JP7588835B2 - Antifouling paint composition - Google Patents

Description

The present invention relates to an antifouling paint composition.

Aquatic fouling organisms such as barnacles, serpula, mussels, moss animals, sea squirts, green laver, sea lettuce, slime, etc. attach to ships (especially the bottom of the ship), fishing equipment such as fishing nets and fishing net accessories, and underwater structures such as power plant water pipes, impairing the functionality of those ships and damaging their appearance.

To prevent such problems, a technology is known in which an antifouling paint composition is applied to a ship or the like to form an antifouling coating film, and the antifouling agent is gradually released from the antifouling coating film, thereby providing antifouling performance over a long period of time (Patent Documents 1 to 4).

However, the antifouling coating films made of (meth)acrylic acid alkoxycarbonyl methyl ester group-containing polymers described in Patent Documents 1 to 4 have extremely low coating film solubility, making it difficult for them to exhibit antifouling properties over a long period of time.
In order to solve these problems, a technique has been proposed that dissolves the coating film and allows the coating film to exhibit antifouling properties over a long period of time (Patent Document 5).

Special Publication No. 63-61989 JP 2003-119420 A JP 2003-119419 A Patent No. 2002-3776 WO2020/045211 publication

The antifouling coating film made of the antifouling coating composition described in Patent Document 5 has improved coating film solubility, but there is a tendency for the coating film solubility to be less uniform at the beginning of immersion and after a long period of time has elapsed. In addition, there is still room for improvement in terms of coating film physical properties such as cracking and peeling. Therefore, there has been a demand for an antifouling coating composition that can maintain excellent coating film surface conditions and antifouling performance for a long period of time.

The present invention was made in consideration of these circumstances, and provides an antifouling paint composition that can maintain excellent coating surface condition and antifouling performance for a long period of time.

According to the present invention, there is provided an antifouling coating composition containing copolymer A and fiber B, in which the copolymer A is a copolymer of monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer (a) is represented by general formula (1).

As a result of extensive research into solving the above problems, the inventors discovered that the above antifouling paint composition can solve the above problems, and thus completed the present invention.

The present invention is explained in detail below.

1. Antifouling Coating Composition The antifouling coating composition of the present invention contains copolymer A and fiber B.

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

<Monomer (a)>
The monomer (a) is represented by the general formula (1).

In the formula, ^R1 represents hydrogen or a methyl group, ^R2 represents hydrogen, a methyl group, or a phenyl group, ^R3 represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of 2 to 10.

^R2 is preferably hydrogen or a methyl group.

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

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

Examples of monomer (a) include poly(oxycarbonylmethyl) methyl (meth)acrylate, poly(oxycarbonylmethyl) ethyl (meth)acrylate, poly(oxycarbonylmethyl) isopropyl (meth)acrylate, poly(oxycarbonylmethyl) n-propyl (meth)acrylate, poly(oxycarbonylmethyl) n-butyl (meth)acrylate, poly(oxycarbonylmethyl) t-butyl (meth)acrylate, poly(oxycarbonylmethyl) 2-ethylhexyl (meth)acrylate, poly(oxycarbonylmethyl) cyclohexyl (meth)acrylate, poly(oxycarbonylmethyl) benzyl (meth)acrylate, poly(oxycarbonylmethyl) phenyl (meth)acrylate, poly(oxycarbonylmethyl) 2-methoxyethyl (meth)acrylate, poly(oxycarbonylmethyl) 4-methacrylate [0113] Examples of the poly(oxycarbonylmethyl) (meth)acrylate include oxybutyl poly(oxycarbonylmethyl), allyl (meth)acrylate poly(oxycarbonylmethyl), vinyl (meth)acrylate poly(oxycarbonylmethyl), methyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], ethyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], n-propyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], isopropyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], n-butyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], t-butyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], methyl (meth)acrylate poly[α-(oxycarbonyl)benzyl], and ethyl (meth)acrylate poly[α-(oxycarbonyl)benzyl]. Preferred examples include methyl (meth)acrylate poly(oxycarbonylmethyl), ethyl (meth)acrylate poly(oxycarbonylmethyl), isopropyl (meth)acrylate poly(oxycarbonylmethyl), n-propyl (meth)acrylate poly(oxycarbonylmethyl), n-butyl (meth)acrylate poly(oxycarbonylmethyl), methyl (meth)acrylate poly[1-(oxypolycarbonylethyl)], ethyl (meth)acrylate poly[1-(oxypolycarbonylethyl)], etc. These monomers (a) can be used alone or in combination of two or more.

The monomer (a) preferably includes those in which n in general formula (1) is 2 and those in which n is 3 to 10, and the mass ratio (n(2)/n(2 to 10)) in terms of solid content is preferably 0.4 to 0.8, more preferably 0.5 to 0.7. In this case, it is preferable from the viewpoint of the coating film solubility and coating film physical properties. Specific examples of this value are 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, and 0.80, and may be within a range between any two of the numerical values exemplified here.

<Monomer (b)>
The monomer (b) is an ethylenically unsaturated monomer other than the monomer (a), and examples thereof include (meth)acrylic acid esters, vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, etc. In this specification, the (meth)acrylic acid ester means an acrylic acid ester or a methacrylic acid ester.

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, propylene glycol monomethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, acrylates such as 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; acrylates such as methoxycarbo(meth)acrylate, nylmethyl, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, t-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyloxycarbonylmethyl (meth)acrylate, phenoxycarbonylmethyl (meth)acrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, 4-methoxybutoxycarbonylmethyl (meth)acrylate, (meth)acrylic acid alkoxycarbonylmethyl esters such as allyloxycarbonylmethyl acrylate, vinyloxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, 1-(ethoxycarbonyl)ethyl (meth)acrylate, 1-(n-propoxycarbonyl)ethyl (meth)acrylate, 1-(isopropoxycarbonyl)ethyl (meth)acrylate, 1-(n-butoxycarbonyl)ethyl (meth)acrylate, 1-(t-butoxycarbonyl)ethyl (meth)acrylate, α-(methoxycarbonyl)benzyl (meth)acrylate, and α-(ethoxycarbonyl)benzyl (meth)acrylate;
Triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, triphenylsilyl meth(meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyls-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, isopropyldiisobutylsilyl (meth)acrylate, isopropyldi-s-butylsilyl (meth)acrylate, t-butyldiisobutylsilyl (meth)acrylate, t-butyl(meth)acrylate Examples of silyl (meth)acrylate esters include diisopentylsilyl, t-butyldiphenylsilyl (meth)acrylate, diisopropylthexylsilyl (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.

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.

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

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

In the present invention, these monomers (b) can be used alone or in combination of two or more. In particular, from the viewpoint of coating film solubility and coating film physical properties, (meth)acrylic acid esters are preferred as monomer (b). In particular, from the viewpoint of crack resistance, methyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like are more preferred. In addition, from the viewpoint of coating film solubility, triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, and the like are more preferred.

1-1-2. Properties and manufacturing method of copolymer A The weight average molecular weight (Mw) of copolymer A is desirably 5000 to 300,000. If the molecular weight is less than 5000, the coating film of the antifouling paint becomes fragile and is prone to peeling and cracking, and if it exceeds 300,000, the viscosity of the polymer solution increases, making it difficult to handle. Specific examples of Mw are 5000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000, and 300,000, and may be within a range between any two of the numerical values exemplified here.

One example of a method for measuring Mw is gel permeation chromatography (GPC).

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

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 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, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, di-t-hexyl peroxide, t-butylperoxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, and 1 , 1,3,3-tetramethylbutylperoxyneodecanoate, t-amylperoxyneodecanoate, t-hexylperoxypivalate, t-amylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and other peroxides. These polymerization initiators can be used alone or in combination of two or more. As the 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-tetramethylbutylperoxy-2-ethylhexanoate are particularly preferred. By appropriately setting the amount of polymerization initiator used, the molecular weight of copolymer A can be adjusted.

Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. Among these, solution polymerization and non-aqueous dispersion polymerization are particularly preferred because they can easily and accurately obtain copolymer A.

In the polymerization reaction, an organic solvent may be used as necessary. The organic solvent is not particularly limited, but examples thereof include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, and propylene glycol 1-monomethyl ether 2-acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
Among these, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene are preferable. These solvents can be used alone or in combination of two or more kinds.

The reaction temperature in the polymerization reaction may be set appropriately depending on 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 under an inert gas atmosphere such as nitrogen gas or argon gas.

1-2. Fiber B
The fiber B of the present invention includes any fiber in the group consisting of natural inorganic fibers, synthetic inorganic fibers, natural organic fibers, synthetic organic fibers and metal fibers or mixtures thereof, and is characterized in that it has one long dimension and two short dimensions.

For example, mineral fibers such as mineral glass fiber, wollastonite fiber, montmorillonite fiber, tobermonite fiber, attapulgite fiber, calcined bauxite fiber, volcanic rock fiber, bauxite fiber, rock wool fiber, mineral fiber processed from mineral wool, polyethylene fiber, polypropylene fiber, cotton fiber, cellulose fiber, polyacrylonitrile fiber, pre-oxidized polyacrylonitrile fiber, and polyester fiber can be mentioned.

The surface of fiber B may or may not be modified (surface treated) by chemical or physical methods. Examples of fiber modification methods include carbonization; silylation; surface oxidation; etching such as treatment with alkali metal hydroxides or treatment with hydrofluoric acid; coating; incorporation of polyelectrolytes into the porous surface structure; adsorption methods; hydrogen bonding methods; cation bonding methods; esterification; anion bonding methods, etc., as well as fiber manufacturing processes.

Of these, particularly preferred are mineral fibers such as mineral glass fiber, wollastonite fiber, montmorillonite fiber, tobermorite fiber, attapulgite fiber, calcined bauxite fiber, volcanic rock fiber, bauxite fiber, rock wool fiber, and mineral fibers processed from mineral wool.

Commercially available products of fiber B include, for example, volcanic rock fiber MS600 (untreated, average fiber length 125 μm, average fiber thickness 5 μm), volcanic rock fiber MS603 (untreated, average fiber length 125 μm, average fiber thickness 5 μm) (all manufactured by Lapinus Fibers BV), rock wool F 554/1 SR (average fiber length 500 μm, average fiber thickness 5 μm), ceramic F 580/1 S (average fiber length 500 μm, average fiber thickness 2.8 μm), polyacrylonitrile F PAC 238/040 (average fiber length 500 μm), polyester/polyamide F PES 231/040 (average fiber length 500 μm, average fiber thickness 10-20 μm), preoxidized polyacrylonitrile F PAC O 245/040 (average fiber length 500 μm, average fiber thickness 10-12 μm), polypropylene fiber F PP 261/040 (average fiber length 500 μm, average fiber thickness 21 μm), polyacrylonitrile fiber F PAC 235/040 (average fiber length 500 μm) (all manufactured by Schwarzwalder Textil-Werke), glass fiber PF E-001 (untreated), PF E-301 (silane-treated), glass fiber SS 05C-404 (silane-treated, average cut length 0.1 mm), glass fiber SS 10-420 (silane-treated, average cut length 0.3 mm) (all manufactured by Nitto Boseki Co., Ltd.), glass fiber EPH 80M-10A (silane-treated, average cut length 80 μm), glass fiber EPH Examples of mineral fibers include 80M-80A (silane-treated, average cut length 80 μm) (all manufactured by Nippon Electric Glass Co., Ltd.), which are preferred for improving mechanical properties.

The content of Fiber B in the composition of the present invention is not particularly limited, but is usually 0.1 to 20 mass %, preferably 1 to 15 mass %, and particularly preferably 4 to 10 mass %, calculated as solid content. Specific examples of the content of Fiber B are 0.1, 1, 2, 4, 5, 6, 7, 8, 9, 10, 15, and 20 mass %, and may be within a range between any two of the numerical values exemplified here.

1-3. Antifouling Agents Antifouling agents include, for example, inorganic agents and organic agents.
Examples of inorganic drugs include cuprous oxide, copper thiocyanate (general name: copper rhodanide), copper powder, etc. Among these, cuprous oxide and copper rhodanide are particularly preferred, and cuprous oxide that has been surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil, etc. is more preferred in terms of long-term stability during storage.
Examples of organic agents include 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), zinc ethylene bisdithiocarbamate (generic name: zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: She-Nine 211), 3,4-dichlorophenyl-N-N-dimethylurea (generic name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (generic name: Irgarol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea 28), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (generic name: medetomidine), and the like.
Among these antifouling agents, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (general name: Econea 28) is particularly preferred from the viewpoint of antifouling performance in an immersion test after a weather resistance test. These antifouling agents can be used alone or in combination of two or more kinds.

The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60 mass %, and preferably 1 to 50 mass %, calculated as solid content. Specific examples of the content of the antifouling agent include 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, and 60 mass %, and may be within a range between any two of the numerical values exemplified here.

1-4. Other Additives Furthermore, to the resin for antifouling coating of the present invention, if necessary, resin components other than copolymer A, dissolution regulators, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents, thixotropic agents, organic solvents, etc. may be added to form an antifouling coating.

As the other resin component, for example, polymer P and the like can be mentioned.
The polymer P is a polymer obtained by polymerizing the monomer (b). The monomer (b) is any ethylenically unsaturated monomer other than the monomer (a). The monomer (b) used in the polymerization of the polymer P may have the same composition as or a different composition from the monomer (b) used in the polymerization of the copolymer A.
In the present invention, the monomer (b) may be used alone or in combination of two or more kinds. In particular, from the viewpoint of compatibility with copolymer A, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, benzyl (meth)acrylate, triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, and the like are preferred.
The polymerization method, initiator, solvent, temperature, other conditions, and the method for measuring Mw can be the same as those described for Copolymer A.
The content of polymer P in the composition of the present invention is not particularly limited, but the content ratio of polymer P to copolymer A is usually 0.1 to 0.5, and preferably 0.1 to 0.3, in terms of solid content, as a mass ratio (polymer P/copolymer A).

Examples of the elution regulator include monocarboxylic acids and their salts, such as rosin, rosin derivatives, naphthenic acid, cycloalkenyl carboxylic acids, bicycloalkenyl carboxylic acids, versatic acid, trimethylisobutenylcyclohexene carboxylic acid, and metal salts thereof, or the above-mentioned alicyclic hydrocarbon resins. These can be used alone or in combination of two or more.
Examples of the rosin 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 (product names, manufactured by Zeon Corporation).
Of these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexene carboxylic acid, or metal salts thereof are preferred.

Examples of the plasticizer include phosphate esters, phthalate esters, adipate esters, sebacate esters, polyesters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, etc. These can be used alone 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, carbodiimidazoles, etc. These 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 mixture containing copolymer A, fiber B, other additives, etc., using a disperser. Alternatively, the antifouling coating composition can be produced by adding fiber B after mixing and dispersing a mixture containing copolymer A, an antifouling agent, other additives, etc., using a disperser.

The mixed liquid is preferably a liquid in which various materials such as copolymer A and fiber B are dissolved or dispersed in a solvent. The solvent may be the same as the organic solvent described above.

As the dispersing machine, for example, one that can be used as a fine grinding machine can be suitably used. For example, a commercially available homomixer, sand mill, bead mill, disperser, paint shaker, etc. can be used. In addition, the mixed liquid may be mixed and dispersed using a container equipped with a stirrer to which glass beads for mixing and dispersion have been added.

3. Antifouling treatment method, antifouling coating film, and coated object The antifouling treatment method of the present invention uses the above-mentioned antifouling paint composition to form an antifouling coating film on the surface of an object to be coated. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface, and the coating surface is constantly renewed, thereby preventing the attachment of aquatic fouling organisms.
Examples of objects on which a coating film is formed include ships (particularly ship bottoms), fishing equipment, underwater structures, and the like.
The thickness of the antifouling coating film may be appropriately set depending on the type of object to be coated, the sailing speed of the ship, the seawater temperature, etc. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700 μm, preferably 100 to 600 μm.

The features of the present invention will be more clearly described below with reference to examples, but the present invention is not limited to these examples.
In each Production Example, Example, and Comparative Example, "%" indicates "mass %." The weight average molecular weight (Mw) is a value determined by GPC (polystyrene equivalent value). The GPC conditions are as follows:
Equipment: Tosoh Corporation HLC-8220GPC
Column: 2 TSKgel SuperHZM-M Flow rate: 0.35 mL/min
Detector: RI
Column thermostat temperature: 40°C
Eluent: THF
The heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Paint component testing method-heating residue".

<Production Example 1 (Production of Monomer a1)>
(First reaction)
A four-neck flask equipped with a thermometer, a condenser, and a stirrer was charged with 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone, and the mixture was stirred for 6 hours at 70 to 80° C. After completion of the reaction, 500 ml of toluene was charged into the reaction solution, and the organic layer was washed with city water, hydrochloric acid, and sodium bicarbonate water in that order, and the solvent was then distilled off by concentration under reduced pressure to obtain 262 g of methoxycarbonylmethyl chloroacetate.

(Second reaction)
Next, 200 g (1.20 mol) of methoxycarbonylmethyl chloroacetate, which is the product of the first reaction, 87 g (1.20 mol) of acrylic acid, 0.1 g of 4-methoxyphenol, and 500 g of ethyl acetate were charged into a four-neck flask equipped with a thermometer, a condenser, a stirrer, and a dropping funnel, and 122 g (1.20 mol) of triethylamine was added dropwise while maintaining the temperature at 40° C. or less under stirring. After the dropwise addition was completed, the mixture was stirred at 70 to 80° C. for 6 hours. After the reaction was completed, the organic layer was washed with city water, hydrochloric acid, and sodium bicarbonate water in that order, and the solvent was distilled off by vacuum concentration to obtain 230.6 g of monomer a1.

<Production Examples 2 to 20 (Production of Monomers a2 to a20)>
Monomers a2 to a20 were obtained by carrying out reactions using the raw materials shown in Table 1 in the same manner as in Production Example 1. The reaction conditions and yields of Production Examples 2 to 20 are shown in Table 1.

Details of the raw materials in Table 1 are as follows:
CANa: Sodium monochloroacetate CAMe: Methyl chloroacetate CAEt: Ethyl chloroacetate NMP: N-methyl-2-pyrrolidone AA: Acrylic acid MAA: Methacrylic acid TEA: Triethylamine MEHQ: 4-methoxyphenol

<Production Example 21 (Production of Copolymer Solution A-1)>
In a four-neck flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel, 50 g of xylene and 50 g of propylene glycol monomethyl ether were charged as a solvent, nitrogen gas was introduced and the temperature was maintained at 88°C while stirring. The monomers (a) and (b) shown in Table 2 and 2.0 g (initial addition) of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate as a polymerization initiator were added thereto, and the resulting mixture was dropped over 3 hours while maintaining the temperature at 88°C. After stirring at 88°C for 1 hour, 0.1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times every hour, and the mixture was further stirred at the same temperature for 2 hours, and then cooled to room temperature to obtain a copolymer solution A-1. The heating residue and Mw of A-1 are shown in Table 2.

<Production Examples 22 to 27 (Production of Copolymer Solutions A-2 to A-5, Polymer Solutions P-1, and P-2)>
Copolymer solutions A-2 to A-5 and polymer solutions P-1 and P-2 were obtained by carrying out the polymerization reaction in the same manner as in Production Example 21, except that the monomers and solvents shown in Table 2 were used. The heating residue and Mw of each solution are shown in Table 2. The numerical values of the blend amounts in the table are mass %.

<Production Example 28 (Production of gum rosin zinc salt solution)>
240 g of Chinese gum rosin (WW) and 360 g of xylene were placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer, and 120 g of zinc oxide was added so that all of the resin acid in the rosin would form a zinc salt, followed by reflux dehydration under reduced pressure at 70 to 80°C for 3 hours. The mixture was then cooled and filtered to obtain a xylene solution of rosin zinc salt (dark brown transparent liquid, solid content 50%). The heating residue of the resulting solution was 50.2%.

2. Examples and Comparative Examples (Production of Coating Compositions)
The components shown in Tables 3 to 5 were blended in the proportions (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.

Details of each component in Tables 3 to 5 are as follows.
<Fiber B>
PF E-001: Untreated cut glass fiber, product name "PF E-001" (manufactured by Nitto Boseki Co., Ltd.)
PF E-301: Silane-based cut glass fiber, product name "PF E-301" (manufactured by Nitto Boseki Co., Ltd.)
SS 05C-404: Silane-based cut glass fiber, product name "SS 05C-404", average cut length 0.1 mm (manufactured by Nitto Boseki Co., Ltd.)
MS600: Rock wool, product name "MS600", average cut length 125 μm (manufactured by Lapinus)
F PAC O 245/040: Polyacrylonitrile, pre-oxidized polyacrylonitrile, trade name "F PAC O 245/040", average cut length 0.5 mm (manufactured by Schwarzwalder Textil-Werke)

<Dissolution Adjustment Agent>
Gum rosin zinc salt solution: The solution produced in Production Example 28 was used. Gum rosin solution: Chinese gum rosin (WW) 50% solids solution in xylene

<Anti-fouling agent>
Cuprous oxide: Product name "NC-301" (manufactured by Nissin Chemco Co., Ltd.)
Copper pyrithione: Product name "Copper Omadin" (manufactured by LONZA Corporation)
Zinc pyrithione: Trade name "Zinc Omadin" (manufactured by LONZA Corporation)
SEANINE 211N: 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by R&H, 30% active ingredient in xylene solution)
ECONEA 028: 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)
SELEKTOPE: Product name "Selktope" (manufactured by ITEC Co., Ltd.)

<Other additives>
Bengala: Product name: Bengala Gold (manufactured by Morishita Bengala Kogyo Co., Ltd.)
Talc: Product name "Talc MS" (manufactured by Nippon Talc Co., Ltd.)
Zinc oxide: Product name "Zinc oxide type 2" (manufactured by Seido Chemical Industry Co., Ltd.)
Titanium oxide: Product name "FR-41" (manufactured by Furukawa Co., Ltd.)
Disparlon A603-20X: fatty acid amide-based thixotropic agent, product name "Disparlon A603-20X" (manufactured by Kusumoto Chemicals Co., Ltd.)
Tetraethoxysilane: Product name "Ethyl Silicate 28" (manufactured by Colcoat Co., Ltd.)
Tricresyl phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)

3. Evaluation The following tests were carried out on the coating compositions of the Examples and Comparative Examples. The test results are shown in Tables 3 to 5. As shown in Tables 3 to 5, in all Examples, the coating film state after 24 months was better than in the Comparative Examples, and the uniformity of the coating film dissolution amount was high. Such an effect was achieved by the combination of copolymer A and fiber B, and the above effect was not achieved in Comparative Examples 1 to 4, which contained copolymer A but not fiber B, and Comparative Examples 5 to 6, which contained polymer P other than copolymer A and fiber B. Moreover, the results of Comparative Examples 7 to 8, which contained polymer P but not fiber B, were comparable to those of Comparative Examples 5 to 6. This shows that the effect of improving the coating film state and uniforming the coating film dissolution amount by adding fiber B is specific to copolymer A.

<Test example (rotary test)>
A rotating drum with a diameter of 515 mm and a height of 440 mm was attached to the center of the tank and rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were also attached.

Test panels were prepared according to the following method.
First, an anti-rust paint (epoxy vinyl A/C) was applied to a titanium plate (71 x 100 x 0.5 mm) so that the thickness after drying was about 100 μm, and then dried to form an anti-rust coating film. Then, the coating compositions obtained in the examples and comparative examples were applied to the titanium plate so that the dry film thickness was about 300 μm, and the plate was 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 of the above-mentioned device so that it was in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this time, the seawater temperature was kept at 25°C and the pH at 8.0 to 8.2, and the seawater was replaced every two weeks.

After 12 months and 24 months of rotary testing, the coating surface of each test panel was observed with the naked eye and a microscope to evaluate the surface condition of the coating.

The coating surface condition was evaluated according to the following criteria.
◎: No abnormalities at all ○: Hair cracks are found on less than 10% of the total coating surface area △: Hair cracks are found on 10-30% of the total coating surface area ×: Hair cracks are found on 30% or more of the total coating surface area

The initial remaining film thickness and the remaining remaining film thickness every 12 months after the start of the test were measured using a Keyence Corporation shape measuring laser microscope VK-X100, and the difference between these measurements was used to calculate the amount of dissolved film, giving the average amount of dissolved film per month (μm/month). The average amount of dissolved film T1 from 0 to 12 months after the start of the test and the average amount of dissolved film T2 from 12 to 24 months after the start of the test were calculated, and the ratio (T1/T2) indicating the uniformity of the amount of dissolved film was calculated.

Claims (1)

An antifouling coating composition comprising a copolymer A and a fiber B,
The copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a),
The antifouling coating composition, wherein the monomer (a) is represented by general formula (1).
(In the formula, ^R1 represents hydrogen or a methyl group, ^R2 represents hydrogen, a methyl group, or a phenyl group, ^R3 represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group, or represents a phenyl group, and n represents an integer of 2 to 10.)