Antifouling coating composition

Abstract

A fouling-resistant coating composition capable of maintaining excellent antifouling performance over a long period is provided. According to the present invention, the fouling-resistant coating composition comprises copolymer A and antifouling agent B, wherein copolymer A comprises monomer (A) and monomers other than monomer (A) and olefinically unsaturated monomer (B), wherein monomer (A) is represented by formula (1), and antifouling agent B is at least one of antifouling agent B1 and antifouling agent B2, wherein antifouling agent B1 is 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole, and antifouling agent B2 is 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole.

Description

Technical Field

[0001] This invention relates to an antifouling coating composition. Background Technology

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

[0003] To prevent such problems, techniques are known to apply antifouling coating compositions to ships or similar objects to form an antifouling film, from which antifouling agents are slowly released, thereby providing long-term antifouling performance (Patent Documents 1-4).

[0004] However, the antifouling coatings formed from polymers containing (meth)acrylate alkoxycarbonyl methyl ester groups as described in Patent Documents 1-4 have very low solubility, making it difficult to maintain antifouling properties for a long time.

[0005] To address these issues, a technology was proposed that can dissolve the coating over a long period of time while maintaining its antifouling properties (Patent Document 5).

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Publication No. 63-61989

[0009] Patent Document 2: Japanese Patent Application Publication No. 2003-119420

[0010] Patent Document 3: Japanese Patent Application Publication No. 2003-119419

[0011] Patent Document 4: Japanese Patent Application Publication No. 2002-3776

[0012] Patent Document 5: International Publication No. 2020 / 045211 Summary of the Invention

[0013] The technical problem that the invention aims to solve

[0014] While the antifouling coating film formed by the antifouling coating composition described in Patent Document 5 improves the solubility of the coating film, there is still room for improvement in maintaining excellent antifouling performance over a long period of time. There is a need for an antifouling coating composition that can solve these problems.

[0015] The present invention was made in view of the following circumstances, and provides a antifouling coating composition that can maintain excellent antifouling performance over a long period of time.

[0016] Methods for solving problems

[0017] The present invention provides an antifouling coating composition containing copolymer A and antifouling agent B, wherein copolymer A contains a copolymer of monomer (a) and an olefinically unsaturated monomer (b) other than monomer (a), wherein monomer (a) is represented by formula (1), and antifouling agent B contains at least one of antifouling agent B1 and antifouling agent B2, wherein antifouling agent B1 is 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole, and antifouling agent B2 is 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazolium.

[0018] In order to solve the above-mentioned problems, the inventors conducted in-depth research and found that the above-mentioned antifouling coating composition can solve the above-mentioned problems, thereby completing the present invention. Detailed Implementation

[0019] The present invention will now be described in detail.

[0020] 1. Antifouling coating composition

[0021] The antifouling coating composition of the present invention contains copolymer A and antifouling agent B.

[0022] 1-1. Copolymer A

[0023] 1-1-1. Composition of copolymer A

[0024] Copolymer A is a copolymer of monomer (a) and an olefinically unsaturated monomer (b) other than monomer (a). Copolymer A contains monomer units derived from monomers (a) and (b). The content of monomer (a) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, relative to the total of monomers (a) and (b). Specifically, for example, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, or within any two values ​​exemplified herein. In this case, the coating film has particularly good solubility.

[0025] <Monomer(a)>

[0026] Monomer (a) is represented by equation (1).

[0027] [Chemistry 1]

[0028]

[0029] (where R is in the formula) 1 R represents hydrogen. 2 R represents hydrogen, methyl, or phenyl. 3This indicates an alkyl or phenyl group with 1 to 8 carbon atoms that can be substituted by an alkoxy or phenyl group with 1 to 8 carbon atoms, where n represents an integer from 2 to 10.

[0030] R 2 Preferably, it is hydrogen or methyl.

[0031] R 3 The number of carbon atoms in the alkoxy or alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, or may be within any range of two values ​​exemplified herein. R 3 Examples of the compounds include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl, benzyl, phenyl, 2-methoxyethyl, 4-methoxybutyl, vinyl, or allyl, with methyl, ethyl, isopropyl, or n-butyl being preferred.

[0032] n represents an integer from 2 to 10, and from the viewpoint of long-term anti-fouling, 2 to 6 is preferred. n can be, for example, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and can be within the range of any two values ​​exemplified here.

[0033] Examples of monomers (a) include, for example, poly(oxycarbonylmethyl) acrylate, poly(oxycarbonylmethyl) acrylate, poly(oxycarbonylmethyl) isopropyl acrylate, poly(oxycarbonylmethyl) n-propyl acrylate, poly(oxycarbonylmethyl) n-butyl acrylate, poly(oxycarbonylmethyl) tert-butyl acrylate, poly(oxycarbonylmethyl) acrylate 2-ethylhexyl acrylate, poly(oxycarbonylmethyl) cyclohexyl acrylate, poly(oxycarbonylmethyl) benzyl acrylate, phenyl poly(oxycarbonylmethyl) acrylate, 2-methoxyethyl poly(oxycarbonylmethyl) acrylate, and 4-methoxybutyl poly(oxycarbonyl) Methyl acrylate, allyl poly(oxycarbonylmethyl) acrylate, vinyl poly(oxycarbonylmethyl) acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[1-(oxycarbonyl)ethyl] acrylate, poly[α-(oxycarbonyl)benzyl] acrylate, poly[α-(oxycarbonyl)benzyl] acrylate. Preferred examples include poly(oxycarbonylmethyl) acrylate, poly(oxycarbonylmethyl) acrylate, poly(oxycarbonylmethyl) isopropyl acrylate, poly(oxycarbonylmethyl) acrylate n-propyl acrylate, poly(oxycarbonylmethyl) acrylate n-butyl acrylate, poly[1-(oxypolycarbonyl)ethyl] acrylate, and poly[1-(oxypolycarbonyl)ethyl] acrylate. These monomers (a) can be used alone or in combination of two or more.

[0034] As monomer (a), monomers containing n=2 in formula (1) and monomers containing n=3 to 10 are preferred. The mass ratio (n(2) / n(2 to 10)) based on solid content is preferably 0.4 to 0.8, more preferably 0.5 to 0.7. This is preferred from the viewpoint of coating solubility and coating properties. Specifically, this value is, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, or 0.80, or may be within the range of any two values ​​exemplified herein.

[0035] <Single(b)>

[0036] Monomer (b) refers to olefinically unsaturated monomers other than monomer (a), such as (meth)acrylates, vinyl compounds, aromatic compounds, dialkyl esters of diacids, etc. Furthermore, in this specification, (meth)acrylate refers to acrylates or methacrylates.

[0037] Examples of (meth)acrylates include monomers (bx) or other (meth)acrylates represented by formula (2).

[0038] [Chemistry 2]

[0039]

[0040] (where R is in the formula) 4 R represents methyl. 5 R represents hydrogen, methyl, or phenyl. 6 This indicates an alkyl or phenyl group with 1 to 8 carbon atoms that can be substituted by an alkoxy or phenyl group with 1 to 8 carbon atoms, where n is an integer from 2 to 10.

[0041] R 5 R 6 The explanation of n and R in equation (1) 1 R 2 The description is the same as for n.

[0042] The content of monomer (bx) relative to the total of monomers (a) and (b) is 0 to 30% by mass, preferably 0 to 10% by mass, and more preferably 0 to 5% by mass. Specifically, the content of monomer (bx) is, for example, 0, 1, 2, 3, 4, 5, 10, 15, 20, 25, or 30% by mass, or may be within any two values ​​exemplified herein.

[0043] In addition, other (meth)acrylates include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, 2-methoxyethyl methacrylate, 2-methoxypropyl methacrylate, 4-methoxybutyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethoxyethyl methacrylate, propylene glycol monomethacrylate, and 2-hydroxyethyl methacrylate. 2-Hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl methacrylate, mono(2-(meth)acryloyloxyethyl)succinate, N-(3-dimethylaminopropyl)(meth)acrylamide, 2-Hydroxyethyl (meth)acrylate, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, N,N'-dimethyl(meth)acrylamide Acrylates, such as methoxycarbonyl methyl methacrylate, ethoxycarbonyl methyl methacrylate, isopropoxycarbonyl methyl methacrylate, n-propoxycarbonyl methyl methacrylate, n-butoxycarbonyl methyl methacrylate, tert-butoxycarbonyl methyl methacrylate, 2-ethylhexyloxycarbonyl methyl methacrylate, cyclohexyloxycarbonyl methacrylate, benzyloxycarbonyl methyl methacrylate, phenoxycarbonyl methacrylate, 2-methoxyethoxycarbonyl methyl methacrylate, 4-methoxybutoxycarbonyl methacrylate Methyl esters, (meth)aryloxycarbonyl methacrylates, (meth)acrylate ethyleneoxycarbonyl methyl esters, (meth)acrylate 1-(methoxycarbonyl)ethyl esters, (meth)acrylate 1-(ethoxycarbonyl)ethyl esters, (meth)acrylate 1-(n-propoxycarbonyl)ethyl esters, (meth)acrylate 1-(isopropoxycarbonyl)ethyl esters, (meth)acrylate 1-(n-butoxycarbonyl)ethyl esters, (meth)acrylate 1-(tert-butoxycarbonyl)ethyl esters, (meth)acrylate α-(methoxycarbonyl)benzyl esters, (meth)acrylate α-(ethoxycarbonyl)benzyl esters, (meth)acrylate alkoxycarbonyl methyl esters;Triisopropylsilyl (meth)acrylate, Triisobutyl (meth)acrylate, Tri-s-butyl (meth)acrylate, Triisopentyl (meth)acrylate, Triphenyl (meth)acrylate, Diisopropylphenyl (meth)acrylate, Diisopropylisobutyl (meth)acrylate, Diisopropylsec-butyl (meth)acrylate, Diisopropylisopentyl (meth)acrylate, Isopropyldiisobutyl (meth)acrylate, Isopropyldisec-butyl (meth)acrylate, Tert-butyldiisopentyl (meth)acrylate, (meth)acrylate Tert-butyl diisopentyl silyl acrylate, tert-butyl diphenyl silyl acrylate, diisopropylhexyl silyl acrylate, diisopropylcyclohexyl silyl acrylate, tricyclohexyl silyl acrylate, tri-1,1-dimethylpentyl silyl acrylate, tri-2,2-dimethylpropyl silyl acrylate, tricyclohexyl methyl silyl acrylate, diisopropylcyclohexyl methyl silyl acrylate, tri-2-ethylhexyl silyl acrylate, tri-2-propylpentyl silyl acrylate, and other silyl acrylates.

[0044] Examples of vinyl compounds include those 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.

[0045] Examples of aromatic compounds include styrene, vinyltoluene, and α-methylstyrene.

[0046] Examples of dialkyl ester compounds that are dicarboxylic acids include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

[0047] In this invention, these monomers (b) can be used alone or in combination of two or more. As monomers (b), from the viewpoint of coating solubility and coating properties, (meth)acrylates are preferred, and especially from the viewpoint of crack resistance, 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. are more preferred. From the viewpoint of coating solubility, triisopropylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, and tri-2-ethylhexyl (meth)acrylate are more preferred.

[0048] 1-1-2. Properties and manufacturing method of copolymer A

[0049] The weight-average molecular weight (Mw) of copolymer A is preferably between 5,000 and 300,000. If the molecular weight is less than 5,000, the antifouling coating film will become brittle and prone to peeling or cracking; if it exceeds 300,000, the viscosity of the polymer solution increases, making it difficult to handle. Specifically, the Mw is, for example, 5,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, 100,000, 200,000, or 300,000, or may be within the range of any two values ​​exemplified herein.

[0050] One method for measuring Mw is gel permeation chromatography (GPC).

[0051] Copolymer A can be a random copolymer, alternating copolymer, periodic copolymer or block copolymer of monomer (a) and monomer (b).

[0052] Copolymer A can be obtained, for example, by polymerizing monomer (a) and monomer (b) in the presence of a polymerization initiator.

[0053] Examples of azo compounds that can act as polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobisisobutyrate, dimethyl 2,2'-azobis(N-butyl-2-methylpropionamide), and others; benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide, and isopropyl peroxide. Peroxides of tert-butyl carbonate, tert-butyl peroxide-2-ethylhexanoate, tert-hexyl peroxide-2-ethylhexanoate, di-tert-hexyl peroxide, tert-butyl peroxide-2-ethylhexyl monocarbonate, di-tert-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanate, tert-pentyl peroxide-neodecanate, tert-hexyl peroxyneodecanate, tert-pentyl peroxyneodecanate, 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. Particularly preferred polymerization initiators are 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobisisobutyronate, and 1,1,3,3-tetramethylbutyl peroxide-2-ethylhexanoate. The molecular weight of copolymer A can be adjusted by appropriately setting the amount of polymerization initiator.

[0054] 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 preferred from the perspective of obtaining copolymer A simply and accurately.

[0055] In polymerization reactions, organic solvents can be used as needed. There are no particular limitations on organic solvents; examples 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-acetic acid; alcohol solvents such as isopropanol, butanol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.

[0056] Preferred solvents include butyl acetate, isobutyl acetate, butanol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene. These solvents can be used alone or in combination of two or more.

[0057] The reaction temperature in the polymerization reaction can be set appropriately according to the type of polymerization initiator, etc., usually 50 to 160°C, preferably 60 to 150°C.

[0058] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0059] 1-2. Antifouling reagent B

[0060] Antifouling agent B includes at least one of antifouling agent B1 and antifouling agent B2. Antifouling agent B1 is 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28), and antifouling agent B2 is 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (generic name: metoprimidine).

[0061] The content of antifouling agent B1 in the composition of the present invention is not particularly limited, but is generally 0.1 to 15% by mass in solids, preferably 0.5 to 10% by mass, and more preferably 1 to 7% by mass. Specifically, the content is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15% by mass, or may be within the range of any two values ​​exemplified herein.

[0062] The content of antifouling agent B2 in the composition of the present invention is not particularly limited, and is generally 0.01 to 5% by mass in solid form, preferably 0.05 to 3% by mass, more preferably 0.1 to 0.3% by mass. Specifically, this content is, for example, 0.01, 0.05, 0.1, 0.2, 0.3, 0.5, 1, 2, 3, 4, 5% by mass, or may be within any two of the values ​​exemplified herein.

[0063] Antifouling agent B may also contain other antifouling agents, such as the following inorganic and organic agents.

[0064] Examples of inorganic agents include cuprous oxide, copper thiocyanate (common name: copper thiocyanate), and copper powder. Among these, cuprous oxide and copper thiocyanate are particularly preferred. From the viewpoint of long-term storage stability, cuprous oxide that has been surface-treated with glycerol, sucrose, stearic acid, lauric acid, lecithin, mineral oil, etc., is even more preferred.

[0065] Examples of organic reagents include, for example, 2-mercaptopyridine-N-oxide copper (common name: copper pyridinethione), 2-mercaptopyridine-N-oxide zinc (common name: zinc pyridinethione), ethylidene didithiocarbamate zinc (common name: Zineb), 4,5-dichloro-2-n-octyl-3-isothiazolinone (common name: Sea nine211), 3,4-dichlorophenyl-NN-dimethylurea (common name: Diuron), and 2-methylthio-4- and tert-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol1051).

[0066] The content of other antifouling agents in the compositions of the present invention is not particularly limited, but is generally 0.1 to 60.0% by mass when converted to solids. The content of antifouling agents 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, or may be within the range of any two values ​​exemplified herein.

[0067] From the viewpoint of antifouling performance in immersion tests after weathering tests, antifouling agent B is particularly preferred to have the following characteristics.

[0068] • Contains antifouling agent B2.

[0069] • Contains both antifouling agent B1 and antifouling agent B2.

[0070] • Contains one or both of antifouling agent B1 and antifouling agent B2, as well as cuprous oxide.

[0071] 1-3. Other additives

[0072] In addition, the antifouling coating resin of the present invention can be supplemented with resin components other than copolymer A, dissolution regulators, plasticizers, fibers, pigments, dyes, defoamers, dehydrating agents, thixotropic agents, organic solvents, etc., as needed to serve as an antifouling coating.

[0073] Other resin components include polymer P, etc.

[0074] Polymer P is a polymer obtained by polymerizing monomer (b). Monomer (b) is any olefinically unsaturated monomer other than monomer (a). The monomer (b) used in the polymerization of polymer P may have the same composition as or different from the monomer (b) used in the polymerization of copolymer A.

[0075] In this invention, monomer (b) can be used alone or in combination of two or more, and particularly from the viewpoint of compatibility with copolymer A, methyl methacrylate, ethyl methacrylate, butyl methacrylate, acrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, ethoxyethyl 2-(meth)acrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, preferably acrylate, benzyl methacrylate, triisopropylsilyl methacrylate, tert-butyldiphenylsilyl methacrylate, tri-2-ethylhexyl methacrylate, etc.

[0076] The polymerization method, initiator, solvent, temperature, other conditions, and Mw measurement method are applicable to the above copolymer A.

[0077] The content of polymer P in the composition of the present invention is not particularly limited, but the mass ratio of polymer P to copolymer A, converted in terms of solid components, is usually 0.1 to 0.5, preferably 0.1 to 0.3.

[0078] Examples of dissolution modifiers include rosin, rosin derivatives, naphthenic acids, cycloalkenylcarboxylic acids, bicycloalkenylcarboxylic acids, tertiary carbonates, trimethylisobutylenylcyclohexenecarboxylic acids and their metal salts, monocarboxylic acids and their salts, or the aforementioned alicyclic hydrocarbon resins. These can be used alone or in combination of two or more.

[0079] Examples of rosin derivatives include hydrogenated rosin, disproportionated rosin, maleic rosin, formylated rosin, and polymerized rosin.

[0080] Commercially available products that are alicyclic hydrocarbon resins include Quinton 1500, 1525L and 1700 (trade names, manufactured by Zeon Corporation of Japan).

[0081] Among them, rosin, rosin derivatives, naphthenic acid, tertiary carbonic acid, trimethylisobutylenylcyclohexenecarboxylic acid or metal salts thereof are preferred.

[0082] Examples of plasticizers include phosphate esters, phthalates, adipates, sebacic acid esters, polyesters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tert-nonyl pentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, and chlorinated paraffin. These can be used alone or in combination of two or more.

[0083] Examples of fibers include mineral glass fibers, wollastonite fibers, montmorillonite fibers, shale fibers, attapulgite fibers, calcined bauxite fibers, volcanic rock fibers, bauxite fibers, rock wool fibers, and mineral fibers processed from mineral wool. These can be used alone or in combination of two or more.

[0084] 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 alone or in combination of two or more.

[0085] 2. Method for manufacturing antifouling coating composition

[0086] The antifouling coating composition of the present invention can be manufactured, for example, by mixing and dispersing a mixture containing copolymer A, antifouling agent B, and other additives using a disperser. Alternatively, antifouling agent B can be added after mixing and dispersing a mixture containing copolymer A and other additives using a disperser.

[0087] The mixture is preferably prepared by dissolving or dispersing various materials, such as copolymer A and antifouling agent B, in a solvent. The same organic solvent as described above can be used as the solvent.

[0088] As a disperser, a disperser that can be used as a micronizer can be appropriately used. For example, commercially available homogenizers, sand mills, bead mills, dispersers, paint vibrators, etc., can be used. Alternatively, the mixture can be mixed and dispersed using glass beads or the like added in a container equipped with a stirrer.

[0089] 3. Antifouling treatment methods, antifouling coatings and coating materials

[0090] In the antifouling treatment method of the present invention, an antifouling coating film is formed on the surface of the substrate using an antifouling coating composition. According to the antifouling treatment method of the present invention, the antifouling coating film gradually dissolves from the surface, and the surface of the coating film is continuously renewed, thereby preventing the adhesion of aquatic fouling organisms.

[0091] Examples of objects to be coated include ships (especially ship bottoms), fishing gear, and underwater structures.

[0092] The thickness of the antifouling coating can be appropriately set according to the type of object to which the coating is formed, the ship's sailing speed, and the seawater temperature. For example, when the object to which the coating is formed is the bottom of a ship, the thickness of the antifouling coating is usually 50 to 700 μm, preferably 100 to 600 μm.

[0093] Example

[0094] The features of the present invention are further illustrated below with examples, etc. However, the present invention is not limited to the examples, etc.

[0095] In each manufacturing example, embodiment, and comparative example, % represents mass%. Weight-average molecular weight (Mw) is a value determined by GPC (polystyrene conversion). The GPC conditions are as follows.

[0096] Device: HLC-8220GPC manufactured by Tosoh Corporation

[0097] Column: 2 TSKgel SuperHZM-M tubes

[0098] Flow rate: 0.35 mL / min

[0099] Detector: RI

[0100] Column constant temperature bath temperature: 40℃

[0101] Elution buffer: THF

[0102] The residual content after heating is determined according to JIS K 5601-1-2:1999 (ISO 3251:1993) "Coatings – Test methods for components – Residual content after heating".

[0103] <Manufacturing Example 1 (Manufacturing of Monomer a1)>

[0104] (First reaction)

[0105] Sodium monochloroacetate: 215 g (1.85 mol), methyl chloroacetate: 201 g (1.85 mol), and N-methyl-2-pyrrolidone: 300 g were added to a four-necked flask equipped with a thermometer, condenser, and stirrer, and stirred at 70–80 °C for 6 hours. After the reaction was complete, toluene: 500 ml was added to the reaction solution, and the organic layer was washed successively with tap water, hydrochloric acid solution, and baking soda solution. The solvent was removed by vacuum distillation to obtain methyl chloroacetate methoxycarbonyl: 262 g.

[0106] (Second reaction)

[0107] Next, the products of the first reaction, methyl chloroacetate methoxycarbonyl ester (200 g, 1.20 mol), acrylic acid (87 g, 1.20 mol), 4-methoxyphenol (0.1 g), and ethyl acetate (500 g), were added dropwise to a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel. While stirring, 122 g (1.20 mol) of triethylamine was added dropwise, maintaining the temperature below 40°C. After the addition was complete, the mixture was stirred at 70–80°C for 6 hours. After the reaction was complete, the organic layer was washed successively with tap water, hydrochloric acid solution, and sodium bicarbonate solution. The solvent was then removed by vacuum distillation to obtain monomer a1: 230.6 g.

[0108] <Manufacturing Examples 2-20 (Manufacturing of monomers a2-a10 and b1-b10)>

[0109] Using the raw materials shown in Table 1, the reaction was carried out in the same manner as in Manufacturing Example 1 to obtain monomers a2 to a10 and monomers b1 to b10. The reaction conditions and yields are shown in Table 1.

[0110] [Table 1]

[0111]

[0112] The detailed information of the raw materials in Table 1 is as follows.

[0113] CANa: Sodium monochloroacetate

[0114] CAMe: Methyl chloroacetate

[0115] CAEt: Ethyl chloroethyl

[0116] NMP: N-methyl-2-pyrrolidone

[0117] AA: Acrylic acid

[0118] MAA: Methacrylic acid

[0119] TEA: Triethylamine

[0120] MEHQ: 4-Methoxyphenol

[0121] <Manufacturing Example 21 (Manufacturing of Copolymer Solution A-1)>

[0122] In a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel, xylene (80 g) and 1-butanol (20 g) were added as solvents. Nitrogen gas was introduced, and the mixture was stirred while maintaining the temperature at 88°C. The following monomers were added dropwise over 3 hours: monomer (a-1): 10 g, monomer (a-3): 4 g, monomer (a-5): 1 g, monomer (a-7): 1 g, monomer (a-9): 1 g; monomer (b): methyl methoxycarbonyl acrylate (33 g), methyl methacrylate (40 g), 2-methoxyethyl acrylate (10 g); and 1,1,3-tetramethylbutylperoxide-2-ethylhexanoate (2.0 g, initially added) as polymerization initiator. Then, after stirring at 88°C for 1 hour, 0.1 g of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate was added three times per hour, and stirred at the same temperature for 2 hours. The mixture was then cooled to room temperature to obtain copolymer solution A-1. The heating residual composition and Mw of A-1 are shown in Table 2.

[0123] <Manufacturing Examples 22-27 (Copolymer Solutions A-2-A-3, P-1-P-4)>

[0124] Except for the monomers and solvents shown in Table 2, the polymerization reaction was carried out in the same manner as in Manufacturing Example 21 to obtain copolymer solutions A-2 to A-3 and P-1 to P-4. The respective heating residual components and Mw are shown in Table 2. The values ​​in the table are by mass%.

[0125] [Table 2]

[0126]

[0127] <Manufacturing Example 28 (Manufacturing of Zinc Salt Solution for Resin)>

[0128] In a flask equipped with a thermometer, reflux condenser, and stirrer, 240g of Chinese-made rosin (WW) and 360g of xylene were added. Further, to ensure all the resin acids in the rosin formed rosin-type zinc salts, 120g of zinc oxide was added. The mixture was then refluxed under reduced pressure at 70–80°C for 3 hours to remove moisture. After cooling and filtration, a xylene solution of rosin zinc salts (dark brown transparent liquid, 50% solids) was obtained. The residual content of the resulting solution upon heating was 50.2%.

[0129] 2. Examples and Comparative Examples (Preparation of Coating Compositions)

[0130] The components shown in Tables 3 to 6 are mixed in the proportions (mass%) shown in the tables and dispersed with glass beads of 1.5 to 2.5 mm in diameter to produce a coating composition.

[0131] [Table 3]

[0132]

[0133] [Table 4]

[0134]

[0135] [Table 5]

[0136]

[0137] [Table 6]

[0138]

[0139] The detailed information for each component in the table is as follows.

[0140] <Antifouling Agent B>

[0141] Econea28: Antifouling Agent B1,2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

[0142] Metopidine: Antifouling agent B2, trade name "Selektope" (manufactured by ITEC).

[0143] Cuprous oxide: Trade name "NC-301" (manufactured by Nisshin Chemco Co., Ltd.)

[0144] Copper pyrithione: Trade name "Copper Omagin" (manufactured by LONZA Corporation)

[0145] Sea Nine: Sea Nine 211: 4,5-Dichloro-2-n-octyl-3-isothiazolidinone (manufactured by R&H, active ingredient 30% xylene solution)

[0146] Zineb: [Ethylene bis(dithiocarbamate)]zinc (manufactured by Ouchi Shinsei Chemical Co., Ltd.)

[0147] Zinc pyrithione: (Manufactured by LONZA Corporation)

[0148] Diuron: Product name "Diuron" (manufactured by Tokyo Kasei Corporation)

[0149] Dissolution regulators

[0150] Zinc rosin salt solution: The solution prepared in Manufacturing Example 28 is used.

[0151] Rosin solution: 50% xylene solution of solid components of rosin (WW) produced in China.

[0152] Pigments

[0153] Iron Dan: Trade name "Bengara Kingyoku" (manufactured by Morishita Bengara Industry Co., Ltd.)

[0154] Talc: Trade name "Talc MS" (manufactured by Talc Corporation, Japan)

[0155] Zinc oxide: Trade name "Zinc Oxide 2 Types" (manufactured by Zhengtong Chemical Industry Co., Ltd.)

[0156] Titanium oxide: Trade name "FR-41" (manufactured by Furukawa Machinery & Metal Co., Ltd.)

[0157] <Other Additives>

[0158] Disparlon A603-20X: A fatty acid amide thixotropic agent, trade name "Disparlon A603-20X" (manufactured by Kusumoto Chemical Co., Ltd.)

[0159] Tetraethoxysilane: Trade name "ethyl silicate 28" (manufactured by Colcoat Co., Ltd.)

[0160] Trimethylbenzene phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)

[0161] 3. Evaluation

[0162] The coating compositions of the Examples and Comparative Examples were tested as follows. The results are shown in Tables 3-6. As shown in the same tables, all Examples exhibited better long-term antifouling performance than all Comparative Examples. Furthermore, a comparison of Examples 13 and 14 shows that the long-term antifouling performance was particularly good when antifouling agent B contained antifouling agent B2. Additionally, a comparison of Examples 11, 13, and 14 shows that the long-term antifouling performance was even better when antifouling agent B contained both antifouling agent B1 and antifouling agent 2. Furthermore, a comparison of Examples 4 and 14, and Examples 6 and 13 shows that the long-term antifouling performance was also particularly good when antifouling agent B contained antifouling agent B1 or antifouling agent 2 and cuprous oxide.

[0163] <Experimental Example (Pollution Prevention Test)>

[0164] The coating compositions obtained in the examples and comparative examples were applied to both sides of a rigid PVC board (100×200×2mm) to achieve a dried coating thickness of approximately 300μm. A test board with a dried coating thickness of approximately 300μm was prepared by drying the obtained coating material at room temperature (25°C) for 3 days. The test board was immersed 1.5m below sea level in Nachikatsuura Town, Wakayama Prefecture, and staining due to adhering substances was observed after 15 and 30 months.

[0165] Evaluation is conducted by visually observing the condition of the coating surface and is judged according to the following criteria.

[0166] ◎: No shellfish, algae or other fouling organisms are attached, and there is almost no mud.

[0167] ○: There is no fouling organism such as shellfish or algae attached, and although there may be a thin layer of slime (to the point where the coating surface is visible), it can be easily removed by gently wiping with a brush.

[0168] △: No fouling organisms such as shellfish and algae adhere to the surface, and although there may be thick (to the point that the coating surface is not visible) slime, it can be removed by wiping with a brush.

[0169] ×: Although there are no fouling organisms such as shellfish or algae attached, the slime is so thick that the coating surface is not visible, and it cannot be removed even by vigorous rubbing with a brush.

[0170] ××: The level of fouling organisms such as shellfish and algae attached to the surface.

Claims

1. An antifouling coating composition comprising copolymer A and antifouling agent B, The copolymer A is a copolymer of monomer (a) and an olefinically unsaturated monomer (b) other than monomer (a). The monomer (a) is represented by equation (1). The antifouling agent B contains antifouling agent B2 and cuprous oxide. The antifouling agent B2 is 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazolium. [Chemistry 1] （1） In the formula, R 1 R represents hydrogen. 2 R represents hydrogen, methyl, or phenyl. 3 It represents an alkyl or phenyl group with 1 to 8 carbon atoms that can be replaced by an alkoxy or phenyl group with 1 to 8 carbon atoms, where n represents an integer from 2 to 10.

2. The antifouling coating composition according to claim 1, The antifouling agent B contains both antifouling agent B1 and antifouling agent B2. The antifouling agent B1 is 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole.

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