CN118591599A - Antifouling coating composition - Google Patents

Abstract

The present invention provides an antifouling coating composition capable of maintaining excellent coating surface state and antifouling performance for a long period of time. According to the present invention, an antifouling coating composition is provided, which contains a copolymer A and an antifouling agent, wherein the copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is composed of a monomer (a1) and a monomer (a2), wherein the monomer (a1) is represented by the general formula (1), and the monomer (a2) is represented by the general formula (2), and the content of the monomer (a1) in the monomer (a) is 50% to 80% by mass.

Description

Antifouling coating composition

Technical Field

The present invention relates to antifouling coating compositions.

Background Art

Due to the attachment of aquatic fouling organisms such as barnacles, cyprinids, blue mussels, bryozoans, tunicates, Enteromorpha, Ulva, and biological slime to ships (especially the bottom of ships), fishing nets, fishing net accessories and other fishing gear, and underwater structures such as water pipes of power stations, there is a problem that the functions of the above-mentioned ships are hindered and their appearance is damaged.

In order to prevent such problems, there is known a technique in which an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is slowly released from the antifouling coating film to thereby exhibit antifouling performance for a long period of time (Patent Documents 1 to 4).

However, the antifouling coating films composed of the polymer containing carbonylmethyl (meth)acrylate groups described in Patent Documents 1 to 4 have significantly poor coating solubility and therefore have difficulty in exhibiting antifouling properties for a long period of time.

In order to solve these problems, a technique has been proposed in which a coating film is dissolved over a long period of time to exhibit antifouling performance (Patent Document 5).

[Prior art literature]

[Patent Document]

Patent Document 1: Japanese Patent Publication No. 63-61989

Patent Document 2: Japanese Patent Application Publication No. 2003-119420

Patent Document 3: Japanese Patent Application Publication No. 2003-119419

Patent Document 4: Japanese Patent Application Publication No. 2002-3776

Patent Document 5: WO2020/045211

Summary of the invention

[Problems to be Solved by the Invention]

Although the antifouling coating film formed from the antifouling coating composition described in Patent Document 5 has improved coating solubility, etc., there is still room for improvement in coating properties such as cracking and peeling, and an antifouling coating composition that can maintain excellent coating surface conditions and antifouling performance for a long period of time is desired.

The present invention has been made in view of the above circumstances, and provides an antifouling coating composition capable of maintaining excellent coating film surface conditions and antifouling performance for a long period of time.

[Methods for solving the problem]

According to the present invention, an antifouling coating composition is provided, which contains a copolymer A and an antifouling agent, wherein the copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), the monomer (a) is composed of a monomer (a1) and a monomer (a2), the monomer (a1) is represented by the general formula (1), the monomer (a2) is represented by the general formula (2), and the content of the monomer (a1) in the monomer (a) is 50% by mass to 80% by mass.

The present inventors have conducted intensive studies to solve the above problems and, as a result, have found that a composition comprising a copolymer A and an antifouling agent can solve the above problems, thereby completing the present invention.

DETAILED DESCRIPTION

Hereinafter, the present invention will be described in detail.

1. Antifouling coating composition

The antifouling coating composition of the present invention contains the copolymer A and the antifouling agent, and may also contain the copolymer B and other additives.

1-1. Copolymer A

Copolymer A is a copolymer containing monomer (a), and the content of monomer (a) is preferably 5% to 95% by mass, and more preferably 10% to 85% by mass. Specifically, for example, it is 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95% by mass, and can be within the range between any two of the numerical values exemplified herein, in which case, the coating solubility is particularly good.

1-1-1. Monomer (a)

Monomer (a) is composed of monomer (a1) and monomer (a2). The content of monomer (a1) in monomer (a) is 50% to 80% by mass, preferably 55% to 75% by mass, and more preferably 60% to 70% by mass. Monomer (a1) has the property of improving film strength and reducing film solubility compared with monomer (a2). Therefore, when the content of monomer (a1) is too little, there is a situation where the film strength becomes too low and the surface state of the film is easy to deteriorate after a long time. On the other hand, when the content of monomer (a1) is too much, there is a situation where the film solubility becomes too low and the antifouling performance decreases. The content of monomer (a1) is, for example, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, 80% by mass, and can be in the range between any two numerical values exemplified here.

<Monomer (a1)>

The monomer (a1) is represented by the general formula (1).

[Chemistry 1]

In formula (1), ^R1 represents hydrogen or a methyl group, ^R2 represents hydrogen, a methyl group or a phenyl group, and ^R3 represents a hydrocarbon group having 5 to 12 carbon atoms or a hydrocarbon group having 2 to 12 carbon atoms and containing a hetero atom.

^R2 is preferably hydrogen or methyl.

The number of carbon atoms of the hydrocarbon group of R ³ is, for example, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within the range between any two of the values exemplified here. The hydrocarbon group of R ³ is, for example, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, isononyl, neononyl, decyl, isodecyl, dodecyl, phenyl, tolyl, benzyl, naphthyl, or biphenyl, preferably n-hexyl, cyclohexyl, 2-ethylhexyl, phenyl, tolyl, or benzyl.

The number of carbon atoms of the heteroatom-containing hydrocarbon group of R ³ is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within the range between any two of the values exemplified herein. The heteroatom is preferably an oxygen atom, a nitrogen atom, or a sulfur atom, and more preferably an oxygen atom. The heteroatom-containing hydrocarbon group of R ³ is, for example, 2-methoxyethyl, 2-ethoxyethyl, 2-methoxyethoxyethyl, 2-phenoxyethyl, furfuryl, or tetrahydrofurfuryl, and preferably 2-methoxyethyl, 2-phenoxyethyl, or tetrahydrofurfuryl.

Examples of the monomer (a1) include:

n-Hexyl(oxycarbonylmethyl)(meth)acrylate

Cyclohexyl(oxycarbonylmethyl)(meth)acrylate

2-Ethylhexyl(oxycarbonylmethyl)(meth)acrylate

Phenyl(oxycarbonylmethyl)(meth)acrylate

Benzyl(oxycarbonylmethyl)(meth)acrylate

2-Methoxyethyl(oxycarbonylmethyl)(meth)acrylate

2-Ethoxyethyl(oxycarbonylmethyl)(meth)acrylate

2-Methoxyethoxyethyl (oxycarbonylmethyl) (meth)acrylate

2-Phenoxyethyl(oxycarbonylmethyl)(meth)acrylate Tetrahydrofurfuryl(oxycarbonylmethyl)(meth)acrylate

<Monomer (a2)>

The monomer (a2) is represented by the general formula (2).

[Chemistry 2]

In formula (2), ^R4 represents hydrogen or methyl, ^R5 represents hydrogen, methyl or phenyl, ^R6 represents a hydrocarbon group having 5 to 12 carbon atoms or a hydrocarbon group having 2 to 12 carbon atoms and containing a heteroatom, and n represents an integer of 2 to 10.

The explanations of ^R5 and ^R6 are the same as those of ^R2 and ^R3 .

n represents an integer of 2 to 10, and from the viewpoint of long-term antifouling properties, it is preferably 2 to 6. n is, for example, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and may be within the range between any two of the values exemplified here.

As the monomer (a2), it is preferred that both a compound in which n is 2 and a compound in which n is 3 or more are contained. In this case, a tendency is observed that stable coating film dissolution continues.

Examples of the monomer (a2) include:

n-Hexyl di(oxycarbonylmethyl) (meth)acrylate

Cyclohexylbis(oxycarbonylmethyl)(meth)acrylate

2-Ethylhexyl di(oxycarbonylmethyl) (meth)acrylate

Phenyl di(oxycarbonylmethyl) (meth)acrylate

Benzyl di(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethyl bis(oxycarbonylmethyl) (meth)acrylate

2-Ethoxyethyl di(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethoxyethyl bis(oxycarbonylmethyl) (meth)acrylate 2-phenoxyethyl bis(oxycarbonylmethyl) (meth)acrylate Tetrahydrofurfuryl bis(oxycarbonylmethyl) (meth)acrylate

n-Hexyl tri(oxycarbonylmethyl) (meth)acrylate

Cyclohexyltri(oxycarbonylmethyl)(meth)acrylate

2-Ethylhexyl tri(oxycarbonylmethyl) (meth)acrylate

Phenyl tris(oxycarbonylmethyl) (meth)acrylate

Benzyl tri(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethyl tris(oxycarbonylmethyl) (meth)acrylate

2-Ethoxyethyl tris(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethoxyethyl tris(oxycarbonylmethyl) (meth)acrylate 2-phenoxyethyl tris(oxycarbonylmethyl) (meth)acrylate Tetrahydrofurfuryl tris(oxycarbonylmethyl) (meth)acrylate

Poly(oxycarbonylmethyl)(meth)acrylate

Cyclohexyl poly(oxycarbonylmethyl) (meth)acrylate

2-Ethylhexyl poly(oxycarbonylmethyl) (meth)acrylate

Poly(oxycarbonylmethyl)phenyl(meth)acrylate

Benzyl poly(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethyl poly(oxycarbonylmethyl) (meth)acrylate

2-Ethoxyethyl poly(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethoxyethyl poly(oxycarbonylmethyl) (meth)acrylate 2-phenoxyethyl poly(oxycarbonylmethyl) (meth)acrylate Tetrahydrofurfuryl poly(oxycarbonylmethyl) (meth)acrylate

Preferred examples include:

Cyclohexyl(oxycarbonylmethyl)(meth)acrylate

Phenyl(oxycarbonylmethyl)(meth)acrylate

2-Methoxyethyl(oxycarbonylmethyl)(meth)acrylate

2-Phenoxyethyl(oxycarbonylmethyl)(meth)acrylate Tetrahydrofurfuryl(oxycarbonylmethyl)(meth)acrylate

Cyclohexylbis(oxycarbonylmethyl)(meth)acrylate

Phenyl di(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethyl bis(oxycarbonylmethyl) (meth)acrylate

2-Phenoxyethyl di(oxycarbonylmethyl) (meth)acrylate Tetrahydrofurfuryl di(oxycarbonylmethyl) (meth)acrylate

Cyclohexyltri(oxycarbonylmethyl)(meth)acrylate

Phenyl tris(oxycarbonylmethyl) (meth)acrylate

2-Methoxyethyl tris(oxycarbonylmethyl) (meth)acrylate

2-Phenoxyethyl tris(oxycarbonylmethyl)(meth)acrylate Tetrahydrofurfuryl tris(oxycarbonylmethyl)(meth)acrylate

Cyclohexyl poly(oxycarbonylmethyl) (meth)acrylate

Poly(oxycarbonylmethyl)phenyl(meth)acrylate

2-Methoxyethyl poly(oxycarbonylmethyl) (meth)acrylate

2-Phenoxyethyl poly(oxycarbonylmethyl) (meth)acrylate Tetrahydrofurfuryl poly(oxycarbonylmethyl) (meth)acrylate

In addition, in this specification, (meth)acrylate means acrylate or methacrylate.

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 monomer (b) used for polymerization of copolymer A includes one or both of monomer (b1) and monomer (b2).

<Monomer (b1)>

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

In formula (3), ^R7 represents hydrogen or a methyl group, and ^R8 to ^R10 each represent, identically or differently, a branched alkyl group having 3 to 8 carbon atoms or a phenyl group.

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 values exemplified herein. Examples of branched alkyl groups include isopropyl, isopropenyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, tert-hexyl, 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. Preferred groups for R ⁸ to R ¹⁰ are, respectively, isopropyl, isopropenyl, sec-butyl, tert-butyl, phenyl, and 2-ethylhexyl, and particularly preferred groups are isopropyl and 2-ethylhexyl.

Examples of the monomer (b1) include triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-sec-butylsilyl (meth)acrylate, triisoamylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropylsec-butylsilyl (meth)acrylate, diisopropylisoamylsilyl (meth)acrylate, isopropyldiisobutylsilyl (meth)acrylate, isopropyldi-sec-butylsilyl (meth)acrylate, tert-butyldiisobutylsilyl (meth)acrylate, Silyl (meth)acrylates such as tert-butyldiisopentylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, diisopropyltert-hexylsilyl (meth)acrylate, diisopropylcyclohexylsilyl (meth)acrylate, tricyclohexylsilyl (meth)acrylate, tri-1,1-dimethylpentylsilyl (meth)acrylate, tri-2,2-dimethylpropylsilyl (meth)acrylate, tricyclohexylmethylsilyl (meth)acrylate, diisopropylcyclohexylmethylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, and tri-2-propylpentylsilyl (meth)acrylate.

These monomers (b1) can be used alone or in combination of two or more.

<Monomer (b2)>

Monomer (b2) is a monomer other than monomer (b1) in monomer (b). In other words, monomer (b2) is a monomer not represented by any one of general formulas (1) to (3). Examples of monomer (b2) include (meth)acrylates, vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, etc., which are not represented by general formulas (1) to (3). It should be noted that in this specification, (meth)acrylate refers to acrylate or methacrylate.

Examples of the (meth)acrylates not represented by the general formulae (1) 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, propylene glycol monomethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 4-methoxybutyl (meth)acrylate. (Meth)acrylic acid esters such as 2-hydroxypropyl 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.

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.

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

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

In copolymer A, these monomers (b) can be used alone or in two or more forms. From the viewpoint of film solubility and film properties, monomer (b) preferably includes (meth) acrylate of monomer (b1) or monomer (b2). From the viewpoint of crack resistance, monomer (b) preferably includes (meth) acrylate of monomer (b2), more preferably includes 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 film solubility, monomer (b) preferably includes monomer (b1), more preferably includes triisopropylsilyl (meth) acrylate, tert-butyldiphenylsilyl (meth) acrylate, tri-2-ethylhexylsilyl (meth) acrylate, etc.

1-1-3. Physical properties and production method of copolymer A

The weight average molecular weight (Mw) of copolymer A is preferably 5000 to 300000. This is because if the molecular weight is less than 5000, the coating film of the antifouling coating becomes fragile and easily causes peeling and cracking. In addition, if it exceeds 300000, the viscosity of the polymer solution increases and it is difficult to handle. The Mw is specifically, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and may also be within the range between any two values exemplified here.

As a method for measuring Mw, gel permeation chromatography (GPC method) is mentioned, for example.

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

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

Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, dimethyl 2,2'-azobisisobutyrate, and 2,2'-azobis(N-butyl-2-methylpropionamide); benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, and tert-butyl peroxide. 2-ethylhexanoic acid tert-butyl ester, peroxy-2-ethylhexanoic acid tert-hexyl ester, di-tert-hexyl peroxide, peroxy-2-ethylhexyl monocarbonate tert-butyl ester, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxy neodecanoate, tert-amyl peroxy neodecanoate, tert-hexyl peroxy pivalate, tert-amyl peroxy pivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate and other peroxides, etc., these polymerization initiators can be used alone or in combination of two or more. As the above-mentioned polymerization initiator, 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 are particularly preferred. The molecular weight of copolymer A can be adjusted by appropriately setting the amount of polymerization initiator used.

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 because the copolymer A can be obtained easily and accurately.

In the above-mentioned polymerization reaction, an organic solvent may be used as needed. The organic solvent is not particularly limited, and examples thereof include aromatic hydrocarbon solvents such as xylene, ethylbenzene, and toluene; aliphatic hydrocarbon solvents; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether 2-acetate, 3-methoxy-3-methylbutyl acetate, diethylene glycol monoethyl ether acetate, butyl propionate, ethyl 2-methylpropionate, 2-methylpropyl 2-methylpropionate, ethyl 3-ethoxypropionate, and other ester solvents. ; Alcohol solvents such as isopropyl alcohol, butanol, propylene glycol monomethyl ether, diacetone alcohol, 2-butoxyethanol, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and 2-phenoxypropanol; ether solvents such as dioxane, diethyl ether, dibutyl ether, tetrahydrofuran, furan, diethylene glycol dimethyl ether, and triethylene glycol dimethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclohexanone, isophorone, and acetophenone, etc. Among them, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether 2-acetate, 3-methoxy-3-methylbutyl acetate, butyl propionate, ethyl 2-methylpropionate, 2-methylpropyl 2-methylpropionate, ethyl 3-ethoxypropionate, butanol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, 2-butoxyethanol, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclohexanone, isophorone, acetophenone, toluene, ethylbenzene, and xylene are preferred. These solvents can be used alone or in combination of two or more.

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

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

1-2. Copolymer B

Copolymer B is a copolymer of monomer (b1) and monomer (b2), comprising monomer units derived from monomer (b1) and monomer (b2). Relative to the total of monomer (b1) and monomer (b2), the content of monomer (b1) is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 70% by mass. Specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, and it is also possible to be in the range between any two of the numerical values exemplified here. At this time, the coating solubility is particularly good.

The methods described in Copolymer A can be applied to the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like.

The content of copolymer B in the composition of the present invention is not particularly limited, and the content ratio of copolymer B to copolymer A is generally 0.05 to 0.9, preferably 0.05 to 0.7, calculated on a solid basis. The mass ratio is, for example, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, or 0.9, and may also be within the range between any two of the values exemplified herein.

1-3. Antifouling agents

Examples of the antifouling agent include inorganic agents and organic agents.

Examples of the inorganic agent include cuprous oxide, copper thiocyanate (common name: copper thiocyanate), copper powder, etc. Among them, cuprous oxide and copper thiocyanate are particularly preferred, and cuprous oxide surface-treated with glycerol, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc. is more preferred from the viewpoint of long-term stability during storage.

Examples of the organic agent include copper 2-pyridinethione-N-oxide (common name: copper pyrithione), zinc 2-pyridinethione-N-oxide (common name: zinc pyrithione), zinc ethylenebisdithiocarbamate (common name: zincineb), 4,5-dichloro-2-n-octyl-3-isothiazolinone (common name: SeaNine 211), 3,4-dichlorophenyl-N-N-dimethylurea (common name: Diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol 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). In addition, there are methods of improving operability and effectiveness by adsorbing these organic agents on activated carbon, or encapsulating them by coating, or converting them into organic salts, or diluting them with various solvents. Organic agents appropriately adjusted by these methods can also be used.

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

The content of the antifouling agent in the composition of the present invention is not particularly limited, and is generally 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 also be within the range between any two of the values exemplified here.

1-4. Other additives

Furthermore, the antifouling coating composition of the present invention can be prepared by adding resin components other than the copolymers A and B, dissolution regulators, plasticizers, pigments, dyes, defoamers, dehydrating agents, thixotropic agents, organic solvents, etc. as needed to the antifouling coating composition.

As other resin components, polymer P etc. are mentioned, for example.

The polymer P is a polymer obtained by polymerizing the above-mentioned monomer (b2).

In the present invention, monomer (b2) can be used alone or in combination of two or more. In particular, from the viewpoint of compatibility with copolymer A, preferred monomers are methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, and the like.

The methods described in Copolymer A can be applied to the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like.

The content of polymer P in the composition of the present invention is not particularly limited, and the content ratio of polymer P to copolymer A is generally 0.05 to 0.7, preferably 0.05 to 0.6, in terms of solid content. The mass ratio is, for example, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, or 0.7, and may also be within the range between any two of the values exemplified here.

Examples of the dissolution modifier include rosin, rosin derivatives, cycloalkanoic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, tert-butyl carboxylic acid, trimethylisobutenylcyclohexene carboxylic acid, and monocarboxylic acids and salts thereof such as metal salts thereof, and the aforementioned alicyclic hydrocarbon resins. These may be used alone or in combination of two or more.

Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.

Examples of commercially available alicyclic hydrocarbon resins include Quintone 1500, 1525L, and 1700 (trade names, manufactured by ZEON Corporation of Japan).

Among them, rosin, rosin derivatives, cycloalkane acid, versatile carbonic acid, trimethylisobutenylcyclohexene carboxylic acid, or metal salts thereof are preferred.

Examples of the plasticizer include phosphates, phthalates, cyclohexanecarboxylates, adipic acid esters, sebacates, polyesters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tert-nonyl pentasulfide, vaseline, polybutene, tri(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, etc. These may be used alone or in combination of two or more.

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

As the above-mentioned organic solvent, there is no particular limitation, for example, solvents recorded as organic solvents in the polymerization reaction of copolymer A, etc. can be cited, wherein preferably butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether 2-acetate, 3-methoxy-3-methylbutyl acetate, butyl propionate, 2-methylethyl propionate, 2-methylpropyl 2-methylpropionate, 3-ethoxyethyl propionate, butanol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, 2-butoxyethanol, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ketone, cyclohexanone, isophorone, acetophenone, toluene, ethylbenzene, xylene. These solvents can be used alone or in combination of two or more.

2. Method for producing antifouling coating composition

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

The mixed solution is preferably a mixed solution in which various materials such as the copolymer and the antifouling agent are dissolved or dispersed in a solvent.

As the above-mentioned dispersing machine, for example, a dispersing machine that can be used as a micro-pulverizer can be preferably used. For example, a commercially available homogeneous mixer, a sand mill, a bead mill, a dispersing machine, etc. can be used. In addition, the above-mentioned mixed solution can also be mixed and dispersed using a device in which glass beads for mixing and dispersing are added to a container equipped with a stirrer.

3. Antifouling treatment methods, antifouling coatings and coatings

The antifouling treatment method of the present invention uses the above-mentioned antifouling coating composition to form an antifouling coating on the surface of the object to be coated. According to the antifouling treatment method of the present invention, the antifouling coating is gradually dissolved from the surface, and the coating surface is always renewed, thereby preventing the attachment of aquatic fouling organisms. Examples of the object to be coated include ships (especially the bottom of a ship), fishing gear, underwater structures, etc.

The thickness of the antifouling coating may be appropriately set according to the type of the coating object, the navigation speed of the ship, the seawater temperature, etc. For example, when the coating object is the bottom of a ship, the thickness of the antifouling coating is usually 50 μm to 700 μm, preferably 100 μm to 600 μm.

[Example]

The features of the present invention will be further clarified by describing examples and the like below, but the present invention is not limited to the examples and the like.

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

Device: HLC-8220GPC manufactured by Tosoh Corporation

Column: TSKgel SuperHZM-M 2 pieces

Flow rate: 0.35mL/min

Detector: RI

Column thermostat temperature: 40°C

Eluent: THF

The heating residual content is a value measured in accordance with JIS K5601-1-2: 1999 (ISO 3251: 1993) "Testing methods for coating components - Heating residual content".

1. Manufacturing Example

1-1. Production Example of Monomer (a1)

<Production Example 1 (Production of Monomer a1-1)>

In a four-necked flask equipped with a thermometer, a cooler, a stirring device and a dropping funnel, 178 g (1.00 mol) of n-hexyl chloroacetate, 72 g (1.00 mol) of acrylic acid, 0.1 g of 4-methoxyphenol, and 500 g of ethyl acetate as a solvent were added, and 101 g (1.00 mol) of triethylamine was added dropwise while stirring and maintaining the temperature below 40°C. After the addition was completed, the mixture was stirred at 70°C to 80°C for 6 hours. After the reaction was completed, the organic layer was washed in the order of tap water, hydrochloric acid water, and sodium bicarbonate water, and the solvent was removed by concentrated distillation under reduced pressure, thereby obtaining 175 g of monomer a 1-1.

<Production Examples 2 to 12 (Production of Monomers a1-2 to a1-12)>

Using the raw materials shown in Table 1, monomers a1-2 to a1-12 were obtained by the same reaction as in Production Example 1. The amounts of raw materials used in Production Examples 2 to 12 and the yields of the obtained products are shown in Table 1 together with the results of Production Example 1.

[Table 1]

<Production Example 13 (Production of Monomer a2-1)>

(First reaction)

In a four-necked flask equipped with a thermometer, a cooler, and a stirring device, sodium monochloroacetate: 233g (2.00mol), n-hexyl chloroacetate: 356g (2.00mol), and N-methyl-2-pyrrolidone: 400g were added, and stirred at 70°C to 80°C for 6 hours. After the reaction was completed, toluene: 500ml was added to the reaction solution, and the organic layer was washed in the order of tap water, hydrochloric acid water, and sodium bicarbonate water, and then the solvent was removed by concentrated distillation under reduced pressure to obtain 400g of n-hexyl 2-(2-chloroacetoxy)acetate [(first reaction) intermediate].

(Second reaction)

Next, 200 g (0.85 mol) of 2-(2-chloroacetoxy)acetic acid n-hexyl ester [(first reaction) intermediate] as the first reaction product, 61 g (0.85 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, a cooler, a stirring device, and a dropping funnel, and 86 g (0.85 mol) of triethylamine were added dropwise while stirring and maintaining the temperature below 40°C. After the addition was completed, the mixture was stirred at 70°C to 80°C for 6 hours. After the reaction was completed, the organic layer was washed with tap water, hydrochloric acid water, and sodium bicarbonate water in this order, and the solvent was removed by concentrated distillation under reduced pressure, thereby obtaining 190 g of monomer a 2-1.

<Production Examples 14 to 55 (Production of Monomers a2-2 to a2-43)>

Using the raw materials shown in Tables 2 to 4, monomers a2-1 to a2-43 were obtained by the same reaction as in Production Example 13. The amounts of raw materials used in Production Examples 14 to 55 and the yields of the obtained monomers are shown in Tables 2 to 4 together with the results of Production Example 13.

[Table 2]

[Table 3]

[Table 4]

<Comparative Production Example 1 (Production of Monomer b2-1)>

In 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 added, and 101 g (1.00 mol) of triethylamine was added dropwise while stirring and maintaining the temperature below 40°C. After the addition was completed, the mixture was stirred at 70°C to 80°C for 6 hours. After the reaction was completed, the organic layer was washed with tap water, hydrochloric acid water and sodium bicarbonate water in this order, and the solvent was removed by concentrated distillation under reduced pressure to obtain 129.7 g of monomer b 2-1.

<Comparative Production Example 2 (Production of Monomer b2-2)>

(First reaction)

In a four-necked flask equipped with a thermometer, a cooler, and a stirring device, sodium monochloroacetate: 233g (2.00mol), methyl chloroacetate: 216g (2.00mol), and N-methyl-2-pyrrolidone: 400g were added, and stirred at 70°C to 80°C for 6 hours. After the reaction was completed, toluene: 500ml was added to the reaction solution, and the organic layer was washed in the order of tap water, hydrochloric acid water, and sodium bicarbonate water, and then the solvent was removed by vacuum concentration and distillation to obtain methyloxycarbonyl chloroacetate [(first reaction) intermediate]: 280g.

(Second reaction)

Next, 200 g (1.20 mol) of methyloxycarbonyl chloroacetate [(first reaction) intermediate] as the first reaction product, 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, a cooler, a stirring device, and a dropping funnel, and 122 g (1.20 mol) of triethylamine was added dropwise while stirring and maintaining the temperature below 40°C. After the addition was completed, the mixture was stirred at 70°C to 80°C for 6 hours. After the reaction was completed, the organic layer was washed in the order of tap water, hydrochloric acid water, and sodium bicarbonate water, and the solvent was removed by concentrated distillation under reduced pressure, thereby obtaining 205 g of monomer b 2-2.

<Comparative Production Examples 3 to 6 (Production of Monomers b2-3 to b2-6)>

Using the raw materials shown in Tables 5 to 7, monomers b2-3 to b2-6 were obtained by the same reaction as in Comparative Preparation Example 2. The amounts of raw materials used and the yields of the obtained monomers in Comparative Preparation Examples 3 to 6 are shown in Tables 5 to 7 together with the results of Comparative Preparation Example 2.

[Table 5]

[Table 6]

[Table 7]

The details of the raw materials in Tables 1 to 7 are as follows.

H: Hydrogen

Me：Methyl

Hx: n-hexyl

Ch：Cyclohexyl

2EtHx: 2-ethylhexyl

Ph: phenyl

2-MeOEt:2-Methoxyethyl

2-PhOEt:2-Phenoxyethyl

THFMe: Tetrahydrofurfuryl

AA: Acrylic acid

MAA: Methacrylic acid

NMP: N-methyl-2-pyrrolidone

CANa: Sodium monochloroacetate

CPANa: Sodium 2-chloropropionate

CAMe: methyl chloroacetate

CAHx: n-hexyl chloroacetate

CACh: Cyclohexyl chloroacetate

CA2-EtHx: 2-ethylhexyl chloroacetate CAPh: phenyl chloroacetate

CA2-MeOEt: 2-methoxyethyl chloroacetate CA2-PhOEt: 2-phenoxyethyl chloroacetate CATHFMe: Tetrahydrofurfuryl chloroacetate

MEHQ: 4-Methoxyphenol

TEA: triethylamine

1-3. Example of Preparation 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, 10 g of xylene, 75 g of n-butyl acetate, 5 g of 1-butanol and 5 g of propylene glycol monomethyl ether as solvents were placed, nitrogen was introduced, and the temperature was maintained at 88°C while stirring. A mixed solution of monomers (a) and (b) in the amounts (g) shown in Table 8 and 2.0 g (initial addition) of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator was added dropwise for 3 hours while being maintained at 88°C. Thereafter, after stirring at 88°C for 1 hour, 0.1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every 1 hour, and after further stirring at the same temperature for 2 hours, the mixture was cooled to room temperature to obtain a copolymer solution A-1. The heating residual component and Mw of A-1 are shown in Table 8.

<Production Examples P2 to P22 (Production of Copolymer Solutions A-2 to A-18, B-1, and C-1 to C-3)>

The monomers and solvents shown in Tables 8 to 11 were used, and except for this, polymerization reactions were carried out in the same manner as in Production Example P1, thereby obtaining copolymer solutions A-2 to A-18, B-1, and C-1 to C-3. The heating residual components and Mw of each polymer are shown in Tables 8 to 11. It should be noted that the unit of the blending amount of the raw materials in the table is g, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator was added in an appropriate amount in each production example so as to obtain the Mw of each copolymer described in Tables 8 to 11.

[Table 8]

[Table 9]

[Table 10]

[Table 11]

1-4. Other manufacturing 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 cooler and a stirrer, and refluxed and dehydrated at 70°C to 80°C under reduced pressure 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%.

<Production Example D2 (Production of Gum Rosin Zinc Salt Solution)>

240 g of Chinese gum rosin (WW) and 360 g of xylene were added to a flask equipped with a thermometer, a reflux cooler and a stirrer, and 120 g of zinc oxide was added to convert all the resin acids in the above rosin into zinc salts. The mixture was refluxed and dehydrated at 70°C to 80°C under reduced pressure for 3 hours. Then, the mixture was cooled and filtered to obtain a xylene solution of gum rosin zinc salt (dense brown transparent liquid, solid content 50%). The heating residue of the obtained solution was 50.2%.

<Production Example D3 (Production of Hydrogenated Rosin Zinc Salt Solution)>

A xylene solution of hydrogenated rosin zinc salt (dark brown transparent liquid, solid content 50%) was obtained by the same method as in Production Example D2 except that the Chinese gum rosin (WW) in Production Example D2 was changed to hydrogenated gum rosin.

<Production Example D4 (Production of Trimethylisobutenylcyclohexenecarboxylic Acid Solution)>

In a flask equipped with a thermometer, a reflux cooler and a stirrer, 320 g of alloocimene, 175 g of methacrylic acid and 0.17 g of MEHQ were added, and heated and stirred at 35°C to 45°C for 24 hours. Then, unreacted raw materials were distilled off under reduced pressure to obtain 73 g of brown viscous trimethylisobutenylcyclohexenecarboxylic acid. Xylene was added thereto to prepare a trimethylisobutenylcyclohexenecarboxylic acid solution (solid content 50%).

2. Examples 1 to 33 and Comparative Examples 1 to 3 (Manufacturing of coating compositions)

The components shown in Tables 12 to 18 were blended in the ratios (mass %) shown in the tables, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to prepare coating compositions.

[Table 12]

[Table 13]

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

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

<Dissolution regulator>

Gum rosin solution: The gum rosin solution prepared in Preparation Example D1 was used.

Gum rosin zinc salt solution: The gum rosin zinc salt solution prepared in Preparation Example D2 was used.

Hydrogenated rosin zinc salt solution: The hydrogenated rosin zinc salt solution prepared in Preparation Example D3 was used.

Trimethylisobutenylcyclohexenecarboxylic acid solution: the trimethylisobutenylcyclohexenecarboxylic acid solution prepared in Preparation Example D4 was used.

<Antifouling Agents>

Cuprous oxide: trade name "NC-301" (manufactured by NISSIN CHEMCO LTD.)

Copper thiocyanate: Cuprous thiocyanate (manufactured by Nippon Chemical Industry Co., Ltd.)

Copper pyrithione: Trade name "Copper Omadine" (manufactured by LONZA Corporation)

Sea Nine: Trade name "Sea Nine 211", 4,5-dichloro-2-octyl-4-isothiazolin-3-one (manufactured by R&H Co.), 30% active ingredient solution in xylene

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

Diuron: Trade name "DIURON" (manufactured by Tokyo Chemical Industry Co., Ltd.)

Tolylfluanid: Trade name "Preventol A5-S (Lanxess)

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.)

<Pigment>

Bengala Kingyoku: Trade name "Bengala Kingyoku" (Morishita Bengara Industries Co., Ltd.)

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

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

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

<Other additives>

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

Tetraethoxysilane: Trade name "Ethyl Silicate 28" (manufactured by Colcoat Co., Ltd.)

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

3. Experiment

The coating compositions of Examples and Comparative Examples were subjected to the following tests. The evaluation results are shown in Tables 12 to 18.

In all the comparative examples, at least one of the results of the rotation test and the immersion test was inferior to that of the examples.

<Test Example 1 (Rotation Test)>

A drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for maintaining the temperature of the seawater at a constant level and a pH automatic controller for maintaining the pH of the seawater at a constant level were installed.

The test plate was prepared as follows.

First, a rust-proof coating (epoxy-based A/C) was applied to a titanium plate (71×100×0.5 mm) so that the thickness after drying was about 100 μm and dried to form a rust-proof coating film. Then, the coating composition obtained in the examples and comparative examples was applied so that the dry film thickness was about 300 μm and dried at 40° C. for 3 days to prepare a test plate.

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

36 months after the start of the test of each test plate, the surface of each coating film was observed with the naked eye and a microscope to evaluate the surface condition of the coating film.

The coating film surface condition was evaluated according to the following criteria.

S: No abnormality at all

A: Fine cracks are observed in less than 10% of the total coating film surface area.

B: Fine cracks are observed in 10% or more and less than 30% of the total area of the coating film surface.

C: Fine cracks are observed in 30% or more and less than 50% of the total area of the coating film surface.

D: Fine cracks are observed over 50% or more of the total surface area of the coating film.

E: Abnormalities of the coating film such as large cracks, blistering, peeling (only the surface or part of the edge of the coating film peels off), and detachment (the entire coating film peels off, and no test coating film remains) are observed.

<Test Example 2 (Immersion Test)>

The coating compositions obtained in the examples and comparative examples were applied to both surfaces of a hard vinyl chloride plate (100×200×2 mm) in such a manner that the thickness of the dry coating film was about 300 μm. The obtained coating 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. The test plate was immersed 1.5 m below the sea surface in Sakai City, Osaka Prefecture, and the staining of the test plate caused by the attached matter was observed after 24 months and 36 months.

Evaluation was performed by visually observing the state of the coating film surface, and judgment was made based on the following criteria.

◎: There is no fouling organisms such as shellfish and algae attached, and there is almost no slime.

○: There is no fouling organisms such as shellfish and algae attached, and slime is thinly attached (to the extent that the coating surface is visible), but it can be removed by lightly wiping with a brush.

△: There is no fouling organisms such as shellfish and algae attached, but the slime is so thick that the coating surface cannot be seen, and it cannot be removed even by strong rubbing with a brush.

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

Claims (2)

1. An antifouling paint composition comprising a copolymer A and an antifouling agent,

The copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a),

The monomer (a) is composed of a monomer (a 1) and a monomer (a 2),

The monomer (a 1) is represented by the general formula (1),

The monomer (a 2) is represented by the general formula (2),

The content of the monomer (a 1) in the monomer (a) is 50 to 80 mass%,

[ Chemical 1]

In the formula (1), R ¹ represents hydrogen or methyl, R ² represents hydrogen, methyl or phenyl, R ³ represents a hydrocarbon group having 5 to 12 carbon atoms or a hydrocarbon group having 2 to 12 carbon atoms and containing a hetero atom,

[ Chemical 2]

In the formula (2), R ⁴ represents hydrogen or methyl, R ⁵ represents hydrogen, methyl or phenyl, R ⁶ represents a hydrocarbon group having 5 to 12 carbon atoms or a hydrocarbon group having 2 to 12 carbon atoms and containing a hetero atom, and n represents an integer of 2 to 10.

2. An antifouling paint composition according to claim 1, wherein,

Further comprises a copolymer B which is used for the polymerization of the monomers,

The monomer (b) is composed of a monomer (b 1) and a monomer (b 2) other than the monomer (b 1),

The monomer (b 1) is represented by the general formula (3),

The copolymer B is a copolymer of the monomer (B1) and the monomer (B2),

[ Chemical 3]

In the formula (3), R ⁷ represents hydrogen or methyl, and R ⁸～R¹⁰ each represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group, the same or different.