Antifouling coating composition

Abstract

The present invention provides an antifouling coating composition capable of maintaining a stable coating film dissolution rate in seawater for a long period of time and capable of maintaining stable antifouling performance without causing coating film abnormalities such as cracking. According to the present invention, an antifouling coating composition is provided, comprising a carboxylate Q represented by the general formula (1) and an antifouling agent.

Description

Technical Field

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

[0002] Aquatic fouling organisms such as barnacles, serrated algae, mussels, mosses, ascidians, green laver, sea lettuce, and sludge attach to ships (especially the bottoms), fishing nets, fishing net accessories, and other fishing tools, as well as underwater structures such as power plant water pipes, causing problems such as functional impairment and deterioration of the appearance of ships.

[0003] In order to prevent such problems, it is known that an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and the antifouling agent is gradually released from the antifouling coating film to provide long-term antifouling properties (Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-17203 Summary of the Invention

[0007] Technical problem to be solved by the invention

[0008] However, even with the technology of Patent Document 1, there are cases where initial coating film dissolution becomes excessive, or coating film abnormalities such as cracks appear after a short period of time, and further improvements are needed.

[0009] The present invention has been made in view of the above circumstances and provides an antifouling coating composition which maintains a stable coating film dissolution rate in seawater for a long period of time, does not cause coating film abnormalities such as cracks, and can maintain stable antifouling performance.

[0010] Methods used to solve problems

[0011] According to the present invention, there is provided an antifouling coating composition comprising a carboxylic acid ester Q represented by the general formula (1) and an antifouling agent.

[0012] The present inventors have conducted intensive studies to solve the above-mentioned problems and, as a result, have found that a composition containing a carboxylic acid ester Q can solve the above-mentioned problems, thereby completing the present invention. DETAILED DESCRIPTION

[0013] The present invention is described in detail below.

[0014] 1. Antifouling coating composition

[0015] The antifouling coating composition of the present invention contains a carboxylate Q and an antifouling agent, and preferably contains at least one of copolymer A, copolymer B, and copolymer C.

[0016] 1-1. Carboxylic acid ester Q

[0017] The carboxylate Q is represented by the general formula (1).

[0018] [Chemistry 1]

[0019]

[0020] (Where R 1 represents a carboxylic acid residue having 20 or less carbon atoms, R 2 represents hydrogen, methyl or phenyl, R 3 represents an alkyl group or phenyl group having 1 to 8 carbon atoms which may be substituted by an alkoxy group or phenyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10.

[0021] R 1 The number of carbon atoms is, for example, 1 to 20, preferably 5 to 20, and more preferably 8 to 20. Specifically, the number of carbon atoms is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, and may be within the range between any two of the values ​​exemplified here. 1 Preferred are gum rosin acid residues, hydrogenated rosin acid residues, hybrid rosin acid residues, versatile carbonic acid residues, or naphthenic acid residues, and more preferred are gum rosin acid residues or hydrogenated rosin acid residues.

[0022] 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 the range between any two of the values ​​exemplified here. 3 It is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl, benzyl, phenyl, 2-methoxyethyl, 4-methoxybutyl, vinyl or allyl, preferably methyl, ethyl, isopropyl or n-butyl.

[0023] From the viewpoint of long-term antifouling properties, n represents an integer of 1 to 10, 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 values ​​exemplified here.

[0024] The carboxylate Q preferably contains both a compound in which n is 1 and a compound in which n is 2 or greater. In this case, the coating film tends to maintain stable dissolution and crack resistance.

[0025] Examples of the carboxylic acid ester Q include methoxycarbonyl methyl ester, ethoxycarbonyl methyl ester, isopropoxycarbonyl methyl ester, n-propoxycarbonyl methyl ester, n-butoxycarbonyl methyl ester, tert-butoxycarbonyl methyl ester, 2-ethylhexyloxycarbonyl methyl ester, cyclohexyloxycarbonyl methyl ester, benzyloxycarbonyl methyl ester, phenoxycarbonyl methyl ester, 2-methoxyethoxycarbonyl methyl ester, 4-methoxybutoxycarbonyl methyl ester, aryloxycarbonyl methyl ester, vinyloxycarbonyl methyl ester, methyl ester, 1-(methoxycarbonyl)ethyl ester, 1-(ethoxycarbonyl)ethyl ester, 1-(n-propoxycarbonyl)ethyl ester, 1-(isopropoxycarbonyl)ethyl ester, 1-(n-butoxycarbonyl)ethyl ester, 1-(tert-butoxycarbonyl)ethyl ester, α-(methoxycarbonyl)benzyl ester, α-(ethoxycarbonyl) ester, methyl bis(oxycarbonylmethyl) ester, ethyl bis(oxycarbonylmethyl) ester, isopropyl bis(oxycarbonylmethyl) ester, n-propyl di bis(oxycarbonylmethyl) ester, n-butyl bis(oxycarbonylmethyl) ester, tert-butyl bis(oxycarbonylmethyl) ester, 2-ethylhexyl bis(oxycarbonylmethyl) ester, cyclohexyl bis(oxycarbonylmethyl) ester, benzyl bis(oxycarbonylmethyl) ester, phenyl bis(oxycarbonylmethyl) ester, 2-methoxyethyl bis(oxycarbonylmethyl) ester, 4-methoxybutyl bis(oxycarbonylmethyl) ester, allyl bis(oxycarbonylmethyl) ester, vinyl bis(oxycarbonylmethyl) ester di[1-(oxypolycarbonyl)ethyl] 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, tert-butyl di[1-(oxypolycarbonyl)ethyl] ester, methyl di[α-(oxycarbonyl)benzyl] ester, ethyl di[α-(oxycarbonyl)benzyl] ester and the like.

[0026] Preferred examples of the carboxylic acid ester Q include methyl di(oxycarbonylmethyl) ester, ethyl di(oxycarbonylmethyl) ester, isopropyl di(oxycarbonylmethyl) ester, n-propyl di(oxycarbonylmethyl) ester, n-butyl di(oxycarbonylmethyl) ester, methyl di[1-(oxypolycarbonylethyl)] ester, ethyl di[1-(oxypolycarbonylethyl)] ester, methyl poly(oxycarbonylmethyl) ester, ethyl poly(oxycarbonylmethyl) ester, isopropyl poly(oxycarbonylmethyl) ester, n-propyl di(oxycarbonylmethyl) ester, Poly(oxycarbonylmethyl) ester, n-butyl poly(oxycarbonylmethyl) ester, tert-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, allyl poly(oxycarbonylmethyl) ester, vinyl poly(oxycarbonylmethyl) ester, methyl poly[1- [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, tert-butyl poly[1-(oxypolycarbonyl)ethyl] ester, methyl poly[α-(oxycarbonyl)benzyl] ester, ethyl poly[α-(oxycarbonyl)benzyl] ester, and more preferably methoxycarbonylmethyl esters of carboxylic acids, ethoxycarbonylmethyl esters, Carbonyl methyl ester, isopropoxycarbonyl methyl ester, n-propoxycarbonyl methyl ester, n-butoxycarbonyl methyl ester, 1-(methoxycarbonyl)ethyl ester, 1-(ethoxycarbonyl)ethyl ester, methyl poly(oxycarbonylmethyl) ester, ethyl poly(oxycarbonylmethyl) ester, isopropyl poly(oxycarbonylmethyl) ester, n-propyl poly(oxycarbonylmethyl) ester, n-butyl poly(oxycarbonylmethyl) ester, methyl poly[1-(oxypolycarbonylethyl)] ester, ethyl poly[1-(oxypolycarbonylethyl)] ester and the like.

[0027] 1-2. Copolymer A

[0028] Copolymer A is a copolymer of monomer (a) and an ethylenically unsaturated monomer (b) other than monomer (a), and contains monomer (a) and monomer units derived from monomer (b). The content of monomer (a) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, relative to the total of monomers (a) and (b). Specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by mass, or within the range of any two of the values ​​exemplified herein. In this case, the coating film solubility is particularly good.

[0029] 1-2-1. Monomer (a)

[0030] Monomer (a) is represented by general formula (2).

[0031] [Chemistry 2]

[0032]

[0033] (Where R 4 represents hydrogen or methyl, R 5 represents hydrogen, methyl or phenyl, R 6 represents an alkyl group or phenyl group having 1 to 8 carbon atoms which may be substituted by an alkoxy group or phenyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10.

[0034] R 5 Preferably, R is hydrogen or methyl. 6 Description and R 3 Same description as .

[0035] 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 exemplified values.

[0036] Monomer (a) includes a compound in which n in general formula (2) is 2 or greater. When a compound in which n is 2 or greater is contained as monomer (a), the solubility of the coating film is improved. Monomer (a) may consist 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.

[0037] Monomer (a) is preferably composed of monomer (a1) and monomer (a2). The content of monomer (a1) in monomer (a) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and particularly preferably 60 to 70% by mass. Compared with monomer (a2), monomer (a1) has the property of improving the strength of the coating and reducing the solubility of the coating. Therefore, if the content of monomer (a1) is too little, the strength of the coating is easily reduced, and the surface state of the coating deteriorates after a long time. On the other hand, if the content of monomer (a1) is too much, the solubility of the coating becomes low, and the antifouling performance is sometimes reduced. The content of monomer (a1) can be, for example, within the range of 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80% by mass. It can also be within the range between any two numerical values ​​exemplified here.

[0038] <Monomer (a1)>

[0039] Monomer (a1) is a compound of the general formula (2) wherein n is 1.

[0040] Examples of the monomer (a1) include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropyloxycarbonylmethyl (meth)acrylate, n-propyloxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, tert-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonyl methacrylate, benzyloxycarbonylmethyl (meth)acrylate, phenoxycarbonyl methacrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, 4-methoxybutoxycarbonylmethyl (meth)acrylate, aryloxycarbonyl methacrylate, vinyloxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)methyl (meth)acrylate, )ethyl (meth)acrylate, 1-(ethoxycarbonyl)ethyl (meth)acrylate, 1-(n-propoxycarbonyl)ethyl (meth)acrylate, 1-(isopropoxycarbonyl)ethyl (meth)acrylate, 1-(n-butoxycarbonyl)ethyl (meth)acrylate, 1-(tert-butoxycarbonyl)ethyl (meth)acrylate, α-(methoxycarbonyl)benzyl (meth)acrylate, α-(ethoxycarbonyl)benzyl (meth)acrylate, preferably methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, 1-(ethoxycarbonyl)ethyl (meth)acrylate.

[0041] <Monomer (a2)>

[0042] The monomer (a2) is a compound wherein n in the general formula (2) is 2 or greater. From the viewpoint of long-term antifouling properties, n in the general formula (2) is preferably 2 to 6.

[0043] As monomer (a2), it is preferred to contain both a compound in which n is 2 and a compound in which n is 3 or greater. Specifically, for example, the mass ratio (n(2) / n(2-10)) based on solid content is preferably 0.4 to 0.8, more preferably 0.5 to 0.7. In this case, the coating film dissolution tends to be continuous and stable. Specifically, this value is, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, or 0.80, and may also be within the range between any two of the numerical values ​​exemplified here.

[0044] Examples of the monomer (a2) include methyl (meth)acrylate di(oxycarbonylmethyl), ethyl (meth)acrylate di(oxycarbonylmethyl), isopropyl (meth)bis(oxycarbonylmethyl)acrylate, n-propyl (meth)acrylate di(oxycarbonylmethyl), n-butyl (meth)bis(oxycarbonylmethyl)acrylate, tert-butyl (meth)bis(oxycarbonylmethyl)acrylate, 2-ethylhexyl (meth)bis(oxycarbonylmethyl)acrylate, cyclohexyl (meth)bis(oxycarbonylmethyl)acrylate, benzyl (meth)acrylate, phenyl (meth)bis(oxycarbonylmethyl)acrylate, 2-methoxyethyl (meth)bis(oxycarbonylmethyl)acrylate, 4-methyl (meth)bis(oxycarbonylmethyl)acrylate. oxybutyl acrylate, (meth)allyl di(oxycarbonylmeth)acrylate, vinyl (meth)acrylate di(oxycarbonylmethyl), methyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], ethyl (meth)acrylate di[1-(oxypolycarbonyl)ethyl], n-propyl (meth)bis[1-(oxypolycarbonyl)ethyl]acrylate, isopropyl (meth)bis[1-(oxypolycarbonyl)ethyl]acrylate, n-butyl (meth)bis[1-(oxypolycarbonyl)ethyl]acrylate, tert-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)ethyl] (oxycarbonylmethyl), ethyl (meth)acrylate bis(oxycarbonylmethyl), isopropyl (meth)bis(oxycarbonylmethyl)acrylate, n-propyl (meth)acrylate bis(oxycarbonylmethyl), n-butyl (meth)bis(oxycarbonylmethyl)acrylate, methyl (meth)acrylate bis[1-(oxypolycarbonylethyl)], ethyl (meth)acrylate bis[1-(oxypolycarbonylethyl)], methyl (meth)acrylate poly(oxycarbonylmethyl), ethyl (meth)acrylate poly(oxycarbonylmethyl), isopropyl (meth)poly(oxycarbonylmethyl)acrylate, n-propyl (meth)acrylate poly(oxycarbonylmethyl), n-butyl (meth)acrylate poly(oxycarbonylmethyl), tert-butyl (meth)acrylate poly(oxycarbonylmethyl), 2-(meth)acrylate ethylhexyl poly(oxycarbonylmethyl), cyclohexyl (meth)acrylate poly(oxycarbonylmethyl), benzyl (meth)polyoxycarbonyl methacrylate), phenyl (meth)poly(oxycarbonylmethyl)acrylate, 2-methoxyethyl (meth)acrylate poly(oxycarbonylmethyl), 4-methoxybutyl (meth)poly(oxycarbonylmethyl)acrylate, allyl (meth)acrylate poly(oxycarbonylmethyl), vinyl (meth)acrylate poly(oxycarbonylmethyl), methyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], ethyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], n-propyl (meth)poly[1-(oxypolycarbonyl)ethyl]acrylate, isopropyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl]acrylate,n-Butyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], t-butyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], methyl (meth)acrylate poly[α-(oxycarbonyl)benzyl], ethyl (meth)acrylate poly[α-(oxycarbonyl)benzyl], preferably methyl (meth)acrylate poly(oxycarbonylmethyl), ethyl (meth)acrylate poly(oxycarbonylmethyl), isopropyl (meth)poly(oxycarbonylmethyl)acrylate, n-propyl (meth)acrylate poly(oxycarbonylmethyl), n-butyl (meth)acrylate poly(oxycarbonylmethyl), methyl (meth)acrylate poly[1-(oxypolycarbonylethyl)], ethyl (meth)acrylate poly[1-(oxypolycarbonylethyl)], etc.

[0045] 1-2-2. Monomer (b)

[0046] Monomer (b) is an ethylenically unsaturated monomer other than monomer (a). Monomer (b) can be divided into monomer (b1) and monomer (b2). Monomer (b) used for polymerization of copolymer A includes one or both of monomer (b1) and monomer (b2).

[0047] <Monomer (b1)>

[0048] The monomer (b1) is represented by the general formula (3).

[0049] [Chemistry 3]

[0050]

[0051] (Where R 7 is hydrogen or methyl, R 8 ~R 10 represents a branched alkyl group or a phenyl group having 3 to 8 carbon atoms, which may be the same or different.

[0052] The number of carbon atoms in the branched alkyl group is, for example, 3, 4, 5, 6, 7, or 8, and may also be within the range between any two of the values ​​exemplified here. Examples of branched alkyl groups include isopropyl, isopropenyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1,1-dimethyl, 1-dimethylbutyl, tert-butyl, cyclohexyl, 1,1-dimethylpentyl, 1-methylhexyl, 1,1-dimethylhexyl, 1-methylheptyl, 2-methylbutyl, 2-ethylbutyl, 2,2-dimethylpropyl, cyclohexylmethyl, 2-ethylhexyl, 2-propylpentyl, and 3-methylpentyl. 8 ~R 10 The same or different groups are preferred, and isopropyl, isopropenyl, sec-butyl, tert-butyl, phenyl and 2-ethylhexyl groups are preferred, with isopropyl and 2-ethylhexyl groups being particularly preferred.

[0053] Examples of the monomer (b1) include triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-sec-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, triphenylsilyl methyl (meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropylsec-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, isopropyldiisobutylsilyl (meth)acrylate, isopropyldisec-butylsilyl (meth)acrylate, tert-butyldiisopentylsilyl (meth)acrylate, Silyl (meth)acrylates such as tert-butyldiisopentylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, diisopropylhexylsilyl (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 are also included. These monomers (c) can be used alone or in combination of two or more.

[0054] <Monomer (b2)>

[0055] Monomer (b2) is obtained by removing monomer (b1) from monomer (b). That is, monomer (b2) is a monomer other than those represented by general formulas (2) to (3). Examples of monomer (b2) include (meth)acrylates, vinyl compounds, aromatic compounds, and dialkyl esters of dibasic acids other than those represented by general formulas (2) to (3). In this specification, (meth)acrylate refers to either acrylate or methacrylate.

[0056] Examples of (meth)acrylates other than those of the general formulae (2) to (3) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-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, (meth)propylene glycol monomethacrylate, 2-hydroxyethyl (meth)acrylate, (Meth)acrylates 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.

[0057] Examples of the vinyl compound 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-vinyl pyrrolidone.

[0058] Examples of the aromatic compound include styrene, vinyltoluene, and α-methylstyrene.

[0059] Examples of the dialkyl ester compound of a dibasic acid include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

[0060] 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 properties, monomer (b) preferably contains a (meth)acrylate of monomer (b1) or monomer (b2). From the viewpoint of crack resistance, monomer (b) preferably contains a (meth)acrylate of monomer (b2), more preferably methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. From the viewpoint of coating film solubility, the monomer (b) preferably contains the monomer (b1), and more preferably contains triisopropylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, or the like.

[0061] 1-2-3. Physical Properties and Production Method of Copolymer A

[0062] 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 antifouling coating film becomes brittle and easily peels or cracks. On the other hand, if the molecular weight exceeds 300,000, when the amount of volatile organic compounds (VOCs) contained in the antifouling coating composition is low, the coating viscosity increases, making handling difficult. Specifically, the Mw is, for example, 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, or 300,000, and may also be within a range between any two of the values ​​exemplified here.

[0063] As a method for measuring Mw, gel permeation chromatography (GPC method) can be mentioned.

[0064] Copolymer A may be a random copolymer, an alternating copolymer, a periodic copolymer or a block copolymer of monomer (a) and monomer (b).

[0065] The copolymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.

[0066] 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, 2,2'-azobisisobutyrate, and 2,2'-azobis(N-butyl-2-methylpropionamide); benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, and tert-butyl peroxycarbonate. Isopropyl ester, tert-butyl peroxidation 2-ethylhexanoate, tert-hexyl peroxidation 2-ethylhexanoate, di-tert-hexyl peroxidation, tert-butyl peroxidation 2-ethylhexyl monocarbonate, di-tert-butyl peroxidation, 1,1,3,3-tetramethylbutyl peroxidation, tertiary peroxides such as amyl peroxidation neodecanoate, tert-hexyl peroxidation pivalate, tert-amyl peroxidation pivalate, peroxidation-2-ethylhexanoic acid, 1,1,3,3-tetramethylbutyl peroxidation-2-ethylhexanoate etc.These polymerization initiators can be used alone or in combination of two or more.As described polymerization initiator, particularly preferred 2,2 '-azobisisobutyronitrile, 2,2 '-azobis(2-methylbutyronitrile), 2,2 '-azobis(2,4-dimethylvaleronitrile), 2,2 '-dimethyl azobisisobutyrate and 1,1,3,3-tetramethylbutyl peroxidation-2-ethylhexanoate. The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.

[0067] Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. Of these, solution polymerization and non-aqueous dispersion polymerization are particularly preferred from the viewpoint of obtaining copolymer A simply and accurately.

[0068] In the polymerization reaction, an organic solvent can be used as needed. As the organic solvent, there is no particular limitation, and 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, propylene glycol 1-monomethyl ether, and 2-monomethyl ether; alcohol solvents such as isopropyl alcohol, butanol, 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.

[0069] Among them, butyl acetate, isobutyl acetate, butanol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene are preferred. These solvents can be used alone or in combination of two or more.

[0070] The reaction temperature in the polymerization reaction can be appropriately set depending on the type of the polymerization initiator, and is usually 50 to 160°C, and preferably 60 to 150°C.

[0071] The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.

[0072] The content of copolymer A in the composition of the present invention is not particularly limited, but the content ratio of copolymer A to carboxylate Q, calculated as a solid content, is generally 0.01 to 0.9, preferably 0.05 to 0.4 by mass (carboxylate Q / copolymer A). This mass ratio is, 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 between any two of the values ​​exemplified herein within the following range.

[0073] 1-3. Copolymer B

[0074] 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) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, relative to the total of monomers (b1) and (b2). Specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by mass, and can be within the range between any two of the values ​​exemplified here. In this case, the coating film solubility is particularly good.

[0075] The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc. can be applied to the method for copolymer A described above.

[0076] The content of copolymer B in the composition of the present invention is not particularly limited, but the mass ratio (carboxylate Q / copolymer B) relative to the content of carboxylate Q, calculated as solid content, is generally 0.01 to 0.9, preferably 0.05 to 0.4. This mass ratio is exemplified by 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 also be within a range between any two of the values ​​exemplified herein.

[0077] 1-4. Copolymer C

[0078] Copolymer C is a copolymer of monomer (b2).

[0079] The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc. can be applied to the method for copolymer A described above.

[0080] The content of copolymer C in the composition of the present invention is not particularly limited, but the mass ratio (carboxylate Q / copolymer C) relative to the content of carboxylate Q, calculated as solids, is generally 0.01 to 0.9, preferably 0.05 to 0.4. This mass ratio is exemplified by 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 also be within a range between any two of the values ​​exemplified herein.

[0081] 1-5. Antifouling reagents

[0082] Examples of the antifouling agent include inorganic agents and organic agents.

[0083] Examples of the inorganic agent include cuprous oxide, copper thiocyanate (common name: endosulfan copper), and copper powder. Among these, cuprous oxide and endosulfan copper are particularly preferred. From the perspective of long-term storage stability, cuprous oxide surface-treated with glycerol, sucrose, stearic acid, lauric acid, lecithin, mineral oil, or the like is more preferred.

[0084] Examples of the organic reagent include copper 2-pyridinethione-N-oxide (common name: copper pyrithione), zinc 2-pyridinethione-N-oxide (common name: zinc pyrithione), zinc ethylenebisdithiocarbamate (common name: Zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (common name: Sea nine 211), 3,4-dichlorophenyl-NN-dimethylurea (common name: Diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (common name: Irgalol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: Econea 28), and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: Medetomidine).

[0085] These antifouling agents can be used alone or in combination of two or more.

[0086] The content of the other antifouling agent in the composition of the present invention is not particularly limited, but is generally 0.1 to 60.0% by mass on a solids basis. Examples of the content of the antifouling agent include 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, and 60% by mass, and may also be within a range between any two of the values ​​exemplified herein.

[0087] 1-6. Other additives

[0088] The antifouling coating resin of the present invention may be added with other resin components other than copolymers A, B and C, dissolution regulators, plasticizers, fibers, pigments, dyes, defoamers, dehydrating agents, thixotropic agents, organic solvents, etc. as needed to prepare an antifouling coating.

[0089] 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.

[0090] Examples of solubility modifiers include rosin, hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, polymerized rosin, cycloalkanoic acid, cycloalkenyl carboxylic acid, dicycloalkenyl carboxylic acid, versatile carbonic acid, trimethyl isobutyl ester and their metal salts, monocarboxylic acids and their salts, and the aforementioned alicyclic hydrocarbon resins. These can be used alone or in combination of two or more.

[0091] Examples of the plasticizer include phosphates, phthalates, adipates, sebacates, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tert-nonyl pentasulfide, vaseline, polybutene, tri(2-ethylhexyl) trimellitate, silicone oil, and chlorinated paraffin. These can be used alone or in combination of two or more.

[0092] Examples of dehydrating agents include calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbondiimidazoles. These can be used alone or in combination of two or more.

[0093] 2. Method for producing antifouling coating composition

[0094] The antifouling coating composition of the present invention can be produced, for example, by mixing and dispersing a mixed solution containing a carboxylate Q, an antifouling agent, and, if necessary, at least one of the copolymers A to C, and other additives using a disperser.

[0095] As a disperser, for example, a disperser that can be suitably used as a fine pulverizer can be used. For example, a commercially available homomixer, sand mill, bead mill, disperser, paint shaker, etc. can be used. Alternatively, the mixed liquid can be mixed and dispersed using glass beads or the like added to a container equipped with an agitator for mixing and dispersing.

[0096] 3. Antifouling treatment methods, antifouling coatings, and coatings

[0097] In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of an object to be coated using an 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 continuously renewed, thereby preventing the adhesion of aquatic fouling organisms.

[0098] Examples of the object to be coated include ships (particularly ship bottoms), fishing gear, and underwater structures.

[0099] The thickness of the antifouling coating can be appropriately set depending on the type of the coating object, the ship's sailing speed, the seawater temperature, etc. For example, when the coating object is a ship bottom, the thickness of the antifouling coating is generally 50 to 700 μm, preferably 100 to 600 μm.

[0100] Example

[0101] In order to further clarify the characteristics of the present invention, examples and the like are shown below. However, the present invention is not limited to the examples and the like.

[0102] % in each of the preparation examples, examples, and comparative examples represents mass %. The weight average molecular weight (Mw) is a value measured by GPC (polystyrene equivalent value). The GPC conditions are as follows.

[0103] Device: HLC-8220GPC manufactured by Tosoh Corporation

[0104] Column: TSKgel SuperHZM-M 2 pieces

[0105] Flow rate: 0.35 mL / min

[0106] Detector: RI

[0107] Column thermostat temperature: 40°C

[0108] Eluent:THF

[0109] The heating residue is a value measured in accordance with JIS K 5601-1-2: 1999 (ISO 3251: 1993) "Test methods for coating components - Heating residue".

[0110] 1. Manufacturing Example

[0111] 1-1. Example of Preparation of Carboxylate Ester Solution

[0112] The carboxylate solution containing the carboxylate Q was prepared by the method shown below.

[0113] <Production Example 1 (Production of Carboxylate Ester Solution q-1)>

[0114] To a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel, 109 g (1.00 mol) of methyl chloroacetate, 335 g of Chinese gum rosin (WW), and 500 g of xylene were added dropwise. While stirring, 101 g (1.00 mol) of triethylamine was maintained below 40°C. After the addition, the mixture was stirred at 70-80°C for 6 hours. After the reaction, the organic layer was washed sequentially with tap water, hydrochloric acid solution, and sodium bicarbonate solution, and the solvent was removed by vacuum concentration and distillation to yield 734 g of a 50% xylene solution of the carboxylic acid ester (carboxylic acid) (carboxylic acid ester solution q-1).

[0115] <Manufacturing Examples 2 to 5 (Manufacturing of Carboxylate Ester Solutions q-2 to q-5)>

[0116] Using the raw materials shown in Table 1, the reaction was carried out in the same manner as in Production Example Q1 to obtain carboxylate ester solutions q-2 to q-5. The reaction conditions and yields of Production Examples 1 to 5 are shown in Table 1.

[0117] [Table 1]

[0118]

[0119] <Production Example 6 (Production of Carboxylate ester q-6)>

[0120] (1st reaction)

[0121] To a four-necked flask equipped with a thermometer, condenser, and stirrer, 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone were added and stirred at 70-80°C for 6 hours. After the reaction, 500 ml of toluene was added to the reaction solution. The organic layer was washed sequentially with tap water, hydrochloric acid, and sodium bicarbonate, and then concentrated under reduced pressure to remove the solvent to yield 262 g of methoxycarbonylmethyl chloroacetate.

[0122] (Second reaction)

[0123] Next, 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 were added to a four-necked flask equipped with a thermometer, condenser, and stirrer. Triethylamine (122 g (1.20 mol)) was added dropwise while stirring, maintaining the temperature below 40°C. After the dropwise addition, the mixture was stirred at 70-80°C for 6 hours. After the reaction was complete, the organic layer was washed sequentially with tap water, hydrochloric acid solution, and sodium bicarbonate solution, and then concentrated under reduced pressure to remove the solvent, yielding 962 g of a 50% xylene solution of the carboxylate (carboxylate solution q-6).

[0124] <Manufacturing Examples 7 to 30 (Manufacturing of Carboxylate Ester Solutions q-7 to q-30)>

[0125] Using the raw materials shown in Table 2, the reaction was carried out in the same manner as in Preparation Example 6 to obtain carboxylate ester solutions q-7 to q-30 shown in Table 2. The reaction conditions and yields of Preparation Examples 6 to 30 are shown in Table 2.

[0126] [Table 2]

[0127]

[0128] The raw materials in Tables 1 and 2 are detailed as follows.

[0129] CA Me: Methyl chloroacetate

[0130] CAEt: ethyl chloroacetate

[0131] Rosin: Gum rosin from China (WW)

[0132] Hydrogenated rosin: Trade name "Hi Pale CH" (manufactured by Arakawa Chemical Industries, Ltd.)

[0133] Versatile carbonic acid: trade name "neodecanoic acid" (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0134] Cyclohexane acid: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

[0135] TEA:Triethylamine

[0136] CANa: sodium monochloroacetate

[0137] NMP: N-methyl-2-pyrrolidone

[0138] 1-2. Production Example of Monomer (a1)

[0139] The monomer (a1) was produced by the method shown below.

[0140] <Production Example 31 (Production of Monomer a1-1)>

[0141] To a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel, add 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. While stirring, add 101 g (1.00 mol) of triethylamine dropwise, maintaining the temperature below 40°C. After the addition is complete, stir at 70-80°C for 6 hours. After the reaction, wash the organic layer with tap water, hydrochloric acid solution, and baking soda solution, then concentrate under reduced pressure to remove the solvent, yielding 129.7 g of monomer a1-1.

[0142] <Production Examples 32 to 33 (Production of Monomers a1-2 to a1-3)>

[0143] Using the raw materials shown in Table 3, the reaction was carried out in the same manner as in Production Example 31 to obtain monomers a1-2 to a1-3. The reaction conditions and yields of Production Examples 31 to 33 are shown in Table 3.

[0144] [Table 3]

[0145]

[0146] 1-3. Production Example of Monomer (a2)

[0147] The monomer (a2) was produced by the method shown below.

[0148] <Production Example 34 (Production of Monomer a2-1)>

[0149] (1st reaction)

[0150] To a four-necked flask equipped with a thermometer, condenser, and stirrer, 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone were added and stirred at 70-80°C for 6 hours. After the reaction was complete, 500 ml of toluene was added to the reaction solution, and the organic layer was washed sequentially with tap water, hydrochloric acid, and sodium bicarbonate. The solvent was then removed by concentration under reduced pressure to obtain 262 g of methoxycarbonylmethyl chloroacetate.

[0151] (Second reaction)

[0152] Next, 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 were added to a four-necked flask equipped with a thermometer, condenser, and stirrer. 122 g (1.20 mol) of triethylamine was added dropwise while stirring, maintaining the temperature below 40°C. After the addition, the mixture was stirred at 70-80°C for 6 hours. After the reaction, the organic layer was washed sequentially with tap water, hydrochloric acid solution, and sodium bicarbonate solution, and the solvent was removed by concentration and distillation under reduced pressure to obtain 230.6 g of monomer a2-1.

[0153] <Production Examples 35 to 48 (Production of Monomers a2-2 to a2-15)>

[0154] Using the raw materials shown in Table 4, the reaction was carried out in the same manner as in Production Example 34 to obtain monomers a2-2 to a2-15 shown in Table 4. The reaction conditions and yields of Production Examples 34 to 48 are shown in Table 4.

[0155] [Table 4]

[0156]

[0157] The raw materials in Tables 3 and 4 are detailed as follows.

[0158] CAMe: Methyl chloroacetate

[0159] CAEt: ethyl chloroacetate

[0160] AA: Acrylic acid

[0161] MAA: Methacrylic acid

[0162] TEA:Triethylamine

[0163] CANa: sodium monochloroacetate

[0164] NMP: N-methyl-2-pyrrolidone

[0165] MEHQ:4-Methoxyphenol

[0166] 1-4. Example of Preparation of Copolymer Solution

[0167] A copolymer solution containing at least one of copolymers A to C was prepared by the method shown below.

[0168] <<Production Example P1 (Production of Copolymer Solution A-1)>

[0169] A four-necked 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, introduced with nitrogen, and maintained at 88°C while stirring. A mixture of monomers (a) and (b) in the amounts (g) shown in Table 5 and 2.0 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (initial addition) as a polymerization initiator was then 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. After stirring at the same temperature for 2 hours, the mixture was cooled to room temperature to obtain copolymer solution A-1. The heating residue and Mw of A-1 are shown in Table 5.

[0170] <Production Examples P2 to P11 (Production of Copolymer Solutions A-2 to A-8, B-1 to B-2, and C-1)>

[0171] Polymerization reactions were carried out in the same manner as in Production Example P1, except that the monomers and solvents shown in Table 5 were used, to obtain copolymer solutions A-2 to A-8, B-1 to B-2, and C-1. The heating residue and Mw of each polymer are shown in Table 5. The values ​​for the raw material amounts in the table are in g.

[0172] [Table 5]

[0173]

[0174] 1-5. Other manufacturing examples

[0175] <Manufacturing Example 49 (Manufacturing of Gum Rosin Solution)>

[0176] 300 g of Chinese gum rosin (WW) and 310 g of xylene were added to a flask equipped with a thermometer, reflux condenser, and stirrer. The mixture was dehydrated under reduced pressure and reflux at 70-80°C for 1 hour to obtain a rosin xylene solution (brown transparent liquid, 50% solids). The heated residue of the resulting solution was 50.3%.

[0177] <Manufacturing Example 50 (Manufacturing of Rosin Zinc Salt Solution)>

[0178] In a flask equipped with a thermometer, reflux condenser, and stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene were added. Furthermore, 120 g of zinc oxide was added to convert all the resin acids in the rosin into rosin-type zinc salts. The mixture was then dehydrated under reduced pressure and reflux 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 solids content of 50%). The resulting solution had a heating residue of 50.2%.

[0179] 2. Examples and Comparative Examples (Production of Coating Compositions)

[0180] The components shown in Tables 6 to 9 were mixed in the ratios (mass %) shown in the same tables, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to prepare coating compositions.

[0181] [Table 6]

[0182]

[0183] [Table 7]

[0184]

[0185] [Table 8]

[0186]

[0187] [Table 9]

[0188]

[0189] Details of the ingredients in the table are as follows.

[0190] <Elution Regulator>

[0191] Rosin zinc salt solution: use the rosin zinc salt solution prepared in Preparation Example 50. Resin rosin solution: use the rosin solution prepared in Preparation Example 49.

[0192] <Antifouling Reagent>

[0193] Cuprous oxide: trade name "NC-301" (manufactured by Nissin Chemco Co., Ltd.)

[0194] Copper pyrithione: Trade name "Copper Omagin" (manufactured by LONZA Co., Ltd.)

[0195] Sea Nine: Sea Nine 211: 4,5-dichloro-2-n-octyl-4-isothiazol-3-one (manufactured by R&H), 30% active ingredient solution in xylene

[0196] Zineb: [ethylene bis(dithiocarbamate)] zinc (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

[0197] Zinc pyrithione: (manufactured by LONZA Co., Ltd.)

[0198] Econea: Trade name "Econea 028" 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

[0199] Medetomidine: (±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (manufactured by Wako Pure Chemical Industries, Ltd.)

[0200] <Other additives>

[0201] Iron Dan: Trade name "Bengara Kingyoku" (manufactured by Morishita Bengara Industry Co., Ltd.)

[0202] Talc: Trade name "Talc MS" (manufactured by Japan Talc Co., Ltd.)

[0203] Zinc oxide: Trade name "Zinc Oxide 2" (manufactured by Shodo Chemical Industry Co., Ltd.)

[0204] Titanium oxide: Trade name "FR-41" (manufactured by Furukawa Machinery & Metal Co., Ltd.)

[0205] Disparlon A603-20X: Amide-based thixotropic agent: Trade name "Disparlon A603-20X" (manufactured by Kusumoto Chemicals Co., Ltd.)

[0206] Tetraethoxysilane: Trade name "ethyl silicate 28" (manufactured by Colcoat Co., Ltd.)

[0207] Rosin ester: Trade name "Ester Gum AA-L" (manufactured by Arakawa Chemical Industries)

[0208] 3. Evaluation

[0209] The coating compositions of Examples and Comparative Examples were subjected to the following tests. The results are shown in Tables 6 to 9.

[0210] As shown in Tables 6-9, all Examples outperformed all Comparative Examples in at least one of the Spin Test and the Anti-fouling Test.

[0211] <Test Example 1 (Rotation Test)>

[0212] A rotating drum with a diameter of 515mm and a height of 440mm is installed in the center of the water tank and rotated by an electric motor. A cooling device is also installed to maintain a constant seawater temperature, and an automatic pH controller is installed to maintain a constant pH value.

[0213] The test plates were prepared according to the following method.

[0214] First, a rust-proof coating (epoxy-vinyl A / C) was applied to a titanium plate (71 × 100 × 0.5 mm) to a dry thickness of approximately 100 μm, and dried to form a rust-proof coating film. Subsequently, the coating compositions obtained in Examples and Comparative Examples were applied to a dry film thickness of approximately 400 μm, and dried at 40°C for 3 days to prepare a test plate.

[0215] The prepared test plate was fixed to the drum of the rotating device of the apparatus so as to contact with the seawater, and the drum was rotated at a speed of 20 knots. During this period, the seawater temperature was maintained at 25°C and the pH was 8.0-8.2, and the seawater was replaced every two weeks.

[0216] The remaining film thickness of each test plate was measured at the initial stage and every six months after the start of the test using a shape measurement laser microscope VK-X100 manufactured by Keyence Corporation. The dissolved film thickness was calculated from the difference to determine the amount of film dissolved per month (μm / month). In addition, when measuring the remaining film thickness 36 months after the rotation test, the surface condition of each coating film was evaluated by observing the surface of each coating film with the naked eye and a microscope.

[0217] The coating film surface conditions were evaluated according to the following criteria.

[0218] ◎: When there is no abnormality at all

[0219] ○: Less than 10% of the total surface area of ​​the coating, hair-like cracks are visible

[0220] △: Hairy cracks are visible on 10-30% of the total surface area of ​​the coating

[0221] ×: Hairy cracks are visible on more than 30% of the total surface area of ​​the coating

[0222] <Test Example 2 (Antifouling Test)>

[0223] The coating compositions obtained in the Examples and Comparative Examples were applied to both sides of rigid PVC panels (100 × 200 × 2 mm) to a dry coating thickness of approximately 300 μm. The resulting coatings were dried at room temperature (25°C) for three days to produce test panels with a dry coating thickness of approximately 300 μm. These panels were immersed 1.5 m below the sea level in Nachikatsuura, Wakayama Prefecture, and the panels were observed for contamination caused by deposits after 12 and 24 months.

[0224] Evaluation was performed by visually observing the state of the coating film surface and judging according to the following criteria.

[0225] ◎: No fouling organisms such as shellfish and algae are attached, and there is almost no slime.

[0226] ○: There is no fouling organisms such as shellfish and algae attached. Although there is thin mud (to the extent that the coating surface is visible), it can be removed by gently wiping with a brush.

[0227] △: Although there are no fouling organisms such as shellfish and algae attached, the slime is so thick that the coating surface cannot be seen and cannot be removed even by rubbing vigorously with a brush.

[0228] ×: Level of fouling organisms such as shellfish and algae attached.

Claims

1. An antifouling coating composition comprising a carboxylate Q represented by the general formula (1) and an antifouling agent, [Chemistry 1] ； Where R 1 represents a rosin acid residue, a hydrogenated rosin acid residue, a hybrid rosin acid residue, a versatile carbonic acid residue or a cyclohexane acid residue, R 2 represents hydrogen, methyl or phenyl, 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 a phenyl group; and n represents an integer of 1 to 10.

2. The antifouling coating composition according to claim 1, Containing at least one of copolymer A, copolymer B and copolymer C, The copolymer A is a copolymer of a monomer (a) represented by the following general formula (2) and an ethylenically unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) contains a compound wherein n is 2 or greater in the general formula (2). The monomer (b) is composed of the monomer (b1) and a monomer (b2) other than the monomer (b1), The monomer (b1) is represented by the general formula (3), The copolymer B is a copolymer of the monomer (b1) and the monomer (b2), The copolymer C is a copolymer of the monomer (b2), [Chemistry 2] ； Where R 4 represents hydrogen or methyl, R 5 represents hydrogen, methyl or phenyl, R 6 represents an alkyl group or phenyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group or phenyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10, [Chemistry 3] ； Where R 7 is hydrogen or methyl, R 8 ~R 10 Each of the groups is the same or different and represents a branched alkyl group or a phenyl group having 3 to 8 carbon atoms.

3. The antifouling coating composition according to claim 2, Contains copolymer A.

4. The antifouling coating composition according to claim 2 or 3, Contains copolymer B.

5. The antifouling coating composition according to claim 2 or 3, Contains copolymer C.

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