hours. After the reaction was complete, the organic layer was washed with tap water, hydrochloric acid, and sodium bicarbonate water, and the solvent was removed by vacuum concentration to obtain 734 g of a 50% xylene solution of carboxylic acid ester (carboxylic acid ester solution q-1).

[0066] <Production Examples 2 to 5 (Production of Carboxylic Acid Ester Solutions q-2 to q-5)> Carboxylic acid ester solutions q-2 to q-5 were obtained by carrying out reactions in the same manner as in Production Example Q1 using the raw materials shown in Table 1. The reaction conditions and yields of Production Examples 1 to 5 are shown in Table 1.

[0067] [Table 1]

[0068] <Production Example 6 (Production of Carboxylic Acid Ester q-6)> (First reaction) A four-necked flask equipped with a thermometer, a condenser, and a stirrer was charged with 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone, and the mixture was stirred for 6 hours at 70 to 80° C. After completion of the reaction, 500 ml of toluene was charged to the reaction solution, and the organic layer was washed with tap water, hydrochloric acid, and sodium bicarbonate water in that order. The solvent was then distilled off by concentration under reduced pressure, yielding 262 g of methoxycarbonylmethyl chloroacetate.

[0069] (Second reaction) Next, a four-neck flask equipped with a thermometer, condenser, stirrer, and dropping funnel was charged with 200 g (1.20 mol) of methoxycarbonylmethyl chloroacetate (the product of the first reaction), 401 g of Chinese gum rosin (WW), and 500 g of xylene, and 122 g (1.20 mol) of triethylamine was added dropwise while stirring, maintaining the temperature below 40°C. After the addition was complete, the mixture was stirred at 70-80°C for 6 hours. After the reaction was complete, the organic layer was washed with tap water, hydrochloric acid, and sodium bicarbonate water, and the solvent was removed by vacuum concentration to obtain 962 g of a 50% xylene solution of carboxylic acid ester (carboxylic acid ester solution q-6).

[0070] <Production Examples 7 to 30 (Production of Carboxylic Acid Ester Solutions q-7 to q-30)> Using the raw materials shown in Table 2, reactions were carried out in the same manner as in Production Example 6 to obtain carboxylic acid ester solutions q-7 to q-30 shown in Table 2. The reaction conditions and yields of Production Examples 6 to 30 are shown in Table 2.

[0071] [Table 2]

[0072] Details of the raw materials in Tables 1 and 2 are as follows: CAMe: methyl chloroacetate CAEt: ethyl chloroacetate Gum rosin: Chinese gum rosin (WW) Hydrogenated rosin: Product name "Hypal CH" (manufactured by Arakawa Chemical Industries, Ltd.) Versatic acid: Trade name "Neodecanoic acid" (Fujifilm Wako Pure Chemical Industries, Ltd.) Naphthenic acid: Fujifilm Wako Pure Chemical Industries, Ltd. TEA: Triethylamine CANa: Sodium monochloroacetate NMP: N-methyl-2-pyrrolidone

[0073] 1-2. Example of production of monomer (a1) Monomer (a1) was produced according to the following method.

[0074] <Production Example 31 (Production of Monomer a1-1)> A four-neck flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was charged with 109 g (1.00 mol) of methyl chloroacetate, 72 g (1.00 mol) of acrylic acid, 0.1 g of 4-methoxyphenol, and 500 g of ethyl acetate, and 101 g (1.00 mol) of triethylamine was added dropwise while stirring, keeping the temperature below 40°C. After the addition was complete, the mixture was stirred at 70-80°C for 6 hours. After the reaction was complete, the organic layer was washed with tap water, hydrochloric acid, and sodium bicarbonate water, in that order, and the solvent was then removed by vacuum concentration to obtain 129.7 g of monomer a1-1. <Production Examples 32 to 33 (Production of Monomers a1-2 to a1-3)> Monomers a1-2 to a1-3 were obtained by carrying out the reaction using the raw materials shown in Table 3 in the same manner as in Production Example 31. Table 3 shows the reaction conditions and yields of Production Examples 31 to 33.

[0075] [Table 3]

[0076] 1-3. Example of production of monomer (a2) Monomer (a2) was produced according to the following method.

[0077] <Production Example 34 (Production of Monomer a2-1)> (First reaction) A four-necked flask equipped with a thermometer, a condenser, and a stirrer was charged with 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone, and the mixture was stirred for 6 hours at 70 to 80° C. After completion of the reaction, 500 ml of toluene was charged to the reaction solution, and the organic layer was washed with tap water, hydrochloric acid, and sodium bicarbonate water in that order. The solvent was then distilled off by concentration under reduced pressure, yielding 262 g of methoxycarbonylmethyl chloroacetate.

[0078] (Second reaction) Next, a four-neck flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel was charged with 200 g (1.20 mol) of methoxycarbonylmethyl chloroacetate (the product of the first reaction), 87 g (1.20 mol) of acrylic acid, 0.1 g of 4-methoxyphenol, and 500 g of ethyl acetate, and 122 g (1.20 mol) of triethylamine was added dropwise while stirring, keeping the temperature below 40°C. After the addition was complete, the mixture was stirred at 70-80°C for 6 hours. After the reaction was complete, the organic layer was washed with tap water, hydrochloric acid, and sodium bicarbonate water, in that order, and the solvent was then removed by vacuum concentration to obtain 230.6 g of monomer a2-1.

[0079] <Production Examples 35 to 48 (Production of Monomers a2-2 to a2-15)> Monomers a2-2 to a2-15 shown in Table 4 were obtained by carrying out the reaction using the raw materials shown in Table 4 in the same manner as in Production Example 34. The reaction conditions and yields of Production Examples 34 to 48 are shown in Table 4.

[0080] [Table 4]

[0081] Details of the raw materials in Tables 3 and 4 are as follows: CAMe: methyl chloroacetate CAEt: ethyl chloroacetate AA: acrylic acid MAA: methacrylic acid TEA: Triethylamine CANa: Sodium monochloroacetate NMP: N-methyl-2-pyrrolidone MEHQ: 4-methoxyphenol

[0082] 1-4. Example of copolymer solution production A copolymer solution containing at least one of Copolymers A to C was produced according to the method described below.

[0083] <Production Example P1 (Production of Copolymer Solution A-1)> A four-neck flask equipped with a thermometer, condenser, stirrer, and dropping funnel was charged with 80 g of xylene and 20 g of 1-butanol as solvents, and nitrogen gas was introduced while stirring and maintaining the temperature at 88°C. A mixture of monomers (a) and (b) in the amounts (g) shown in Table 5 and 2.0 g (initial addition) of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator was added dropwise over 3 hours while maintaining the temperature at 88°C. After stirring at 88°C for 1 hour, 0.1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every hour. The mixture was then stirred at the same temperature for another 2 hours and then cooled to room temperature to obtain copolymer solution A-1. The heating residue and Mw of A-1 are shown in Table 5.

[0084] <Production Examples P2 to P11 (Production of Copolymer Solutions A-2 to A-8, B-1 to B-2, and C-1)> Copolymer solutions A-2 to A-8, B-1 to B-2, and C-1 were obtained by carrying out the polymerization reaction in the same manner as in Production Example P1, except that the monomers and solvents shown in Table 5 were used. The heating residue and Mw of each polymer are shown in Table 5. The numerical values ​​for the amounts of raw materials blended in the table are in grams.

[0085] [Table 5]

[0086] 1-5.Other manufacturing examples <Production Example 49 (Production of gum rosin solution)> 300 g of Chinese gum rosin (WW) and 310 g of xylene were placed in a flask equipped with a thermometer, reflux condenser, and stirrer, and the mixture was refluxed under reduced pressure at 70-80°C for 1 hour to dehydrate, yielding a xylene solution of gum rosin (brown, transparent liquid, 50% solids). The residual content of the resulting solution was 50.3%.

[0087] <Production Example 50 (Production of Rosin Zinc Salt Solution)> 240 g of Chinese gum rosin (WW) and 360 g of xylene were placed in a flask equipped with a thermometer, reflux condenser, and stirrer. 120 g of zinc oxide was then added so that all of the resin acid in the rosin would form zinc salts. The mixture was refluxed and dehydrated under reduced pressure at 70-80°C for 3 hours. The mixture was then cooled and filtered to obtain a xylene solution of rosin zinc salt (a dark brown, transparent liquid with a solid content of 50%). The residual content of the resulting solution was 50.2%.

[0088] 2. Examples and Comparative Examples (Production of Coating Compositions) The components shown in Tables 6 to 9 were blended in the proportions (mass %) shown in the tables, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce coating compositions.

[0089] [Table 6]

[0090] [Table 7]

[0091] [Table 8]

[0092] [Table 9]

[0093] Details of the components in the table are as follows:

[0094] <Dissolution modifier> Rosin zinc salt solution: Use the solution prepared in Example 50 Gum rosin solution: Use the solution prepared in Example 49

[0095] <Anti-fouling agent> Cuprous oxide: Product name "NC-301" (manufactured by Nisshin Chemco Co., Ltd.) Copper pyrithione: Product name "Copper Omajin" (manufactured by LONZA Corporation) Sea Nine: Brand name "Sea Nine 211", 4,5-dichloro-2-octyl-4-isothiazolin-3-one (manufactured by R&H), 30% active ingredient in xylene solution Zineb: [ethylenebis(dithiocarbamate)] zinc (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Zinc pyrithione: (manufactured by LONZA Corporation) Econea: Trade name "Econea 028" 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP) Medetomidine: (±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (Wako Pure Chemical Industries, Ltd.)

[0096] <Other additives> Bengala: Product name: "Bengara Gold" (manufactured by Morishita Bengala Kogyo Co., Ltd.) Talc: Product name "Talc MS" (manufactured by Nippon Talc Co., Ltd.) Zinc oxide: Product name "Zinc Oxide Type 2" (manufactured by Seido Chemical Industry Co., Ltd.) Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.) Disparlon A603-20X: Amide-based thixotropic agent: Product name "Disparlon A603-20X" (Kusumoto Chemicals Co., Ltd.) Tetraethoxysilane: Product name "Ethyl Silicate 28" (manufactured by Colcoat Co., Ltd.) Rosin ester: Product name "Ester Gum AA-L" (manufactured by Arakawa Chemical Industries)

[0097] 3. Evaluation The coating compositions of the Examples and Comparative Examples were subjected to the following tests, the results of which are shown in Tables 6 to 9.

[0098] As shown in Tables 6 to 9, all of the Examples were superior to all of the Comparative Examples in at least one of the rotary test and the antifouling test.

[0099] <Test Example 1 (Rotary Test)> A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the tank and was rotated by a motor. It was also equipped with a cooling device to keep the seawater temperature constant and an automatic pH controller to keep the seawater pH constant.

[0100] Test panels were prepared according to the following method.

[0101] First, an anti-rust paint (epoxy vinyl A / C) was applied to a titanium plate (71 × 100 × 0.5 mm) to a dry thickness of approximately 100 μm, and then dried to form an anti-rust coating film. Then, the coating compositions obtained in the examples and comparative examples were applied to a dry film thickness of approximately 400 μm, and the plate was dried at 40°C for 3 days to prepare a test plate.

[0102] The test plate was fixed to the rotating drum of the rotating device of the above-mentioned equipment so that it would come into contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this time, the seawater temperature was kept at 25°C and the pH at 8.0 to 8.2, and the seawater was replaced every two weeks.

[0103] The remaining film thickness of each test panel was measured initially and every six months after the start of the test using a Keyence VK-X100 shape measuring laser microscope, and the amount of dissolved film per month (μm / month) was obtained by calculating the difference between the measured values. In addition, when measuring the remaining film thickness after 36 months of rotary testing, the surface of each coating was observed with the naked eye and with a microscope to evaluate the surface condition of the coating.

[0104] The coating surface condition was evaluated according to the following criteria. ◎: No abnormalities at all ○: Hair cracks are observed on less than 10% of the total coating surface area △: Hair cracks are observed on 10-30% of the total coating surface area. ×: Hair cracks are observed on more than 30% of the total surface area of ​​the coating film.

[0105] <Test Example 2 (Anti-fouling test)> The coating compositions obtained in the Examples and Comparative Examples were applied to both sides of a rigid PVC board (100 x 200 x 2 mm) to a dry coating thickness of approximately 300 μm. The resulting coating was dried at room temperature (25°C) for 3 days to produce a test board with a dry coating thickness of approximately 300 μm. This test board was immersed 1.5 m below sea level in Owase City, Mie Prefecture, and the damage to the test board by deposits was observed after 12 and 24 months.

[0106] The evaluation was carried out by visually observing the state of the coating surface and was judged according to the following criteria. ◎: No adhesion of fouling organisms such as shellfish or algae, and almost no slime. ○: No fouling organisms such as shellfish or algae are attached, and although there is a thin layer of slime (enough to make the coating surface visible), it can be removed by lightly wiping with a brush. △: No adhesion of fouling organisms such as shellfish or algae, but the slime is so thick that the coating surface is not visible and cannot be removed even by wiping vigorously with a brush. ×: Level of fouling organisms such as shellfish and algae adhering

Claims

1. An antifouling coating composition containing a carboxylic acid ester Q represented by general formula (1) and an antifouling agent, The antifouling coating composition comprises at least one of copolymer A, copolymer B, and copolymer C, The copolymer A is a copolymer of a monomer (a) represented by general formula (2) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer (a) includes a compound in which n in the general formula (2) is 2 or more, the monomer (b) is composed of a monomer (b1) and a monomer (b2) other than the monomer (b1); The monomer (b1) is represented by general formula (3): The copolymer B is a copolymer of the monomer (b1) and the monomer (b2), The copolymer C is a copolymer of a (meth)acrylic acid ester, The antifouling coating composition, wherein the (meth)acrylic acid ester comprises 2-methoxyethyl (meth)acrylate. 【Chemistry 1】 (In the formula, R 1 represents a gum rosin acid residue, a hydrogenated rosin acid residue, a disproportionated rosin acid residue, a versatic acid residue, or a naphthenic acid residue; R ２ represents hydrogen, a methyl group, or a phenyl group; R ３ represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of 1 to 10. 【Chemistry 2】 (In the formula, R 4 represents hydrogen or a methyl group, R 5 represents hydrogen, a methyl group, or a phenyl group, R 6 represents a phenyl group or an alkyl group having 1 to 8 carbon atoms 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.) 【Transformation 3】 (wherein R 7 is hydrogen or a methyl group, and R 8 to R 10 are the same or different and each represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group).

2. The antifouling coating composition according to claim 1, An antifouling coating composition comprising copolymer A.

3. An antifouling coating composition according to claim 1 or claim 2, An antifouling coating composition comprising copolymer B.

4. An antifouling coating composition according to any one of claims 1 to 3, An antifouling coating composition comprising copolymer C.

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