Antifouling coating composition

Abstract

Provided is a composition for forming a high-gloss coating film which, despite having a comparatively slow coating film dissolution rate, exhibits good long-term antifouling performance, and in which coating film anomalies such as cracks do not occur even after long-term immersion in seawater.　The present invention provides an antifouling coating composition comprising a copolymer A, a rosin ester B, another rosin component C, and an antifouling agent D, wherein: the copolymer A is a copolymer of a monomer (a1) and an ethylenically unsaturated monomer (a2) other than the monomer (a1); the monomer (a1) is represented by general formula (1); the rosin ester B is a reaction product of a polyalcohol (b1) and a rosin or rosin derivative (b2); and the other rosin component C is a rosin or rosin derivative, or a metal salt of a rosin or rosin derivative.

Description

Antifouling paint composition

[0001] The present invention relates to an antifouling paint composition.

[0002] Aquatic fouling organisms such as barnacles, serpulids, mussels, bryozoans, ascidians, green laver, sea lettuce, and slime adhere to ships (especially the bottom part), fishing gears such as fishing nets and fishing net accessories, and underwater structures such as the intake pipes of power plants, causing problems such as impairment of the functions of these ships and damage to their appearance. To prevent such problems, a technique is known in which an antifouling paint composition is applied to ships and the like to form an antifouling paint film, and an antifouling agent is slowly released from the antifouling paint film to exhibit antifouling performance over a long period (Patent Document 1).

[0003] JP-A-2000-17203

[0004] However, even when the technique of Patent Document 1 is adopted, the initial dissolution of the paint film may become excessively large, or coating film abnormalities such as cracks may occur after a relatively short period of time, and further improvement is required. In addition, the paint film using the technique of Patent Document 1 tends to have low gloss, and a high-gloss paint film surface may be required to improve the aesthetic appearance of shipbuilding. The present invention has been made in view of such circumstances, and provides a composition for forming a paint film that exhibits good long-term antifouling performance despite a relatively slow paint film dissolution rate, does not cause coating film abnormalities such as cracks even after being immersed in seawater for a long time, and forms a high-gloss paint film.

[0005] According to the present invention, there is provided an antifouling paint composition containing a copolymer A, a rosin ester B, other rosin components C, and an antifouling agent D, wherein the copolymer A is a copolymer of a monomer (a1) and an ethylenically unsaturated monomer (a2) other than the monomer (a1), the monomer (a1) is represented by the general formula (1), the rosin ester B is a reaction product of polyhydric alcohols (b1) and rosin or a rosin derivative (b2), and the other rosin component C is a rosin or a rosin derivative or a metal salt of a rosin or a rosin derivative.

[0006] The inventors of this invention conducted extensive research to solve the above problems and, as a result, discovered that the aforementioned composition can solve the problems, thus completing the present invention.

[0007] The present invention will be described in detail below. In this specification, "(meth)acrylic" means acrylic or methacrylic.

[0008] 1. Antifouling paint composition The antifouling paint composition of the present invention comprises copolymer A, rosin ester B, other rosin component C, and antifouling agent D.

[0009] 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).

[0010] <Monomer (a1)> Monomer (a1) is the triorganosilyl (meth)acrylate monomer, and is represented by general formula (1). (In the formula, R １ R is a hydrogen atom or a methyl group. ２ ~R ４ (Each of these represents the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms.)

[0011] R ２ ~R ４ Examples of branched alkyl groups having 3 to 8 carbon atoms include isopropyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methylheptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group, and 3-methylpentyl group. Preferred R2 to R4 groups are isopropyl group, s-butyl group, t-butyl group, phenyl group, and 2-ethylhexyl group. Particularly preferred are isopropyl group and 2-ethylhexyl group.

[0012] Examples of monomers (a1) include triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyl-s-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, isopropyldiisobutylsilyl (meth)acrylate, isopropyl-s-butylsilyl (meth)acrylate, t-butyldiisobutylsilyl (meth)acrylate, and meth)acrylate. Examples include silyl esters of (meth)acrylates such as t-butyldiisopentylsilyl lylate, t-butyldiphenylsilyl (meth)acrylate, diisopropyltexylsilyl (meth)acrylate, diisopropylcyclohexylsilyl (meth)acrylate, tricyclohexylsilyl (meth)acrylate, tri-1,1-dimethylpentylsilyl (meth)acrylate, tri-2,2-dimethylpropylsilyl (meth)acrylate, tricyclohexylmethylsilyl (meth)acrylate, diisopropylcyclohexylmethylsilyl (meth)acrylate, tri-2-ethylhexylsilyl (meth)acrylate, and tri-2-propylpentylsilyl (meth)acrylate. These monomers (a1) can be used individually or in combination of two or more.

[0013] <Monomer (a2)> Monomer (a2) is an ethylenically unsaturated monomer other than monomer (a1), and examples include (meth)acrylic acid esters, vinyl compounds, aromatic compounds, dialkyl ester compounds of dibasic acids, etc.

[0014] Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, and 2-ethoxy (meth)acrylate. Ethyl, Propylene glycol monomethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, Glycidyl (meth)acrylate, Furfuryl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, Dimethylaminoethyl (meth)acrylate, Diethylaminoethyl (meth)acrylate, 2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl methacrylate, Mono(2-(meth)acryloyloxyethyl) succinate , N-(3-dimethylaminopropyl)(meth)acrylamide, 2-[2-(2-methoxyethoxy)ethoxy]ethyl (meth)acrylate, N,N'-dimethyl(meth)acrylamide, 2-(2-methoxyethoxy)ethyl (meth)acrylate, (meth)acrylic acid, hydroxypropyl acrylate, 2-(acetoacetyloxy)ethyl methacrylate, 2-(2-hydroxyethoxy)ethyl methacrylate, N-vinyl-2-pyrrolidone, 2-[2-(2-ethoxyethoxy)ethoxy]ethyl methacrylate Examples include acrylic acid esters such as xyethyl, 4-hydroxybutyl acrylate glycidyl ether, N-isopropyl acrylamide, 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, and 3-methoxybutyl acrylate.

[0015] Examples of vinyl compounds include vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and vinylpyrrolidone, which have functional groups.

[0016] Examples of aromatic compounds include styrene, vinyltoluene, and α-methylstyrene.

[0017] Examples of dialkyl ester compounds of dibasic acids include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.

[0018] In the present invention, these monomers (a2) can be used individually or in combination of two or more. In particular, from the viewpoint of coating film properties, (meth)acrylic acid esters are preferred as monomers (a2), and from the viewpoint of crack resistance, methyl methacrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, etc. are more preferred.

[0019] The content of monomer (a1) in the monomer mixture used for polymerization of copolymer A is preferably 25 to 75% by mass, and more preferably 30 to 60% by mass.

[0020] The monomer (a1) content is preferably, for example, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, or 75% by mass, and may be within the range of any two of the values ​​exemplified herein.

[0021] 1-1-2. Physical Properties and Manufacturing Method of Copolymer A The weight-average molecular weight (Mw) of copolymer A is preferably between 5,000 and 100,000. If the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and prone to peeling and cracking. If it exceeds 100,000, the viscosity of the polymer solution increases, 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, and may also be within the range of any two of the values ​​exemplified here.

[0022] One method for measuring Mw is gel permeation chromatography (GPC).

[0023] Copolymer A may be any of the following copolymers: a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer of monomer (a1) and monomer (a2).

[0024] Copolymer A can be obtained, for example, by polymerizing monomer (a1) and monomer (a2) in the presence of a polymerization initiator.

[0025] Examples of polymerization initiators include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobisisobutyrate, dimethyl-2,2'-azobisisobutyrate, 2,2'-azobis(N-butyl-2-methylpropionamide, etc. azo compounds; benzoyl peroxide, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy-2-ethylhexanoate, di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1 Examples of polymerization initiators include peroxides such as 1,3,3-tetramethylbutyl peroxyneodecanoate, t-amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. 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-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, and 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate. The molecular weight of copolymer A can be adjusted by appropriately setting the amount of polymerization initiator used.

[0026] Polymerization methods include, for example, 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 allows for the simple and accurate acquisition of copolymer A.

[0027] In the polymerization reaction described above, organic solvents may be used as needed. The organic solvents are not particularly limited, but 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-acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol, and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether, and dibutyl ether; and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among these, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene, and xylene are preferred. These solvents can be used individually or in combination of two or more.

[0028] The reaction temperature in the polymerization reaction can be set appropriately depending on the type of polymerization initiator, etc., and is usually 50 to 160°C, preferably 60 to 150°C. The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen gas or argon gas.

[0029] 1-2. Rosin Ester B Rosin ester B is a reaction product of polyhydric alcohols (b1) and rosin or rosin derivatives (b2).

[0030] <Polyhydric alcohols (b1)> Polyhydric alcohols (b1) are organic compounds having two or more alcoholic hydroxyl groups in one molecule. The number of carbon atoms in polyhydric alcohols (b1) is preferably 2 to 5, specifically, for example, 2, 3, 4, or 5. Polyhydric alcohols (b1) are preferably dihydric to tetrahydric (dihydric, trihydric, or tetrahydric) alcohols. Therefore, polyhydric alcohols (b1) are preferably at least one selected from dihydric to tetrahydric alcohols, having 2 to 5 carbon atoms.

[0031] Examples of polyhydric alcohols (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-bis(hydroxymethyl)cyclopropane, glycerin, 1,2,3-butanetriol, 1,2,4-butanetriol, 2-(hydroxymethyl)propane-1,3-diol, trimethylolethane, erythritol, pentylene glycol, pentaerythritol, and other alcohols, with glycerin being particularly preferred.

[0032] <Rosin or rosin derivative (b2)> Examples of rosin include gum rosin, tall oil rosin, and wood rosin. Examples of rosin derivatives include disproportionated rosin, hydrogenated rosin, polymerized rosin, maleated rosin, and rosin esters other than rosin ester B.

[0033] Rosin ester B is produced, for example, by an esterification reaction or transesterification reaction between polyhydric alcohols (b1) and rosin or a rosin derivative (b2).

[0034] Examples of rosin ester B include compounds such as rosin glycerin ester, disproportionate rosin glycerin ester, hydrogenated rosin glycerin ester, rosin pentaerythritol ester, disproportionate rosin pentaerythritol ester, hydrogenated rosin pentaerythritol ester, disproportionate maleic acid rosin ester, and polymerized rosin pentaerythritol. Rosin glycerin ester, hydrogenated rosin glycerin ester, rosin pentaerythritol ester, and hydrogenated rosin pentaerythritol ester are particularly preferred. These rosin esters B can be used individually or in combination of two or more.

[0035] Commercially available products can be used as rosin ester B, such as Permalyn 5095, Permalyn 5110, Foralyn 90, and Foralyn 110 (manufactured by Eastman Chemical Corporation).

[0036] The content of rosin ester B in the composition of the present invention is not particularly limited, but in combination with copolymer A, the content of rosin ester B in the total mass of copolymer A and rosin ester B is preferably 5 to 90% by mass, particularly preferably 10 to 75% by mass, and more preferably 10 to 60% by mass, from the viewpoint of aesthetics and coating film solubility. Specifically, this content is, for example, 5, 10, 20, 30, 40, 50, 60, 70, 75, 80, and 90% by mass, and may be in the range between any two of the values ​​exemplified here.

[0037] 1-3. Other Rosin Component C Other rosin component C is rosin or a rosin derivative, or a metal salt of rosin or a rosin derivative.

[0038] Rosin and rosin derivatives are as described in "Rosin or Rosin Derivatives (b2)". Examples of rosin metal salts include rosin zinc salt, rosin copper salt, and rosin calcium salt. Examples of rosin derivative metal salts include hydrogenated rosin zinc salt, hydrogenated rosin copper salt, hydrogenated rosin calcium salt, disproportionated rosin zinc salt, disproportionated rosin copper salt, and disproportionated rosin calcium salt.

[0039] The content of other rosin component C in the composition of the present invention is not particularly limited, but from the viewpoint of aesthetics and coating film solubility, the content of other rosin component C in the total mass of copolymer A, rosin ester B, and other rosin component C is preferably 5 to 90% by mass, particularly preferably 10 to 75% by mass, and more preferably 10 to 60% by mass. Specifically, this content is, for example, 5, 10, 20, 30, 40, 50, 60, 70, 75, 80, and 90% by mass, and may be in the range of any two of the values ​​exemplified here.

[0040] 1-4. Antifouling agent D The antifouling agent D is a chemical that has a killing or repellent effect on aquatic fouling organisms. Examples of the antifouling agent D include inorganic chemicals and organic chemicals.

[0041] Examples of the inorganic chemicals include cuprous oxide, copper thiocyanate (common name: rhodan copper), copper powder, etc. Among these, cuprous oxide and rhodan copper are particularly preferred. Cuprous oxide that is surface-treated with glycerin, sucrose, stearic acid, lauric acid, lecithin, mineral oil, etc. is more preferred in terms of long-term stability during storage.

[0042] Examples of the organic chemicals include copper 2-mercaptopyridine-N-oxide (common name: copper pyrithione), zinc 2-mercaptopyridine-N-oxide (common name: zinc pyrithione), zinc ethylene bisdithiocarbamate (common name: zineb), 4,5-dichloro-2-n-octyl-3-isothiazolone (common name: Sea-Nine 211), 3,4-dichlorophenyl-N-N-dimethylurea (common name: diuron), 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine (common name: Irgarol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: Econazole 28), 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: medetomidine), etc. These antifouling agents can be used alone or in combination of two or more.

[0043] The content rate of the antifouling agent in the composition of the present invention is not particularly limited, but in terms of solid content conversion, usually 0.1 to 60% by mass is preferred. The content rate 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, 60% by mass, and it may also be within the range between any two of the values exemplified here.

[0044] 1-5. Other additives Furthermore, to the resin for the antifouling paint of the present invention, other resin components other than the copolymer A, elution regulators, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents, thixotropic agents, organic solvents, etc. can be added as necessary to make an antifouling paint. [[ID=1 4]]

[0045] As other resin components, for example, (meth)acrylic resins, polyester resins, vinyl resins, petroleum resins, metal-containing resins, bipolar ion compound-containing resins, silicone resins, alicyclic hydrocarbon resins, etc. can be mentioned.

[0046] As the elution regulator, for example, rosin, hydrogenated rosin, disproportionated rosin, maleated rosin, polymerized rosin, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, versatic acid, trimethylisobutenyl cyclohexene carboxylic acid, and metal salts thereof, etc., or the above-mentioned alicyclic hydrocarbon resin can be mentioned. These can be used alone or in combination of two or more.

[0047] As the plasticizer, for example, phosphate esters, phthalate esters, adipate esters, sebacate esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, petrolatum, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, diisononyl cyclohexane-1,2-dicarboxylate, triethyl acetyl citrate, tributyl acetyl citrate, dipropylene glycol dibenzoate, etc. can be mentioned. These can be used alone or in combination of two or more.

[0048] As the dehydrating agent, for example, calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, carbodiimidazoles, etc. can be mentioned. These can be used alone or in combination of two or more.

[0049] 2. Method for producing the antifouling paint composition The antifouling paint composition of the present invention can be produced, for example, by mixing and dispersing a mixed liquid containing copolymer A, rosin ester B, other rosin components C, antifouling agent D, and other additives, etc. using a disperser.

[0050] As the aforementioned disperser, one that can be used as a fine grinder is preferably used. For example, commercially available homomixers, sand mills, bead mills, dispersers, etc. can be used. Alternatively, the mixture may be mixed and dispersed using a container equipped with a stirrer and containing glass beads for mixing and dispersion.

[0051] 3. Antifouling treatment method, antifouling coating, and coated object The antifouling treatment method of the present invention forms an antifouling coating on the surface of an object to be coated using the above-mentioned antifouling paint composition. According to the antifouling treatment method of the present invention, the antifouling coating gradually dissolves from the surface and the coating surface is constantly renewed, thereby preventing the adhesion of aquatic fouling organisms. Examples of objects to be coated include ships (especially the bottom of the ship), fishing gear, underwater structures, etc. The thickness of the antifouling coating can be appropriately set according to the type of object to be coated, the ship's cruising speed, seawater temperature, etc. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating is usually 50 to 700 μm, preferably 100 to 600 μm.

[0052] The following examples illustrate the features of the present invention. However, the present invention is not limited to these examples. Percentages in each manufacturing example, example, and comparative example represent mass percentages. Numerical values ​​for composition in the table also represent mass percentages. The weight-average molecular weight (Mw) is the value obtained by GPC (polystyrene equivalent). The GPC conditions are as follows: Apparatus: HLC-8220GPC manufactured by Tosoh Corporation Column: TSKgel SuperHZM-M 2 columns Flow rate: 0.35 mL / min Detector: RI Column constant temperature bath temperature: 40°C Eluent: THF The heat residue was measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Test method for paint components - Heat residue".

[0053] 1. Manufacturing Examples <Manufacturing Example 1 (Manufacturing of Copolymer Solution A-1)> 32 g of xylene was placed in a four-necked flask equipped with a thermometer, condenser, stirrer, and dropping funnel. Nitrogen gas was introduced, and the temperature was maintained at 88°C while stirring. A mixture of 40 g of triisopropylsilyl methacrylate, 27.5 g of 2-methoxyethyl acrylate, 32.5 g of methyl meacrylate, and 0.42 g of 1,1,3,3-tetramethylbutyl peroxy-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 peroxy-2-ethylhexanoate was added twice at 20-minute intervals 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 heat residue was 50.8%, and the Mw was 49,000.

[0054] <Production Examples 2-7 (Production of Copolymer Solutions A-2 to A-6 and Comparative Copolymer Solution R-1)> Polymerization reactions were carried out using the monomer mixtures shown in Table 1 in the same manner as in Production Example 1. The reaction temperature, solvent amount, and initiator amount were adjusted as appropriate to obtain copolymer solutions A-2 to A-6 and comparative copolymer solution R-1 shown in Table 1. The viscosity, heating residue, and Mw of each obtained copolymer solution are shown in Table 1.

[0055]

[0056] <Production Example 8 (Preparation of Comparative Copolymer Solution R-2)> 200 g of Laroflex MP-25 (BASF) and 300 g of xylene were placed in a flask equipped with a thermometer, reflux condenser, and stirrer, and stirred at 70-80°C for 1 hour to obtain comparative copolymer solution R-2 (solid content 40%).

[0057] <Production Example 9 (Preparation of Rosin Ester Solution B-1)> 300 g of rosin glycerin ester and 300 g of xylene were placed in a flask equipped with a thermometer, reflux condenser, and stirrer, and stirred at 70-80°C for 1 hour to obtain Rosin Ester Solution B-1 (brown transparent liquid, solid content 50%).

[0058] <Production Examples 10-12 (Production of Rosin Ester Solutions B-2 to B-3 and Z-1)> Rosin ester solutions B-2 to B-3 and Z-1 were obtained by performing the same procedure as in Production Example 9 using the rosin esters shown in Table 2. Each of the obtained solutions is shown in Table 2.

[0059]

[0060] <Production Example 13 (Preparation of Gum Rosin Solution C-1)> 300 g of Chinese gum rosin (WW) and 300 g of xylene were placed in a flask equipped with a thermometer, reflux condenser, and stirrer, and stirred at 70-80°C for 1 hour to obtain a gum rosin xylene solution (brown transparent liquid, solid content 50%).

[0061] <Production Example 14 (Production of Hydrogenated Rosin Solution C-2)> 300 g of hydrogenated rosin from China and 300 g of xylene were placed in a flask equipped with a thermometer, reflux condenser, and stirrer, and stirred at 70-80°C for 1 hour to obtain a xylene solution of hydrogenated rosin (brown transparent liquid, solid content 50%).

[0062] <Production Example 15 (Preparation of Gum Rosin Zinc Salt Solution C-3)> In a flask equipped with a thermometer, reflux condenser, and stirrer, 240 g of Chinese gum rosin (WW) and 360 g of xylene were placed in the flask. Further, 120 g of zinc oxide was added so that all of the resin acid in the rosin would form a zinc salt, and reflux dehydration was carried out under reduced pressure at 70-80°C for 3 hours. After that, the solution was cooled and filtered to obtain a xylene solution of gum rosin zinc salt (dark brown transparent liquid, solid content 50%). The heating residue of the obtained solution was 50.2%.

[0063] <Production Example 16 (Production of Hydrogenated Rosin Zinc Salt Solution C-4)> A xylene solution of hydrogenated rosin zinc salt (dark brown transparent liquid, 50% solids content) was obtained using the same method as in Production Example 15, except that the Chinese-made gum rosin (WW) was replaced with hydrogenated gum rosin.

[0064] 2. Examples and Comparative Examples (Preparation of Paint Compositions) Paint compositions were prepared by mixing and dispersing the components shown in Tables 3 to 7 in the proportions (mass%) shown in the same tables with glass beads with a diameter of 2 mm.

[0065]

[0066]

[0067]

[0068]

[0069]

[0070] The details of the components in Tables 2 to 7 are as follows:

[0071] <Rosin Ester B> Rosin Glycerin Ester: Product name "Permalyn 5095" (manufactured by Eastman Chemical Company) Hydrogenated Rosin Glycerin Ester: Product name "Foralyn 90" (manufactured by Eastman Chemical Company) Hydrogenated Rosin Pentaerythritol Ester: Product name "Foralyn 110" (manufactured by Eastman Chemical Company) Rosin Methyl Ester: Product name "Metalyn 200" (manufactured by Eastman Chemical Company)

[0072] <Other Rosin Components C> Gum rosin solution C-1: The one prepared in Production Example 13 was used. Hydrogenated rosin solution C-2: The one prepared in Production Example 14 was used. Gum rosin zinc salt solution C-3: The one prepared in Production Example 15 was used. Hydrogenated rosin zinc salt solution C-4: The one prepared in Production Example 16 was used.

[0073] <Anti-fouling agent D> Cuprous oxide: Product name "NC-301" (manufactured by Nisshin Chemco Co., Ltd.) Copper pyrithione: Product name "Copper omazine" (manufactured by LONZA Co., Ltd.)

[0074] <Pigments and other additives> Zinc oxide: Product name "Zinc Oxide Type 2" (manufactured by Seido Chemical Industry Co., Ltd.) Titanium dioxide: Product name "FR-41" (manufactured by Furukawa Machinery & Metal Co., Ltd.) Red iron oxide: Product name "Red Iron Oxide Kingyoku" (manufactured by Morishita Red Iron Oxide Industry Co., Ltd.) Talc: Product name "Talc MS" (manufactured by Nippon Talc Co., Ltd.) Ethyl silicate: Product name "Ethyl Silicate 28" (manufactured by Colcoat Co., Ltd.) Chlorinated paraffin: Product name "Cereclar 42" (manufactured by INEOS) Cyclohexane-1,2-dicarboxylate diisononyl: Product name "HEXAMOLL® DINCH®" (manufactured by BASF) Triethyl acetyl citrate: Manufactured by Tokyo Chemical Industry Co., Ltd. Dipropylene glycol dibenzoate: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Disparon A603-20X: Aamide-based thixotropic agent: Product name "Disparon A603-20X" (manufactured by Kusumoto Chemical Co., Ltd.) Disparon 4200-20: Polyethylene oxide-based thixotropic agent: Product name "Disparon 4200-20" (manufactured by Kusumoto Chemical Co., Ltd.)

[0075] <Test Example 1 (Anti-fouling Test)> The coating compositions obtained in the Examples and Comparative Examples were applied to both sides of a rigid PVC board (100 x 200 x 2 mm) to a dry coating thickness of approximately 300 μm. The resulting coatings were dried at room temperature (25°C) for 3 days to prepare a test board with a dry coating thickness of approximately 300 μm. This test board was immersed 1.5 m below sea level in Owase City, Mie Prefecture, and the fouling of the test board by attached substances was observed after 12 months, 24 months, and 30 months.

[0076] The evaluation was conducted by visually observing the condition of the paint film surface, and the following criteria were used for judgment: ◎: No fouling organisms such as shellfish or algae attached, and almost no slime. 〇: No fouling organisms such as shellfish or algae attached, and although a thin layer of slime is attached (enough to allow the paint film surface to be seen), it can be easily wiped off with a brush. △: No fouling organisms such as shellfish or algae attached, but a thick layer of slime is attached to the paint film surface, to the point where it cannot be seen, and cannot be removed even with vigorous wiping with a brush. ×: Fouling organisms such as shellfish or algae are attached.

[0077] <Test Example 2 (Rotary Test)> A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank and made rotatable by a motor. A cooling device to maintain a constant seawater temperature and an automatic pH controller to maintain a constant seawater pH were also installed. A test plate was prepared according to the following method. First, a rust-preventive coating film was formed on a titanium plate (71 × 100 × 0.5 mm) by applying a rust-preventive paint (epoxy vinyl A / C) to a dry thickness of approximately 100 μm and allowing it to dry. Then, the paint compositions obtained in the examples and comparative examples were applied to a dry film thickness of approximately 400 μm and dried at 40°C for 3 days to prepare the test plate. The prepared test plate was fixed to the rotating drum of the above apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this time, the seawater temperature was maintained at 25°C and the pH at 8.0 to 8.2, and the seawater was changed every two weeks. The initial thickness of each test plate and the remaining thickness every six months after the start of the test were measured using a one-shot 3D shape measuring machine VR-5000 (manufactured by Keyence Corporation). The average amount of dissolved coating film per month (μm / month) was obtained by calculating the difference between these measurements.

[0078] Furthermore, when measuring the remaining film thickness 12 months and 24 months after the rotary test, the surface condition of each coating was evaluated by observing it with the naked eye and using a microscope. The evaluation of the coating surface condition was performed according to the following criteria: ○: No abnormalities at all △: Hairline cracks partially visible on the coating surface ×: Hairline cracks visible throughout the coating surface ××: Cracks visible on the coating surface

[0079] <Test 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 x 200 x 1 mm) to a dry coating thickness of approximately 200 μm. The resulting coating was dried at 40°C for one day to prepare a test plate with a dry coating thickness of approximately 200 μm.

[0080] The gloss value of the dried coating surface was measured at 60 degrees Celsius using a Microtrigloss gloss meter (BYK Gardner). Generally, a higher gloss value indicates a higher gloss and superior aesthetics of the coating surface; therefore, in this test, coatings showing high gloss values ​​were evaluated as preferable.

[0081] <Test Results> From the results of Test Examples 1 to 3, it was found that the coating films of the examples exhibited high gloss values, demonstrated good long-term antifouling performance despite relatively low amounts of coating dissolution, and did not develop coating abnormalities such as cracks even after prolonged immersion in seawater. On the other hand, the coating films of the comparative examples were inferior to the coating films of the examples in at least one of the following aspects: gloss value, long-term antifouling performance, and resistance to coating abnormalities.

Claims

1. An antifouling paint composition comprising copolymer A, rosin ester B, other rosin component C, and antifouling agent D, wherein copolymer A is a copolymer of monomer (a1) and an ethylenically unsaturated monomer (a2) other than monomer (a1), monomer (a1) is represented by general formula (1), rosin ester B is a reaction product of polyhydric alcohols (b1) and rosin or a rosin derivative (b2), and other rosin component C is rosin or a rosin derivative, or a metal salt of rosin or a rosin derivative. (In the formula, R １ R is a hydrogen atom or a methyl group. ２ ~R ４ (Each of these represents the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms.) 2. The antifouling coating composition according to claim 1, wherein the rosin ester B is a hydrogenated rosin glycerin ester.

3. The antifouling coating composition according to claim 1, wherein the content of rosin ester B is 5 to 90% by mass of the total mass of copolymer A and rosin ester B.

4. The antifouling coating composition according to claim 1, wherein the content of the other rosin component C is 5 to 90% by mass of the total mass of the copolymer A, the rosin ester B, and the other rosin component C.

5. The antifouling coating composition according to any one of claims 1 to 4, wherein the polyhydric alcohol (b1) is at least one selected from dihydric to tetrahydric alcohols having 2 to 5 carbon atoms.

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