WO2023145634A1 - Antifouling coating material composition - Google Patents

Abstract

Provided is an antifouling coating material composition capable of maintaining the surface of a coating film in an excellent condition and also maintaining the antifouling performance at an excellent level for a long period of time.　According to the present invention, an antifouling coating material composition is provided, which comprises a copolymer A and an antifouling chemical substance, in which the copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) that is different from the monomer (a), the monomer (a) comprises a monomer (a1) and a monomer (a2), the monomer (a1) is represented by general formula (1), the monomer (a2) is represented by general formula (2), and the content of the monomer (a1) in the monomer (a) is 50 to 80% by mass.

Description

antifouling paint composition

The present invention relates to an antifouling paint composition.

Aquatic fouling organisms such as barnacles, serpra, mussels, mussels, sea squirts, green laver, sea lettuce, and slimes may be found on ships (especially on the bottom of ships), fishing nets, fishing tools such as fishing net accessories, and underwater structures such as power plant water pipes. There are problems such as the deterioration of the functions of the ships and the like and the deterioration of the appearance due to the adhesion.
In order to prevent such problems, 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, thereby providing long-term antifouling. Techniques for exhibiting performance are known (Patent Documents 1 to 4).
However, the antifouling coating film composed of a polymer containing a (meth)acrylic acid alkoxycarbonylmethyl ester group described in Patent Documents 1 to 4 has remarkably low coating film solubility, and therefore exhibits antifouling properties over a long period of time. It was difficult to demonstrate.
In order to solve these problems, a technique has been proposed in which the coating film dissolves over a long period of time to exhibit antifouling performance (Patent Document 5).

Japanese Patent Publication No. 63-61989 Japanese Patent Application Laid-Open No. 2003-119420 Japanese Patent Application Laid-Open No. 2003-119419 JP-A-2002-3776 WO2020/045211

The antifouling coating film made of the antifouling coating composition described in Patent Document 5 has improved coating film solubility, etc., but there is still room for improvement in terms of coating film physical properties such as cracks and peeling. There has been a demand for an antifouling coating composition capable of maintaining excellent coating film surface conditions and antifouling performance over a long period of time.
The present invention has been made in view of such circumstances, and provides an antifouling coating composition capable of maintaining excellent coating film surface conditions and antifouling performance over a long period of time.

According to the present invention, an antifouling coating composition containing a copolymer A and an antifouling agent, wherein the copolymer A comprises a monomer (a) and A copolymer of an ethylenically unsaturated monomer (b), wherein the monomer (a) is composed of a monomer (a1) and a monomer (a2), and 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 An antifouling coating composition is provided that is 50 to 80% by weight.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that a composition containing copolymer A and an antifouling agent can solve the above problems, and have completed the present invention.

The present invention will be described in detail below.
1. Antifouling Paint Composition The antifouling paint composition of the present invention contains the copolymer A and an antifouling agent, and may 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, more preferably 10 to 85% by mass. Specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95% by mass, where It may be within a range between any two of the exemplified numerical values, in which case the coating film 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, more preferably 60 to 70% by mass. The monomer (a1) has the property of increasing the coating film strength and lowering the coating film solubility as compared with the monomer (a2). Therefore, if the content of the monomer (a1) is too small, the strength of the coating film becomes too low, and the surface condition of the coating film tends to deteriorate after a long period of time. On the other hand, if the content of the monomer (a1) is too high, the coating film solubility may become too low, resulting in a decrease in the antifouling performance. The content of the monomer (a1) is, for example, 50, 55, 60, 65, 70, 75, 80% by mass, and may be within a range between any two of the numerical values exemplified here. .

<Monomer (a1)>
The monomer (a1) is represented by general formula (1).
(In the formula, R ¹ represents hydrogen or a methyl group, R ² represents hydrogen, a methyl group, or a phenyl group, and R ³ represents a hydrocarbon group having 5 to 12 carbon atoms or a hetero group having 2 to 12 carbon atoms. indicates a hydrocarbon group containing atoms.)

R ² is preferably hydrogen or a methyl group.

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

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

Examples of the monomer (a1) include
(meth) n-hexyl acrylate (oxycarbonylmethyl),
(meth)cyclohexyl acrylate (oxycarbonylmethyl),
(meth) 2-ethylhexyl acrylate (oxycarbonylmethyl),
(meth) phenyl (oxycarbonylmethyl) acrylate,
benzyl (oxycarbonylmethyl) (meth)acrylate,
(meth) 2-methoxyethyl (oxycarbonylmethyl) acrylate,
(meth) 2-ethoxyethyl acrylate (oxycarbonylmethyl),
(meth) 2-methoxyethoxyethyl (oxycarbonylmethyl) acrylate,
(meth) 2-phenoxyethyl acrylate (oxycarbonylmethyl),
(meth)acrylate tetrahydrofurfuryl(oxycarbonylmethyl)acrylate,
is mentioned.

<Monomer (a2)>
The monomer (a2) is represented by general formula (2).
In the formula, R ⁴ represents hydrogen or a methyl group, R ⁵ represents hydrogen, a methyl group, or a phenyl group, and R ⁶ represents a hydrocarbon group having 5 to 12 carbon atoms or a heteroatom having 2 to 12 carbon atoms. and n is an integer of 2-10. )

The descriptions of ^R5 and ^R6 are the same as for ^R2 and ^R3 .

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

The monomer (a2) preferably includes both a compound in which n is 2 and a compound in which n is 3 or more. In this case, there is a tendency for stable coating film dissolution to continue.

Examples of the monomer (a2) include
(meth) n-hexyl di(oxycarbonylmethyl)acrylate,
(meth)cyclohexyl di(oxycarbonylmethyl)acrylate,
(meth) 2-ethylhexyl di(oxycarbonylmethyl) acrylate,
(meth) phenyl di(oxycarbonylmethyl)acrylate,
benzyl di(oxycarbonylmethyl) (meth)acrylate,
(meth) 2-methoxyethyl di(oxycarbonylmethyl) acrylate,
(meth) 2-ethoxyethyl di(oxycarbonylmethyl) acrylate,
(meth) 2-methoxyethoxyethyl di(oxycarbonylmethyl) acrylate,
(meth) 2-phenoxyethyl di(oxycarbonylmethyl) acrylate,
(meth)acrylate tetrahydrofurfuryl di(oxycarbonylmethyl)acrylate,

(meth) n-hexyl tri(oxycarbonylmethyl)acrylate,
(meth)cyclohexyl tri(oxycarbonylmethyl)acrylate,
(meth) 2-ethylhexyl tri(oxycarbonylmethyl) acrylate,
(meth) phenyl tri(oxycarbonylmethyl)acrylate,
benzyl tri(oxycarbonylmethyl) (meth)acrylate,
(meth) 2-methoxyethyl tri(oxycarbonylmethyl) acrylate,
(meth) 2-ethoxyethyl tri(oxycarbonylmethyl) acrylate,
(meth) 2-methoxyethoxyethyl tri(oxycarbonylmethyl)acrylate,
(meth) 2-phenoxyethyl tri(oxycarbonylmethyl) acrylate,
(meth)acrylate tetrahydrofurfuryl tri(oxycarbonylmethyl)acrylate,

(meth) n-hexyl acrylate poly(oxycarbonylmethyl),
(meth)cyclohexyl acrylate poly(oxycarbonylmethyl),
(meth) 2-ethylhexyl acrylate poly(oxycarbonylmethyl),
(meth)phenyl poly(oxycarbonylmethyl)acrylate,
benzyl (meth)acrylate poly(oxycarbonylmethyl),
2-methoxyethyl (meth)acrylate poly(oxycarbonylmethyl),
2-ethoxyethyl (meth)acrylate poly(oxycarbonylmethyl),
(meth) 2-methoxyethoxyethyl poly(oxycarbonylmethyl) acrylate,
(meth) 2-phenoxyethyl acrylate poly(oxycarbonylmethyl),
(meth)acrylate tetrahydrofurfurylpoly(oxycarbonylmethyl)acrylate,
are mentioned,

Preferably,
(meth)cyclohexyl acrylate (oxycarbonylmethyl),
(meth) phenyl (oxycarbonylmethyl) acrylate,
(meth) 2-methoxyethyl (oxycarbonylmethyl) acrylate,
(meth) 2-phenoxyethyl acrylate (oxycarbonylmethyl),
(meth)acrylate tetrahydrofurfuryl(oxycarbonylmethyl)acrylate,

(meth)cyclohexyl di(oxycarbonylmethyl)acrylate,
(meth) phenyl di(oxycarbonylmethyl)acrylate,
(meth) 2-methoxyethyl di(oxycarbonylmethyl) acrylate,
(meth) 2-phenoxyethyl di(oxycarbonylmethyl) acrylate,
(meth)acrylate tetrahydrofurfuryl di(oxycarbonylmethyl)acrylate,

(meth)cyclohexyl tri(oxycarbonylmethyl)acrylate,
(meth) phenyl tri(oxycarbonylmethyl)acrylate,
(meth) 2-methoxyethyl tri(oxycarbonylmethyl) acrylate,
(meth) 2-phenoxyethyl tri(oxycarbonylmethyl) acrylate,
(meth)acrylate tetrahydrofurfuryl tri(oxycarbonylmethyl)acrylate,

(meth)cyclohexyl acrylate poly(oxycarbonylmethyl),
(meth)phenyl poly(oxycarbonylmethyl)acrylate,
2-methoxyethyl (meth)acrylate poly(oxycarbonylmethyl),
(meth) 2-phenoxyethyl acrylate poly(oxycarbonylmethyl),
(Meth)acrylic acid tetrahydrofurfurylpoly(oxycarbonylmethyl).

In this specification, (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester.

1-1-2. monomer (b)
Monomer (b) is an ethylenically unsaturated monomer other than monomer (a). The monomer (b) can be classified into a monomer (b1) and a monomer (b2). ) and monomer (b2), or both.

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

The number of carbon atoms in the branched alkyl group is, for example, 3, 4, 5, 6, 7, or 8, and may be within a range between any two of the numerical values exemplified here. Branched alkyl groups include, for example, isopropyl group, isopropenyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-dimethyl propyl group, 1,1-dimethylbutyl group, thexyl 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 and the like. R ⁸ to R ¹⁰ are preferably the same or different and are preferably isopropyl, isopropenyl, s-butyl, t-butyl, phenyl, and 2-ethylhexyl, particularly preferably isopropyl and 2-ethylhexyl groups.

Examples of the monomer (b1) include triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, meth (Meth)triphenylsilyl acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyl s-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, (meth)acrylate Isopropyldiisobutylsilyl acrylate, isopropyldi-s-butylsilyl (meth)acrylate, t-butyldiisobutylsilyl (meth)acrylate, t-butyldiisopentylsilyl (meth)acrylate, t-(meth)acrylate Butyldiphenylsilyl, diisopropylthexylsilyl (meth)acrylate, diisopropylcyclohexylsilyl (meth)acrylate, tricyclohexylsilyl (meth)acrylate, tri-1,1-dimethylpentylsilyl (meth)acrylate, (meth)acrylic Tri-2,2-dimethylpropylsilyl acid, tricyclohexylmethylsilyl (meth)acrylate, diisopropylcyclohexylmethylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, tri-2-propyl (meth)acrylate (meth)acrylic acid silyl esters such as pentylsilyl, and the like. etc. These monomers (c) can be used individually or in combination of 2 or more types.

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

<Monomer (b2)>
The monomer (b2) is obtained by removing the monomer (b1) from the monomer (b). In other words, the monomer (b2) is a monomer not represented by any of general formulas (1) to (3). Examples of the monomer (b2) include (meth)acrylic acid esters, vinyl compounds, aromatic compounds, and dialkyl ester compounds of dibasic acids, which are not represented by the general formulas (1) to (3). In addition, in this specification, (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester.

Examples of (meth)acrylic acid esters not represented by general formulas (1) to (3) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate. , t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, (meth)acrylic Acid 4-methoxybutyl, 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, methacryl Acid 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl, succinic acid mono(2-(meth)acryloyloxyethyl), N-(3-dimethylaminopropyl)(meth)acrylamide, (meth)acryl (Meth)acrylic acid esters such as 2-hydroxyethyl acid, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate and N,N'-dimethyl(meth)acrylamide.

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, and N-vinylpyrrolidone. be done.

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

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

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

1-1-3. Physical Properties and Production Method of Copolymer A The weight average molecular weight (Mw) of Copolymer A is preferably 5,000 to 300,000. If the molecular weight is less than 5,000, the coating film of the antifouling paint will be brittle and easily peeled off or cracked. Specifically, this Mw is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000. may be within the range.

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

Copolymer A is a random copolymer, alternating copolymer, periodic copolymer, or block copolymer of monomer (a) and monomer (b). may

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

Examples of the polymerization initiator include 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 and other azo compounds; benzoylper oxide, di-tert-butylperoxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, t- Peroxides such as amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. -methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate is preferred, and the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.

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

In the polymerization reaction, an organic solvent may be used as necessary. The organic solvent is not particularly limited, but for example, xylene, ethylbenzene, aromatic hydrocarbon solvents such as 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, 3-ethoxypropionic acid Ester solvents such as ethyl; isopropyl alcohol, butyl alcohol, propylene glycol monomethyl ether, diacetone alcohol, 2-butoxyethanol, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, 2-phenoxypropanol alcohol solvents such as dioxane, diethyl ether, dibutyl ether, tetrahydrofuran, furan, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether; A ketone-based solvent such as acetophenone and the like are included.
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-methylpropionate 2- Methyl propyl, ethyl 3-ethoxypropionate, butyl alcohol, 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 mono Butyl 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 according to the type of polymerization initiator, etc., and is usually 50 to 160°C, preferably 60 to 150°C.

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

1-2. Copolymer B
Copolymer B is a copolymer of monomer (b1) and monomer (b2), and contains monomer units derived from monomer (b1) and monomer (b2). The content of the monomer (b1) with respect to the sum of the monomers (b1) and (b2) is preferably 10 to 90% by mass, more preferably 20 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, the numerical values exemplified here It may be in the range between any two. In this case, the coating film solubility is particularly good.

Regarding the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc., the methods described above for copolymer A can be applied.

The content of the copolymer B in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A is converted to solid content, and the mass ratio (copolymer B/copolymer A) is It is usually 0.05 to 0.9, preferably 0.05 to 0.7. This mass ratio is, for example, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, where may be within a range between any two of the numerical values exemplified in .

1-3. Antifouling Agents Antifouling agents include, for example, inorganic agents and organic agents.
Examples of inorganic chemicals include cuprous oxide, copper thiocyanate (common name: rhodan copper), and copper powder. Among these, cuprous oxide and rhodan copper are particularly preferable, and cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, lycithin, mineral oil, etc. is preferred for long-term storage stability. is more preferable.
Examples of organic agents include copper 2-mercaptopyridine-N-oxide (generic name: copper pyrithione), zinc 2-mercaptopyridine-N-oxide (generic name: zinc pyrithione), zinc ethylene bisdithiocarbamate (generic name: Zineb ), 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: Seanine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: Irgalol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: medetomidine) and the like. In addition, these organic agents can be adsorbed on activated carbon, encapsulated by coating, converted into organic salts, or diluted with various solvents to improve handling and effectiveness. Organic agents that are appropriately adjusted by the technique can also be used.
These antifouling agents can be used singly or in combination of two or more.

Although the content of the antifouling agent in the composition of the present invention is not particularly limited, it 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 a range between any two of the numerical values exemplified here.

1-4. Other Additives Further, the antifouling paint composition of the present invention may optionally contain resin components other than copolymers A and B, elution modifiers, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents, An antifouling paint can be prepared by adding a thixotropic agent, an organic solvent, or the like.

Examples of other resin components include polymer P and the like.
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 the copolymer A, methyl (meth)acrylate and ethyl (meth)acrylate , Butyl (meth)acrylate, Isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-(meth)acrylate Ethoxyethyl, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate and the like are preferred.
The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like can be applied to the method described above for copolymer A.

The content of the polymer P in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A, in terms of solid content, the mass ratio (polymer P / copolymer A) is usually 0 0.05 to 0.7, preferably 0.05 to 0.6. This mass ratio is, for example, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7. It may be within a range between two.

Dissolution modifiers include, for example, monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. salts or the above alicyclic hydrocarbon resins. These can be used singly or in combination of two or more.
Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
Examples of the alicyclic hydrocarbon resin include commercially available products such as Quinton 1500, 1525L, and 1700 (trade names, manufactured by Nippon Zeon Co., Ltd.).
Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferred.

Examples of the plasticizer include phosphates, phthalates, cyclohexanecarboxylic acid esters, adipates, sebacates, polyesters, epoxidized soybean oil, alkyl vinyl ether polymers, and polyalkylene glycols. , t-nonylpentasulfide, vaseline, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, and the like. These can be used singly or in combination of two or more.

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

The organic solvent is not particularly limited, but includes, for example, the solvents described as the organic solvent in the polymerization reaction of the copolymer A. 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, butyl alcohol, propylene glycol monomethyl ether, Propylene glycol 1-monomethyl ether 2-acetate, 2-butoxyethanol, ethylene glycol propyl ether, 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.

2. Method for producing antifouling coating composition The antifouling coating composition of the present invention can be prepared, for example, by mixing and dispersing a mixture containing a copolymer, an antifouling agent, other additives, etc. using a disperser. can be manufactured.
It is preferable that the mixed liquid is prepared by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.
As the disperser, for example, one that can be used as a fine pulverizer can be suitably used. For example, a commercially available homomixer, sand mill, bead mill, disper, etc. can be used. Alternatively, the mixed liquid may be mixed and dispersed using a container equipped with a stirrer to which glass beads or the like for mixing and dispersing are added.

3. Antifouling Treatment Method, Antifouling Coating Film, and Coated Object In the antifouling treatment method of the present invention, the antifouling coating composition is used to form an antifouling coating film on the surface of a coating film-forming object. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing adhesion of aquatic fouling organisms.
Examples of the object to be coated include ships (particularly ship bottoms), fishing tools, underwater structures, and the like.
The thickness of the antifouling coating film may be set as appropriate according to the type of object to be coated, sailing speed of the ship, seawater temperature, and the like. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating is usually 50-700 μm, preferably 100-600 μm.

Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to the examples and the like.
% in each Production Example, Example and Comparative Example indicates % by mass. The weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC. The conditions for GPC are as follows.
Apparatus: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSKgel SuperHZM-M 2 Flow rate: 0.35 mL/min
Detector... RI
Column constant temperature bath temperature: 40°C
Eluent... THF
The heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Coating component test method-heating residue".

1. Production Example 1-1. Production Example of Monomer (a1) <Production Example 1 (Production of Monomer a1-1)>
A four-neck flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, normal hexyl chloroacetate: 178 g (1.00 mol), acrylic acid: 72 g (1.00 mol), 4-methoxyphenol: 0.1 g, Ethyl acetate: 500 g was charged as a solvent, and triethylamine: 101 g (1.00 mol) was added dropwise while stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed in order with city water, hydrochloric acid water, and sodium bicarbonate water, and the solvent was distilled off by vacuum concentration to obtain 175 g of monomer a1-1.

<Production Examples 2 to 12 (production of monomers a1-2 to a1-12)>
Monomers a1-2 to a1-12 were obtained by performing reactions in the same manner as in Production Example 1 using the raw materials shown in Table 1. Table 1 shows the amount of each raw material used and the yield of the product obtained in Production Examples 2 to 12 together with the results of Production Example 1.

<Production Example 13 (production of monomer a2-1)>
(First reaction)
Sodium monochloroacetate: 233 g (2.00 mol), normal hexyl chloroacetate: 356 g (2.00 mol), N-methyl-2-pyrrolidone: 400 g were placed in a four-necked flask equipped with a thermometer, a condenser, and a stirrer. After charging, the mixture was stirred at 70 to 80° C. for 6 hours. After completion of the reaction, 500 ml of toluene was added to the reaction mixture, and the organic layer was washed in this order with city water, hydrochloric acid, and sodium bicarbonate. [(First reaction) intermediate]: 400 g was obtained.

(Second reaction)
Next, normal-hexyl 2-(2-chloroacetoxy)acetate, which is the product of the first reaction [(first reaction) intermediate], was added to a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel. : 200 g (0.85 mol), acrylic acid: 61 g (0.85 mol), 4-methoxyphenol: 0.1 g, and ethyl acetate: 500 g. It was dripped while maintaining. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in that order, and the solvent was distilled off by vacuum concentration to obtain 190 g of monomer a2-1.

<Production Examples 14 to 55 (production of monomers a2-2 to a2-43)>
Monomers a2-1 to a2-43 were obtained by performing reactions in the same manner as in Production Example 13 using starting materials shown in Tables 2 to 4. Tables 2 to 4 show the amounts of raw materials used and the yields of the obtained monomers in Production Examples 14 to 55 together with the results of Production Example 13.

<Comparative Production Example 1 (production of monomer b2-1)>
In a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, methyl chloroacetate: 109 g (1.00 mol), acrylic acid: 72 g (1.00 mol), 4-methoxyphenol: 0.1 g, Ethyl acetate: 500 g was charged, and triethylamine: 101 g (1.00 mol) was added dropwise while stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in that order, and the solvent was distilled off by vacuum concentration to obtain 129.7 g of monomer b2-1.

<Comparative Production Example 2 (production of monomer b2-2)>
(First reaction)
A four-necked flask equipped with a thermometer, a condenser, and a stirrer was charged with 233 g (2.00 mol) of sodium monochloroacetate, 216 g (2.00 mol) of methyl chloroacetate, and 400 g of N-methyl-2-pyrrolidone. , and stirred at 70-80° C. for 6 hours. After completion of the reaction, 500 ml of toluene was added to the reaction solution, and the organic layer was washed in this order with city water, hydrochloric acid water, and sodium bicarbonate water. Intermediate]: 280 g were obtained.

(Second reaction)
Then, 200 g (1.20 mol) of the product of the first reaction, methoxycarbonylmethyl chloroacetate [(first reaction) intermediate]: 200 g (1.20 mol) ), acrylic acid: 87 g (1.20 mol), 4-methoxyphenol: 0.1 g, and ethyl acetate: 500 g were charged, and triethylamine: 122 g (1.20 mol) was added dropwise with stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in that order, and the solvent was distilled off by vacuum concentration to obtain 205 g of monomer b2-2.

<Comparative Production Examples 3 to 6 (production of monomers b2-3 to b2-6)>
Monomers b2-3 to b2-6 were obtained by performing reactions in the same manner as in Comparative Production Example 2 using the starting materials shown in Tables 5 to 7. Tables 5 to 7 show the amounts of raw materials used and the yields of the obtained monomers in Comparative Production Examples 3 to 6 together with the results of Comparative Production Example 2.

The details of the raw materials in Tables 1 to 7 are as follows.
H: hydrogen Me: methyl group Hx: normal hexyl group Ch: cyclohexyl group 2EtHx: 2-ethylhexyl group Ph: phenyl group 2-MeOEt: 2-methoxyethyl group 2-PhOEt: 2-phenoxyethyl group THFMe: tetrahydrofurfuryl group

AA: acrylic acid MAA: methacrylic acid NMP: N-methyl-2-pyrrolidone CANa: sodium monochloroacetate CPANa: sodium 2-chloropropionate CAMe: methyl chloroacetate CAHx: normal 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. Production Example of Copolymer Solution <Production Example P1 (Production of Copolymer Solution A-1)>
A four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel was charged with xylene: 10 g, n-butyl acetate: 75 g, 1-butanol: 5 g, and propylene glycol monomethyl ether: 5 g as solvents, Nitrogen gas was introduced and the temperature was maintained at 88° C. while stirring. Then, the monomer (a) and the monomer (b) in the amount (g) shown in Table 8 and 1,1,3,3-tetramethylbutylperoxy-2-ethyl as a polymerization initiator Hexanoate: A mixture of 2.0 g (initial addition) was added dropwise over 3 hours while maintaining the temperature at 88°C. Then, after stirring at 88 ° C. for 1 hour, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate: 0.1 g was added 3 times every hour, and the temperature was the same. After stirring for 2 hours at , the mixture was cooled to room temperature to obtain a copolymer solution A-1. Table 8 shows the heating residue and Mw of A-1.

<Production Examples P2 to P22 (production of copolymer solutions A-2 to A-18, B-1, and C-1 to C-3)>
Copolymer solutions A-2 to A-18, B-1, and C were obtained by performing a polymerization reaction in the same manner as in Production Example P1, except that the monomers and solvents shown in Tables 8 to 11 were used. -1 to C-3 were obtained. Tables 8 to 11 show the heating residue and Mw of each polymer. The unit of numerical values for the amounts of raw materials in the tables is g, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, which is a polymerization initiator, In each production example, an appropriate amount was added so as to obtain the Mw of each copolymer described in .

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 are placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer, and dehydrated under reduced pressure at 70-80° C. for 1 hour under reduced pressure to obtain xylene of gum rosin. A solution (brown clear liquid, 50% solids) was obtained. The heating residue of the resulting solution was 50.3%.

<Production Example D2 (Production of gum rosin zinc salt solution)>
In a flask equipped with a thermometer, a reflux condenser, and a stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene are added to the flask, and 120 g of zinc oxide is added so that all the resin acids in the rosin form zinc salts. was added, and dehydration was carried out under reduced pressure at 70 to 80° C. for 3 hours. Thereafter, the mixture was cooled and filtered to obtain a xylene solution of gum rosin zinc salt (dark brown transparent liquid, solid content 50%). The heating residue of the resulting 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 in the same manner as in Production Example D2, except that Chinese gum rosin (WW) in Production Example D2 was changed to hydrogenated gum rosin.

<Production Example D4 (Production of trimethylisobutenylcyclohexenecarboxylic acid solution)>
320 g of alloocimene, 175 g of methacrylic acid and 0.17 g of MEHQ were placed in a flask equipped with a thermometer, a reflux condenser and a stirrer, and heated and stirred at 35-45° C. for 24 hours. Thereafter, unreacted raw materials were distilled off under reduced pressure to obtain 73 g of trimethylisobutenylcyclohexenecarboxylic acid with brown viscosity. Xylene was added to this to prepare a trimethylisobutenylcyclohexenecarboxylic acid solution (solid content: 50%).

2. Examples 1 to 33 and Comparative Examples 1 to 3 (production of coating composition)
A coating composition was produced by blending the components shown in Tables 12 to 18 at the ratios (% by mass) shown in the same tables and mixing and dispersing the mixture with glass beads having a diameter of 1.5 to 2.5 mm.

The details of the components in the table are as follows.
<Elution modifier>
Gum rosin solution: Use the one produced in Production Example D1 Gum rosin zinc salt solution: Use the one produced in Production Example D2 Hydrogenated rosin zinc salt solution: Use the one produced in Production Example D3 Trimethylisobutenylcyclohexenecarboxylic acid solution : Use the one produced in Production Example D4.

<Anti-fouling agent>
Cuprous oxide: trade name “NC-301” (manufactured by Nisshin Chemco Co., Ltd.)
Rhodan copper: Cuprous thiocyanate (manufactured by Nippon Kagaku Sangyo Co., Ltd.)
Copper pyrithione: trade name “Copper Omagin” (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% active ingredient in xylene solution Zineb: [ethylene bis(dithiocarbamate)] zinc (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
Diuron: Product name “Diuron” (manufactured by Tokyo Chemical Industry Co., Ltd.)
Tolylfluanid: trade name "Preventol A 5-S (manufactured by 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>
Bengara: Product name "Bengara goldfish" (manufactured by Morishita Bengara Kogyo Co., Ltd.)
Talc: Product name “Talc MS” (manufactured by Nippon Talc Co., Ltd.)
Zinc oxide: Product name “Type 2 zinc oxide” (manufactured by Seido Chemical Industry Co., Ltd.)
Titanium oxide: trade name “FR-41” (manufactured by Furukawa Co., Ltd.)

<Other additives>
Disparlon A603-20X: amide-based thixotropic agent: trade name "Disparlon A603-20X" (manufactured by Kusumoto Kasei Co., Ltd.)
Tetraethoxysilane: trade name “Ethyl Silicate 28” (manufactured by Colcoat Co., Ltd.)
Tricresyl phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)

3. Tests The following tests were performed on the coating compositions of Examples and Comparative Examples. Evaluation results are shown in Tables 12 to 18.
All comparative examples did not perform as well in at least one of the rotary test and immersion test as compared to the examples.

<Test Example 1 (rotary test)>
A rotating drum with a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank, and it was made to rotate by a motor. In addition, a cooling device for keeping the seawater temperature constant and a pH automatic controller for keeping the seawater pH constant were installed.
A test plate was prepared according to the following method.
First, on a titanium plate (71×100×0.5 mm), an antirust paint (epoxy vinyl A/C) is applied so that the thickness after drying is about 100 μm, and dried to form an antirust coating film. bottom. After that, the coating compositions obtained in Examples and Comparative Examples were applied so that the dry film thickness was about 300 μm, and dried at 40° C. for 3 days to prepare a test panel.
The prepared test plate was fixed to the rotating drum of the rotating device of the apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this period, the temperature of the seawater was kept at 25°C and the pH at 8.0-8.2, and the seawater was replaced every two weeks.
After 36 months from the start of the test on each test plate, the surface condition of the coating film was evaluated by observing the surface of each coating film with the naked eye and a microscope.
The coating film surface condition was evaluated according to the following criteria.
S: No abnormality A: Hair cracks observed in less than 10% of the total coating surface area.
B: Hair cracks observed in 10% or more and less than 30% of the total coating surface area.
C: Hair cracks observed in 30% or more and less than 50% of the total coating surface area.
D: Hair cracks observed in 50% or more of the total coating surface area.
E: Abnormalities in the paint film such as large cracks, blisters or peeling (only the surface of the paint film and part of the edge are peeled off), peeling (the entire paint film is peeled off and no test paint film remains). What can be done.

<Test Example 2 (immersion test)>
The coating compositions obtained in Examples and Comparative Examples were applied to both sides of a hard PVC board (100×200×2 mm) so that the thickness of the dry coating film would be about 300 μm. A test plate having a dry coating film having a thickness of about 300 μm was prepared by drying the obtained coated material at room temperature (25° C.) for 3 days. This test plate was immersed 1.5 m below the sea surface in Sakai City, Osaka Prefecture, and the fouling of the test plate due to deposits was observed after 24 months and 36 months.

The evaluation was carried out by visually observing the state of the coating film surface, and judged according to the following criteria.
⊚: No attachment of fouling organisms such as shellfish and algae, and almost no slime.
◯: No fouling organisms such as shellfish and algae adhered, and slime was thinly adhered (to the extent that the coating film surface was visible), but could be removed by lightly wiping with a brush.
Δ: No fouling organisms such as shellfish or algae adhered, but the slime adhered so thickly that the coating film surface was not visible, and could not be removed by wiping strongly with a brush.
x: Level at which fouling organisms such as shellfish and algae adhere.

Claims (2)

1. An antifouling paint composition containing 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 (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),
   An antifouling paint composition, wherein the content of the monomer (a1) in the monomer (a) is 50 to 80% by mass.
   (In the formula, R ¹ represents hydrogen or a methyl group, R ² represents hydrogen, a methyl group, or a phenyl group, and R ³ represents a hydrocarbon group having 5 to 12 carbon atoms or a hetero group having 2 to 12 carbon atoms. indicates a hydrocarbon group containing atoms.)
   (In the formula, R ⁴ represents hydrogen or a methyl group, R ⁵ represents hydrogen, a methyl group, or a phenyl group, and R ⁶ represents a hydrocarbon group having 5 to 12 carbon atoms or a hetero group having 2 to 12 carbon atoms. represents a hydrocarbon group containing atoms, and n represents an integer of 2 to 10.)
2. The antifouling paint composition according to claim 1,
   Furthermore, it contains a copolymer B,
   The monomer (b) is composed of a monomer (b1) and a monomer (b2) other than the monomer (b1),
   The monomer (b1) is represented by the general formula (3),
   The antifouling coating composition, wherein the copolymer B is a copolymer of the monomer (b1) and the monomer (b2).
   (In the formula, R ⁷ is hydrogen or a methyl group, and R ⁸ to R ¹⁰ are the same or different and represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group.)