Antifouling coating composition

Abstract

Provided is an antifouling coating composition capable of forming an antifouling coating film having good antifouling properties or good surface state of the coating film for a long period of time. The present invention provides an antifouling coating composition containing a copolymer A and an antifouling agent, the copolymer A being a copolymer of a monomer (a) represented by the following formula (1) and a monomer (b) represented by the following formula (2), and a copolymer of the monomer (a) and a monomer (c) other than (b) that is an ethylenically unsaturated monomer.

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 slime attach to ships (especially the hull), fishing nets, fishing net accessories and other fishing gear, as well as underwater structures such as power plant pipes, causing problems such as functional damage and deterioration of the appearance of ships.

[0003] To prevent such problems, known technologies include applying an antifouling coating composition to a ship or similar object to form an antifouling film, thereby slowly releasing the antifouling agent from the antifouling film to provide long-term antifouling performance (Patent Documents 1-4).

[0004] However, the antifouling coatings described in Patent Documents 1-4, which are composed of polymers containing (meth)acrylic acid alkoxycarbonyl methyl ester groups, have very low solubility and therefore cannot maintain their antifouling properties for a long time.

[0005] To address these issues, a technique was proposed that dissolves the coating over a longer period and provides 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: WO2020 / 045211 Publication Summary of the Invention

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

[0014] Patent Document 5 evaluated the coating properties and antifouling performance over a period of up to 24 months. The inventors further evaluated the antifouling coating composition disclosed in Patent Document 5 over a longer period and found problems such as decreased antifouling performance and coating abnormalities like cracking. Therefore, there is a need for an antifouling coating composition that can form an antifouling coating that maintains good antifouling performance and a good coating surface condition for a longer period than the antifouling coating composition of Patent Document 5.

[0015] The present invention was made in view of the following circumstances, and its object is to provide an antifouling coating composition that can form an antifouling film with good antifouling properties and can improve the duration of good coating surface condition.

[0016] Problem Solving Methods

[0017] According to the present invention, an antifouling coating composition containing copolymer A and an antifouling agent is provided, wherein copolymer A contains monomer (a) represented by formula (1) and monomer (b) represented by formula (2), and copolymer with olefinically unsaturated monomer (c) other than said monomers (a) and (b).

[0018] The inventors conducted in-depth research to solve the above-mentioned problems and found that a composition containing copolymer A and an antifouling agent could solve the above-mentioned problems, thus 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 an antifouling agent.

[0022] 1-1. Copolymer A

[0023] Copolymer A is a copolymer of monomers (a) and (b) with an olefinically unsaturated monomer (c) other than monomers (a) and (b).

[0024] The content of monomers (a) and (b) relative to the total amount of monomers (a), (b), and (c) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass. Specifically, for example, it is 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by mass, or it can be within any two values ​​exemplified herein. In this case, the coating film has particularly good solubility.

[0025] The content of monomer (a) is preferably 10 to 90% by mass, more preferably 20 to 80% 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, or 90% by mass, or any range between any two values ​​exemplified herein. In this case, the coating film solubility and physical properties are particularly good.

[0026] 1-1-1. Monomer (a)

[0027] Monomer (a) is represented by equation (1).

[0028] [Chemistry 1]

[0029]

[0030] In the formula, R 1 R represents hydrogen, methyl, or phenyl. 2 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 1 to 10.

[0031] R 1 Preferably, it is hydrogen or methyl.

[0032] R 2 The number of carbon atoms in the alkoxy or alkyl group is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, or can be within any range of two values ​​exemplified here. R 2 Examples of the compounds are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl, benzyl, phenyl, 2-methoxyethyl, 4-methoxybutyl, vinyl or allyl, preferably methyl, ethyl, isopropyl or n-butyl.

[0033] n represents an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any two of the values ​​listed here.

[0034] The monomer (a) preferably contains a compound in formula (1) where n is 2 or more. By using a compound with n of 2 or more as monomer (a), the solubility of the coating film is improved. The monomer (a) may consist solely of a compound with n of 2 or more, or it may be a mixture of a compound with n of 1 and a compound with n of 2 or more.

[0035] Monomer (a) is preferably composed of monomer (a1) and monomer (a2). The content of monomer (a1) in monomer (a) is preferably 20-100% by mass, more preferably 30-60% by mass, and particularly preferably 35-55% by mass. Specifically, this content is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, and 100% by mass, which can be within the range of any two values ​​listed herein. Compared with monomer (a2), monomer (a1) has the property of increasing coating film strength and reducing coating film solubility. Therefore, if the content of monomer (a1) is too low, the strength of the coating film tends to decrease, and the surface condition of the coating film deteriorates after a long period of time.

[0036] <Single (a1)>

[0037] The monomer (a1) is a compound in formula (1) where n is 1.

[0038] Examples of monomers (a1) include methoxycarbonyl methyl methacrylate, ethoxycarbonyl methyl methacrylate, isopropoxycarbonyl methyl methacrylate, n-propoxycarbonyl methyl methacrylate, n-butoxycarbonyl methyl methacrylate, tert-butoxycarbonylmethyl methacrylate, 2-ethylhexyloxycarbonyl methyl methacrylate, cyclohexyloxycarbonyl methyl methacrylate, benzyloxycarbonyl methyl methacrylate, phenoxycarbonyl methyl methacrylate, 2-methoxyethoxycarbonyl methyl methacrylate, 4-methoxybutoxycarbonyl methyl methacrylate, aryloxycarbonyl methyl methacrylate, ethyleneoxycarbonyl methyl methacrylate, 1-(methoxycarbonyl)ethyl methacrylate, and so on. The following are preferred: 1-(ethoxycarbonyl)ethyl methacrylate, 1-(n-propoxycarbonyl)ethyl methacrylate, 1-(isopropoxycarbonyl)ethyl methacrylate, 1-(n-butoxycarbonyl)ethyl methacrylate, 1-(tert-butoxycarbonyl)ethyl methacrylate, α-(methoxycarbonyl)benzyl methacrylate, α-(ethoxycarbonyl)benzyl methacrylate, preferably methyl methoxycarbonyl methacrylate, methyl ethoxycarbonyl methacrylate, methyl isopropoxycarbonyl methacrylate, methyl n-propoxycarbonyl methacrylate, methyl n-butoxycarbonyl methacrylate, 1-(methoxycarbonyl)ethyl methacrylate, and 1-(ethoxycarbonyl)ethyl methacrylate.

[0039] <Single (a2)>

[0040] The monomer (a2) is a compound in formula (1) where n is 2 or more. From the viewpoint of long-term antifouling properties, n in formula (1) is preferably 2 to 6.

[0041] The monomer (a2) preferably contains both a compound with n=2 and a compound with n=3 or more. Specifically, for example, the mass ratio of solid components (n(2) / n(2-10)) is preferably 0.2-0.8, more preferably 0.3-0.7. In this case, there is a tendency for stable film dissolution to continue. Specifically, this value is, for example, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, or may be within the range of any two values ​​listed herein.

[0042] Examples of monomers (a2) include dimethyl methacrylate (di(oxycarbonylmethyl)), diethyl methacrylate (di(oxycarbonylmethyl)), diisopropyl methacrylate (di(oxycarbonylmethyl)), dipropyl methacrylate (di(oxycarbonylmethyl)), dibutyl methacrylate (di(oxycarbonylmethyl)), ditert-butyl methacrylate (di(oxycarbonylmethyl)), 2-ethylhexyl methacrylate (di(oxycarbonylmethyl)), cyclohexyl methacrylate (di(oxycarbonylmethyl)), dibenzyl methacrylate (di(oxycarbonylmethyl)), phenyl methacrylate (di(oxycarbonylmethyl)), methyl 2-methoxyethyl di(oxycarbonylmethacrylate)), 4-methoxybutyl di(oxycarbonylmethyl) methacrylate, and allyl di(oxycarbonylmethyl) methacrylate. Vinyl di(oxycarbonylmethyl) methacrylate, methyl methacrylate di[1-(oxypolycarbonyl)ethyl], ethyl methacrylate di[1-(oxypolycarbonyl)ethyl], n-propyl methacrylate di[1-(oxypolycarbonyl)ethyl], isopropyl methacrylate di[1-(oxypolycarbonyl)ethyl], n-butyl methacrylate di[1-(oxypolycarbonyl)ethyl], tert-butyl methacrylate di[1-(oxypolycarbonyl)ethyl], methyl methacrylate di[α-(oxycarbonyl)benzyl], ethyl methacrylate di[α-(oxycarbonyl)benzyl], preferably methyl methacrylate di(oxycarbonylmethyl), ethyl methacrylate di(oxycarbonylmethyl), isopropyl methacrylate di(oxycarbonylmethyl), n-propyl methacrylate Di(oxycarbonylmethyl), di(oxycarbonyl-n-butyl) methacrylate, dimethyl methacrylate [1-(polyoxycarbonylethyl)], diethyl methacrylate [1-(oxypolycarbonylethyl)], poly(oxycarbonylmethyl) methyl methacrylate, poly(oxycarbonylmethyl) ethyl methacrylate, poly(oxycarbonylmethyl) isopropyl methacrylate, poly(oxycarbonylmethyl) n-propyl methacrylate, poly(oxycarbonylmethyl) n-butyl methacrylate, poly(oxycarbonylmethyl) tert-butyl methacrylate, poly(oxycarbonylmethyl) 2-ethyl hexyl methacrylate, di(oxycarbonylmethyl) cyclohexyl methacrylate, di(oxycarbonylmethyl) benzyl methacrylate, phenyl di(oxycarbonylmethyl) methacrylate, 2-methyl methacrylate Oxyethyl poly(oxycarbonylmethyl), 4-methoxybutyl methacrylate poly(oxycarbonylmethyl), propyl methacrylate poly(oxycarbonylmethyl), vinyl methacrylate poly(oxycarbonylmethyl), methyl methacrylate poly[1-(oxypolycarbonylethyl)], ethyl methacrylate poly[1-(oxypolycarbonylethyl)], n-propyl methacrylate poly[1-(oxypolycarbonyl)ethyl], isopropyl methacrylate poly[1-(oxypolycarbonyl)ethyl], methyl methacrylate poly[1-(oxypolycarbonyl)ethyl], n-butyl methacrylate poly[1-(oxypolycarbonyl)ethyl], tert-butyl methacrylate poly[1-(oxypolycarbonyl)ethyl], methyl methacrylate poly[α-(oxycarbonyl)benzyl], ethyl methacrylate poly[α-(oxycarbonyl)benzyl], and preferably others can be listed.Methyl methacrylate poly(oxycarbonylmethyl), ethyl methacrylate poly(oxycarbonylmethyl), isopropyl methacrylate poly(oxycarbonylmethyl), n-propyl methacrylate poly(oxycarbonylmethyl), methacrylate polyester (oxypolycarbonylmethyl) n-butyl, methyl methacrylate poly[1-(oxypolycarbonylethyl)], ethyl methacrylate poly[1-(oxypolycarbonylethyl)], etc.

[0043] 1-1-2. Monomer (b)

[0044] Monomer (b) is represented by equation (2).

[0045] [Chemistry 2]

[0046]

[0047] In the formula, R 3 R represents hydrogen, methyl, and phenyl. 4 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 1 to 10.

[0048] R 3 and R 4 The explanation of R in equation (1) 1 and R 2 The explanation is the same. The explanation of n is the same as that of n in equation (1).

[0049] Monomer (b) preferably contains a compound in formula (2) where n is 2 or more. When a compound with n is 2 or more is used as monomer (b), the solubility of the coating film is improved. Monomer (b) may consist only of a compound with n is 2 or more, or it may be a mixture of a compound with n is 1 and a compound with n is 2 or more.

[0050] Monomer (b) preferably consists of monomer (b1) and monomer (b2). The content of monomer (b1) in monomer (b) is preferably 20-100% by mass, more preferably 30-60% by mass, and particularly preferably 35-55% by mass. Specifically, this content is, for example, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100% by mass, or within any two values ​​exemplified here. Compared with monomer (b2), monomer (b1) has the property of increasing coating strength and reducing coating solubility. Therefore, if the content of monomer (b1) is too low, the strength of the coating is easily reduced, and the surface condition of the coating will deteriorate over time. On the other hand, if the content of monomer (b1) is too high, the solubility of the coating decreases, and the antifouling performance may sometimes decrease.

[0051] <Single (b1)>

[0052] Monomer (b1) is a compound in formula (2) where n is 1.

[0053] As monomer (b1), acrylates of the monomers listed in the monomer (a1) above can be included.

[0054] <Single (b2)>

[0055] The monomer (b2) is a compound in formula (2) where n is 2 or more. From the viewpoint of long-term antifouling properties, n in formula (2) is preferably 2 to 6.

[0056] The monomer (b2) preferably contains compounds with n=2 or more and compounds with n=3 or more. Specifically, for example, the mass ratio (n(2) / n(2-10)) converted from solid content is preferably 0.2-0.8, more preferably 0.3-0.7. In this case, there is a tendency for stable film dissolution to continue. Specifically, this value is, for example, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, or may be within any two values ​​listed herein.

[0057] As monomer (b2), acrylates of the monomers listed in monomer (a2) above can be included.

[0058] 1-1-3. Monomer (c)

[0059] Monomer (c) is an olefinic unsaturated monomer other than monomer (a) and monomer (b).

[0060] As monomer (c), examples include (meth)acrylates, vinyl compounds, aromatic compounds, dialkyl esters of dicarboxylic acids, etc., not represented in formulas (1) to (2). Furthermore, in this specification, (meth)acrylates refer to acrylates or methacrylates.

[0061] Examples of (meth)acrylates not represented in formulas (1) to (2) include methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauric acid methacrylate, 2-methoxyethyl methacrylate, 2-methoxypropyl methacrylate, 4-methoxybutyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2-ethoxyethyl methacrylate, propylene glycol monomethyl methacrylate, 2-(meth)acrylate hydroxyethyl ester, 2- Hydroxypropyl methacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl methacrylate, mono(2-(meth)acryloyloxyethyl)succinate, N-(3-dimethylaminopropyl)(meth)acrylamide, 2-hydroxyethyl methacrylate, 2-[2-(2-methoxyethoxy)ethoxy](meth)acrylate, N,N'-dimethyl(meth)acrylamide, and other methacrylates.

[0062] Triisopropylsilyl methacrylate, tert-butyldiphenylsilyl methacrylate, tri-n-octylsilyl methacrylate, tri-2-ethylhexyl methacrylate, and other meth acrylate silyl esters, etc.

[0063] Examples of ethylene 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.

[0064] Examples of aromatic compounds include styrene, vinyltoluene, and α-methylstyrene.

[0065] Examples of dialkyl ester compounds that are dicarboxylic acids include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

[0066] In copolymer A, these monomers (c) can be used alone or in combination of two or more. From the viewpoint of coating solubility and coating properties, monomer (c) preferably contains (meth)acrylate. From the viewpoint of crack resistance, monomer (c) preferably contains (meth)acrylate, and more preferably contains 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, triisopropylsilyl (meth)acrylate, tert-butyldiphenylsilyl (meth)acrylate, tri-n-octyl (meth)acrylate, tri-2-ethylhexyl (meth)acrylate, etc.

[0067] 1-1-4. Properties and Manufacturing Method of Copolymer A

[0068] The weight-average molecular weight (Mw) of copolymer A is preferably between 5,000 and 300,000. If the molecular weight is below 5,000, the antifouling coating becomes brittle and prone to peeling or cracking, or when 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, 300,000, or may be within any two of the numbers exemplified here.

[0069] Gel permeation chromatography (GPC) is one example of a method used to measure Mw.

[0070] Copolymer A can be any copolymer of monomer (a), random copolymer of monomer (b) and monomer (c), alternating copolymer, periodic copolymer, or block copolymer.

[0071] For example, copolymer A can be obtained by polymerizing monomers (a), (b), and (c) in the presence of a polymerization initiator.

[0072] Examples of polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobisisobutyrate, 2,2'-azobis(N-butyl-2-methylpropionamide), and other azo compounds; benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide, isopropyl tert-butyl peroxide 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 peroxide-neodecanoate, tert-pentyl peroxide-neodecanoate, tert-pentyl peroxide-neodecanoate, tert-pentyl peroxide-neodecanoate, etc. Peroxides such as 1,1,3,3-tetramethylbutylperoxide-2-ethylhexanoate are used. 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'-azobisisobutyrate, and 1,1,3,3-tetramethylbutylperoxide-2-ethylhexanoate. By appropriately setting the amount of polymerization initiator, the molecular weight of the resulting polymer A can be adjusted. Furthermore, chain transfer agents can be used to adjust the molecular weight of the resulting polymer. Examples of chain transfer agents include thiols such as n-dodecyl mercaptan; thioglycolates such as octyl mercaptoacetate; α-methylstyrene dimers; and terpinene.

[0073] Examples of polymerization methods include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. From the perspective of obtaining copolymer A simply and accurately, solution polymerization or non-aqueous dispersion polymerization is particularly preferred.

[0074] In polymerization reactions, organic solvents can be used as needed. There are no particular restrictions on organic solvents, such as aromatic hydrocarbon solvents like xylene and toluene; aliphatic hydrocarbon solvents; ester solvents like ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, and propylene glycol 1-monomethyl ether 2-acetic acid; alcohol solvents like isopropanol, butanol, and propylene glycol monomethyl ether; ether solvents like dioxane, diethyl ether, and dibutyl ether; and ketone solvents like methyl ethyl ketone and methyl isobutyl ketone.

[0075] 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.

[0076] 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.

[0077] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0078] 1-2. Antifouling reagent

[0079] Inorganic and organic reagents can be listed as antifouling agents.

[0080] Examples of inorganic reagents 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.

[0081] Examples of organic reagents include 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 Nine 211), 3,4-dichlorophenyl-NN-dimethylurea (common name: Diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-triazine (common name: Irgalol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: Econea 28), and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: metopridine), etc.

[0082] These antifouling agents can be used in combination with one or more of them.

[0083] The content of the antifouling agent in the composition 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 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, or may be within the range of any two values ​​exemplified herein.

[0084] 1-3. Other additives

[0085] In addition, the antifouling coating composition of the present invention can be supplemented as needed with resin components other than copolymer A, dissolution regulators, plasticizers, pigments, dyes, defoamers, dehydrating agents, thixotropic agents, organic solvents, etc., as an antifouling coating.

[0086] Other resin components include, for example, polymer P, which can be listed below.

[0087] Polymer P is a polymer that can be obtained by polymerizing the monomer (c).

[0088] In this invention, monomer (c) can be used alone or in combination of two or more. In particular, from the viewpoint of compatibility with copolymer A, methyl methacrylate, ethyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, triisopropylsilyl methacrylate, tert-butyldiphenylsilyl methacrylate, tri-n-octyl methacrylate, tri-2-ethylhexyl methacrylate, etc.

[0089] The polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, etc., can be applied to the methods described for copolymer A.

[0090] The content of polymer P in the compositions of the present invention is not particularly limited, but the mass ratio of polymer P to copolymer A, converted to solid components, is typically 0.1 to 0.5, preferably 0.1 to 0.3. This mass ratio is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, or may be within any range of two values ​​exemplified herein.

[0091] 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.

[0092] Examples of rosin derivatives include hydrogenated rosin, disproportionated rosin, maleic rosin, formylated rosin, and polymerized rosin.

[0093] Commercially available products that can be cited as alicyclic hydrocarbon resins include Quinton 1500, 1525L, and 1700 (trade names, manufactured by Zeon Co., Ltd. of Japan).

[0094] Among them, rosin, rosin derivatives, naphthenic acid, tertiary carbonic acid, trimethylisobutylenylcyclohexenic acid, or metal salts thereof are preferred.

[0095] Examples of plasticizers include phosphate esters, phthalates, adipates, sebacic acid esters, polyester epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tert-nonyl pentasulfide, petrolatum, polybutene, tri(2-ethylhexyl) trimellitate, silicone oil, and chlorinated paraffin. These can be used alone or in combination.

[0096] 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.

[0097] 2. Method for manufacturing antifouling coating composition

[0098] The antifouling coating composition of the present invention can be manufactured, for example, by mixing and dispersing a mixture containing copolymers, antifouling agents, other additives, etc. using a disperser.

[0099] The mixture is preferably prepared by dissolving or dispersing various materials, such as copolymers and antifouling agents, in a solvent.

[0100] As the dispersant, a dispersant capable of being used as a micronizer can be appropriately used, for example. Commercially available homogenizers, sand mills, bead mills, dispersers, etc., can be used. Alternatively, a container equipped with a stirrer can be used to add glass beads or the like for mixing and dispersing to mix and disperse the liquid.

[0101] 3. Antifouling treatment methods, antifouling coatings and coating materials

[0102] 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 coating surface is continuously renewed, thereby preventing the adhesion of aquatic fouling organisms.

[0103] Examples of objects to be coated include ships (especially ship bottoms), fishing gear, and underwater structures.

[0104] 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.

[0105] [Example]

[0106] The features of the present invention are further illustrated below with examples, etc. However, the present invention is not limited to the examples, etc.

[0107] 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.

[0108] Device: HLC-8220GPC manufactured by Tosoh Corporation

[0109] Column: 2 TSKgel SuperHZM-M tubes

[0110] Flow rate: 0.35 mL / min

[0111] Detector: RI

[0112] Column constant temperature bath temperature: 40℃

[0113] Elution buffer: THF

[0114] 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".

[0115] 1. Manufacturing Example

[0116] 1-1. Example of manufacturing monomer (a1)

[0117] <Manufacturing Example 1 (Manufacturing of Monomer a1-1)>

[0118] In a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel, methyl chloroacetate: 109 g (1.00 mol), methacrylic acid: 86 g (1.00 mol), 4-methoxyphenol: 0.1 g, and ethyl acetate: 500 g were added. While stirring, triethylamine: 101 g (1.00 mol) was added dropwise while 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 concentration under reduced pressure to obtain monomer a1-1: 142.3 g.

[0119] <Manufacturing Examples 2-7 (Manufacturing of monomers a1-2 and b1-1-b1-5)>

[0120] Using the raw materials shown in Table 1, monomers a1-2 and b1-1 to b1-5 were obtained by reacting in the same manner as in Manufacturing Example 1. The reaction conditions and yields of Manufacturing Examples 1 to 7 are shown in Table 1.

[0121] [Table 1]

[0122]

[0123] 1-2. Manufacturing examples of monomer (a2)

[0124] <Manufacturing Example 8 (Manufacturing of Monomer a2-1)>

[0125] (Reaction 1)

[0126] 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 concentration under reduced pressure to obtain methoxycarbonylmethyl chloroacetate: 262 g.

[0127] (Reaction 2)

[0128] Then, in a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel, 200 g (1.20 mol) of methyl chloroacetate methoxycarbonyl ester, 103 g (1.20 mol) of methacrylic acid, 0.1 g of 4-methoxyphenol, and 500 g of ethyl acetate, the products (intermediates) of the first reaction, were added dropwise while stirring and 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, and the solvent was removed by distillation under reduced pressure to obtain monomer a2-1: 230.6 g.

[0129] <Manufacturing Examples 9-42 (Manufacturing of monomers a2-2 to a2-10 and b2-1 to b2-25)>

[0130] Using the raw materials shown in Tables 2 to 4, monomers a2-2 to a2-10 and b2-1 to b2-25 as shown in Table 2 were obtained by performing the reaction in the same manner as in Manufacturing Example 8. The reaction conditions and yields of Manufacturing Examples 8 to 42 are shown in Tables 2 to 4.

[0131] [Table 2]

[0132]

[0133] [Table 3]

[0134]

[0135] [Table 4]

[0136]

[0137] The raw materials listed in Tables 1 to 4 are detailed below.

[0138] AA: Acrylic acid

[0139] MAA: Methacrylic acid

[0140] NMP: N-methyl-2-pyrrolidone

[0141] CANa: Sodium monochloroacetate

[0142] CPANa: Sodium 2-chloropropionate

[0143] CAMe: Methyl chloroacetate

[0144] CAEt: Ethyl chloroacetate

[0145] CAiPr: Isopropyl chloroacetate

[0146] CANBu: n-Butyl chloroacetate

[0147] CPAMe: Methyl 2-chloropropionate

[0148] MEHQ: 4-Methoxyphenol

[0149] TEA: Triethylamine

[0150] 1-3. Examples of Copolymer Solution Preparation

[0151] <Manufacturing Example P1 (Manufacturing of Copolymer Solution A-1)>

[0152] Xylene (50 g) and butyl acetate (50 g) were added as solvents to a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel. Nitrogen gas was introduced, and the mixture was maintained at 88°C with stirring. Then, monomers (a), (b), and (c) in proportions (g) as shown in Table 5, along with 1,1,3,3-tetramethylperoxy-2-ethylhexanoate (2.0 g, initially added) as a polymerization initiator, were added dropwise over 3 hours while maintaining the mixture at 88°C. After stirring at 88°C for 1 hour, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (0.1 g) was added three times every hour, and the mixture was stirred at the same temperature for another 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 5.

[0153] <Manufacturing Examples P2~P24 (Manufacturing of copolymer solutions A-2~A-20, R-1~R-4)>

[0154] In addition to using the monomers, polymerization initiators, and solvents shown in Tables 5 to 7, copolymer solutions A-2 to A-20 and R-1 to R-4 were obtained by reacting in the same manner as in Manufacturing Example P1. The heating residual composition and Mw of each polymer are shown in Tables 5 to 7. The unit of the proportions of raw materials in the tables is g.

[0155] [Table 5]

[0156]

[0157] [Table 6]

[0158]

[0159] [Table 7]

[0160]

[0161] 1-4. Other manufacturing examples

[0162] <Manufacturing Example D1 (Manufacturing of Rosin Solution)>

[0163] 300g of Chinese-made rosin (WW) and 310g of xylene were added to a flask equipped with a thermometer, reflux condenser, and stirrer. The mixture was dehydrated by reflux under reduced pressure at 70–80°C for 1 hour to obtain a rosin-xylene solution (brown transparent liquid, 50% solids). The residual content of the resulting solution after heating was 50.3%.

[0164] <Manufacturing Example D2 (Manufacturing of Hydrogenated Rosin Solution)>

[0165] Except for replacing the Chinese-origin rosin (WW) in Manufacturing Example D1 with hydrogenated rosin, a xylene solution of hydrogenated rosin (brown transparent liquid, 50% solids) was obtained using the same method as in Manufacturing Example D1. The residual content of the resulting solution upon heating was 50.1%.

[0166] <Manufacturing Example D3 (Manufacturing of Zinc Salt Solution of Gum Rosin)>

[0167] In a flask equipped with a thermometer, reflux condenser, and stirrer, 240 g of Chinese-made resin rosin (WW) and 360 g of xylene were added, along with 120 g of zinc oxide, until the resin acid was completely dissolved. Rosin-type zinc salt was then added, and the mixture was refluxed under reduced pressure at 70–80 °C for 3 hours to remove moisture. After cooling and filtration, a xylene solution of rosin zinc salt (dark brown transparent liquid, 50% solids) was obtained. The residual content of the resulting solution upon heating was 50.2%.

[0168] <Manufacturing Example D4 (Manufacturing of Hydrogenated Rosin Zinc Salt Solution)>

[0169] Except for replacing the Chinese-origin rosin (WW) in Manufacturing Example D3 with hydrogenated rosin, a xylene solution of hydrogenated rosin zinc salt (dark brown transparent liquid, 50% solids) was obtained using the same method as in Manufacturing Example D3. The residue of the resulting solution upon heating was 50.5%.

[0170] 2. Examples 1-36 and Comparative Examples 1-4 (Preparation of Coating Compositions)

[0171] The coating composition is prepared by mixing and dispersing the components shown in Tables 8 to 11 at the ratios (mass %) shown in the tables with glass beads of 1.5 to 2.5 mm in diameter.

[0172] [Table 8]

[0173]

[0174] [Table 9]

[0175]

[0176] [Table 10]

[0177]

[0178] [Table 11]

[0179]

[0180] The ingredients in the table are detailed below.

[0181] <Dissolution regulator>

[0182] Hydrogenated rosin zinc solution: The solution prepared in Manufacturing Example D4 is used. Rosin zinc salt solution: The solution prepared in Manufacturing Example D3 is used. Rosin solution: The solution prepared in Manufacturing Example D1 is used.

[0183] Hydrogenated rosin solution: The solution prepared in manufacturing example D2 is used.

[0184] <Antifouling reagent>

[0185] Cuprous oxide: Trade name "NC-301" (manufactured by Nisshin Chemco Co., Ltd.)

[0186] Copper pyrithione: Trade name "Copper Omagin" (manufactured by LONZA Corporation)

[0187] Sea Nine: Trade name "Sea Nine211", 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (manufactured by R&H), 30% xylene solution of active ingredient.

[0188] Zineb: [Ethylene bis(dithiocarbamate)] Zinc (manufactured by Ouchi Shinsei Chemical Co., Ltd.)

[0189] Zinc pyrithione: (Manufactured by LONZA Corporation)

[0190] Econea 028: Trade name "Econea 028" 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (manufactured by Janssen PMP)

[0191] Metopidine: (±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (manufactured by Wako Pure Chemical Industries, Ltd.)

[0192] <Pigment>

[0193] Iron Dan: Trade name "Bengara Kingyoku" (manufactured by Morishita Bengara Industry Co., Ltd.)

[0194] Talc: Trade name "Talc MS" (manufactured by Talc Corporation, Japan)

[0195] Zinc oxide: Trade name "Zinc Oxide 2 Types" (manufactured by Zhengtong Chemical Industry Co., Ltd.)

[0196] Titanium oxide: Trade name "FR-41" (manufactured by Furukawa Machinery & Metal Co., Ltd.)

[0197] <Other Additives>

[0198] Disparlon A603-20X: Amide-based thixotropic agent: Trade name "Disparlon A603-20X" (manufactured by Kusumoto Chemical Co., Ltd.)

[0199] Tetraethoxysilane: Trade name "ethylsilicate 28" (manufactured by Colcoat Co., Ltd.)

[0200] Trimethylbenzene phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)

[0201] Chlorinated paraffin: Trade name "Paraffin Chlorlated (Cl: 40%)" (manufactured by Wako Pure Chemical Industries, Ltd.)

[0202] 3. Experiment

[0203] The coating compositions of the examples and comparative examples were subjected to the following tests. The evaluation results are shown in Tables 8 to 11.

[0204] All comparative examples showed poor results in either the rotation test or the anti-fouling test.

[0205] <Experimental Example 1 (Rotation Test)>

[0206] A rotating drum with a diameter of 515 mm and a height of 440 mm is installed in the center of the tank, and is rotated by an electric motor. In addition, a cooling device to maintain a constant seawater temperature and an automatic pH controller to maintain a constant seawater pH are also installed.

[0207] The test plate was prepared according to the following method.

[0208] First, an anti-rust coating (epoxy-based A / C) was applied to a titanium plate (71×100×0.5mm) to a thickness of approximately 100μm after drying, forming an anti-rust film after drying. Then, the coating compositions obtained in the examples and comparative examples were applied to achieve a dry film thickness of approximately 300μm, and dried at 40°C for 3 days to prepare test panels.

[0209] The prepared test plate was fixed onto the rotating drum of the rotating device described above, so that it came into contact with seawater, and the rotating drum rotated at a speed of 20 knots. During this period, the seawater temperature was maintained at 25°C, the pH value was maintained at 8.0-8.2, and the seawater was changed every two weeks.

[0210] The residual film thickness of each test plate was measured using a shape measurement laser microscope VK-X100 manufactured by Keyence Co., Ltd. at the initial stage and every 6 months after the start of the test. The amount of film dissolved per month (μm / month) was calculated by calculating the difference in the thickness of the dissolved coating. In addition, when measuring the residual film thickness after 36 months of rotational testing, the surface condition of each coating was evaluated by observing the surface of each coating with the naked eye and a microscope.

[0211] The surface condition of the coating is evaluated according to the following criteria.

[0212] ◎: When there are absolutely no abnormalities

[0213] ○: Hair-like cracks are visible on less than 10% of the total surface area of ​​the coating.

[0214] △: Hair-like cracks are visible in 10-30% of the total surface area of ​​the coating.

[0215] ×: Hair-like cracks are visible in more than 30% of the total surface area of ​​the coating.

[0216] ××: Visible coating abnormalities, such as large cracks, blistering, or peeling (peeling only on the surface or part of the edge of the coating), or delamination (the entire coating peels off, with no test coating residue), etc.

[0217] <Experimental Example 2 (Pollution Prevention Test)>

[0218] The coating compositions obtained in the examples and comparative examples were applied to both sides of a rigid polyvinyl chloride (PVC) sheet (100×200×2mm) to achieve a dried coating thickness of approximately 300μm. A test panel 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 panel was immersed at a depth of 1.5m below sea level in Owashi City, Mie Prefecture, and fouling due to adhering substances was observed after 12 months, 24 months, and 36 months.

[0219] The evaluation is conducted by visually observing the condition of the coating surface, and the judgment is made according to the following criteria.

[0220] ◎: No shellfish, algae or other fouling organisms adhere to it, and almost no mud.

[0221] ○: No fouling organisms such as shellfish or algae adhere to the surface. There is a thin layer of slime (visible on the coating surface), but it can be easily removed by gently wiping with a brush.

[0222] △: Although there are no fouling organisms such as shellfish or algae attached, the slime is so thick that the surface of the coating is not visible and cannot be removed by scrubbing vigorously with a brush.

[0223] ×: The level of fouling organisms such as shellfish and algae attached to the surface.

Claims

1. A stain-resistant coating composition comprising copolymer A and a stain-resistant agent, characterized in that, The copolymer A is a copolymer of monomer (a) represented by formula (1) and monomer (b) represented by formula (2) with an olefinically unsaturated monomer (c) other than monomer (a) and (b). [Chemistry 1] （1） In the formula, R 1 R represents hydrogen, methyl, and phenyl. 2 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 represents an integer from 1 to 10. [Chemistry 2] （2） In the formula, R 3 R represents hydrogen, methyl, and phenyl. 4 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 represents an integer from 1 to 10. The content of monomer (a) is 10-90% by mass relative to the total of monomer (a) and monomer (b). The monomer (a) is a mixture of compounds with n=1 and n=2 or more in formula (1) above. The monomer (b) is a mixture of a compound with n=1 and a compound with n=2 or more in the above formula (2).

2. The antifouling coating composition according to claim 1, characterized in that, It also contains dissolution regulators.

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