Antifouling coating composition

Abstract

Provided is a composition for forming a high-gloss coating film which has a relatively slow dissolution rate, can exhibit good antifouling performance, and does not cause coating film abnormalities such as cracking even if immersed in seawater for a long period of time. According to the present invention, provided is an antifouling coating composition containing a copolymer A, a rosin ester B, and an antifouling agent C. The copolymer A is a copolymer of a monomer (a1) represented by general formula (1) and an ethylenically unsaturated monomer (a2) other than the monomer (a1), the rosin ester B is a reaction product of a polyol (b1) and rosin or a derivative (b2) thereof.

Description

Technical Field

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

[0002] If aquatic fouling organisms such as barnacles, slugs, mussels, bryozoans, sea squirts, sea lettuce, sea lettuce, and slime attach to ships (especially the hull), fishing nets, fishing net attachments and other fishing gear, as well as underwater structures such as power plant water pipes, problems such as functional damage and cosmetic damage may occur.

[0003] To prevent such problems, there is a known technology that involves applying an antifouling coating composition to the surface of a ship or similar vessel to form an antifouling film, thereby providing long-term antifouling performance by slowly releasing the antifouling agent from the antifouling film (Patent Document 1).

[0004] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2000-17203 Summary of the Invention

[0005] The technical problem that the invention aims to solve

[0006] However, even with the technology in Patent Document 1, there are sometimes abnormalities in the coating, such as excessive initial dissolution or cracking after a short period of time, which require further improvement.

[0007] Furthermore, coatings obtained using the technology in Patent Document 1 often have low gloss, while a high-gloss coating surface is sometimes required to improve the aesthetics of shipbuilding.

[0008] The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a coating film that has a relatively slow dissolution rate but can exert good antifouling properties, and will not cause coating abnormalities such as cracking even when immersed in seawater for a long time, and has a high gloss.

[0009] Technical means for solving technical problems

[0010] According to the present invention, an antifouling coating composition is provided, comprising copolymer A, rosin ester B and antifouling agent C, wherein copolymer A is a copolymer of monomer (a1) and vinyl unsaturated monomer (a2) other than said monomer (a1), said monomer (a1) being represented by general formula (1), and said rosin ester B is a reaction product of polyol (b1) and rosin or its derivative (b2).

[0011] In order to solve the above problems, the inventors conducted in-depth research and found that the composition can solve the above problems, thus completing the present invention. Detailed Implementation

[0012] The present invention will now be described in detail. In this specification, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0013] 1. Antifouling coating composition The antifouling coating composition of the present invention contains copolymer A, rosin ester B, and antifouling agent C.

[0014] 1-1. Copolymer A 1-1-1. Composition of copolymer A Copolymer A is a copolymer of monomer (a1) and polymerizable unsaturated monomer (a2) other than monomer (a1). Copolymer A contains monomer units derived from monomers (a1) and (a2).

[0015] <Single (a1)> The monomer (a1) is a triorganosilyl (meth)acrylate monomer, represented by general formula (1).

[0016]

Chemistry 1

[0017] (In the formula, R¹ represents a hydrogen atom or a methyl group, R²~R 4 (Whether they are the same or different, they represent branched alkyl or phenyl groups with 3 to 8 carbon atoms) As R²~R 4 Branched alkyl groups having 3 to 8 carbon atoms, examples include: isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpropyl, 1-methylbutyl, 1-methylpentyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, tert-hexyl, cyclohexyl, 1,1-dimethylpentyl, 1-methylhexyl, 1,1-dimethylhexyl, 1-methylheptyl, 2-methylbutyl, 2-ethylbutyl, 2,2-dimethylpropyl, cyclohexylmethyl, 2-ethylhexyl, 2-propylpentyl, 3-methylpentyl, etc. As R² to R... 4 The preferred compounds are isopropyl, sec-butyl, tert-butyl, phenyl, and 2-ethylhexyl. Isopropyl and 2-ethylhexyl are particularly preferred.

[0018] As monomers (a1), examples include: triisopropylsilyl (meth)acrylate, triisobutyl (meth)acrylate, trisec-butyl (meth)acrylate, triisopentyl (meth)acrylate, triphenyl (meth)acrylate, diisopropylphenyl (meth)acrylate, diisopropyl isobutyl (meth)acrylate, diisopropyl sec-butyl (meth)acrylate, diisopropyl isopentyl (meth)acrylate, isopropyl diisobutyl (meth)acrylate, isopropyl disec-butyl (meth)acrylate, tert-butyl diisobutyl (meth)acrylate, and so on. Tert-butyl diisopentyl silyl acrylate, tert-butyl diphenyl silyl acrylate, diisopropyl tert-hexyl silyl acrylate, diisopropyl cyclohexyl silyl acrylate, tricyclohexyl silyl acrylate, tri(1,1-dimethylpentyl) silyl acrylate, tri(2,2-dimethylpropyl) silyl acrylate, tri(cyclohexylmethyl) silyl acrylate, diisopropyl(cyclohexylmethyl) silyl acrylate, tri(2-ethylhexyl) silyl acrylate, tri(2-propylpentyl) silyl acrylate, and other silyl acrylates. These monomers (a1) can be used alone or in combination of two or more.

[0019] <Single (a2)> Monomer (a2) is an ethylene-unsaturated monomer other than monomer (a1), such as (meth)acrylates, vinyl compounds, aromatic compounds, dialkyl esters of dicarboxylic acids, etc.

[0020] Examples of (meth)acrylates include: 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 monomethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl methacrylate, and mono(2-(meth)acryloyloxyethyl) succinate. Ester, N-(3-dimethylaminopropyl)(meth)acrylamide, 2-[2-(2-methoxyethoxy)ethoxy]ethyl methacrylate, N,N'-dimethyl(meth)acrylamide, 2-(2-methoxyethoxy)ethyl methacrylate, (meth)acrylic acid, hydroxypropyl acrylate, 2-(acetylacetoxy)ethyl methacrylate, 2-(2-hydroxyethoxy)ethyl methacrylate, N-vinyl-2-pyrrolidone, 2-[2- Acrylates such as [2-ethoxyethoxy]ethoxy]ethyl ester, 4-hydroxybutyl acrylate glycidyl ether, N-isopropylacrylamide, 2-(dimethylamino)ethyl acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, 4-hydroxybutyl acrylate, tetrahydrofurfuryl acrylate, 3-chloro-2-hydroxypropyl acrylate, 2-[2-(2-ethoxyethoxy)ethoxy]ethyl methacrylate, N,N'-diethylacrylamide, 3-methoxybutyl acrylate, etc.

[0021] Examples of vinyl compounds include vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, N-vinylpyrrolidone, and other vinyl compounds with functional groups.

[0022] Examples of aromatic compounds include styrene, vinyltoluene, and α-methylstyrene.

[0023] Examples of dialkyl esters of dicarboxylic acids include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

[0024] In this invention, these monomers (a2) can be used alone or in combination of two or more. In particular, from the viewpoint of coating properties, (meth)acrylate is preferred as monomer (a2), and more preferably from the viewpoint of crack resistance, methyl methacrylate, butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.

[0025] The monomer (a1) content in copolymer A is preferably 25-75% by mass, more preferably 30-60% by mass.

[0026] Specifically, the content of monomer (a1) is preferably 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75% by mass, or may be within any two values ​​listed herein.

[0027] 1-1-2. Properties and manufacturing method of copolymer A The weight-average molecular weight (Mw) of copolymer A is preferably between 5,000 and 100,000. This is because if the molecular weight is less than 5,000, the antifouling coating film will become brittle and prone to peeling or cracking, while if it exceeds 100,000, the viscosity of the polymer solution will increase, making it difficult to handle. Specifically, Mw can be, for example, 5,000, 10,000, 20,000, 25,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or within any two values ​​listed herein.

[0028] Methods for determining Mw include, for example, gel permeation chromatography (GPC).

[0029] Copolymer A can be any one of random copolymer, alternating copolymer, periodic copolymer or block copolymer of monomer (a1) and monomer (a2).

[0030] Copolymer A can be obtained, for example, by polymerizing monomers (a1) and (a2) in the presence of a polymerization initiator.

[0031] Examples of polymerization initiators include, for instance, azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), dimethyl-2,2'-azobisisobutyrate, and 2,2'-azobis(N-butyl-2-methylpropionamide); benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxide, and tert-butyl percarbonate. Peroxides such as propyl ester, 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-tetramethyl butyl peroxide-neodecanoate, tert-amyl peroxide-neodecanoate, tert-hexyl peroxide-tert-amyl peroxide-tert-amyl peroxide, and 1,1,3,3-tetramethyl butyl peroxide-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-tetramethyl butyl peroxide-2-ethylhexanoate. The molecular weight of copolymer A can be adjusted by appropriately setting the amount of polymerization initiator used.

[0032] 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 because it can easily and accurately obtain copolymer A.

[0033] In the polymerization reaction, organic solvents may be used as needed. There are no particular limitations on the 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.

[0034] 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.

[0035] 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.

[0036] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon.

[0037] 1-2. Rosin Ester B Rosin ester B is a reaction product of polyols (b1) and rosin or its derivatives (b2).

[0038] <Polyols (b1)> Polyols (b1) are organic compounds having two or more hydroxyl groups in one molecule. The polyol (b1) preferably has 2 to 5 carbon atoms, specifically, for example, 2, 3, 4, or 5. Polyols (b1) are preferably 2 to 4-membered (2-, 3-, or 4-membered) alcohols. Therefore, polyol (b1) is preferably selected from at least one 2 to 4-membered alcohol with 2 to 5 carbon atoms.

[0039] Examples of polyols (b1) include: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 2,4-pentanediol, 3-methyl-1,3-butanediol, 2,2-dimethyl-1,3-propanediol, 2-methyl-1,3-propanediol, 2-methylene-1,3-propanediol, 1,1-di(hydroxymethyl)cyclopropane, glycerol, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-hydroxymethyl-1,3-propanediol, trimethylolethane, erythritol, pentanediol, pentaerythritol, etc., with glycerol being particularly preferred.

[0040] <Rosin or its derivatives (b2)> Examples of rosin include: resin rosin, tall oil rosin, and wood rosin. Examples of derivatives of rosin include: disproportionated rosin, hydrogenated rosin, polymerized rosin, maleic rosin, and rosin esters other than rosin ester B.

[0041] Rosin ester B is manufactured, for example, by esterification or transesterification of a polyol (b1) with rosin or its derivative (b2).

[0042] Examples of rosin ester B include: rosin glycerol ester, disproportionated rosin glycerol ester, hydrogenated rosin glycerol ester, pentaerythritol rosin ester, disproportionated pentaerythritol rosin ester, hydrogenated pentaerythritol rosin ester, disproportionated maleic acid rosin ester, and polymerized pentaerythritol rosin ester, with rosin glycerol ester, hydrogenated rosin glycerol ester, and pentaerythritol rosin ester being particularly preferred. These rosin esters B can be used alone or in combination of two or more.

[0043] As rosin ester B, commercially available products can also be used, such as: Permalyn 5095, Permalyn 5110, Foralyn 90, Foralyn 110 (manufactured by Eastman Chemical Company), etc.

[0044] The content of rosin ester B in the composition of the present invention is not particularly limited, but in combination with copolymer A, especially from the viewpoint of aesthetics and coating solubility, the content ratio of rosin ester B in the total mass of copolymer A and rosin ester B is preferably 5 to 90% by mass, and particularly preferably 10 to 60% by mass. Specifically, this content is, for example, 5, 10, 20, 30, 40, 50, 60, 70, 80, or 90% by mass, and may also be within the range of any two values ​​exemplified herein.

[0045] 1-3. Antifouling agent C As antifouling agents C, examples include inorganic and organic reagents.

[0046] Examples of inorganic reagents include cuprous oxide, copper thiocyanate (common name: Rhodane copper), and copper powder. Among these, cuprous oxide and Rhodane copper are particularly preferred. Cuprous oxide that has been surface-treated with glycerol, sucrose, stearic acid, lauric acid, lecithin, mineral oil, etc., is even more preferred in terms of long-term stability during storage.

[0047] Examples of organic reagents include: 2-mercaptopyridine-N-copper oxide (common name: copper pyridinethione), 2-mercaptopyridine-N-zinc oxide (common name: zinc pyridinethione), zinc ethylidene didithiocarbamate (common name: zineb), 4,5-dichloro-2-n-octyl-3-isothiazolidinone (common name: Sea-Nine 211), 3,4-dichlorophenyl-N,N-dimethylurea (common name: diuron), 2-methylthio-4-tert-butylamino-6-cyclopropylamino-triazine (common name: Irgarol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: Econea 28), and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: metopril), etc.

[0048] These antifouling agents can be used in combination with one or more. The content of the antifouling agent in the composition of the present invention is not particularly limited, but when converted to solid components, it is generally preferred to be 0.1 to 60% by mass. The content of the antifouling agent is preferably, 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, or 60% by mass, or may be within the range of any two values ​​listed herein.

[0049] Other additives Furthermore, in the antifouling coating resin of the present invention, other resin components besides copolymer A, dissolution modifiers, plasticizers, pigments, dyes, defoamers, dehydrating agents, thixotropic agents, organic solvents, etc., may be added as needed to prepare an antifouling coating.

[0050] Other resin components include, for example, (meth)acrylic resin, polyester resin, vinyl resin, petroleum resin, metal-containing resin, zwitterionic resin, organosilicon resin, alicyclic hydrocarbon resin, etc.

[0051] Examples of dissolution modifiers include, for example, rosin, hydrogenated rosin, disproportionated rosin, maleic rosin, polymerized rosin, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, tertiary carbonate, trimethylisobutylenylcyclohexene carboxylic acid and its metal salts, or the aforementioned alicyclic hydrocarbon resins. These can be used alone or in combination of two or more.

[0052] Examples of plasticizers include: phosphate esters, phthalates, adipates, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, tert-nonyl pentasulfide, petrolatum, polybutene, tri(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, diisononyl cyclohexane-1,2-dicarboxylic acid, triethyl acetylglucosyl citrate, tributyl acetylglucosyl citrate, dipropylene glycol dibenzoate, etc. These can be used alone or in combination of two or more.

[0053] Examples of dehydrating agents include: calcium sulfate, synthetic zeolite adsorbents, orthoesters, silicates or isocyanates such as tetramethoxysilane and tetraethoxysilane, carbodiimides, and carbonyl diimidazoles. These can be used alone or in combination of two or more.

[0054] 2. Method for manufacturing antifouling coating composition The antifouling coating composition of the present invention can be manufactured, for example, by mixing and dispersing a mixture containing copolymer A, rosin ester B, antifouling agent C and other additives using a disperser.

[0055] As the dispersant, equipment suitable for use as a micro-pulverizer can be used, for example. Commercially available homogenizers, sand mills, bead mills, dispersers, etc., can be used. Alternatively, glass beads or similar materials for mixing and dispersing can be added to a container equipped with a stirrer to mix and disperse the mixture.

[0056] 3. Antifouling treatment methods, antifouling coatings and coating materials The antifouling treatment method of the present invention is a method of forming an antifouling coating film on the surface of a film-forming object using the above-described 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.

[0057] Examples of objects to be coated include ships (especially ship bottoms), fishing gear, and underwater structures.

[0058] 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, seawater temperature, etc. 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. Example

[0059] The following examples are shown to further illustrate the features of the invention. However, the invention is not limited to these examples.

[0060] In the manufacturing examples, embodiments, and comparative examples, "%" indicates "mass %". The composition values ​​in the table represent mass %. The weight-average molecular weight (Mw) is a value obtained through GPC (polystyrene conversion). The GPC conditions are as follows.

[0061] Device... HLC-8220GPC manufactured by Tosoh Corporation Chromatographic column... TSKgel SuperHZM-M 2 columns Flow rate: 0.35 mL / min Detector RI The column thermostat temperature is 40℃. Elution buffer...THF The residual composition after heating was determined according to JIS K 5601-1-2:1999 (ISO 3251:1993) "Coatings - Test methods for components - Residual composition after heating".

[0062] 1. Manufacturing Example <Manufacturing Example 1 (Manufacturing of Copolymer Solution A-1)> In a four-necked flask equipped with a thermometer, cooler, stirrer, and dropping funnel, 32 g of xylene was added, nitrogen gas was introduced, and the mixture was stirred and maintained at 88°C. A mixture of 40 g of triisopropylsilyl methacrylate, 27.5 g of 2-methoxyethyl acrylate, 32.5 g of methyl methacrylate, and 0.42 g of 1,1,3,3-tetramethylbutyl peroxide (2-ethylhexanoate) was added dropwise 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-tetramethylbutyl peroxide (2-ethylhexanoate) was added twice every 20 minutes to complete the polymerization reaction. 64 g of xylene was added, and the mixture was cooled to room temperature to obtain copolymer solution A-1. The viscosity of the obtained copolymer solution A-1 was 580 mPa·s (25°C), the residual composition after heating was 50.8%, and the Mw was 49,000.

[0063] <Manufacturing Examples 2-7 (Manufacturing of copolymer solutions A-2-A-6, and comparative copolymer solution R-1)> Polymerization was carried out using the monomer mixtures shown in Table 1, following the same procedure as in Manufacturing Example 1. By appropriately adjusting the reaction temperature, solvent volume, and initiator dosage, copolymer solutions A-2 to A-6 and comparative copolymer solution R-1, as shown in Table 1, were obtained. The viscosity, residual composition upon heating, and Mw of each polymer solution are shown in Table 1.

[0064] Table 1

[0065] <Manufacturing Example 8 (Manufacturing of Comparative Copolymer Solution R-2)> In a flask equipped with a thermometer, reflux cooler and stirrer, add 200g of Laroflex MP-25 (manufactured by BASF) and 300g of xylene, and stir at 70-80°C for 1 hour to obtain comparative copolymer solution R-2 (40% solids).

[0066] <Manufacturing Example 9 (Manufacturing of Rosin Ester Solution B-1)> In a flask equipped with a thermometer, reflux cooler and stirrer, add 300g of rosin glycerol ester and 300g of xylene, and stir at 70-80℃ for 1 hour to obtain rosin ester solution B-1 (brown transparent liquid, 50% solid content).

[0067] <Manufacturing Examples 10-12 (Manufacturing of Rosin Ester Solutions B-2-B-3 and Z-1)> Rosin ester solutions B-2 to B-3 and Z-1 were obtained by performing the same operations as in Manufacturing Example 9 on the rosin esters shown in Table 2. The resulting solutions are shown in Table 2.

[0068] Table 2

[0069] <Manufacturing Example 13 (Manufacturing of Gum Rosin Solution)> In a flask equipped with a thermometer, reflux cooler and stirrer, add 300g of Chinese rosin (WW) and 300g of xylene, stir at 70-80℃ for 1 hour to obtain a xylene solution of rosin (brown transparent liquid, 50% solids).

[0070] <Manufacturing Example 14 (Manufacturing of Hydrogenated Rosin Solution)> In a flask equipped with a thermometer, reflux condenser and stirrer, add 300g of Chinese-made hydrogenated rosin and 300g of xylene, and stir at 70-80°C for 1 hour to obtain a xylene solution of hydrogenated rosin (brown transparent liquid, 50% solids).

[0071] 2. Examples and Comparative Examples (Preparation of Coating Compositions) The components shown in Tables 3 to 6 are combined in the proportions (mass%) shown in the tables and dispersed with glass beads of 2 mm in diameter to produce a coating composition.

[0072] Table 3

[0073] Table 4

[0074] Table 5

[0075] Table 6

[0076] The detailed information of the components in Tables 2 to 6 is as follows.

[0077] <Rosin Ester B> Rosin glyceryl esters: Trade name "Permalyn 5095" (manufactured by Eastman Chemical Company) Hydrogenated rosin glycerol esters: Trade name "Foralyn 90" (manufactured by Eastman Chemical Company) Hydrogenated rosin pentaerythritol ester: Trade name "Foralyn 110" (manufactured by Eastman Chemical Company) Rosin methyl ester: Trade name "Metalyn 200" (manufactured by Eastman Chemical Company) <Dissolution modifier> Gum rosin solution: Used in the product manufactured in manufacturing example 13.

[0078] Hydrogenated rosin solution: Used in the product manufactured in Manufacturing Example 14.

[0079] <Antifouling Agent C> Cuprous oxide: Trade name "NC-301" (manufactured by Nichijin Kogyo Co., Ltd.) Copper pyrithione: Trade name "Copper Omadine" (manufactured by LONZA Corporation) Zinc mancozeb: Zinc ethylene bis(dithiocarbamate) (manufactured by Ouchi Shinsei Chemical Co., Ltd.) Sea-Nine: Trade name "Sea-Nine 211", 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (manufactured by R&H Company), a 30% xylene solution of the active ingredient. Metopidine: (±)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (manufactured by Wako Pure Chemical Industries, Ltd.) Pigments and other additives Zinc oxide: Trade name "Zinc Oxide 2 Types" (manufactured by Zhengtong Chemical Industry Co., Ltd.) Titanium oxide: Trade name "FR-41" (manufactured by Furukawa Machinery & Metal Co., Ltd.) Tetsudan: Trade name "Bengala Kingyoku" (manufactured by Morishita Benpaku Kogyo Co., Ltd.) Talc: Trade name "Talc MS" (manufactured by Talc Corporation of Japan) Ethyl silicate: Trade name "Ethyl silicate 28" (manufactured by Colcoat Co., Ltd.) Chlorinated paraffin: Trade name "Cereclor 42" (manufactured by INEOS) Cyclohexane-1,2-dicarboxylic acid diisononyl ester: Trade names "HEXAMOLL (registered trademark) DINCH (registered trademark)" (manufactured by BASF). Triethyl acetyl citrate: Manufactured by Tokyo Chemical Co., Ltd. Dipropylene glycol dibenzoate: Manufactured by Fujifilm and Kojun Pharmaceutical Co., Ltd. Disparlon A603-20X: Amide-based thixotropic agent: Trade name "Disparlon A603-20X" (manufactured by Kusumoto Chemical Co., Ltd.) Disparlon 4200-20: Thixotropic agent for oxidized polyethylene: Trade name "Disparlon 4200-20" (manufactured by Kusumoto Chemical Co., Ltd.) <Experimental Example 1 (Pollution Prevention Test)> 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 300 μm. The resulting coating was dried at room temperature (25°C) for 3 days to obtain a test panel with a dried coating thickness of approximately 300 μm. The test panel was immersed at a depth of 1.5 m below sea level in Owashi City, Mie Prefecture, and the fouling caused by adhering substances was observed after 12 months and 24 months.

[0080] The coating surface was evaluated by visual inspection, and the following criteria were used for judgment.

[0081] ◎: No fouling organisms such as shellfish or algae adhere to it, and there is almost no slime.

[0082] ○: No fouling organisms such as shellfish or algae adhere to the surface. Although there may be a thin layer of slime (visible on the coating surface), it can be easily removed by gently wiping with a brush.

[0083] △: No shellfish or algae or other fouling organisms adhere to the surface, but there is a layer of slime of an invisible thickness on the coating surface that cannot be removed even with vigorous scrubbing with a brush.

[0084] ×: Level where fouling organisms such as shellfish or algae are attached.

[0085] <Experimental Example 2 (Rotation Test)> A rotating drum with a diameter of 515 mm and a height of 440 mm is installed in the center of the tank, and it is powered by a motor. In addition, a cooling device is installed to maintain a constant seawater temperature, and an automatic pH controller is installed to maintain a constant seawater pH.

[0086] The test plate was made according to the following method.

[0087] First, an anti-rust coating (epoxy vinyl-based A / C) was applied to a titanium plate (71×100×0.5mm) to a thickness of approximately 100μm after drying, and then dried to form an anti-rust coating film. Next, the coating compositions obtained in the examples and comparative examples were applied to a dry film thickness of approximately 400μm and dried at 40°C for 3 days to prepare a test panel.

[0088] The prepared test plate was fixed onto the rotating drum of the rotating mechanism 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 period, the seawater temperature was maintained at 25°C and the pH was maintained at 8.0-8.2, and the seawater was changed every two weeks.

[0089] The residual film thickness of each test plate was measured at the initial stage and every 6 months after the start of the test using a VR-5000 one-click 3D profile measuring instrument (manufactured by Keyence Corporation). The thickness of the dissolved coating was calculated from the difference, thereby obtaining the average amount of coating dissolved per month (μm / month).

[0090] In addition, the surface of each coating was observed with the naked eye and a microscope to evaluate the surface condition of the coating when the residual film thickness was measured 12 months and 24 months after the rotation test.

[0091] The surface condition of the coating is evaluated according to the following criteria.

[0092] ○: No abnormalities at all △: Microcracks (hair cracks) are visible in some areas of the coating surface. ×: Microcracks are visible throughout the coating surface. ××: Cracks are visible on the coating surface. <Experimental Example 3 (Gloss Value Measurement)> The coating compositions obtained in the examples and comparative examples were applied to one side of a frosted glass plate (100×200×1mm) to achieve a dried coating thickness of approximately 200μm. The resulting coating was dried at 40°C for 1 day to obtain a test plate with a dried coating thickness of approximately 200μm.

[0093] The gloss value of the dried coating surface was measured at 60 degrees using a Micro-Tri-Gloss meter (manufactured by BYK Gardner). Generally, a higher gloss value indicates a higher gloss level and better aesthetics of the coating surface; therefore, in this experiment, coatings exhibiting high gloss values ​​were rated as superior.

[0094] <Experimental Results> According to the results of Test Examples 1 to 3, compared with the coating of the comparative example which does not contain at least one of copolymer A and rosin ester B, the coating of the embodiment formed using the composition containing copolymer A and rosin ester B showed a higher gloss value, and although the amount of coating dissolved was less, it still performed well in antifouling performance, and no coating abnormalities such as cracking occurred after long-term immersion in seawater.

Claims

1. A stain-resistant coating composition comprising copolymer A, rosin ester B, and stain-resistant agent C, characterized in that, The copolymer A is a copolymer of monomer (a1) and an vinyl unsaturated monomer (a2) other than monomer (a1). The monomer (a1) is represented by the general formula (1). The rosin ester B is a reaction product of a polyol (b1) and rosin or its derivative (b2). In the formula, R¹ represents a hydrogen atom or a methyl group, and R² ~ R 4 The terms "identical" or "different" refer to branched alkyl or phenyl groups with 3 to 8 carbon atoms.

2. The antifouling coating composition according to claim 1, characterized in that, The content ratio of rosin ester B in the total mass of copolymer A and rosin ester B is 5 to 90 by mass.

3. The antifouling coating composition according to claim 1 or 2, characterized in that, The polyol (b1) is selected from at least one of 2 to 4 polyols having 2 to 5 carbon atoms.

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