Patent Description:
Aquatic fouling organisms such as barnacles, tubeworms, common mussels, Bugula neritina, sea squirts, green laver, sea lettuce, and slimes adhere to ships (especially, on the bottom of ships), fishing tools such as fishing nets and fishing net accessories, and underwater structures such as power plant aqueducts, thereby causing problems such as impaired functionality and appearance of the ships and the like. Examples may be found in Patent Literature <NUM>-<NUM>.

In order to prevent such problems, there are known techniques in which an antifouling coating composition is applied onto a ship or the like to form an antifouling coating film such that an antifouling agent is gradually released from the antifouling coating film, which allows antifouling performance to be exhibited over a long period of time (Patent Literature <NUM>).

However, even with the technique of Patent Literature <NUM>, coating film dissolution at the initial stage may become excessively large or coating film defects such as cracks may occur after a relatively short period of time, so there is a need for further improvement.

The present invention has been made in view of such circumstances, and provides an antifouling coating composition capable of maintaining a stable coating film dissolution rate in seawater over a long period of time, and capable of maintaining stable antifouling performance without causing coating film defects such as cracks.

According to the present invention, there is provided an antifouling coating composition comprising a carboxylic acid ester Q represented by general formula (<NUM>) and an antifouling agent.

As a result of diligent research to solve the above problems, the present inventors have found that the composition comprising the carboxylic acid ester Q can solve the above problems and have completed the present invention.

An antifouling coating composition of the present invention contains a carboxylic acid ester Q and an antifouling agent which is selected from cuprous oxide, copper thiocyanate, copper powder, copper <NUM>-mercaptopyridine-N-oxide, zinc <NUM>-mercaptopyridine-N-oxide, zinc ethylene-bis-dithiocarbamate, <NUM>,<NUM>-dichloro-<NUM>-n-octyl-<NUM>-isothiazolone, <NUM>,<NUM>-dichlorophenyl-N,N-dimethylurea, <NUM>-methylthio-<NUM>-t-butylamino-<NUM>-cyclopropylamino-s-triazine, <NUM>-(p-chlorophenyl)-<NUM>-cyano-<NUM>-bromo-<NUM>-trifluoromethylpyrrole, and <NUM>-[<NUM>-(<NUM>,<NUM>-dimethylphenyl)ethyl]-<NUM>-imidazole, and preferably contains at least one of a copolymer A, a copolymer B, and a copolymer C.

The carboxylic acid ester Q is represented by general formula (<NUM>). <CHM>
wherein R<NUM> 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<NUM> represents hydrogen, a methyl group, or a phenyl group, R<NUM> is an alkyl group having <NUM> to <NUM> carbon atoms optionally substituted with an alkoxy group having <NUM> to <NUM> carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of <NUM> to <NUM>.

R<NUM> is a gum rosin acid residue, a hydrogenated rosin acid residue, a disproportionated rosin acid residue, a versatic acid residue, or a naphthenic acid residue. Still more preferably R<NUM> may be a gum rosin acid residue or a hydrogenated rosin acid residue.

The number of carbon atoms in the alkoxy group or alkyl group of R<NUM> is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here. R<NUM> is, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a t-butyl group, a <NUM>-ethylhexyl group, a cyclohexyl group, a benzyl group, a phenyl group, a <NUM>-methoxyethyl group, a <NUM>-methoxybutyl group, a vinyl group, or an allyl group, and is preferably a methyl group, an ethyl group, an isopropyl group, or a n-butyl group.

n represents an integer of <NUM> to <NUM>, and preferably <NUM> to <NUM>, from the viewpoint of long-term antifouling property. n is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here.

The carboxylic acid ester Q preferably contains both a compound in which n is <NUM> and a compound in which n is <NUM> or more. In this case, stable dissolution of coating film and crack resistance tend to continue.

Examples of the carboxylic acid ester Q include methoxycarbonylmethyl ester, ethoxycarbonylmethyl ester, n-propoxycarbonylmethyl ester, n-butoxycarbonylmethyl ester, t-butoxycarbonylmethyl ester, <NUM>-ethylhexyloxycarbonylmethyl ester, cyclohexyloxycarbonylmethyl ester, benzyloxycarbonylmethyl ester, phenoxycarbonylmethyl ester, <NUM>-methoxyethoxycarbonylmethyl ester, <NUM>-methoxybutoxycarbonylmethyl ester, allyloxycarbonylmethyl ester, vinyloxycarbonylmethyl ester, <NUM>-(methoxycarbonyl)ethyl ester, <NUM>-(ethoxycarbonyl)ethyl ester, <NUM>-(n-propoxycarbonyl)ethyl ester, <NUM>-(isopropoxycarbonyl)ethyl ester, <NUM>-(n-butoxycarbonyl)ethyl ester, <NUM>-(t-butoxycarbonyl)ethyl ester, α-(methoxycarbonyl)benzyl ester, α-(ethoxycarbonyl)ester, methyldi(oxycarbonylmethyl) ester, ethyldi(oxycarbonylmethyl) ester, isopropyldi(oxycarbonylmethyl) ester, n-propyldi(oxycarbonylmethyl) ester, n-butyldi(oxycarbonylmethyl) ester, t-butyldi(oxycarbonylmethyl) ester, <NUM>-ethylhexyldi(oxycarbonylmethyl) ester, cyclohexyldi(oxycarbonylmethyl) ester, benzyldi(oxycarbonylmethyl) ester, phenyldi(oxycarbonylmethyl) ester, <NUM>-methoxyethyldi(oxycarbonylmethyl) ester, <NUM>-methoxybutyldi(oxycarbonylmethyl) ester, allyldi(oxycarbonylmethyl) ester, vinyldi(oxycarbonylmethyl) ester, methyldi[<NUM>-(oxypolycarbonyl)ethyl] ester, ethyldi[<NUM>-(oxypolycarbonyl)ethyl]ester, n-propyldi[<NUM>-(oxypolycarbonyl)ethyl]ester, isopropyldi[<NUM>-(oxypolycarbonyl)ethyl] ester, n-butyldi[<NUM>-(oxypolycarbonyl)ethyl] ester, t-butyldi[<NUM>-(oxypolycarbonyl)ethyl] ester, methyldi[α-(oxycarbonyl)benzyl] ester, and ethyldi[α-(oxycarbonyl)benzyl] ester of carboxylic acids.

Preferred examples of the carboxylic acid ester Q include methyldi(oxycarbonylmethyl) ester, ethyldi(oxycarbonylmethyl) ester, isopropyldi(oxycarbonylmethyl) ester, isopropyldi(oxycarbonylmethyl) ester, n-propyldi(oxycarbonylmethyl) ester, n-butyldi(oxycarbonylmethyl) ester, methyldi[<NUM>-(oxypolycarbonylethyl)] ester, ethyl di[<NUM>-(oxypolycarbonylethyl)] ester, methylpoly(oxycarbonylmethyl) ester, ethyl poly(oxycarbonylmethyl) ester, isopropyl poly(oxycarbonylmethyl) ester, n-propyl poly(oxycarbonylmethyl) ester, n-butyl poly(oxycarbonylmethyl) ester, t-butyl poly(oxycarbonylmethyl) ester, <NUM>-ethylhexyl poly(oxycarbonylmethyl) ester, cyclohexylpoly(oxycarbonylmethyl) ester, benzylpoly(oxycarbonylmethyl) ester, phenylpoly(oxycarbonylmethyl) ester, <NUM>-methoxyethyl poly(oxycarbonylmethyl) ester, <NUM>-methoxybutyl poly(oxycarbonylmethyl) ester, allyl poly(oxycarbonylmethyl) ester, vinylpoly(oxycarbonylmethyl) ester, methylpoly[<NUM>-(oxypolycarbonyl)ethyl] ester, ethylpoly[<NUM>-(oxypolycarbonyl)ethyl] ester, n-propyl poly[<NUM>-(oxypolycarbonyl)ethyl] ester, isopropylpoly[<NUM>-(oxypolycarbonyl)ethyl] ester, n-butylpoly[<NUM>-(oxypolycarbonyl)ethyl] ester, t-butylpoly[<NUM>-(oxypolycarbonyl)ethyl] ester, methylpoly[α-(oxycarbonyl)benzyl] ester, andethylpoly[α-(oxycarbonyl)benzyl] ester; and still more preferred examples thereof include methoxycarbonylmethyl ester, ethoxycarbonylmethyl ester, isopropoxycarbonylmethyl ester, n-propoxycarbonylmethyl ester, n-butoxycarbonylmethyl ester, <NUM>-(methoxycarbonyl)ethyl ester, <NUM>-(ethoxycarbonyl)ethyl ester, methylpoly(oxycarbonylmethyl) ester, ethylpoly(oxycarbonylmethyl) ester, isopropylpoly(oxycarbonylmethyl) ester, n-propylpoly(oxycarbonylmethyl) ester, n-butylpoly(oxycarbonylmethyl) ester, methylpoly[<NUM>-(oxypolycarbonylethyl)] ester, and ethylpoly[<NUM>-(oxypolycarbonylethyl)] ester.

The copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and contains monomer units derived from the monomer (a) and the monomer (b). The content of the monomer (a) with respect to the total of the monomer (a) and the monomer (b) is preferably <NUM> to <NUM>% by mass, and still more preferably <NUM> to <NUM>% by mass. Specifically, the content thereof is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>% by mass, and may be within the range between any two numerical values exemplified here. In this case, the coating film dissolubility is particularly good.

The monomer (a) is represented by general formula (<NUM>). <CHM>
wherein R<NUM> represents a methyl group, R<NUM> represents hydrogen, a methyl group, or a phenyl group, R<NUM> is an alkyl group having <NUM> to <NUM> carbon atoms optionally substituted with an alkoxy group having <NUM> to <NUM> carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of <NUM> to <NUM>.

R<NUM> is preferably hydrogen or a methyl group. The description of R<NUM> is similar to that of R<NUM>.

n represents an integer of <NUM> to <NUM>, and n is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here.

The monomer (a) contains a compound represented by general formula (<NUM>) in which n is <NUM> or more. When the compound in which n is <NUM> or more is contained as the monomer (a), the coating film dissolubility is increased. The monomer (a) may only be constituted by a compound in which n is <NUM> or more, or may be a mixture of a compound in which n is <NUM> and a compound in which n is <NUM> or more.

The monomer (a) is preferably constituted by a monomer (a1) and a monomer (a2). The content of the monomer (a1) in the monomer (a) is preferably <NUM> to <NUM>% by mass, more preferably <NUM> to <NUM>% by mass, and particularly preferably <NUM> to <NUM>% by mass. The monomer (a1) has the property of increasing the coating film strength and decreasing the coating film dissolubility as compared with the monomer (a2). Therefore, when the content of the monomer (a1) is too small, the strength of the coating film tends to decrease, and the coating film surface condition may deteriorate after a long period of time. On the other hand, when the content of the monomer (a1) is too large, the coating film dissolubility decreases, and the antifouling performance may deteriorate. The content of the monomer (a1) is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>% by mass, and may be within the range between any two numerical values exemplified here.

The monomer (a1) is a compound represented by general formula (<NUM>) in which n is <NUM>.

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, <NUM>-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyloxycarbonylmethyl (meth)acrylate, phenoxycarbonylmethyl (meth)acrylate, <NUM>-methoxyethoxycarbonylmethyl (meth)acrylate, <NUM>-methoxybutoxycarbonylmethyl (meth)acrylate, allyloxycarbonylmethyl (meth)acrylate, vinyloxycarbonylmethyl (meth)acrylate, <NUM>-(methoxycarbonyl)ethyl (meth)acrylate, <NUM>-(ethoxycarbonyl)ethyl (meth)acrylate, <NUM>-(n-propoxycarbonyl)ethyl (meth)acrylate, <NUM>-(isopropoxycarbonyl)ethyl (meth)acrylate, <NUM>-(n-butoxycarbonyl)ethyl (meth)acrylate, <NUM>-(t-butoxycarbonyl)ethyl (meth)acrylate,α-(methoxycarbonyl)benzyl (meth)acrylate, and α-(ethoxycarbonyl)benzyl (meth)acrylate, and preferred examples thereof include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, <NUM>-(methoxycarbonyl)ethyl (meth)acrylate, and <NUM>-(ethoxycarbonyl)ethyl (meth)acrylate.

The monomer (a2) is a compound represented by general formula (<NUM>) in which n is <NUM> or more. n in general formula (<NUM>) is preferably <NUM> to <NUM> from the viewpoint of long-term antifouling property.

The monomer (a2) preferably contains both a compound in which n is <NUM> and a compound in which n is <NUM> or more. Specifically, the mass ratio (n(<NUM>)/n(<NUM> to <NUM>)) in terms of solid content is preferably, for example, <NUM> to <NUM>, and more preferably <NUM> to <NUM>. In this case, stable dissolution of the coating film tends to continue. Specifically, the value is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here.

Examples of the monomer (a2) include di(oxycarbonylmethyl) methyl (meth)acrylate, di(oxycarbonylmethyl) ethyl (meth)acrylate, di(oxycarbonylmethyl) isopropyl (meth)acrylate, di(oxycarbonylmethyl) n-propyl (meth)acrylate, di(oxycarbonylmethyl) n-butyl (meth)acrylate, di(oxycarbonylmethyl) t-butyl (meth)acrylate, di(oxycarbonylmethyl) <NUM>-ethylhexyl (meth)acrylate, di(oxycarbonylmethyl) cyclohexyl (meth)acrylate, di(oxycarbonylmethyl) benzyl (meth)acrylate, di(oxycarbonylmethyl) phenyl (meth)acrylate, di(oxycarbonylmethyl) <NUM>-methoxyethyl (meth)acrylate, di(oxycarbonylmethyl) <NUM>-methoxybutyl (meth)acrylate, di(oxycarbonylmethyl) allyl (meth)acrylate, di(oxycarbonylmethyl) vinyl (meth)acrylate, di[<NUM>-(oxypolycarbonyl)ethyl] methyl (meth)acrylate, di[<NUM>-(oxypolycarbonyl)ethyl] ethyl (meth)acrylate, di[<NUM>-(oxypolycarbonyl)ethyl] n-propyl (meth)acrylate, di[<NUM>-(oxypolycarbonyl)ethyl] isopropyl (meth)acrylate, di[<NUM>-(oxypolycarbonyl)ethyl] n-butyl (meth)acrylate, di[<NUM>-(oxypolycarbonyl)ethyl] t-butyl (meth)acrylate, di[α-(oxycarbonyl)benzyl] methyl (meth)acrylate, and di[α-(oxycarbonyl)benzyl] ethyl (meth)acrylate, preferred examples thereof include di(oxycarbonylmethyl) methyl (meth)acrylate, di(oxycarbonylmethyl) ethyl (meth)acrylate, di(oxycarbonylmethyl) isopropyl (meth)acrylate, di(oxycarbonylmethyl) n-propyl (meth)acrylate, di(oxycarbonylmethyl) n-butyl (meth)acrylate, di[<NUM>-(oxypolycarbonylethyl)] methyl (meth)acrylate, di[<NUM>-(oxypolycarbonylethyl)] ethyl (meth)acrylate, poly(oxycarbonylmethyl) methyl (meth)acrylate, poly(oxycarbonylmethyl) ethyl (meth)acrylate, poly(oxycarbonylmethyl) isopropyl (meth)acrylate, poly(oxycarbonylmethyl) n-propyl (meth)acrylate, poly(oxycarbonylmethyl) n-butyl (meth)acrylate, poly(oxycarbonylmethyl) t-butyl (meth)acrylate, poly(oxycarbonylmethyl) <NUM>-ethylhexyl (meth)acrylate, poly(oxycarbonylmethyl) cyclohexyl (meth)acrylate, poly(oxycarbonylmethyl) benzyl (meth)acrylate, poly(oxycarbonylmethyl) phenyl (meth)acrylate, poly(oxycarbonylmethyl) <NUM>-methoxyethyl (meth)acrylate, poly(oxycarbonylmethyl) <NUM>-methoxybutyl (meth)acrylate, poly(oxycarbonylmethyl) allyl (meth)acrylate, poly(oxycarbonylmethyl) vinyl (meth)acrylate, poly[<NUM>-(oxypolycarbonyl)ethyl] methyl (meth)acrylate, poly[<NUM>-(oxypolycarbonyl)ethyl] ethyl (meth)acrylate, poly[<NUM>-(oxypolycarbonyl)ethyl] n-propyl (meth)acrylate, poly[<NUM>-(oxypolycarbonyl)ethyl] isopropyl (meth)acrylate, poly[<NUM>-(oxypolycarbonyl)ethyl] n-butyl (meth)acrylate, poly[<NUM>-(oxypolycarbonyl)ethyl] t-butyl (meth)acrylate, poly[α-(oxycarbonyl)benzyl] methyl (meth)acrylate, and poly[α-(oxycarbonyl)benzyl] ethyl (meth)acrylate, preferred examples thereof include poly(oxycarbonylmethyl) methyl (meth)acrylate, poly(oxycarbonylmethyl) ethyl (meth)acrylate, poly(oxycarbonylmethyl) isopropyl (meth)acrylate, poly(oxycarbonylmethyl) n-propyl (meth)acrylate, poly(oxycarbonylmethyl) n-butyl (meth)acrylate, poly[<NUM>-(oxypolycarbonylethyl)] methyl (meth)acrylate, and poly[<NUM>-(oxypolycarbonylethyl)] ethyl (meth)acrylate.

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), and the monomer (b) used in the polymerization of the copolymer A contains one or both of the monomer (b1) and the monomer (b2).

The monomer (b1) is represented by general formula (<NUM>). <CHM>
wherein R<NUM> is hydrogen or a methyl group, and R<NUM> to R<NUM> are the same as or different from each other and each represent a branched alkyl group having <NUM> to <NUM> carbon atoms or a phenyl group.

The number of carbon atoms in the branched alkyl group is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here. Examples of the branched alkyl group include an isopropyl group, an isopropenyl group, an isobutyl group, a s-butyl group, a t-butyl group, a <NUM>-ethylpropyl group, a <NUM>-methylbutyl group, a <NUM>-methylpentyl group, a <NUM>,<NUM>-dimethylpropyl group, a <NUM>,<NUM>-dimethylbutyl group, a hexyl group, a cyclohexyl group, a <NUM>,<NUM>-dimethylpentyl group, a <NUM>-methylhexyl group, a <NUM>,<NUM>-dimethylhexyl group, a <NUM>-methylheptyl group, a <NUM>-methylbutyl group, a <NUM>-ethylbutyl group, a <NUM>,<NUM>-dimethylpropyl group, a cyclohexylmethyl group, a <NUM>-ethylhexyl group, a <NUM>-propylpentyl group, and a <NUM>-methylpentyl group. Preferred as R<NUM> to R<NUM> are the same as or different from each other and are an isopropyl group, an isopropenyl group, a s-butyl group, a t-butyl group, a phenyl group, and a <NUM>-ethylhexyl group, and particularly preferred are an isopropyl group and a <NUM>-ethylhexyl group.

Examples of the monomer (b1) include (meth)acrylic acid silyl esters such as triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyl s-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, isopropyl diisobutylsilyl (meth)acrylate, isopropyl di-s-butylsilyl (meth)acrylate, t-butyl diisobutylsilyl (meth)acrylate, t-butyl diisopentylsilyl (meth)acrylate, t-butyl diphenylsilyl (meth)acrylate, diisopropylhexylsilyl (meth)acrylate, diisopropylcyclohexylsilyl (meth)acrylate, tricyclohexylsilyl (meth)acrylate, tri-<NUM>,<NUM>-dimethylpentylsilyl (meth)acrylate, tri-<NUM>,<NUM>-dimethylpropylsilyl (meth)acrylate, tricyclohexylmethylsilyl (meth)acrylate, diisopropylcyclohexylmethylsilyl (meth)acrylate, tri-<NUM>-ethylhexylsilyl (meth)acrylate, and tri-<NUM>-propylpentylsilyl (meth)acrylate. These monomers (c) may be used singly, or two or more thereof may be used in combination.

The monomer (b2) is the monomer (b) excluding the monomer (b1). In other words, the monomer (b2) is a monomer not represented by any of general formulas (<NUM>) to (<NUM>). Examples of the monomer (b2) include (meth)acrylic acid esters, vinyl compounds, aromatic compounds and dialkyl ester compounds of dibasic acids, which are not represented by general formulas (<NUM>) to (<NUM>). As used herein, (meth)acrylic acid esters mean acrylic acid esters or methacrylic acid esters.

Examples of the (meth)acrylic acid esters not represented by general formulas (<NUM>) to (<NUM>) include (meth)acrylic acid esters, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, <NUM>-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, <NUM>-methoxyethyl (meth)acrylate, <NUM>-methoxypropyl (meth)acrylate, <NUM>-methoxybutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, <NUM>-ethoxyethyl (meth)acrylate, propylene glycol monomethyl (meth)acrylate, <NUM>-hydroxyethyl (meth)acrylate, <NUM>-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, <NUM>-[<NUM>-(<NUM>-hydroxyethoxy)ethoxy]ethoxy]ethyl methacrylate, mono(<NUM>-(meth)acryloyloxyethyl) succinate, N-(<NUM>-dimethylaminopropyl) (meth)acrylamide, <NUM>-hydroxyethyl (meth)acrylate, <NUM>-[<NUM>-(<NUM>-methoxyethoxy)ethoxy]ethyl (meth)acrylate, and N,N'-dimethyl (meth)acrylamide.

Examples of the 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.

Examples of the aromatic compounds include styrene, vinyltoluene, and α-methylstyrene.

Examples of the dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

In the copolymer A, these monomers (b) may be used singly, or two or more thereof may be used in combination. From the viewpoint of coating film dissolubility and coating film property, the monomer (b) preferably contains a (meth)acrylic acid ester of the monomer (b1) or the monomer (b2). From the viewpoint of crack resistance, the monomer (b) preferably contains a (meth)acrylic acid ester of the monomer (b2), and more preferably contains methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, <NUM>-ethylhexyl (meth)acrylate, <NUM>-methoxyethyl (meth)acrylate, <NUM>-ethoxyethyl (meth)acrylate, <NUM>-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, or the like. From the viewpoint of coating film dissolubility, the monomer (b) preferably contains the monomer (b1), and more preferably contains triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, tri-<NUM>-ethylhexylsilyl (meth)acrylate, or the like.

The weight-average molecular weight (Mw) of the copolymer A is preferably <NUM>,<NUM> to <NUM>,<NUM>. When the molecular weight is less than <NUM>,<NUM>, the coating film formed of the antifouling coating material becomes fragile and easily peels off or cracks, and when the molecular weight exceeds <NUM>,<NUM>, the viscosity of the polymer solution increases and handling becomes difficult. Specifically, the Mw is, for example, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, <NUM>,<NUM>, or <NUM>,<NUM> and may be within the range between any two numerical values exemplified here.

Examples of the method for measuring Mw include gel permeation chromatography (GPC method).

The copolymer A may be a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of the monomer (a) and the monomer (b).

The copolymer A may be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.

Examples of the polymerization initiator include azo compounds such as <NUM>,<NUM>'-azobisisobutyronitrile, <NUM>,<NUM>'-azobis(<NUM>-methylbutyronitrile), <NUM>,<NUM>'-azobis(<NUM>,<NUM>-dimethylvaleronitrile), dimethyl-<NUM>,<NUM>'-azobisisobutyrate, dimethyl-<NUM>,<NUM>'-azobisisobutyrate, and <NUM>,<NUM>'-azobis(N-butyl-<NUM>-methylpropionamide); peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-<NUM>-ethylhexanoate, t-hexylperoxy-<NUM>-ethylhexanoate, di-t-hexyl peroxide, t-butylperoxy-<NUM>-ethylhexyl monocarbonate, di-t-butyl peroxide, <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutylperoxyneodecanoate, t-amylperoxyneodecanoate, t-hexylperoxypivalate, t-amylperoxypivalate, and <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutylperoxy-<NUM>-ethylhexanoate. These polymerization initiators may be used singly, or two or more thereof may be used in combination. Particularly preferred as the polymerization initiator are <NUM>,<NUM>'-azobisisobutyronitrile, <NUM>,<NUM>'-azobis(<NUM>-methylbutyronitrile), <NUM>,<NUM>'-azobis(<NUM>,<NUM>-dimethylvaleronitrile), dimethyl <NUM>,<NUM>'-azobisisobutyrate, and <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutylperoxy-<NUM>-ethylhexanoate. The amount of the polymerization initiator used may be set as appropriate to adjust the molecular weight of the copolymer A.

Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. Among these, solution polymerization or non-aqueous dispersion polymerization is particularly preferred in that the copolymer A simply and accurately can be obtained therethrough.

In the polymerization reaction, an organic solvent may be used as necessary. Examples of the organic solvent include, but are not limited to, aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methoxy propyl acetate, and propylene glycol <NUM>-monomethyl ether <NUM>-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, preferred are butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol <NUM>-monomethyl ether <NUM>-acetate, toluene, and xylene. These solvents may be used singly, or two or more thereof may be used in combination.

The reaction temperature in the polymerization reaction may be set as appropriate according to the type of the polymerization initiator and the like, and is usually <NUM> to <NUM>, preferably <NUM> to <NUM>.

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

The content of the copolymer A in the composition of the present invention is not particularly limited, but the mass ratio (carboxylic acid ester Q/copolymer A) as the content ratio with respect to the carboxylic acid ester Q is usually <NUM> to <NUM>, and preferably <NUM> to <NUM>, in terms of solid content. The mass ratio is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here.

The copolymer B is a copolymer of the monomer (b1) and the monomer (b2), and contains monomer units derived from the monomer (b1) and the monomer (b2). The content of the monomer (b1) with respect to the total of the monomer (b1) and the monomer (b2) is preferably <NUM> to <NUM>% by mass, and still more preferably <NUM> to <NUM>% by mass. Specifically, the content thereof is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>% by mass, and may be within the range between any two numerical values exemplified here. In this case, the coating film dissolubility is particularly good.

The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like may be applied to the method described above for the copolymer A.

The content of the copolymer B in the composition of the present invention is not particularly limited, but the mass ratio (carboxylic acid ester Q/copolymer B) as the content ratio with respect to the carboxylic acid ester Q is usually <NUM> to <NUM>, and preferably <NUM> to <NUM>, in terms of solid content. The mass ratio is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here.

The copolymer C is a copolymer of the monomer (b2).

The content of the copolymer C in the composition of the present invention is not particularly limited, but the mass ratio (carboxylic acid ester Q/copolymer C) as the content ratio with respect to the carboxylic acid ester Q is usually <NUM> to <NUM>, and preferably <NUM> to <NUM>, in terms of solid content. The mass ratio is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>, and may be within the range between any two numerical values exemplified here.

The antifouling agent is selected from cuprous oxide, copper thiocyanate (generic name: copper rhodanide), and copper powder. Among these, preferred are cuprous oxide and copper rhodanide, and more preferred is cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, lecithin, mineral oil and the like in view of long-term stability during storage.

The antifouling agent is further selected from copper <NUM>-mercaptopyridine-N-oxide (generic name: copper pyrithione), zinc <NUM>-mercaptopyridine-N-oxide (generic name: zinc pyrithione), zinc ethylene-bis-dithiocarbamate (generic name: Zineb), <NUM>,<NUM>-dichloro-<NUM>-n-octyl-<NUM>-isothiazolone (generic name: SEA-NINE <NUM>), <NUM>,<NUM>-dichlorophenyl-N,N-dimethylurea (generic name: Diuron), <NUM>-methylthio-<NUM>-t-butylamino-<NUM>-cyclopropylamino-s-triazine (generic name: Irgarol <NUM>), <NUM>-(p-chlorophenyl)-<NUM>-cyano-<NUM>-bromo-<NUM>-trifluoromethylpyrrole (generic name: Econea <NUM>), and <NUM>-[<NUM>-(<NUM>,<NUM>-dimethylphenyl)ethyl]-<NUM>-imidazole (generic name: medetomidine).

These antifouling agents may be used singly, or two or more thereof may be used in combination.

The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually <NUM> to <NUM>% by mass, in terms of solid content. The content of the antifouling agent is, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, or <NUM>% by mass, and may be within the range between any two numerical values exemplified here.

If necessary, a resin component other than the copolymers A, B and C, a release modifier, a plasticizer, a pigment, a dye, an antifoaming agent, a dehydrating agent, a thixotropic agent, an organic solvent, or the like may be further added to the resin for the antifouling coating material of the present invention to obtain the antifouling coating material.

Examples of the other resin component include polyester resins, vinyl resins, petroleum resins, metal-containing resins, zwitterionic compound-containing resins, silicone resins, and alicyclic hydrocarbon resins.

Examples of the release modifier include rosin, hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, polymerized rosin, monocarboxylic acid and salts thereof, such as naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, versatic acid, trimethyl isobutenyl cyclohexene carboxylic acid, and metal salts thereof, and alicyclic hydrocarbon resins described above. These may be used singly or in combination of two or more thereof.

Examples of the plasticizer include phosphate esters, phthalate esters, adipate esters, sebacate esters, epoxidized soybean oil, alkyl vinyl ether polymer, polyalkylene glycols, t-nonyl pentasulfide, vaseline, polybutene, tris(<NUM>-ethylhexyl) trimellitate, silicone oil, and chlorinated paraffin. These may be used singly or in combination of two or more thereof.

Examples of the dehydrating agent include calcium sulfate, synthetic zeolite adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These may be used singly, or two or more thereof may be used in combination.

The antifouling coating composition of the present invention may be produced, for example, by mixing and dispersing a mixed solution containing the carboxylic acid ester Q and an antifouling agent, and optionally, at least one of the copolymers A to C, other additives, and the like, using a disperser.

A disperser that may be used as a fine pulverizer may be suitably used, for example, as the disperser. For example, commercially available homomixers, sand mills, bead mills, dispersers, or the like may be used. Alternatively, glass beads or the like for mixing and dispersing may be charged into a container equipped with a stirrer and used for mixing and dispersing the mixed solution.

In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of an object to be coated with the above antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing adhesion of aquatic fouling organisms.

Examples of the object to be coated include ships (in particular, ship bottoms), fishing tools, and underwater structures.

The thickness of the antifouling coating film may be set as appropriate according to the type of object to be coated, sailing speed of the ship, seawater temperature, and the like. For example, in a case where the object to be coated is the bottom of a ship, the thickness of the antifouling coating film is usually <NUM> to <NUM>, and preferably <NUM> to <NUM>.

The features of the present invention will be further clarified by Examples and the like to be described below. The present invention, however, is not limited to these Examples and the like.

In each of Production Examples, Examples, and Comparative Examples, "%" represents "% by mass". The weight-average molecular weight (Mw) is a value obtained by GPC (polystyrene equivalent). The conditions for GPC were as follows.

The non-volatile matter is a value measured in accordance with JIS K <NUM>-<NUM>-<NUM>:<NUM> (ISO <NUM>:<NUM>) "Testing Methods for Paint Components: Determination Of Non-Volatile matter".

The carboxylic acid ester solution containing carboxylic acid ester Q was produced in accordance with the method described below.

Into a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, <NUM> (<NUM> mol) of methyl chloroacetate, <NUM> of Chinese gum rosin, and <NUM> of xylene were charged, and <NUM> (<NUM> mol) of triethylamine was added dropwise to the mixture with stirring while maintaining the temperature at <NUM> or lower. After completion of the dropwise addition, the mixture was stirred at <NUM> to <NUM> for <NUM> hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in this order, and then the solvent was removed by concentration under reduced pressure to give <NUM> of a <NUM>% xylene solution of carboxylic acid ester (carboxylic acid ester solution q-<NUM>).

Carboxylic acid ester solutions q-<NUM> to q-<NUM> were obtained by performing reactions in the same manner as in Production Example <NUM> using the raw materials shown in Table <NUM>. The reaction conditions and yields of Production Examples <NUM> to <NUM> are shown in Table <NUM>.

Into a four-necked flask equipped with a thermometer, a condenser, and a stirrer, <NUM> (<NUM> mol) of sodium monochloroacetate, <NUM> (<NUM> mol) of methyl chloroacetate, and <NUM> of N-methyl-<NUM>-pyrrolidone were charged, and the mixture was stirred at <NUM> to <NUM> for <NUM> hours. After completion of the reaction, <NUM> of toluene was added to the reaction solution, and the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in this order, and then the solvent was removed by concentration under reduced pressure to give <NUM> of methyl methoxycarbonyl methyl chloroacetate.

Subsequently, into a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, <NUM> (<NUM> mol) of methoxycarbonyl methyl chloroacetate, which is the product of the first reaction, <NUM> of Chinese gum rosin (WW), and <NUM> of xylene were charged, and <NUM> (<NUM> mol) of triethylamine was added dropwise to the mixture with stirring while maintaining the temperature at <NUM> or lower. After completion of the dropwise addition, the mixture was stirred at <NUM> to <NUM> for <NUM> hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in this order, and then the solvent was removed by concentration under reduced pressure to give <NUM> of a <NUM>% xylene solution of carboxylic acid ester (carboxylic acid ester solution q-<NUM>).

Carboxylic acid ester solutions q-<NUM> to q-<NUM> shown in Table <NUM> were obtained by performing reactions in the same manner as in Production Example <NUM> using the raw materials shown in Table <NUM>. The reaction conditions and yields of Production Examples <NUM> to <NUM> are shown in Table <NUM>.

The details of the raw materials in Tables <NUM> and <NUM> are as follows.

The monomer (a1) was produced in accordance with the method described below.

Into a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, <NUM> (<NUM> mol) of methyl chloroacetate, <NUM> (<NUM> mol) of acrylic acid, <NUM> of <NUM>-methoxyphenol, and <NUM> of ethyl acetate were charged, and <NUM> (<NUM> mol) of triethylamine was added dropwise to the mixture with stirring while maintaining the temperature at <NUM> or lower. After completion of the dropwise addition, the mixture was stirred at <NUM> to <NUM> for <NUM> hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in this order, and the solvent was removed by concentration under reduced pressure to give <NUM> of a monomer a1-<NUM>.

Monomers a1-<NUM> to a1-<NUM> were obtained by performing reactions in the same manner as in Production Example <NUM> using the raw materials shown in Table <NUM>. The reaction conditions and yields of Production Examples <NUM> to <NUM> are shown in Table <NUM>.

The monomer (a2) was produced in accordance with the method described below.

Subsequently, into a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, <NUM> (<NUM> mol) of methoxycarbonyl methyl chloroacetate, which is the product of the first reaction, <NUM> (<NUM> mol) of acrylic acid, <NUM> of <NUM>-methoxyphenol, and <NUM> of ethyl acetate were charged, and <NUM> (<NUM> mol) of triethylamine was added dropwise to the mixture with stirring while maintaining the temperature at <NUM> or lower. After completion of the dropwise addition, the mixture was stirred at <NUM> to <NUM> for <NUM> hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in this order, and the solvent was removed by concentration under reduced pressure to give <NUM> of a monomer a2-<NUM>.

Monomers a2-<NUM> to a2-<NUM> shown in Table <NUM> were obtained by performing reactions in the same manner as in Production Example <NUM> using the raw materials shown in Table <NUM>. The reaction conditions and yields of Production Examples <NUM> to <NUM> are shown in Table <NUM>.

The copolymer solution containing at least one of the copolymers A to C was produced in accordance with the method described below.

Into a four-necked flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, <NUM> of xylene and <NUM> of <NUM>-butanol were charged as solvents, nitrogen gas was introduced, and the mixture was stirred while maintaining the temperature <NUM>. Then, a mixed solution of the monomer (a) and the monomer (b) in the amounts (g) shown in Table <NUM> and <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutylperoxy-<NUM>-ethylhexanoate as a polymerization initiator (initial addition) was added dropwise over <NUM> hours while maintaining the temperature at <NUM>. Thereafter, after stirring at <NUM> for <NUM> hour, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutylperoxy-<NUM>-ethylhexanoate was added <NUM> times every hour, and after stirring for <NUM> hours at the same temperature, the mixture was cooled to room temperature to obtain a copolymer solution A-<NUM>. The non-volatile matter and Mw of A-<NUM> are shown in Table <NUM>.

Copolymer solutions A-<NUM> to A-<NUM>, B-<NUM> to B-<NUM>, and C-<NUM> were obtained by performing a polymerization reaction in the same manner as in Production Example P1 except that the monomers and solvents shown in Table <NUM> were used. The non-volatile matter and Mw of each polymer are shown in Table <NUM>. The unit of numerical values for the amounts of raw materials in the table is g.

Into a flask equipped with a thermometer, a refluxing condenser, and a stirrer, <NUM> of Chinese gum rosin (WW) and <NUM> of xylene were added, and the mixture was refluxed and dehydrated under reduced pressure at <NUM> to <NUM> for <NUM> hour to obtain a xylene solution of gum rosin (brown transparent liquid, solid content: <NUM>%). The non-volatile matter of the resulting solution was <NUM>%.

Into a flask equipped with a thermometer, a refluxing condenser, and a stirrer, <NUM> of Chinese gum rosin (WW) and <NUM> of xylene were added, and <NUM> of zinc oxide was further added thereto so that all the resin acids in the rosin form zinc salts, and the mixture was refluxed and dehydrated under reduced pressure at <NUM> to <NUM> for <NUM> hours. Thereafter, the mixture was cooled and filtered to obtain a xylene solution of rosin zinc salt (dark brown transparent liquid, solid content: <NUM>%). The non-volatile matter of the resulting solution was <NUM>%.

The components shown in Tables <NUM> to <NUM> were blended in the proportions (% by mass) shown in the same tables, and the coating compositions were produced by mixing and dispersing the mixture with glass beads of <NUM> to <NUM> in diameter.

The details of the components in the table are as follows.

Rosin zinc salt solution: solution produced in Production Example <NUM> was used.

Gum rosin solution: solution produced in Production Example <NUM> was used.

The coating compositions of Examples and Comparative Examples were subjected to the following tests. The results are shown in Tables <NUM> to <NUM>.

As shown in Tables <NUM> to <NUM>, all Examples were superior to all Comparative Examples in at least one of the rotary test and the antifouling test.

A water tank was provided with, in the center thereof, a rotary drum having a diameter of <NUM> and a height of <NUM>, which was configured to be rotatable by a motor. The tank was also provided with a cooling apparatus for keeping the seawater temperature constant, and an automatic pH controller for keeping the seawater pH constant.

Test plates were prepared in accordance with the following method.

First, an anti-corrosion coating material (an epoxy vinyl A/C) was applied onto a titanium plate (<NUM> × <NUM> × <NUM>) such that the thickness after drying was about <NUM>, and dried to form an anti-corrosion coating film. Thereafter, each of the coating compositions obtained in Examples and Comparative Examples was applied thereon such that the dry film thickness was about <NUM>, and dried at <NUM> for <NUM> days to prepare a test plate.

The test plate thus prepared was fixed to the rotary drum of the rotating apparatus of the above equipment so as to be in contact with seawater, and the rotary drum was rotated at a speed of <NUM> knots. During the test, the temperature and the pH of the seawater were maintained at <NUM> and at <NUM> to <NUM>, respectively, and the seawater was replaced every two weeks.

The initial film thickness and remaining film thickness were measured at the initial stage and every <NUM> months after the start of the test for each of the testing plates using a shape measurement laser microscope VK-X100 manufactured by Keyence Corporation, and the dissolved coating film thickness was calculated from the difference between the two values, to obtain the coating film dissolution amount per month (µm/month). Further, when measuring the remaining film thickness after <NUM> months of the rotary test, the surface of each coating film was observed with naked eyes and a microscope to evaluate the surface condition of the coating film.

Evaluation of the coating film surface condition was made in accordance with the following criteria.

Each of the coating compositions obtained in Examples and Comparative Examples was applied onto both sides of a PVC plate (<NUM> × <NUM> × <NUM>) such that the thickness of the dry coating film was about <NUM>. The resulting coated product was dried at room temperature (<NUM>) for <NUM> days to prepare a test plate with a dry coating film having a thickness of about <NUM>. The test plate was immersed <NUM> below sea level in Owase City, Mie Prefecture, Japan, and fouling of the test plates by adhered materials was observed after <NUM> months and <NUM> months.

Claim 1:
An antifouling coating composition comprising:
a carboxylic acid ester Q represented by general formula (<NUM>); and
an antifouling agent which is selected from cuprous oxide, copper thiocyanate, copper powder, copper <NUM>-mercaptopyridine-N-oxide, zinc <NUM>-mercaptopyridine-N-oxide, zinc ethylene-bis-dithiocarbamate, <NUM>,<NUM>-dichloro-<NUM>-n-octyl-<NUM>-isothiazolone, <NUM>,<NUM>-dichlorophenyl-N,N-dimethylurea, <NUM>-methylthio-<NUM>-t-butylamino-<NUM>-cyclopropylamino-s-triazine, <NUM>-(p-chlorophenyl)-<NUM>-cyano-<NUM>-bromo-<NUM>-trifluoromethylpyrrole, and <NUM>-[<NUM>-(<NUM>,<NUM>-dimethylphenyl)ethyl]-<NUM>-imidazole,
<CHM>
wherein R<NUM> 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<NUM> represents hydrogen, a methyl group, or a phenyl group, R<NUM> is an alkyl group having <NUM> to <NUM> carbon atoms optionally substituted with an alkoxy group having <NUM> to <NUM> carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of <NUM> to <NUM>.