Antifouling paint composition

Abstract

Provided is an antifouling coating composition which has high storage stability and with which a stable coating film-dissolving rate is maintained over a long period of time in seawater, and stable antifouling performance can be maintained without causing coating film abnormalities such as cracks.　According to the present invention, provided is an antifouling coating composition containing a copolymer A, an ester compound C, and an antifouling chemical agent D, wherein: the copolymer A is a copolymer of a monomer (a) represented by general formula (1) and an ethylenically unsaturated monomer (b) other than the monomer (a); the monomer (a) includes a compound in which n in general formula (1) is at least 2; and the ester compound C includes at least one ester compound represented by chemical formulae (3)-(8).

Description

Technical Field

[0001] The present invention relates to an antifouling paint composition.

Background Art

[0002] Aquatic fouling organisms such as barnacles, serpulids, mussels, bryozoans, ascidians, green laver, sea lettuce, and slime attach to ships (especially the bottom part), fishing nets, fishing gear such as fishing net accessories, and underwater structures such as power plant intake pipes, causing problems such as impairment of the functions of these ships and damage to their appearance. To prevent such problems, a technique is known in which an antifouling paint composition is applied to a ship or the like to form an antifouling paint film, and an antifouling agent is gradually released from the antifouling paint film to exhibit antifouling performance over a long period (Patent Documents 1 to 4). However, the antifouling paint film composed of a (meth)acrylic acid alkoxysicarbonylmethyl ester group-containing polymer described in Patent Documents 1 to 4 has extremely low film solubility, making it difficult to exhibit antifouling properties over a long period. To solve these problems, a technique has been proposed in which the film dissolves over a long period to exhibit antifouling performance (Patent Document 5).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0004] Although the antifouling coating film made of the antifouling paint composition described in Patent Document 5 has improved coating film solubility and the like, when a long period of time has passed after immersion in seawater, the coating film dissolution may become excessively large, or coating film abnormalities such as cracks may occur, and further improvement is required. In addition, if the period from paint production to painting is long, the performance of the original paint composition may not be exhibited, and a paint composition with high storage stability is required.

[0005] The present invention has been made in view of such circumstances, and provides a highly storage-stable antifouling paint composition that can maintain a stable coating film dissolution rate and stable antifouling performance without causing coating film abnormalities such as cracks over a long period of time in seawater.

Means for Solving the Problems

[0006] According to the present invention, there is provided an antifouling paint composition containing a copolymer A, an ester compound C, and an antifouling agent D, wherein the copolymer A is a copolymer of a monomer (a) represented by the general formula (1) and an ethylenically unsaturated monomer (b) other than the monomer (a), the monomer (a) includes a compound in which n in the general formula (1) is 2 or more, and the ester compound C contains at least one ester compound represented by chemical formulas (3) to (8).

[0007] As a result of intensive studies to solve the above problems, the present inventor has found that a composition containing a copolymer A, an ester compound C, and an antifouling agent D can solve the above problems, and has completed the present invention.

Embodiments for Carrying Out the Invention

[0008] Hereinafter, the present invention will be described in detail. 1. Antifouling Paint Composition The antifouling paint composition of the present invention contains a copolymer A, an ester compound C, and an antifouling agent D.

[0009] 1-1. Copolymer A The copolymer A is a copolymer of monomer (a) and ethylenically unsaturated monomer monomer (b) other than monomer (a), and contains monomer units derived from monomer (a) and monomer (b). The content of monomer (a) relative to the total of monomer (a) and monomer (b) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass. Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and may be within the range between any two of the values exemplified herein. In this case, the coating film solubility is particularly good.

[0010] 1-1-1. Monomer (a) Monomer (a) is represented by the general formula (1).

[0011]

Chemical formula

[0012] In the formula, R 1 represents hydrogen or a methyl group, and R 2 represents hydrogen, a methyl group, or a phenyl group, and R 3 is an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of 1 to 10.

[0013] R 2 is preferably hydrogen or a methyl group.

[0014] R 3 The number of carbon atoms of the alkoxy group or alkyl group of is, for example, 1, 2, 3, 4, 5, 6, 7, 8, and may be within the range between any two of the values exemplified herein. R 3 is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, a 2-ethylhexyl group, a cyclohexyl group, a benzyl group, a phenyl group, a 2-methoxyethyl group, a 4-methoxybutyl group, a vinyl group, or an allyl group, and is preferably a methyl group, an ethyl group, an isopropyl group, or an n-butyl group.

[0015] n represents an integer from 1 to 10. n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, and may also be within the range between any two of the exemplified numerical values.

[0016] Monomer (a) includes a compound in which n in the general formula (1) is 2 or more. When a compound in which n is 2 or more is included as monomer (a), the solubility of the coating film becomes high. Monomer (a) may be composed only of a compound in which n is 2 or more, or may be a mixture of a compound in which n is 1 and a compound in which n is 2 or more.

[0017] 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. Monomer (a1) has the property of increasing the coating film strength and decreasing the coating film solubility compared to monomer (a2). For this reason, when the content of monomer (a1) is too small, the coating film strength tends to be low, and the surface state of the coating film may easily deteriorate after a long period. On the other hand, when the content of monomer (a1) is too large, the coating film solubility becomes low, and the antifouling performance may decrease.

[0018] <Monomer (a1)> Monomer (a1) is a compound in which n in the general formula (1) is 1.

[0019] Examples of the monomer (a1) include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, t-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyloxycarbonylmethyl (meth)acrylate, phenoxycarbonylmethyl (meth)acrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, 4-methoxybutoxycarbonylmethyl (meth)acrylate, allyloxycarbonylmethyl (meth)acrylate, vinyloxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)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-(t-butoxycarbonyl)ethyl (meth)acrylate, α-(methoxycarbonyl)benzyl (meth)acrylate, and α-(ethoxycarbonyl)benzyl (meth)acrylate. Preferred examples include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, and 1-(ethoxycarbonyl)ethyl (meth)acrylate.

[0020] <Monomer (a2)> The monomer (a2) is a compound in which n in the general formula (1) is 2 or more. From the viewpoint of long-term antifouling properties, n in the general formula (1) is preferably 2 to 6.

[0021] As the monomer (a2), it is preferable to include both a compound where n is 2 and a compound where n is 3 or more. Specifically, for example, in terms of solid content conversion, the mass ratio (n(2) / n(2~10)) is preferably 0.4 to 0.8, and more preferably 0.5 to 0.7. In this case, there is a tendency for stable dissolution of the coating film to continue. This value is specifically, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, and it may also be within the range between any two of the values exemplified here.

[0022] Examples of the monomer (a2) include methyl (meth)acrylate bis(oxycarbonylmethyl), ethyl (meth)acrylate bis(oxycarbonylmethyl), isopropyl (meth)acrylate bis(oxycarbonylmethyl), n-propyl (meth)acrylate bis(oxycarbonylmethyl), n-butyl (meth)acrylate bis(oxycarbonylmethyl), t-butyl (meth)acrylate bis(oxycarbonylmethyl), 2-ethylhexyl (meth)acrylate bis(oxycarbonylmethyl), cyclohexyl (meth)acrylate bis(oxycarbonylmethyl), benzyl (meth)acrylate bis(oxycarbonylmethyl), phenyl (meth)acrylate bis(oxycarbonylmethyl), 2-methoxyethyl (meth)acrylate bis(oxycarbonylmethyl), 4-methoxybutyl (meth)acrylate bis(oxycarbonylmethyl), allyl (meth)acrylate bis(oxycarbonylmethyl), vinyl (meth)acrylate bis(oxycarbonylmethyl), methyl (meth)acrylate bis[1-(oxypolycarbonyl)ethyl], ethyl (meth)acrylate bis[1-(oxypolycarbonyl)ethyl], n-propyl (meth)acrylate bis[1-(oxypolycarbonyl)ethyl], isopropyl (meth)acrylate bis[1-(oxypolycarbonyl)ethyl], n-butyl (meth)acrylate bis[1-(oxypolycarbonyl)ethyl], t-butyl (meth)acrylate bis[1-(oxypolycarbonyl)ethyl], methyl (meth)acrylate bis[α-(oxycarbonyl)benzyl], and ethyl (meth)acrylate bis[α-(oxycarbonyl)benzyl]. Preferably, methyl (meth)acrylate bis(oxycarbonylmethyl), ethyl (meth)acrylate bis(oxycarbonylmethyl), isopropyl (meth)acrylate bis(oxycarbonylmethyl), n-propyl (meth)acrylate bis(oxycarbonylmethyl), n-butyl (meth)acrylate bis(oxycarbonylmethyl), methyl (meth)acrylate bis[1-(oxypolycarbonylethyl)], ethyl (meth)acrylate bis[1-(oxypolycarbonylethyl)], methyl (meth)acrylate poly(oxycarbonylmethyl), and ethyl (meth)acrylate poly(oxycarbonylmethyl).(Meth)acrylic acid isopropyl poly(oxycarbonylmethyl), (meth)acrylic acid n-propyl poly(oxycarbonylmethyl), (meth)acrylic acid n-butyl poly(oxycarbonylmethyl), (meth)acrylic acid t-butyl poly(oxycarbonylmethyl), (meth)acrylic acid 2-ethylhexyl poly(oxycarbonylmethyl), (meth)acrylic acid cyclohexyl poly(oxycarbonylmethyl), (meth)acrylic acid benzyl poly(oxycarbonylmethyl), (meth)acrylic acid phenyl poly(oxycarbonylmethyl), (meth)acrylic acid 2-methoxyethyl poly(oxycarbonylmethyl), (meth)acrylic acid 4-methoxybutyl poly(oxycarbonylmethyl), (meth)acrylic acid allyl poly(oxycarbonylmethyl), (meth)acrylic acid vinyl poly(oxycarbonylmethyl), (meth)acrylic acid methyl poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid ethyl poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid n-propyl poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid isopropyl poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid n-butyl poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid t-butyl poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid methyl poly[α-(oxycarbonyl)benzyl], (meth)acrylic acid ethyl poly[α-(oxycarbonyl)benzyl] may be mentioned, and preferably, (meth)acrylic acid methyl poly(oxycarbonylmethyl), (meth)acrylic acid ethyl poly(oxycarbonylmethyl), (meth)acrylic acid isopropyl poly(oxycarbonylmethyl), (meth)acrylic acid n-propyl poly(oxycarbonylmethyl), (meth)acrylic acid n-butyl poly(oxycarbonylmethyl), (meth)acrylic acid methyl poly[1-(oxypolycarbonyl ethyl)], (meth)acrylic acid ethyl poly[1-(oxypolycarbonyl ethyl)] and the like may be mentioned.,

[0023] 1-1-2. Monomer (b) Monomer (b) is an ethylenically unsaturated monomer other than monomer (a). Monomer (b) can be classified into monomer (b1) and monomer (b2), and the monomer (b) used in the polymerization of copolymer A contains one or both of monomer (b1) and monomer (b2).

[0024] <Monomer (b1)> Monomer (b1) is represented by the general formula (2).

[0025] [Chemical formula]

[0026] In the formula, R 4 is hydrogen or a methyl group, and three Rs 5 each independently represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group.

[0027] The number of carbon atoms of the branched alkyl group is, for example, 3, 4, 5, 6, 7, or 8, and may be within the range between any two of the exemplified values. Examples of the branched alkyl group include isopropyl group, isopropenyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methylheptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group, 3-methylpentyl group, etc. Preferred as Rs 5 are each independently an isopropyl group, an isopropenyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group, and particularly preferred are an isopropyl group and a 2-ethylhexyl group.

[0028] Examples of the monomer (b1) include (meth) acrylic acid triisopropylsilyl, (meth) acrylic acid triisobutylsilyl, (meth) acrylic acid tris-butylsilyl, (meth) acrylic acid triisopentylsilyl, (meth) acrylic acid triphenylsilyl, (meth) acrylic acid diisopropylphenylsilyl, (meth) acrylic acid diisopropylisobutylsilyl, (meth) acrylic acid diisopropyls-butylsilyl, (meth) acrylic acid diisopropylisopentylsilyl, (meth) acrylic acid isopropyldiisobutylsilyl, (meth) acrylic acid isopropyldi-s-butylsilyl, (meth) acrylic acid t-butyldiisoptylsilyl, (meth) acrylic acid t-butyldiisopentylsilyl, (meth) acrylic acid t-butyldiphenylsilyl, (meth) acrylic acid diisopropyltexylsilyl, (meth) acrylic acid diisopropylcyclohexylsilyl, (meth) acrylic acid tricyclohexylsilyl, (meth) acrylic acid tri-1,1-dimethylpentylsilyl, (meth) acrylic acid tri-2,2-dimethylpropylsilyl, (meth) acrylic acid tricyclohexylmethylsilyl, (meth) acrylic acid diisopropylcyclohexylmethylsilyl, (meth) acrylic acid tri-2-ethylhexylsilyl, (meth) acrylic acid tri-2-propylpentylsilyl and other (meth) acrylic acid silyl esters. These monomers (b1) can be used alone or in combination of two or more.

[0029] <Monomer (b2)> The monomer (b2) is what remains after removing the monomer (b1) from the monomer (b). In other words, the monomer (b2) is a monomer not represented by either of the general formulas (1) and (2). Examples of the monomer (b2) include (meth) acrylic acid esters, vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, etc. that are not represented by either of the general formulas (1) and (2). In this specification, the (meth) acrylic acid ester means an acrylic acid ester or a methacrylic acid ester.

[0030] Examples of (meth)acrylic acid esters not represented by either general formula (1) or (2) include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, propylene glycol monomethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 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, succinic acid mono(2-(meth)acryloyloxyethyl), N-(3-dimethylaminopropyl)(meth)acrylamide, 2-hydroxyethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, N,N'-dimethyl(meth)acrylamide, and the like.

[0031] Examples of vinyl compounds include vinyl compounds having functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, N-vinylpyrrolidone, and the like.

[0032] Examples of aromatic compounds include styrene, vinyltoluene, α-methylstyrene, and the like.

[0033] Examples of dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, dimethyl fumarate, and the like.

[0034] In copolymer A, these monomers (b) can be used alone or in combination of two or more. From the viewpoints of coating film solubility and coating film physical properties, monomer (b) preferably contains a (meth)acrylate ester of monomer (b1) or monomer (b2). From the viewpoint of crack resistance, monomer (b) preferably contains a (meth)acrylate ester of monomer (b2), and more preferably contains methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. From the viewpoint of coating film solubility, monomer (b) preferably contains monomer (b1), and more preferably contains triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, etc.

[0035] 1-1-3. Physical Properties and Production Method of Copolymer A The weight average molecular weight (Mw) of copolymer A is preferably from 5000 to 300000. If the molecular weight is less than 5000, the coating film of the antifouling paint becomes fragile and is liable to peel or crack. If it exceeds 300000, the viscosity of the polymer solution increases and handling becomes difficult. Specifically, this Mw is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and may be within the range between any two of the values exemplified herein.

[0036] Examples of the method for measuring Mw include gel permeation chromatography (GPC method).

[0037] Copolymer A may be any copolymer such as a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of monomer (a1), monomer (a2), and monomer (b).

[0038] The copolymer A can be obtained, for example, by polymerizing monomer (a1), monomer (a2), and monomer (b) in the presence of a polymerization initiator.

[0039] Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis(N-butyl-2-methylpropionamide); peroxides such as benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, t-amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. These polymerization initiators can be used alone or in combination of two or more. Particularly preferred as the polymerization initiator are 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. The molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used. Further, a chain transfer agent can be used to adjust the molecular weight of the resulting polymer. Examples of the chain transfer agent include mercaptans such as n-dodecyl mercaptan; thioglycolic acid esters such as octyl thioglycolate; α-methylstyrene dimer, terpinolene.

[0040] Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization, etc. Among these, solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that copolymer A can be obtained simply and with high precision.

[0041] In the polymerization reaction, an organic solvent may be used if necessary. The organic solvent is not particularly limited, 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, and propylene glycol 1-monomethyl ether 2-acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among them, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene are preferable. These solvents can be used alone or in combination of two or more. The reaction temperature in the polymerization reaction may be appropriately set according to the type of polymerization initiator, etc., and is usually 50 to 160°C, preferably 60 to 150°C.

[0042] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.

[0043] 1-2. Ester Compound C The ester compound C of the present invention contains at least one ester compound (3) to (8) represented by chemical formulas (3) to (8). In the present specification, the ester compound means a carboxylic acid ester composed of a carboxylic acid and an alcohol, and the aforementioned carboxylic acid includes hydroxycarboxylic acids such as lactic acid and citric acid, and their O-acetylhydroxycarboxylic acids. The ester compound C is preferably a compound other than very volatile organic compounds (VVOC) and volatile organic compounds (VOC) defined by the World Health Organization (WHO). Specifically, the ester compound C preferably remains as a non-volatile component when the paint composition is measured for the content of volatile components in accordance with ASTM D2369-07.

[0044] <Ester compound (3)> The ester compound (3) has a structure represented by chemical formula (3). The ester compound (3) is, for example, an aliphatic ester or an aromatic ester, and is, for example, an ester compound in which a monocarboxylic acid and a monoalcohol are ester-bonded by dehydration condensation. When the ester compound (3) is an aliphatic ester, R 7 R 8 Preferably, at least one of them, or both, contains a branched structure, a cyclic structure, or a heteroatom. When the ester compound (3) is an aromatic ester, R 7 R 8 It is only necessary that one or both of them have an aromatic ring. When R 7 contains an aromatic ring, it is preferable that the aromatic ring is directly bonded to the carbon atom of the carbonyl group.

[0045] [Chemical formula] (In the formula, R 7 ~R 8 are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and this hydrocarbon group is aliphatic or aromatic, linear or branched, or has a cyclic structure.)

[0046] R 7 R8 The number of carbon atoms in the hydrocarbon group is preferably 2 to 20, specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, and it may also be within the range between any two of the numerical values exemplified herein. R 7 and R 8 The total number of carbon atoms is preferably 6 or more. R 7 , R 8 Examples of the heteroatom of R, R include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Among these, a structure containing an oxygen atom is preferable.

[0047] Specific examples of the ester compound (3) include, in the case of aliphatic esters, decyl decanoate, geranyl acetate, octyl stearate, cetyl stearate, octyl epoxy stearate, 3,7-dimethyl-6-octen-1-yl acetate, terpinyl acetate, 4-tert-butylcyclohexyl acetate, menthyl acetate, isobornyl acetate, isobornyl ethylate, isobornyl stearate, methyl dihydrojasmonate, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl stearate, cyclohexyl hexanoate, cyclohexyl cyclohexanecarboxylate, ethyl hexyl acetoacetate, butyl ricinoleate, methyl acetyl ricinoleate, isopentyl lactate, menthyl lactate, hexadecyl lactate, 3-hydroxy-2,2,4-trimethylpentyl isobutyrate, glycerol monooleate, glycerol monoisostearate, tetrahydrofurfuryl acetate, ethyl 3-phenylglycidate, ethyl 3-methyl-3-phenylglycidate, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, epoxidized fatty acid isobutyl, epoxidized fatty acid 2-ethylhexyl, and the like.

[0048] Specific examples of the ester compound (3) include, in the case of aromatic esters, isoamyl phenylacetate, benzyl isovalerate, benzyl acetoacetate, p-tolyl n-octanoate, benzyl stearate, benzyl epoxy stearate, isoamyl phenylacetate, 2-ethylhexyl benzoate, hexyl hydroxybenzoate, benzyl benzoate, 2-isopropoxyethyl benzoate, benzyl hydroxybenzoate, benzyl 4-benzyloxybenzoate, furfuryl acetate, ethyl 2-furancarboxylate, tetrahydrofurfuryl propionate, n-octyl 2-furancarboxylate, isoamyl 2-furancarboxylate, and the like.

[0049] <Ester Compound (4)> The ester compound (4) has a structure represented by Chemical Formula (4). The ester compound (4) is, for example, an aliphatic ester or an aromatic ester, and is, for example, an ester compound composed of one dicarboxylic acid and two monoalcohols. When the ester compound (4) is an aliphatic ester, R 9 , R 10 , or any one or all of X preferably contains at least one of a branched structure, a cyclic structure, or a heteroatom. Among these, it is more preferable that R 9 , R 10 contains a branched structure, and it is more preferable that X contains a cyclic structure. When the ester compound (4) is an aromatic ester, it is sufficient that any one of R 9 , R 10 , and X has at least one aromatic ring. Among these, a structure in which X contains an aromatic ring is preferable, and when X contains an aromatic ring, it is more preferable that the aromatic ring is directly bonded to the carbon atom of the carbonyl group.

[0050] [Chemical Formula] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and R 9 to R 10 are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and X and R9 ~R 10 The hydrocarbon groups of ~R are each aliphatic or aromatic, linear or branched, or have a cyclic structure.)

[0051] X and R 9 、R 10 The number of carbon atoms of the hydrocarbon group of ~R is preferably 2 to 20, specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, and it may also be within the range between any two of the numerical values exemplified here. X and R 9 、R 10 Examples of the heteroatom of ~R include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Among these, a structure containing an oxygen atom is preferred.)

[0052] When the hydrocarbon group of X has a cyclic structure, this cyclic structure preferably has at least one of an aromatic ring structure, an aliphatic six-membered ring structure, and a heteroatom-containing cyclic structure.)

[0053] Specific examples of the ester compound (4) include, in the case of aliphatic esters, di-2-ethylhexyl succinate, diisononyl succinate, di-2-ethylhexyl maleate, diisononyl maleate, diisodecyl maleate, di-2-ethylhexyl fumarate, diisononyl fumarate, diisopropyl adipate, diisobutyl adipate, di-2-ethylhexyl adipate, diisononyl adipate, diisodecyl adipate, di-2-butoxyethyl adipate, heptyl nonyl adipate, 1-benzyl 6-[2-(2-methoxyethoxy)ethyl] adipate, diisopropyl azelate, di-2-ethylhexyl azelate, diisononyl azelate, diisopropyl sebacate, di-2-ethylhexyl sebacate, diisononyl sebacate, diisodecyl sebacate, diisopropyl dodecanoate, di-2-ethylhexyl dodecanoate, diisononyl dodecanoate, diisodecyl dodecanoate. Specific examples in which X contains a cyclic structure include diethyl 1,1-cyclohexanedicarboxylate, diethyl 4-oxocyclohexane-1,1-dicarboxylate, diethyl 1,2-cyclohexanedicarboxylate, diisopropyl 1,2-cyclohexanedicarboxylate, diglycidyl 1,2-cyclohexanedicarboxylate, dibutyl 1,2-cyclohexanedicarboxylate, di-2-ethylhexyl 1,2-cyclohexanedicarboxylate, diisononyl 1,2-cyclohexanedicarboxylate, diisodecyl 1,2-cyclohexanedicarboxylate, diethyl 1,3-cyclohexanedicarboxylate, diisopropyl 1,3-cyclohexanedicarboxylate, di-2-ethylhexyl 1,3-cyclohexanedicarboxylate, diisononyl 1,3-cyclohexanedicarboxylate, dimethyl 2-oxocyclohexane-1,3-dicarboxylate, dimethyl 2-oxocyclohexane-1,3-dicarboxylate, dimethyl 5-hydroxycyclohexane-1,3-dicarboxylate, dimethyl 1,4-cyclohexanedicarboxylate, diethyl 1,4-cyclohexanedicarboxylate, diallyl 1,4-cyclohexanedicarboxylate, dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate, diethyl 1,4-cyclohexanedione-2,5-dicarboxylate, di-2-ethylhexyl 1,4-cyclohexanedicarboxylate, 1,Diisononyl 4 - cyclohexanedicarboxylate, diethyl 4 - cyclohexene - 1,2 - dicarboxylate, di(2 - ethylhexyl) 4 - cyclohexene - 1,2 - dicarboxylate, diisononyl 4 - cyclohexene - 1,2 - dicarboxylate, diethyl 4,5 - epoxycyclohexane - 1,2 - dicarboxylate, di(2 - ethylhexyl) 4,5 - epoxycyclohexane - 1,2 - dicarboxylate, diisononyl 4,5 - epoxycyclohexane - 1,2 - dicarboxylate, distearyl 4,5 - epoxycyclohexane - 1,2 - dicarboxylate, diepoxystearyl 4,5 - epoxycyclohexane - 1,2 - dicarboxylate, dimethyl 1,3 - adamantanedicarboxylate, di(2 - ethylhexyl) 3,4 - tetrahydrofuran - carboxylate, diethyl 2,5 - tetrahydrofuran - carboxylate, diisononyl 2,5 - tetrahydrofuran - carboxylate, diisodecyl 2,5 - tetrahydrofuran - carboxylate, etc. can be mentioned.,

[0054] Specific examples of the ester compound (4) include, in the case of aromatic esters, benzyl octyl adipate, isopropyl phthalate, isobutyl phthalate, cyclohexyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, butyl cyclohexyl phthalate, butyl nonyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, butyl phthalyl ethyl glycolate, diphenyl phthalate, dibenzyl phthalate, benzyl butyl phthalate, octyl benzyl phthalate, benzyl 2-ethylhexyl phthalate, benzyl isononyl phthalate, benzyl isodecyl phthalate, hydroxyethyl 2-ethylhexyl phthalate, diethyl isophthalate, diisopropyl isophthalate, cyclohexyl isophthalate, di-n-octyl isophthalate, di-2-ethylhexyl isophthalate, diisononyl isophthalate, diisodecyl isophthalate, diethyl terephthalate, isopropyl terephthalate, cyclohexyl terephthalate, di-n-octyl terephthalate, di-2-ethylhexyl terephthalate, diisononyl terephthalate, diisodecyl terephthalate, diethyl 2,5-furandicarboxylate, diisopropyl 2,5-furandicarboxylate, di-2-ethylhexyl 2,5-furandicarboxylate, diisononyl 2,5-furandicarboxylate, di-2-ethylhexyl 3,4-furandicarboxylate, di-n-decyl 3,4-furandicarboxylate, and the like.

[0055] <Ester Compound (5)> The ester compound (5) has a structure represented by Chemical Formula (5). The ester compound (5) is, for example, an aliphatic ester or an aromatic ester, and is, for example, an ester compound composed of one tricarboxylic acid and three monoalcohols. When the ester compound (5) is an aliphatic ester, R 11 ~R 13 , or any one, or all parts of X, preferably contain at least one of a branched structure, a cyclic structure, or a heteroatom. When the ester compound (5) is an aromatic ester, R 11 ~R 13It suffices to have at least one aromatic ring in any of X. Among these, a structure in which X contains an aromatic ring is preferable. When X contains an aromatic ring, it is more preferable that the aromatic ring is directly bonded to the carbon atom of the carbonyl group.

[0056] [Chemical formula] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and R 11 ~R 13 are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom. The hydrocarbon groups of X and R 11 ~R 13 are each aliphatic or aromatic, linear or branched, or have a cyclic structure.)

[0057] X and R 11 ~R 13 Preferably have 2 to 18 carbon atoms in the hydrocarbon group. Specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, and may be within the range between any two of the numerical values exemplified here. As the heteroatom of X and R 11 ~R 13 Examples include an oxygen atom, a sulfur atom, a nitrogen atom, etc. Among these, it is preferable to contain an oxygen atom.

[0058] When the hydrocarbon group of X has a cyclic structure, this cyclic structure preferably has at least one of an aromatic ring structure, an aliphatic six-membered ring structure, and a heteroatom-containing cyclic structure.

[0059] Specific examples of the ester compound (5) include, as aliphatic esters, triethyl methane tricarboxylate, triethyl citrate, triethyl acetylcitrate, tributyl citrate, tributyl acetylcitrate, trihexyl butyrylcitrate, trihexyl acetylcitrate, 2-ethylhexyl citrate, 2-ethylhexyl acetylcitrate, tri-2-ethylhexyl 1,3,4-cyclopentanetricarboxylate, triethyl 1,2,4-cyclohexanetricarboxylate, tri-2-ethylhexyl 1,2,4-cyclohexanetricarboxylate, triisononyl 1,2,4-cyclohexanetricarboxylate, tris(2,2,4-trimethylpentyl) 1,2,4-cyclohexanetricarboxylate, and the like.

[0060] Specific examples of the ester compound (5) include, as aromatic esters, tributyl trimellitate, tri-2-ethylhexyl trimellitate, tri-n-octyl trimellitate, triisononyl trimellitate, tri-2-ethylhexyl 1,3,5-benzenetricarboxylate, triisononyl 1,3,5-benzenetricarboxylate, and the like.

[0061] <Ester Compound (6)> The ester compound (6) has a structure represented by Chemical Formula (6). The ester compound (6) is, for example, an aliphatic ester or an aromatic ester, and is, for example, an ester compound composed of one tetracarboxylic acid and four monoalcohols. When the ester compound (6) is an aliphatic ester, R 14 ~R 17 , or any one, or all parts of X preferably contain at least one of a branched structure, a cyclic structure, or a heteroatom. Among these, it is more preferable that R 14 ~R 17 contains a branched structure. When the ester compound (6) is an aromatic ester, R 14 ~R 17 only needs to have at least one aromatic ring in any of them. Among these, a structure in which X contains an aromatic ring is preferable, and when X contains an aromatic ring, it is more preferable that the aromatic ring is directly bonded to the carbon atom of the carbonyl group.

[0062] [Chemical formula] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and R 14 ~R 17 are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and the hydrocarbon groups of X and R 14 ~R 17 are each aliphatic or aromatic, linear or branched, or have a cyclic structure.)

[0063] X and R 14 ~R 17 preferably have 2 to 18 carbon atoms in the hydrocarbon group, specifically, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, and may be within the range between any two of the exemplified numerical values. As the hetero atom of X and R 14 ~R 17 oxygen atom, sulfur atom, nitrogen atom, etc. may be mentioned, and among these, it is preferable to contain an oxygen atom.

[0064] When the hydrocarbon group of X has a cyclic structure, this cyclic structure preferably has at least one of an aromatic ring structure, an aliphatic six-membered ring structure, and a hetero atom-containing cyclic structure.

[0065] Specific examples of the ester compound (6) include, as aliphatic esters, tetraethyl 1,2,4,5-cyclohexanetetracarboxylate, tetraisopropyl 1,2,4,5-cyclohexanetetracarboxylate, tetra-2-ethylhexyl 1,2,4,5-cyclohexanetetracarboxylate, tetran-octyl 1,2,4,5-cyclohexanetetracarboxylate, isononyl 1,2,4,5-cyclohexanetetracarboxylate, triethyl tetrahydrofuran-2,3,4,5-tetracarboxylate, 2-ethylhexyl tetrahydrofuran-2,3,4,5-tetracarboxylate, etc.

[0066] Specific examples of the ester compound (6) include aromatic esters such as tetraethyl pyromellitate, tetraisopropyl pyromellitate, tetra-2-ethylhexyl pyromellitate, tetran-octyl pyromellitate, and isononyl pyromellitate.

[0067] <Ester compound (7)> The ester compound (7) has a structure represented by the chemical formula (7). The ester compound (7) is, for example, an aliphatic ester or an aromatic ester, and is, for example, an ester compound composed of one diol and two monocarboxylic acids. When the ester compound (7) is an aliphatic ester, R 18 ~R 19 , or any one or all of X preferably contains at least one of a branched structure, a cyclic structure, or a heteroatom. Among these, it is more preferable that the X portion contains a branched structure, a cyclic structure, or a heteroatom. When the ester compound (7) is an aromatic ester, R 18 ~R 19 only needs to have at least one aromatic ring in any one of them. Among these, it is preferable that R 18 ~R 19 contains a structure having an aromatic ring, and when R 18 ~R 19 contains an aromatic ring, it is more preferable that the aromatic ring is directly bonded to the carbon atom of the carbonyl group.

[0068]

Chemical formula

[0069] When the hydrocarbon group of X has a cyclic structure, this cyclic structure preferably has at least one of an aromatic ring structure, an aliphatic six-membered ring structure, and a heteroatom-containing cyclic structure.

[0070] Specific examples of the ester compound (7) include aliphatic esters such as propylene glycol diacetate, dipropylene glycol diacetate, 1,3-butylene glycol diacetate, 1,2-pentanediol diacetate, 1,6-hexanediol diacetate, 2,2,4-trimethyl-1,3-pentanediol diacetate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 2,2,4-trimethyl-1,3-pentanediol di-2-methylbutyrate, 1,4-cyclohexanedimethanol diisovalerate, 2,2,4-trimethyl-1,3-pentanediol di-2-ethylhexanoate, 1,4-cyclohexanedimethanol bis(2-ethylhexanoate), triethylene glycol di(2-ethylhexanoate), propylene glycol dilaurate, di-2-ethylhexanoate isosorbide, and the like.

[0071] Specific examples of the ester compound (7) include aromatic esters such as 2,5-diacetoxytoluene, 2,5-dibutoxytoluene, 2,2,4-trimethyl-1,3-pentanediol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and the like.

[0072] <Ester compound (8)> The ester compound (8) has a structure represented by the chemical formula (8). The ester compound (8) is, for example, an aliphatic ester or an aromatic ester, and is, for example, an ester compound composed of one triol and three monocarboxylic acids. When the ester compound (8) is an aliphatic ester, R 20 ~R 22、or any or all parts of X preferably contain at least one of a branched structure, a cyclic structure, or a heteroatom, and among these, it is more preferable for the X part to contain a branched structure, a cyclic structure, or a heteroatom. When the ester compound (8) is an aromatic ester, R 20 ~R 22 only needs to have at least one aromatic ring in any of them, and among these, it is preferable for the structure containing an aromatic ring to be in R 20 ~R 22 , and when R 20 ~R 22 contains an aromatic ring, it is more preferable that the aromatic ring is directly bonded to the carbon atom of the carbonyl group.

[0073] [Chemical formula] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and R 20 ~R 22 are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and the hydrocarbon groups of X and R 20 ~R 22 are each aliphatic or aromatic, linear or branched, or have a cyclic structure.)

[0074] When the hydrocarbon group of X has a cyclic structure, this cyclic structure preferably has at least one of an aromatic ring structure, an aliphatic six-membered ring structure, and a heteroatom-containing cyclic structure.

[0075] Specific examples of the ester compound (8) as an aliphatic ester include glycerol triacetate, glycerol tributyrate, glycerol tris(2-ethylhexanoate), glycerol trioctanoate, glycerol trilaurate, glycerol tristearate, glycerol trioleate, diacetyllauroylglycerol, epoxidized soybean oil, epoxidized linseed oil, and the like.

[0076] Specific examples of the ester compound (8) include, among aromatic esters, 1,2,4-triacetoxybenzene, 1,2,4-isopropoxybenzene, 2-benzylglycerol diacetate, and the like.

[0077] <Method for obtaining or manufacturing ester compound C, compounding method, compounding amount> The ester compound C can be used without particular limitation, such as those produced by known methods, commercially available products, reagents, etc. that can be obtained.

[0078] Known production methods include, for example, dehydration condensation reactions between carboxylic acids and alcohols, transesterification reactions between esters and alcohols, and ester synthesis reactions between carboxylic acid chlorides and alcohols. Also, some ester compounds can be produced by epoxidizing or hydrogenating the unsaturated parts of similar compounds available as commercial products, or by partial conversion of commercial ester compounds such as substitution reactions and coupling reactions.

[0079] 1-3. Antifouling agent D Examples of antifouling agents include inorganic agents and organic agents. Examples of inorganic agents include, for example, cuprous oxide, copper thiocyanate (common name: rhodan copper), copper powder, etc. Among these, cuprous oxide and rhodan copper are particularly preferred, and cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, lecithin, mineral oil, etc. is more preferred in terms of long-term storage stability. Examples of the organic agents include copper 2-mercaptopyridine-N-oxide (common name: copper pyrithione), zinc 2-mercaptopyridine-N-oxide (common name: zinc pyrithione), zinc ethylenebis(dithiocarbamate) (common name: zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (common name: Sea-Nine 211), 3,4-dichlorophenyl-N-N-dimethylurea (common name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: Econea 28), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: medetomidine), and the like. These antifouling agents can be used alone or in combination of two or more.

[0080] The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60.0% by mass in terms of solid content. The content of the antifouling agent is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and may be within the range between any two of the exemplified values.

[0081] 1-4. Other Additives Furthermore, to the resin for the antifouling paint of the present invention, resin components other than copolymer A, elution regulators, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents, thixotropic agents, organic solvents, etc. can be added as necessary to obtain an antifouling paint.

[0082] Examples of the other resin components include copolymer B, polymer P, and the like. The copolymer B is a copolymer of monomer (b1) and monomer (b2), and contains monomer units derived from monomer (b1) and monomer (b2). The content of monomer (b1) relative to the total of monomer (b1) and monomer (b2) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass. Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and may be within the range between any two of the numerical values exemplified herein. In this case, the coating film solubility is particularly good.

[0083] For the polymerization method, initiator, solvent, temperature, other conditions, the method for measuring Mw, etc., the methods already described for copolymer A can be applied. The content of copolymer B in the composition of the present invention is not particularly limited, but the content ratio with copolymer A, in terms of solid content, the mass ratio (copolymer B / copolymer A) is usually 0.1 to 0.9, preferably 0.3 to 0.7. This mass ratio is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and may be within the range between any two of the numerical values exemplified herein.

[0084] The polymer P is a polymer obtained by polymerizing the monomer (b2). In the present invention, the monomer (b2) can be used alone or in combination of two or more. In particular, from the viewpoint of compatibility with copolymer A, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, etc. are preferred. For the polymerization method, initiator, solvent, temperature, other conditions, the method for measuring Mw, etc., the methods already described for copolymer A can be applied. The content of polymer P in the composition of the present invention is not particularly limited, but the content ratio with copolymer A, in terms of solid content, the mass ratio (polymer P / copolymer A) is usually 0.1 to 0.5, preferably 0.1 to 0.3. This mass ratio can be, for example, 0.1, 0.2, 0.3, 0.4, 0.5, and may also be within the range between any two of the numerical values exemplified herein.

[0085] Examples of the dissolution regulator include monocarboxylic acids and their salts such as rosin, rosin derivatives, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, versatic acid, trimethylisobutenyl cyclohexene carboxylic acid, and metal salts thereof, or the above-mentioned alicyclic hydrocarbon resins. These can be used alone or in combination of two or more. Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, polymerized rosin, etc. Examples of the alicyclic hydrocarbon resins include commercially available products such as Quintone 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.). Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenyl cyclohexene carboxylic acid, or metal salts thereof are preferred.

[0086] Examples of the dehydrating agent include calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, carbodiimidazoles, etc. These can be used alone or in combination of two or more.

[0087] 2. Method for producing the antifouling paint composition The antifouling paint composition of the present invention can be produced, for example, by mixing and dispersing a mixed liquid containing a copolymer, an antifouling agent, and other additives using a disperser. The mixed liquid is preferably one in which various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent. As the disperser, for example, those that can be used as a fine pulverizer can be preferably used. For example, commercially available homomixers, sand mills, bead mills, disper, etc. can be used. Alternatively, a container equipped with a stirrer and added with glass beads for mixing and dispersion may be used to mix and disperse the mixed solution.

[0088] 3. Antifouling treatment method, antifouling coating film, and coated object The antifouling treatment method of the present invention forms an antifouling coating film on the surface of the object to be coated film using the above antifouling paint 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 updated, thereby preventing the adhesion of aquatic fouling organisms. Examples of the object to be coated film include ships (especially the bottom of the ship), fishing gear, underwater structures, etc. The thickness of the antifouling coating film may be appropriately set according to the type of the object to be coated film, the sailing speed of the ship, the seawater temperature, etc. For example, when the object to be coated film is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700 μm, preferably 100 to 600 μm.

Examples

[0089] Hereinafter, examples, etc. are shown to make the features of the present invention clearer. However, the present invention is not limited to examples, etc. % in each production example, example and comparative example represents mass%. The weight average molecular weight (Mw) is the value obtained by GPC (polystyrene conversion value). The conditions of GPC are as follows. Apparatus... HLC-8220GPC manufactured by Tosoh Corporation Column... Two TSKgel SuperHZM-M Flow rate... 0.35 mL / min Detector... RI Column thermostat temperature... 40°C Eluent... THF The heat residue is the value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Paint component test method - Heat residue".

[0090] 1. Production Example 1-1. Production Example of Monomer (a1) <Production Example 1 (Production of Monomer a1-1)> Into a four-necked flask equipped with a thermometer, a cooler, a stirrer, and a dropping funnel, 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 were charged, and while stirring, 101 g (1.00 mol) of triethylamine was added dropwise while maintaining the temperature at 40 °C or lower. After completion of the dropwise addition, the mixture was stirred at 70 to 80 °C for 6 hours. After completion of the reaction, the organic layer was washed with tap water, hydrochloric acid water, and aqueous sodium bicarbonate in that order, and the solvent was distilled off by concentration under reduced pressure to obtain 129.7 g of monomer a1-1. <Production Examples 2 to 3 (Production of Monomers a1-2 to a1-3)> Using the raw materials shown in Table 1, the reaction was carried out in the same manner as in Production Example 1 to obtain monomers a1-2 to a1-3. The reaction conditions and yields of Production Examples 1 to 3 are shown in Table 1.

[0091]

Table 1

[0092] 1-2. Production Example of Monomer (a2) <Production Example 4 (Production of Monomer a2-1)> (First Reaction) Into a four-necked flask equipped with a thermometer, a cooler, and a 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 charged, and the mixture was stirred at 70 to 80 °C for 6 hours. After completion of the reaction, 500 ml of toluene was charged into the reaction solution, and the organic layer was washed with tap water, hydrochloric acid water, and aqueous sodium bicarbonate in that order, and the solvent was distilled off by concentration under reduced pressure to obtain 262 g of methoxycarbonylmethyl chloroacetate.

[0093] (Second Reaction) Next, into a four-necked flask equipped with a thermometer, a cooler, a stirrer, and a dropping funnel, 200 g (1.20 mol) of methoxycarbonylmethyl chloroacetate, which is 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 charged, and 122 g (1.20 mol) of triethylamine was added dropwise while maintaining the temperature at 40 °C or lower with stirring. After completion of the dropwise addition, the mixture was stirred at 70 to 80 °C for 6 hours. After completion of the reaction, the organic layer was washed in the order of city water, hydrochloric acid water, and aqueous sodium bicarbonate, and the solvent was distilled off by concentration under reduced pressure to obtain 230.6 g of monomer a2-1.

[0094] <Production Examples 5 to 18 (Production of Monomers a2-2 to a2-15)> Using the raw materials shown in Table 2, the reaction was carried out in the same manner as in Production Example 4 to obtain the monomers a2-2 to a2-15 shown in Table 2. The reaction conditions and yields of Production Examples 4 to 18 are shown in Table 2.

[0095]

Table 2

[0096] Details of the raw materials in Tables 1 to 2 are as follows. CAMe: Methyl chloroacetate CAEt: Ethyl chloroacetate AA: Acrylic acid MAA: Methacrylic acid TEA: Triethylamine MEHQ: 4-Methoxyphenol CANa: Sodium monochloroacetate NMP: N-Methyl-2-pyrrolidone

[0097] 1-3. Production Example of Copolymer Solution <Production Example P1 (Production of Copolymer Solution A-1)> Into a four-necked flask equipped with a thermometer, a cooler, a stirring device, and a dropping funnel, 80 g of xylene and 20 g of 1-butanol were charged as solvents, nitrogen gas was introduced, and the temperature was maintained at 88 °C while stirring. Then, a mixed solution of monomer (a1), monomer (a2), and monomer (b) in the amounts shown in Table 3 (g) and 2.0 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (initial addition) as a polymerization initiator was added dropwise over 3 hours while maintaining the temperature at 88 °C. Thereafter, after stirring at 88 °C for 1 hour, 0.1 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate was added 3 times at 1-hour intervals, and after further stirring at the same temperature for 2 hours, the mixture was cooled to room temperature to obtain copolymer solution A-1. The heat residue and Mw of A-1 are shown in Table 3.

[0098] <Production Examples P2 to P5 (Production of Copolymer Solutions A-2 to 5)> Copolymer solutions A-2 to A-5 were obtained by carrying out a polymerization reaction in the same manner as in Production Example P1, except that the monomers, polymerization initiator, and solvent shown in Table 3 were used. The heat residue and Mw of each polymer are shown in Table 3. The unit of the numerical values of the amounts of the raw materials in the table is g.

[0099]

Table 3

[0100] <Production Example P6 (Production of Copolymer Solution B-1)> 200 g of xylene was charged into a flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel. While stirring at 85 ± 5 °C under a nitrogen atmosphere, a mixed solution of 270 g of triisopropylsilyl acrylate, 200 g of methyl methacrylate, 25 g of 2-methoxyethyl acrylate, 5 g of tetrahydrofurfuryl acrylate, and 2.4 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate as a polymerization initiator was added dropwise over 2 hours. After stirring at the same temperature for 1 hour, 0.3 g of 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate was added 5 times at 1-hour intervals to complete the polymerization reaction. Then, xylene was added and dissolved so that the heating residue became 50% to obtain a triorganosilyl ester-containing copolymer solution B-1. The viscosity of the obtained copolymer solution was 300 mPa·s (25 °C), the heating residue was 49.5%, and Mw was 48,000.

[0101] 1-4. Other Production Examples <Production Example D1 (Production of Gum Rosin Solution)> 300 g of Chinese gum rosin (WW) and 310 g of xylene were placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer, and refluxed and dehydrated under reduced pressure at 70 to 80 °C for 1 hour to obtain a xylene solution of gum rosin (brown transparent liquid, solid content 50%). The heating residue of the obtained solution was 50.3%.

[0102] <Production Example D2 (Production of Hydrogenated Rosin Solution)> A xylene solution of hydrogenated rosin (brown transparent liquid, solid content 50%) was obtained in the same manner as in Production Example D1 except that the Chinese gum rosin (WW) in Production Example D1 was changed to hydrogenated rosin. The heating residue of the obtained solution was 50.1%.

[0103] <Production Example D3 (Production of Zinc Salt Solution of Gum Rosin)> Into a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene were placed. Further, 120 g of zinc oxide was added so that all the resin acids in the rosin formed zinc salts, and reflux dehydration was carried out under reduced pressure at 70 to 80 °C for 3 hours. Then, after cooling and filtration, a xylene solution of gum rosin zinc salt (dark brown transparent liquid, solid content 50%) was obtained. The heating residue of the obtained solution was 50.2%.

[0104] <Production Example D4 (Production of Hydrogenated Rosin Zinc Salt Solution)> A xylene solution of hydrogenated rosin zinc salt (dark brown transparent liquid, solid content 50%) was obtained in the same manner as in Production Example D3, except that the Chinese gum rosin (WW) in Production Example D3 was changed to hydrogenated rosin. The heating residue of the obtained solution was 50.5%.

[0105] 2. Examples 1 to 91 and Comparative Examples 1 to 16 (Production of Paint Compositions) The components shown in Tables 4 to 13 were blended at 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 produce a paint composition.

[0106]

Table 4

[0107]

Table 5

[0108]

Table 6

[0109]

Table 7

[0110]

Table 8

[0111]

Table 9

[0112]

Table 10

[0113]

Table 11

[0114]

Table 12

[0115]

Table 13

[0116] The details of the components in the table are as follows.

[0117] <Ester Compound C> <<Ester Compound (3)>> DAD: Decyl Decanoate: Trade name "Decyl Decanoate" (manufactured by Tokyo Chemical Industry Co., Ltd.) PAiPr: Isopropyl Palmitate: Trade name "Isopropyl Palmitate" (manufactured by Tokyo Chemical Industry Co., Ltd.) MENTA: Menthyl Acetate: Trade name "(-)-Menthyl Acetate" (manufactured by Tokyo Chemical Industry Co., Ltd.) i-BoAc: Isobornyl Acetate: Trade name "Isobornyl Acetate" (manufactured by Tokyo Chemical Industry Co., Ltd.) LAHD: Hexadecyl Lactate: Trade name "Hexadecyl Lactate" (manufactured by Tokyo Chemical Industry Co., Ltd.) MISAG: Glycerol Monoisostearate: Trade name "Glycerol Monoisostearate" (manufactured by Wako Pure Chemical Industries, Ltd.) ARAM: Methyl O-Acetylricinoleate: Trade name "Methyl O-Acetylricinoleate" (manufactured by Tokyo Chemical Industry Co., Ltd.) DHJAM: Methyl Dihydrojasmonate: Trade name "Methyl Dihydrojasmonate" (manufactured by Tokyo Chemical Industry Co., Ltd.) E-6000: 2-Ethylhexyl Epoxidized Fatty Acid: Trade name "Sansosizer E-6000" (manufactured by Shin Nippon Rika Co., Ltd.) ECHECH: 3,4-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate: Trade name "3',4'-Epoxycyclohexylmethyl 3,4-Epoxycyclohexanecarboxylate" (manufactured by Wako Pure Chemical Industries, Ltd.) PATHF: Tetrahydrofurfuryl Propionate: Trade name "Tetrahydrofurfuryl Propionate" (manufactured by Tokyo Chemical Industry Co., Ltd.) BAEH: 2-Ethylhexyl Benzoate: Trade name "2-Ethylhexyl Benzoate" (manufactured by Tokyo Chemical Industry Co., Ltd.) n-OFA: n-Octyl 2-Furancarboxylate: Trade name "n-Octyl 2-Furancarboxylate" (manufactured by Tokyo Chemical Industry Co., Ltd.) MPhGAE: Ethyl 3-Methyl-3-phenylglycidate: Trade name "Ethyl 3-Methyl-3-phenylglycidate" (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0118] <<Ester Compound (4)>> AADBE: Bis(2-butoxyethyl) Adipate: Trade name "Bis(2-butoxyethyl) Adipate" (manufactured by Tokyo Chemical Industry Co., Ltd.) AAEH: Bis(2-ethylhexyl) Adipate: Trade name "Bis(2-ethylhexyl) Adipate" (manufactured by Tokyo Chemical Industry Co., Ltd.) AADiN: Diisononyl Adipate: Trade name "Diisononyl Adipate" (manufactured by Wako Pure Chemical Industries, Ltd.) AADiD: Diisodecyl Adipate: Trade name "Diisodecyl Adipate" (manufactured by Wako Pure Chemical Industries, Ltd.) AzAEH: Di-2-ethylhexyl azelate: Trade name "Bis(2-ethylhexyl) Azelate" (manufactured by Tokyo Chemical Industry Co., Ltd.) DOS: Di-2-ethylhexyl sebacate: Trade name "Sunsoftizer DOS" (manufactured by Shin Nippon Rika Co., Ltd.) DECH: Diethyl 1,1-cyclohexanedicarboxylate: Trade name "Diethyl 1,1-Cyclohexanedicarboxylate" (manufactured by Tokyo Chemical Industry Co., Ltd.) DGCH: Diglycidyl 1,2-cyclohexanedicarboxylate: Trade name "Diglycidyl 1,2-Cyclohexanedicarboxylate" (manufactured by Tokyo Chemical Industry Co., Ltd.) DMCDO: Dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate: Trade name "Dimethyl 1,4-Cyclohexanedione-2,5-dicarboxylate" (manufactured by Tokyo Chemical Industry Co., Ltd.) DINCH: Diisononyl 1,2-cyclohexanedicarboxylate: Trade name "HEXAMOLL® DINCH®" (manufactured by BASF) DEHTH: Di-2-ethylhexyl 4-cyclohexene-1,2-dicarboxylate: Trade name "Sunsoftizer DEHTH" (manufactured by Shin Nippon Rika Co., Ltd.) E-PS: Di-2-ethylhexyl 4,5-epoxycyclohexane-1,2-dicarboxylate: Trade name "Sunsoftizer E-PS" (manufactured by Shin Nippon Rika Co., Ltd.) EP-18: Distearyl 4,5-epoxycyclohexane-1,2-dicarboxylate: Trade name "Licaflo EP-18" (manufactured by Shin Nippon Rika Co., Ltd.) E-PO: Diepoxystearyl 4,5-epoxycyclohexane-1,2-dicarboxylate: Trade name "Sunsoftizer E-PO" (manufactured by Shin Nippon Rika Co., Ltd.) DEHP: Di-2-ethylhexyl phthalate: Trade name "Bis(2-ethylhexyl) Phthalate" (manufactured by Wako Pure Chemical Industries, Ltd.) DINP: Diisononyl phthalate: Trade name "Diisononyl Phthalate" (manufactured by Wako Pure Chemical Industries, Ltd.) DIDP: Diisodecyl phthalate: Trade name "Diisodecyl Phthalate" (manufactured by Wako Pure Chemical Industries, Ltd.) EPEG: Ethyl phthalyl ethyl glycolate: Trade name "Ethyl Phthalyl Ethyl Glycolate" (manufactured by Tokyo Chemical Industry Co., Ltd.) BPBG: Butyl phthalyl butyl glycolate: Trade name "Butyl Phthalyl Butyl Glycolate" (manufactured by Tokyo Chemical Industry Co., Ltd.) m-PAEH: Di-2-ethylhexyl isophthalate: Trade name "Bis(2-ethylhexyl) Isophthalate" (manufactured by Tokyo Chemical Industry Co., Ltd.) p-PAEH: Di-2-ethylhexyl terephthalate: Trade name "Bis(2-ethylhexyl) terephthalate" (manufactured by SIGMA-ALDRICH)

[0119] <<Ester compound (5)>> TECA: Triethyl citrate: Trade name "Triethyl Citrate" (manufactured by Tokyo Chemical Industry Co., Ltd.) TEACA: Triethyl O-acetylcitrate: Trade name "Triethyl O-Acetylcitrate" (manufactured by Tokyo Chemical Industry Co., Ltd.) TBACA: Tributyl O-acetylcitrate: Trade name "Tributyl O-Acetylcitrate" (manufactured by Tokyo Chemical Industry Co., Ltd.) TEHACA: 2-Ethylhexyl O-acetylcitrate: Trade name "CITROFOL® AHII" (manufactured by Jungbunzlauer) BTHC: Trihexyl O-butyrylcitrate: Trade name "Trihexyl O-Butyrylcitrate" (manufactured by Tokyo Chemical Industry Co., Ltd.) TEHTM: Tris(2-ethylhexyl) trimellitate: Trade name "Tris(2-ethylhexyl) Trimellitate" (manufactured by Tokyo Chemical Industry Co., Ltd.) TiNTM: Triisononyl trimellitate: Trade name "ADEKA SAIZER C-9N" (manufactured by ADEKA Corporation)

[0120] <<Ester compound (6)>> UL-80: Tetra-2-ethylhexyl pyromellitate: Trade name "ADEKA Sizer UL-80" (manufactured by ADEKA CORPORATION) UL-100: Mixed linear alkyl ester of pyromellitic acid: Trade name "ADEKA Sizer L-100" (manufactured by ADEKA CORPORATION)

[0121] <<Ester Compound (7)>> TMPIB: 2,2,4-Trimethyl-1,3-pentanediol diisobutyrate: Trade name "2,2,4-Trimethyl-1,3-pentanediol Diisobutyrate" (manufactured by Tokyo Chemical Industry Co., Ltd.) CHMEH: 1,4-Cyclohexanedimethanol bis(2-ethylhexanoate) HDOA: 1,6-Hexanediol diacetate: Trade name "1,6-Diacetoxyhexane" (manufactured by Tokyo Chemical Industry Co., Ltd.) P-1783: Triethylene glycol di(2-ethylhexanoate): Trade name "Proviplast 1783" (manufactured by Sanko Co., Ltd.) DEGDB: Diethylene glycol dibenzoate: Trade name "Diethylene Glycol Dibenzoate" (manufactured by Tokyo Chemical Industry Co., Ltd.) DPGDB: Dipropylene glycol dibenzoate: Trade name "Di(propylene glycol) dibenzoate" (manufactured by Sigma-Aldrich)

[0122] <<Ester Compound (8)>> TAAG: Glycerol triacetate: Trade name "Triacetin" (manufactured by Tokyo Chemical Industry Co., Ltd.) TBAG: Glycerol tributyrate: Trade name "Tributyrin" (manufactured by Wako Pure Chemical Industries, Ltd.) TEHAG: Glycerol tris(2-ethylhexanoate): Trade name "Glycerol tris(2-ethylhexanoate)" (manufactured by Wako Pure Chemical Industries, Ltd.) TOAG: Glyceryl trioleate: Trade name "Glyceryl trioleate" (manufactured by Sigma-Aldrich) E-2000H: Epoxidized soybean oil: Trade name "Sunsoizer E-2000H" (manufactured by Shin Nippon Rika Co., Ltd.) E-9000H: Epoxidized linseed oil: Trade name "Sunsoizer E-9000H" (manufactured by Shin Nippon Rika Co., Ltd.)

[0123] <Antifouling agent D> Copper oxide: Trade name "NC-301" (manufactured by Nisshin Kemco Co., Ltd.) Copper pyrithione: Trade name "Copper Omazine" (manufactured by LONZA Co., Ltd.) Sea Nine: Trade name "Sea Nine 211", 4,5-dichloro-2-octyl-4-isothiazolin-3-one (manufactured by R&H), 30% xylene solution of active ingredient Zineb: Zinc [ethylenebis(dithiocarbamate)] (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.) Zinc pyrithione: (manufactured by LONZA Co., Ltd.) Econea 028: Trade name "Econea 028", 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP) Medetomidine: (±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (manufactured by Wako Pure Chemical Industries, Ltd.) Copper rhodanide: Cuprous thiocyanate (manufactured by Nippon Chemical Industry Co., Ltd.) Diuron: Trade name "Diuron" (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0124] <Dissolution regulator> Hydrogenated rosin zinc solution: Use the one manufactured in Production Example D4 Gum rosin zinc salt solution: Use the one manufactured in Production Example D3 Gum rosin solution: Use the one manufactured in Production Example D1 Hydrogenated rosin solution: Use the one manufactured in Production Example D2

[0125] <Pigment> Red iron oxide: Trade name "Red iron oxide Kinkyoaku" (manufactured by Morishita Benkei Industry Co., Ltd.) Talc: Trade name "Talc MS" (manufactured by Nippon Talc Co., Ltd.) Zinc Oxide: Trade name "Two Kinds of Zinc Oxide" (manufactured by Shohdo Chemical Industry Co., Ltd.) Titanium Oxide: Trade name "FR-41" (manufactured by Furukawa Machinery Metal Co., Ltd.)

[0126] <Other Additives> Disparlon A603-20X: Amide-based thixotropic agent: Trade name "Disparlon A603-20X" (manufactured by Kusumoto Chemicals, Ltd.) Tricresyl Phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.) Lutonal A-25: Alkyl vinyl ether polymer: (manufactured by BASF) PEG400: Polyethylene glycol: Trade name "Polyethylene Glycol400" (manufactured by Tokyo Chemical Industry Co., Ltd.) Polybutene: Trade name "Polybutene 0N" (manufactured by Nippon Oil & Fats Co., Ltd.) Liquid Paraffin: Moresco White P-100 (manufactured by MORESCO Corporation) Tetraethoxysilane: Trade name "Ethyl Silicate 28" (manufactured by Colcoat Co., Ltd.)

[0127] <Solvent> Denatured Alcohol: Trade name "Clin Ace High" (manufactured by Imazu Pharmaceutical Industry Co., Ltd.)

[0128] 3. Tests All of the paint compositions of the examples and comparative examples were put into sealed containers within 1 hour after production and allowed to stand for 30 days in a thermostatic device set at 50°C (accelerated deterioration treatment), and then used. The following tests were conducted on the paints that had undergone the above treatment. The evaluation results are shown in Tables 4 to 12. In all of the comparative examples, the results were not as good as those of the examples in either the rotary test or the antifouling test.

[0129] <Test Example 1 (Rotary Test)> A rotating drum with a diameter of 515 mm and a height of 440 mm was installed at the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and a pH automatic controller for keeping the pH of the seawater constant were installed.

[0130] The test plates were prepared according to the following method.

[0131] First, a rust-preventive paint (epoxy vinyl-based A / C) was applied onto a titanium plate (71×100×0.5 mm) so that the thickness after drying was about 100 μm, and then dried to form a rust-preventive coating film. Thereafter, the paint compositions obtained in the examples and comparative examples were applied so that the dry film thickness was about 450 μm, and dried at 40 °C for 3 days to prepare test plates.

[0132] The prepared test plates were fixed to the rotating drum of the rotating device of the above apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During that time, the temperature of the seawater was maintained at 25 °C, the pH was maintained at 8.0 - 8.2, and the seawater was replaced every two weeks.

[0133] The residual film thickness of each test plate at the initial stage and 24 months after the start of the test was measured with a shape measurement laser microscope VK-X100 manufactured by Keyence Corporation, and the dissolved film thickness was calculated from the difference to obtain the film dissolution amount per month (μm / month), and the solubility of the coating film was evaluated according to the following criteria.

[0134] ◎: The average dissolution amount per month (μm / month) is 5 μm or more and less than 10 μm, which is an ideal dissolution amount. ○: The average dissolution amount per month (μm / month) is 2 μm or more and less than 5 μm, and the dissolution amount is slightly small. △: The average dissolution amount per month (μm / month) is 10 μm or more, and it is slightly over-dissolved. ×: The average dissolution amount per month (μm / month) is less than 2 μm, and it is not dissolved at all. ××: All the coating films were dissolved or peeled off within 24 months, and it was clearly over-dissolved. -: After the accelerated degradation treatment, problems such as thickening or gelation occurred in the paint, and the target test could not be performed.

[0135] Also, when measuring the residual film thickness 24 months after the rotary test, the surface state of each coating film was evaluated by observing the surface of each coating film with the naked eye and a microscope.

[0136] The evaluation of the coating film surface state was carried out according to the following criteria. ◎: When there is no abnormality at all ○: Hair cracks are observed in less than 10% of the total area of the coating film surface △: Hair cracks are observed in 1 - 30% of the total area of the coating film surface ×: Hair cracks are observed in 30% or more of the total area of the coating film surface ××: Abnormalities are observed in the coating film, such as large cracks, blisters, or peeling (only the surface or a part of the edge of the coating film peels off), detachment (the entire coating film peels off and no test coating film remains) -: After the accelerated deterioration treatment, problems such as thickening or gelling occurred in the paint, and the target test could not be carried out.

[0137] <Test Example 2 (Antifouling Test)> The coating compositions obtained in the examples and comparative examples were applied to both sides of a rigid PVC plate (100 × 200 × 2 mm) so that the thickness as a dry coating film would be about 300 μm. The obtained coated article was dried at room temperature (25°C) for 3 days to prepare a test plate having a dry coating film with a thickness of about 300 μm. This test plate was immersed 1.5 m below the sea surface in Owase City, Mie Prefecture, and the fouling of the test plate by adherents was observed after 18 months and 36 months.

[0138] The evaluation was carried out by visually observing the state of the coating film surface and judged according to the following criteria. ◎: There is no adhesion of fouling organisms such as shellfish and algae, and there is almost no slime. ○: There is no adhesion of fouling organisms such as shellfish and algae, and the slime adheres thinly (to the extent that the coating film surface can be seen) and can be lightly wiped off with a brush. △: There is no adhesion of fouling organisms such as shellfish and algae, but the slime adheres thickly to the extent that the coating film surface cannot be seen and cannot be removed even by strongly wiping with a brush. ×: The level at which fouling organisms such as shellfish and algae are attached -: After the accelerated deterioration treatment, problems such as thickening or gelling occurred in the paint, and the target test could not be carried out.

Claims

1. An antifouling paint composition containing a copolymer A, an ester compound C, and an antifouling agent D, wherein the copolymer A is a copolymer of a monomer (a) represented by the general formula (1) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer (a) includes a compound in which n in the general formula (1) is 2 or more, the ester compound C contains at least one ester compound represented by chemical formulas (3) to (8), the antifouling paint composition. 【Chemical 1】 (wherein R １ represents hydrogen or a methyl group, and R ２ represents hydrogen, a methyl group, or a phenyl group, and R ３ is an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of 1 to 10.) 【Chemical Formula 3】 (In the formula, R ７ ~R ８ each represents a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and this hydrocarbon group is aliphatic or aromatic, linear or branched, or has a cyclic structure.) [Chemical Formula 4] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and R ９ ~R １０ are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and the hydrocarbon groups of X and R ９ ~R １０ are each aliphatic or aromatic, linear or branched, or have a cyclic structure.) 【Chemical Formula 5】 (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and R １１ to R １３ are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and the hydrocarbon groups of X and R １１ to R １３ are each aliphatic or aromatic, linear or branched, or have a cyclic structure.) [Chemical Formula 6] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and R １４ ~R １７ are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a hetero atom, and the hydrocarbon groups of X and R １４ ~R １７ are each aliphatic or aromatic, linear or branched, or have a cyclic structure.) 【Chemical Formula 7】 (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and R １８ ~R １９ are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and the hydrocarbon groups of X and R １８ ~R １９ are each aliphatic or aromatic, linear or branched, or have a cyclic structure.) [Chemical Formula 8] (In the formula, X is a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and R ２０ ~R ２２ are each a hydrocarbon group having 1 to 25 carbon atoms which may contain a heteroatom, and the hydrocarbon groups of X and R ２０ ~R ２２ are each aliphatic or aromatic, linear or branched, or have a cyclic structure.)

2. The antifouling paint composition according to claim 1, wherein the ester compound C contains an ester compound represented by the chemical formulas (4) to (6).

3. The antifouling paint composition according to claim 2, wherein the hydrocarbon group of X in the chemical formulas (4) to (6) has a cyclic structure.

4. The antifouling paint composition according to claim 3, wherein the cyclic structure of the hydrocarbon group of X in the chemical formulas (4) to (6) has an aromatic ring structure.

5. The antifouling paint composition according to claim 3 or claim 4, wherein the cyclic structure of the hydrocarbon group of X in the chemical formulas (4) to (6) has an aliphatic six-membered ring structure.

6. The antifouling paint composition according to any one of claims 3 to 5, wherein the cyclic structure of the hydrocarbon group of X in the chemical formulas (4) to (6) has a heteroatom-containing cyclic structure.

7. The antifouling paint composition according to claim 2, wherein the hydrocarbon group of X in the chemical formulas (4) to (6) is linear or branched.

8. The antifouling paint composition according to claim 1, wherein the ester compound C contains an ester compound represented by the chemical formulas (7) to (8).

9. The antifouling paint composition according to claim 8, wherein the hydrocarbon group of X in the chemical formulas (7) to (8) has a cyclic structure.

10. The antifouling paint composition according to claim 9, wherein the cyclic structure of the hydrocarbon group of X in the chemical formulas (7) to (8) has at least one of an aromatic ring structure, an aliphatic six-membered ring structure, and a heteroatom-containing cyclic structure.

11. The antifouling paint composition according to claim 8, wherein the hydrocarbon group of X in the chemical formulas (7) to (8) is linear or branched.

12. The antifouling paint composition according to any one of claims 8 to 11, wherein the hydrocarbon group of X in the chemical formulas (7) to (8) has a heteroatom.

13. A coated article having on its surface an antifouling coating film formed using the antifouling paint composition according to any one of claims 1 to 12.

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