Underwater antifouling coating composition

Abstract

One embodiment of the present invention relates to an underwater antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating film or a method for producing the same, or an antifouling method for a substrate, wherein the underwater antifouling coating composition contains a rosin-based compound (A) and a pigment (B), the rosin-based compound (A) contains a rosin-based compound monomer (A1) and a rosin-based compound multimer (A2), the content of the multimer (A2) with respect to 1 part by mass of the content of the monomer (A1) is 0.1-5 parts by mass, and the content of xylene-insoluble components in the underwater antifouling coating composition is 50-90 mass% with respect to 100 mass% of the solids content of the underwater antifouling coating composition.

Description

Underwater antifouling paint composition

[0001] One embodiment of the present invention relates to an underwater antifouling paint composition, an antifouling coating film, a substrate with an antifouling coating film or a method for producing the same, or a method for antifouling a substrate.

[0002] In order to prevent underwater structures such as the bottom of a ship from suffering economic losses due to increased propulsion resistance caused by the adhesion of aquatic organisms and damage caused by erosion by aquatic organisms, a method of antifouling the underwater structures is generally adopted in which an antifouling coating film is formed by applying an antifouling coating composition to the surface of the underwater structures.

[0003] As such an antifouling coating composition, for example, Patent Document 1 describes an antifouling coating composition that can exhibit long-term performance in preventing adhesion of aquatic organisms.

[0004] Japanese Patent Application Publication No. 10-030071

[0005] Among aquatic organisms, barnacles are particularly strong adhesive creatures and can bite into antifouling coatings. Therefore, when attempts are made to remove barnacles from an antifouling coating, the entire coating can come off or become uneven, causing great damage and requiring repairs.

[0006] When an antifouling coating film is formed by applying an antifouling coating composition to the bottom of a ship or the like and allowing it to dry (naturally), the applied antifouling coating composition may be exposed to wind (natural wind) during the drying process. It has been found that when an antifouling coating film is formed from an antifouling coating composition containing a rosin compound, exposure to such wind tends to cause wrinkles on the surface of the formed antifouling coating film.

[0007] It has been found that conventional antifouling coating compositions such as those described in Patent Document 1 have room for improvement in terms of suppressing the occurrence of such wrinkles and preventing barnacles from adhering to and biting into antifouling coating films formed from the antifouling coating compositions.

[0008] One embodiment of the present invention provides an underwater antifouling paint composition that can form an antifouling coating film that is less likely to wrinkle even when exposed to wind, and that can suppress the attachment and intrusion of barnacles.

[0009] As a result of extensive research, the present inventors have found that the above-mentioned problems can be solved by the following configuration example.

[0010] [1] An underwater antifouling coating composition comprising a rosin compound (A) and a pigment (B), wherein the rosin compound (A) comprises a rosin compound monomer (A1) and a rosin compound multimer (A2), the content of the multimer (A2) per 1 part by mass of the monomer (A1), is 0.1 to 5 parts by mass, and the content of xylene-insoluble matter in the underwater antifouling coating composition is 50 to 90% by mass relative to 100% by mass of the solids content of the underwater antifouling coating composition.

[0011] [2] The underwater antifouling coating composition according to [1], wherein the content of the multimer (A2) is 1 to 20 mass% relative to 100 mass% of the solids content of the underwater antifouling coating composition.

[0012] [3] The underwater antifouling coating composition according to [1] or [2], wherein the content of the rosin compound (A) is 10 to 50 mass% relative to 100 mass% of the solids content of the underwater antifouling coating composition.

[0013] [4] The underwater antifouling coating composition according to any one of [1] to [3], wherein the pigment (B) comprises a flat pigment. [5] The underwater antifouling coating composition according to any one of [1] to [4], wherein the pigment (B) comprises talc.

[0014] [6] The underwater antifouling coating composition according to any one of [1] to [5], further comprising an antifouling agent (C). [7] The underwater antifouling coating composition according to [6], wherein the antifouling agent (C) contains cuprous oxide, and the content of the cuprous oxide is 10 to 70 mass% relative to 100 mass% of the solids content of the underwater antifouling coating composition.

[0015] [8] The underwater antifouling coating composition according to [6] or [7], wherein the total content of the pigment (B) and the antifouling agent (C) is 40 to 90 mass% relative to 100 mass% of the solids content of the underwater antifouling coating composition.

[0016] [9] The underwater antifouling coating composition according to any one of [1] to [8], further comprising a monocarboxylic acid compound (D) other than the rosin-based compound (A).

[10] The underwater antifouling coating composition according to [9], wherein the monocarboxylic acid compound (D) comprises a branched aliphatic carboxylic acid having 3 to 30 carbon atoms.

[0017]

[11] An antifouling coating film formed from the underwater antifouling coating composition according to any one of [1] to

[10] .

[12] A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to

[11] .

[0018]

[13] A method for producing a substrate with an antifouling coating film, comprising the steps of applying the underwater antifouling coating composition according to any one of [1] to

[10] to at least a part of a substrate, and then drying the composition.

[0019]

[14] A method for antifouling a substrate, comprising the step of forming the antifouling coating film according to

[11] on at least a part of the substrate.

[0020] According to one embodiment of the present invention, it is possible to form an antifouling coating film that is less likely to wrinkle even when exposed to wind during formation. Furthermore, according to one embodiment of the present invention, it is possible to form an antifouling coating film that has high antifouling properties (adhesion inhibition properties) against aquatic organisms, particularly barnacles, and that, even if aquatic organisms, particularly barnacles, do attach, inhibits the barnacles from biting into the film, allowing the barnacles to be removed by a simple method such as washing with water. Therefore, according to one embodiment of the present invention, it is possible to form an antifouling coating film that inhibits damage caused by aquatic organisms, particularly barnacles, and the need for repair due to such damage.

[0021] <Underwater Antifouling Coating Composition> An underwater antifouling coating composition according to one embodiment of the present invention (hereinafter also referred to as "the composition") comprises a rosin compound (A) and a pigment (B), wherein the rosin compound (A) comprises a rosin compound monomer (A1) and a rosin compound multimer (A2), the content of the multimer (A2) per part by mass of the content of the monomer (A1) is 0.1 to 5 parts by mass, and the content of xylene-insoluble matter in the composition is 50 to 90% by mass relative to 100% by mass of the solids content of the composition.

[0022] The content of xylene insoluble matter in the composition is 50 to 90% by mass, preferably 52 to 85% by mass, and more preferably 55 to 80% by mass, based on 100% by mass of the solids content of the composition. By using the composition having a xylene insoluble matter content within this range, it is possible to form an antifouling coating film that is less likely to wrinkle even when exposed to wind during formation. The content of xylene insoluble matter is specifically measured by the method described in the examples below.

[0023] The "solid content" of the present composition refers to the components other than the solvent in the present composition, and is the solid content obtained by drying the present composition in a hot air dryer at 105°C for 1 hour.

[0024] <Rosin Compound (A)> The rosin compound (A) contains a rosin compound monomer (A1) and a rosin compound multimer (A2). Examples of the rosin compound include compounds containing abietic acid, palustric acid, isopimaric acid, or the like as main components.

[0025] The presence of the monomer (A1) and the multimer (A2) in the compound (A) can be determined, for example, by observing multiple peaks in the measurement results measured under the following GPC conditions: The content ratio of the monomer (A1) and the multimer (A2) in the compound (A) can be calculated, for example, from the ratio of the peak area of ​​the peak identified as the monomer (A1) to the peak area of ​​the peak identified as the multimer (A2) among the multiple peaks in the measurement results measured under the following GPC conditions:

[0026] GPC conditions Apparatus: "HLC-8420GPC" (manufactured by Tosoh Corporation) Columns: "TSKgel guard column Super H-L" (manufactured by Tosoh Corporation, 4.6 mm (inner diameter), 3.5 cm (length)) x 1, "TSKgel Super H2000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)) x 1, "TSKgel Super H4000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)) x 2 Eluent: tetrahydrofuran (THF) Flow rate: 0.600 mL / min Detector: RI Column thermostat temperature: 40°C Standard material: polystyrene Sample preparation method: Compound (A) whose concentration was adjusted with THF to a solid content of 1.5% by mass was filtered through a membrane filter (0.45 μm), and the resulting filtrate was used as a GPC measurement sample.

[0027] The content of compound (A) in the composition is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass, based on 100% by mass of the solids content of the composition. When the content of compound (A) is within this range, wrinkles are less likely to occur during coating film formation, and an antifouling coating film having high antifouling properties (adhesion inhibition properties) against aquatic organisms, particularly barnacles, can be easily formed.

[0028] The present composition contains compound (A), which is a plant-derived component, and in one embodiment of the present invention, the binder component in the present composition can be substantially compound (A) alone. In this case, the present composition has a high content of plant-derived components and is a composition that uses less fossil resources than conventional compositions. Such a composition can contribute to suppressing the increase in carbon dioxide concentration in the atmosphere and reducing environmental impact.

[0029] [Rosin-Based Compound Monomer (A1)] Examples of the rosin-based compound monomer (A1) include rosin, rosin derivatives, rosin metal salts, and pine tar. Among these, rosin is preferred because it enhances the effects of the present composition. Examples of the rosin include gum rosin, wood rosin, and tall oil rosin, with gum rosin being preferred. Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, and formylated rosin. Examples of the rosin metal salt include zinc rosinate, calcium rosinate, copper rosinate, magnesium rosinate, and reaction products of other metal compounds with rosin. The monomer (A1) used in the present composition may be one type or two or more types.

[0030] The content of the monomer (A1) in the present composition is preferably 5 to 45 mass%, more preferably 10 to 40 mass%, and even more preferably 15 to 35 mass%, based on 100 mass% of the solids content of the present composition. When the content of the monomer (A1) is within this range, an antifouling coating film having high antifouling properties (adhesion inhibition properties) against aquatic organisms, particularly barnacles, can be easily formed.

[0031] [Rosin Compound Multimer (A2)] The rosin compound multimer (A2) is a multimer of the monomer (A1). The multimer is preferably a dimer. The multimer (A2) can be obtained by multimerizing (e.g., dimerizing) the monomer (A1) by, for example, the method described in JP-A-2002-201433. The multimer (A2) used in the present composition may be one type or two or more types.

[0032] The content of multimer (A2) in the composition is 0.1 to 5 parts by mass, preferably 0.11 to 3 parts by mass, more preferably 0.12 to 1 part by mass, more preferably 0.12 to 0.8 parts by mass, more preferably 0.12 to 0.7 parts by mass, even more preferably 0.13 to 0.5 parts by mass, and particularly preferably 0.14 to 0.3 parts by mass, relative to 1 part by mass of monomer (A1) in the composition. When the content of multimer (A2) relative to the content of monomer (A1) is within the above range, an antifouling coating film that has good water resistance when immersed in water and excellent durability of antifouling properties can be easily formed.

[0033] The content of the multimer (A2) in the present composition is preferably 1 to 20 mass%, more preferably 1.5 to 15 mass%, and even more preferably 2 to 10 mass%, based on 100 mass% of the solids content of the present composition. When the content of the multimer (A2) relative to the solids content of the present composition is within the above range, an antifouling coating film that has good water resistance when immersed in water and excellent durability of antifouling properties can be easily formed.

[0034] <Pigment (B)> The pigment (B) is not particularly limited, and a conventionally known pigment can be used. Examples of the pigment (B) include flat pigments (B1), zinc oxide (B2), and other pigments (B3) other than these. The pigment (B) used in the present composition may be one type or two or more types.

[0035] The content of pigment (B) in the composition is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 15 to 55% by mass, based on 100% by mass of the solids content of the composition. When the content of pigment (B) is within this range, a composition with excellent coating workability can be easily obtained, the occurrence of wrinkles during coating film formation can be suppressed, stress relaxation within the coating film can be achieved, and an antifouling coating film with excellent adhesion to the substrate and excellent water resistance when immersed in water can be easily formed.

[0036] [Flat Pigment (B1)] The use of a flat pigment (B1) in the present composition tends to suppress cracks that may occur in the antifouling coating film to be formed, and an antifouling coating film with reduced internal stress can be easily formed. When a flat pigment (B1) is used in the present composition, the flat pigment (B1) used may be one type or two or more types.

[0037] Examples of the flat pigment (B1) include talc, mica, glass flakes, aluminum flakes, scaly iron oxide, stainless steel flakes, and plastic flakes. Among these, talc and mica are preferred, and talc is more preferred, from the viewpoint of being able to further suppress the cracks.

[0038] The median diameter (D50) of the flat pigment (B1) is preferably 5 to 200 μm. The average aspect ratio (median diameter / average thickness) of the flat pigment (B1) is preferably 3 to 150, more preferably 5 to 100.

[0039] In this specification, D50 can be measured using a laser scattering diffraction particle size distribution analyzer, for example, "SALD 2200" (manufactured by Shimadzu Corporation). The average thickness can be calculated as the average value of the thicknesses of several tens to several hundreds of pigment particles by observing the main surface of the flat pigment (B1) from a direction horizontal to the main surface using a scanning electron microscope (SEM), for example, "XL-30" (manufactured by Philips).

[0040] When the present composition contains the flat pigment (B1), the content thereof is preferably 1 to 30 mass %, more preferably 3 to 20 mass %, relative to 100 mass % of the solids content of the present composition, from the viewpoint that an antifouling coating film having the above-mentioned effects can be easily formed.

[0041] [Zinc oxide (B2)] The use of zinc oxide (B2) in the present composition tends to facilitate the formation of an antifouling coating film that has sufficient antifouling properties and excellent water resistance. The shape, median diameter (D50), etc. of zinc oxide (B2) are not particularly limited, and when zinc oxide (B2) is used in the present composition, two or more types of zinc oxide (B2) that differ in shape, D50, etc. may be used.

[0042] The D50 of zinc oxide (B2) is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, from the viewpoint of making zinc oxide (B2) more easily dispersible in the composition and improving the antifouling properties of the antifouling coating film obtained, and is preferably 10 μm or less, more preferably 5 μm or less.

[0043] When the present composition contains zinc oxide (B2), the content thereof is preferably 1 to 50 mass %, more preferably 3 to 40 mass %, relative to 100 mass % of the solids content of the present composition, from the viewpoint that an excellent antifouling coating film can be easily formed due to the above-mentioned effects, etc.

[0044] [Other Pigments (B3)] The present composition may contain other pigments (B3) other than the flat pigment (B1) and zinc oxide (B2), for example, for the purpose of coloring the antifouling coating film or concealing the base, or for the purpose of adjusting the strength of the antifouling coating film to an appropriate level. When other pigments (B3) are used in the present composition, the other pigments (B3) used may be one type or two or more types.

[0045] Examples of other pigments (B3) include extender pigments such as silica, zinc phosphate, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, calcium sulfate, and zinc sulfide; and color pigments such as red iron oxide (red iron oxide), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, and phthalocyanine blue.

[0046] When the present composition contains other pigments (B3), the total content thereof may be appropriately set depending on the coloring property and hiding property required for the antifouling coating film to be formed, the viscosity required for the present composition, etc., but is preferably 1 to 40% by mass, more preferably 3 to 30% by mass, relative to 100% by mass of the solids content of the present composition.

[0047] <Other Optional Components> The present composition may contain optional components other than the rosin compound (A) and pigment (B) as needed. Examples of such optional components include an antifouling agent (C), a monocarboxylic acid compound (D), a polybasic acid (E), a solvent (F), a plasticizer (G), an anti-sagging agent / anti-settling agent (H), other binder components, an antifoaming agent, a wetting and dispersing agent, and a dehydrating agent. When other optional components are used in the present composition, the other optional components used may each be one type or two or more types.

[0048] [Antifouling Agent (C)] In order to improve the antifouling properties of the antifouling coating film formed from the present composition, the present composition preferably further contains an antifouling agent (C). When the antifouling agent (C) is used in the present composition, the antifouling agent (C) used may be one type or two or more types.

[0049] When the present composition contains the antifouling agent (C), the content thereof is preferably 1 to 80 mass %, more preferably 10 to 70 mass %, relative to 100 mass % of the solids content of the present composition, from the viewpoint that an antifouling coating film having sufficient antifouling properties can be easily formed.

[0050] Furthermore, when the present composition contains an antifouling agent (C), the total content of the pigment (B) and the antifouling agent (C) is preferably 40 to 90% by mass, more preferably 45 to 85% by mass, and even more preferably 50 to 80% by mass, relative to 100% by mass of the solids content of the present composition, from the viewpoint of being able to easily form an antifouling coating film that is excellent in water resistance and has high antifouling properties (adhesion inhibition properties) against aquatic organisms.

[0051] Examples of the antifouling agent (C) include (+ / -)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (also known as medetomidine); 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (also known as tralopyril); metal pyrithione compounds such as copper pyrithione and zinc pyrithione; 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT); borane-nitrogen base adducts such as pyridinetriphenylborane and 4-isopropylpyridine(N-B)methyl(diphenyl)borane; N,N-dimethyl-N'-(3,4-dichlorophenyl)urea; Maleimide compounds such as N-(2,4,6-trichlorophenyl)maleimide, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, and 2,3-dichloro-N-(2'-ethyl-6'-methylphenyl)maleimide; 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine; 2,4,5,6-tetrachloroisophthalonitrile; carbamate compounds such as bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, zinc dimethyldithiocarbamate, and zinc ethylenebisdithiocarbamate; disulfide compounds such as chloromethyl-n-octyl disulfide and tetraalkylthiuram disulfide; N',N'-dimethyl-N-phenyl-(N-fluorodichloromethylthio)sulfamide; and copper compounds such as cuprous oxide, copper oxide, copper (metallic copper), and copper thiocyanate (also known as copper rhodanide). Among these, the antifouling agent (C) preferably contains at least one selected from medetomidine, tralopyril, DCOIT, a metal pyrithione compound (e.g., copper pyrithione, zinc pyrithione), and a copper compound (e.g., cuprous oxide, copper rhodanide), more preferably contains at least one selected from a metal pyrithione compound and cuprous oxide, and particularly preferably contains a metal pyrithione compound and cuprous oxide, in view of being able to easily form an antifouling coating film having high antifouling properties (adhesion inhibitory properties) against aquatic organisms, particularly barnacles.

[0052] Medetomidine has optical isomerism, and when medetomidine is used in the present composition, only one of the optical isomers may be used, or a mixture of the optical isomers in any ratio may be used. Furthermore, the medetomidine may be an imidazolium salt of medetomidine or an adduct of medetomidine with a metal or the like. In this case, the imidazolium salt or the adduct with a metal or the like may be used as a raw material when preparing the present composition, and the imidazolium salt or the adduct with a metal or the like may be formed in the present composition or the antifouling coating film.

[0053] Cuprous oxide: The cuprous oxide is preferably in the form of particles having a median diameter (D50) of about 0.1 to 30 μm, since this allows for the easy formation of an antifouling coating film that has long-lasting antifouling properties. Furthermore, cuprous oxide that has been surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, or the like is preferred, since this allows for the easy production of a composition that has excellent long-term stability during storage.

[0054] When the present composition contains cuprous oxide, the content thereof is preferably 10 to 70 mass%, more preferably 15 to 65 mass%, and even more preferably 20 to 60 mass%, relative to 100 mass% of the solids content of the present composition, from the viewpoint that an antifouling coating film having sufficient antifouling properties can be easily formed.

[0055] Metal pyrithione compounds: Copper pyrithione and zinc pyrithione are preferred as the metal pyrithione compounds, with copper pyrithione being preferred from the viewpoint of easily forming an antifouling coating film that is excellent in water resistance, crack resistance, and antifouling properties. When the present composition contains a metal pyrithione, the content thereof is preferably 0.5 to 20% by mass, more preferably 2 to 15% by mass, relative to 100% by mass of the solids content of the present composition, from the viewpoint of easily forming an antifouling coating film that has sufficient antifouling properties.

[0056] [Monocarboxylic acid compound (D)] The present composition may contain a monocarboxylic acid compound (D). When the present composition contains the compound (D), it improves the surface renewal of the formed antifouling coating film in water, and when the antifouling coating film contains an antifouling agent, it can enhance the antifouling properties of the antifouling coating film by promoting the release of the antifouling agent into water, and it also has the function of imparting appropriate water resistance to the antifouling coating film, and further, the coating workability of the present composition also tends to be improved. When the compound (D) is used in the present composition, the compound (D) used may be one type or two or more types.

[0057] Compound (D) is not particularly limited as long as it is a compound other than compound (A). Examples of compound (D) include compounds represented by R-COOH (R is a saturated or unsaturated aliphatic hydrocarbon group having 10 to 40 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 40 carbon atoms, or a group in which any of these groups is partially substituted with a heteroatom), and derivatives thereof (e.g., metal esters). Among these, in terms of the above-mentioned effects being more excellent, compound (D) is preferably a branched aliphatic carboxylic acid having 3 to 30 carbon atoms (which may contain at least one selected from a heteroatom and a double bond).

[0058] Suitable examples of compound (D) include trimethylisobutenylcyclohexenecarboxylic acid, versatic acid, stearic acid, and naphthenic acid, and among these, versatic acid is particularly preferred because it can easily form an antifouling coating film with excellent coating film properties. Versatic acid is a general term for a mixture of highly branched carboxylic acids having 9 to 11 carbon atoms, mainly 10 carbon atoms.

[0059] Examples of the metal ester include zinc ester and copper ester. When the present composition contains the metal ester, the metal ester may be used as a raw material for preparing the present composition, or the metal ester may be formed in the present composition or the antifouling coating film.

[0060] When the present composition contains compound (D), the content thereof is preferably 0.5 to 10 mass %, more preferably 1 to 7 mass %, relative to 100 mass % of the solids content of the present composition, from the viewpoints that the present composition having excellent coating workability can be easily obtained and an antifouling coating film having excellent water resistance can be easily formed.

[0061] [Polybasic acid (E)] The present composition may contain a polybasic acid (E). Examples of the polybasic acid (E) include maleic acid, fumaric acid, itaconic acid, citraconic acid, dimer acid, and citric acid. When a polybasic acid (E) is used in the present composition, the polybasic acid (E) used may be one type or two or more types.

[0062] When the present composition contains a polybasic acid (E), the content thereof is preferably 0.5 to 5 mass %, more preferably 1 to 3 mass %, relative to 100 mass % of the solids content of the present composition, from the viewpoint that an antifouling coating film having excellent water resistance can be easily formed, etc.

[0063] [Solvent (F)] The present composition may contain a solvent (F) such as water or an organic solvent, as needed, for the purpose of adjusting the viscosity of the composition, etc. The solvent (F) is preferably an organic solvent, and preferably does not substantially contain water. In other words, the present composition is preferably an organic solvent-based composition rather than a water-based composition. Here, "substantially does not contain water" means that the proportion of water in the solvent (F) is 10% by mass or less, preferably 2% by mass or less. When a solvent (F) is used in the present composition, the solvent (F) used may be one type or two or more types.

[0064] Examples of the organic solvent include aromatic organic solvents such as xylene, toluene, and ethylbenzene; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic monohydric alcohols (having 1 to 10 carbon atoms, preferably about 2 to 5 carbon atoms) such as ethanol, isopropyl alcohol, n-butanol, isobutanol, and propylene glycol monomethyl ether; and ester solvents such as ethyl acetate and butyl acetate.

[0065] The content of solvent (F) in the composition may be 0% by mass, but when the composition contains solvent (F), it is preferable to appropriately set the content so as to obtain a desired viscosity depending on the coating method of the composition, and it is usually preferably 10 to 50% by mass, more preferably 15 to 40% by mass, based on 100% by mass of the composition. If the content of solvent (F) is too high, problems such as a decrease in anti-sagging properties may occur.

[0066] [Plasticizer (G)] The present composition may contain a plasticizer (G) for the purpose of imparting plasticity to the antifouling coating film to be formed, etc. When a plasticizer (G) is used in the present composition, the plasticizer (G) used may be one type or two or more types.

[0067] Examples of the plasticizer (G) include tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), acetyl tributyl citrate, and adipic acid diester.

[0068] When the present composition contains a plasticizer (G), the content thereof is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, relative to 100 mass % of the solids content of the present composition, from the viewpoint of being able to maintain good plasticity of the antifouling coating film to be formed, etc.

[0069] [Anti-sagging agent / anti-settling agent (H)] The present composition may contain an anti-sagging agent / anti-settling agent (H) for the purpose of adjusting the viscosity of the composition, etc. When an anti-sagging agent / anti-settling agent (H) is used in the present composition, the anti-sagging agent / anti-settling agent (H) used may be one type or two or more types.

[0070] Examples of the anti-sagging agent / anti-settling agent (H) include organic clay waxes (e.g., stearate salts of Al, Ca, and Zn, lecithin salts, and alkylsulfonates), organic waxes (e.g., polyethylene wax, oxidized polyethylene wax, amide wax, polyamide wax, and hydrogenated castor oil wax), mixtures of organic clay waxes and organic waxes, and synthetic finely powdered silica.

[0071] When the present composition contains an anti-sagging agent / anti-settling agent (H), the content thereof is preferably 0.01 to 10 mass %, more preferably 0.1 to 3 mass %, relative to 100 mass % of the solid content of the present composition.

[0072] [Other Binder Components] The present composition may contain other binder components other than the compound (A) for the purpose of imparting static antifouling properties, water resistance, crack resistance, and strength to the antifouling coating film to be formed. When other binder components are used in the present composition, the other binder components to be used may be one type or two or more types. Examples of the other binder components include polyester-based (co)polymers, (meth)acrylic (co)polymers ((meth)acrylic resins), vinyl-based (co)polymers (including polyvinyl ethyl ether, etc.), silyl ester-based (co)polymers, metal (e.g., zinc, copper) ester-based (co)polymers, chlorinated paraffin, n-paraffin, terpene phenol resins, petroleum resins, and ketone resins.

[0073] <Method for preparing the present composition> The present composition can be prepared by a method similar to that for preparing a known general antifouling coating composition. Specifically, the present composition can be prepared by adding the compound (A), the pigment (B), and, if necessary, the other optional components to a container all at once or sequentially, and stirring and mixing them.

[0074] <Antifouling Coating Film, Substrate with Antifouling Coating Film, Manufacturing Method Thereof, and Method for Antifouling a Substrate> An antifouling coating film according to one embodiment of the present invention (hereinafter also referred to as "the present coating film") is formed from the present composition and can usually be formed by drying the present composition. The present coating film is usually formed on a substrate and used as a substrate with the present coating film, comprising the substrate and the present coating film. A suitable example of a method for manufacturing a substrate with the present coating film includes a step of applying the present composition to at least a portion of the substrate and then drying the composition. Furthermore, a method for antifouling a substrate according to one embodiment of the present invention includes a step of forming the present coating film on at least a portion of the substrate. Because the method for manufacturing a substrate with the present coating film includes a step of forming the present coating film on at least a portion of the substrate, it can also be said to be a method for antifouling a substrate.

[0075] The substrate is not particularly limited, but since the present composition is preferably used for antifouling substrates in a wide range of industrial fields such as ships, fisheries, and underwater structures, examples of the substrate include ships (e.g., hull shells for large steel ships such as container ships and tankers, fishing boats, FRP boats, wooden boats, yachts, etc., including both new ships and repaired ships); fishing materials (e.g., ropes, fishing nets, fishing gear, floats, buoys); diver suits; underwater goggles; oxygen cylinders; swimsuits; torpedoes; structures such as oil pipelines, water supply and discharge pipes, circulating water pipes, water supply and discharge outlets for thermal and nuclear power plants, submarine cables, seawater utilization equipment (e.g., seawater pumps), megafloats, coastal roads, undersea tunnels, port facilities, various underwater civil engineering structures in canals and waterways, etc. Among these, ships, underwater structures, and fishery materials are preferred, ships and underwater structures are more preferred, and ships are particularly preferred.

[0076] The substrate may be a substrate treated with other treatment agents such as a rust inhibitor, a substrate having a coating film such as a primer formed on its surface, or a substrate having the present coating film formed thereon. The type of object with which the present coating film comes into direct contact is not particularly limited.

[0077] The method for applying the present composition to at least a part of a substrate is not particularly limited, and examples thereof include a method of coating the present composition on a substrate and a method of immersing the substrate in the present composition (impregnating the substrate with the present composition). Examples of the coating method include known methods such as methods using a brush, a roller, or a spray.

[0078] The drying method includes, for example, leaving the coating at room temperature (e.g., 25°C) for preferably about 0.5 to 14 days, more preferably about 1 to 7 days. The drying may be carried out under heating or while blowing air. According to one embodiment of the present invention, even when drying is carried out while blowing air, an antifouling coating film that is less likely to wrinkle due to the wind can be easily formed.

[0079] The thickness of the present coating film after drying may be selected as desired depending on the degree of wear of the present coating film, the intended use and period of use of the present coating film, etc., but is preferably, for example, about 30 to 1,000 μm. Methods for forming an antifouling coating film of this thickness include methods in which the present composition is applied one or more times so as to obtain a dried coating film of a thickness of preferably 10 to 300 μm, more preferably 30 to 200 μm per application.

[0080] The substrate with the present coating film can also be produced by a method including step (I) of forming the present coating film and step (II) of attaching the obtained present coating film to a substrate. Step (I) is not particularly limited, and an example thereof includes a method in which the present composition is applied to at least a portion of a substrate, and a support that has been subjected to a release treatment as necessary is used instead of the substrate. Step (II) is also not particularly limited, and an example thereof includes a method described in JP 2013-129724 A.

[0081] Hereinafter, one embodiment of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Note that the "solid content" of each component used in the examples refers to the component excluding volatile components contained in each component as a solvent, and the solid content is defined as the content obtained by drying each component in a hot air dryer at 105°C for 1 hour.

[0082] [Examples 1 to 13 and Comparative Examples 1 to 3] Underwater antifouling paint compositions were prepared by mixing and stirring the components in the proportions (parts by mass) shown in Table 1. The amount of each component shown in Table 1 indicates the amount blended as is. For example, in Example 2, the amount of fatty acid amide blended as is (total) was 1.0 part by mass. The solid content of the fatty acid amide was 20% by mass, so the amount of fatty acid amide itself blended in Example 2 was 0.2 parts by mass. Details of each component used in the examples and comparative examples are shown in Table 2.

[0083] <Amount of Xylene Insolubles in the Solids of the Paint> The amount of xylene insolubles in the solids of the paint (the content of xylene insolubles in the solids of the underwater antifouling coating composition) was specifically measured and calculated, for example, by a method involving the following steps (1) to (6). (1) A portion of the prepared underwater antifouling coating composition was weighed, and the weighed underwater antifouling coating composition and approximately 10 times the mass of xylene were placed in a centrifuge tube and thoroughly mixed. (2) After 30 minutes of centrifugation at 0°C and 3,500 rpm, the supernatant was removed and transferred to another container. (3) The residue after removing the supernatant in (2) was again mixed with the same amount of xylene as in (1), and centrifuged under the same conditions. The supernatant was removed and added to the container containing the first supernatant. This procedure was repeated once more. (4) The residue after the three centrifugations was dried in a hot air dryer at 105°C for 1 hour, and the mass of the remaining solids was measured. (5) A portion of the remaining underwater antifouling coating composition weighed in (1) above was dried for 1 hour in a hot air dryer at 105°C, and the solids content of the underwater antifouling coating composition was calculated. (6) The solids content of the underwater antifouling coating composition weighed in (1) above was calculated from the solids content of the underwater antifouling coating composition calculated in (5) above, and the amount of xylene-insoluble matter in the solids content of the paint (the content of xylene-insoluble matter in the solids content of the underwater antifouling coating composition) was calculated from this solids content and the solids content calculated in (4) above.

[0084] <Film Formability> Each of the prepared underwater antifouling coating compositions was applied once to a vinyl chloride plate measuring 150 mm long x 70 mm wide x 3 mm thick so that the dry film thickness was 300 μm. The vinyl chloride plate coated with the composition was then placed in a draft chamber at 25°C for 1 hour with air blowing parallel to the coated composition surface at a speed of approximately 2 m / s to dry, thereby forming a coating film. If the formed coating film did not wrinkle, it was rated as "AA," and if wrinkles were present, it was rated as "BB." The results are shown in Table 1.

[0085] <Evaluation of barnacle resistance> An epoxy resin-based anticorrosive paint composition (trade name "Banno 1500", manufactured by Chugoku Toryo Co., Ltd.) was applied to a sandblasted steel plate (100 mm long x 200 mm wide x 2.3 mm thick) to a dry film thickness of 150 μm and dried, and then an epoxy resin-based binder paint composition (trade name "Banno 1500RZ", manufactured by Chugoku Toryo Co., Ltd.) was applied to a dry film thickness of 100 μm and dried. Subsequently, each of the prepared underwater antifouling paint compositions was applied once to give an antifouling coating film with a dry film thickness of 100 μm, and the resulting coating was dried at 25° C. for 7 days to prepare a test plate.

[0086] The prepared test panels were fixed to the inner wall of a cylinder generating a rotating water current at a surface speed of 10 knots and placed in a dynamic immersion environment in 30°C seawater for three months. They were then immersed in Hiroshima Bay approximately 2 meters below the water surface with the antifouling coating film oriented approximately parallel to the water surface. Three months after the start of immersion, the barnacle adhesion area on the antifouling coating film was measured, and the barnacle resistance of the antifouling coating film was evaluated according to the antifouling performance evaluation criteria based on barnacle adhesion area described below. After three months of immersion in Hiroshima Bay, the test panels were removed from the water and subjected to high-pressure water rinsing until all barnacles attached to the antifouling coating film were removed. After high-pressure water rinsing, the antifouling coating film surface was visually observed, the area of ​​any defects in the antifouling coating film was measured, and damage to the antifouling coating film due to barnacle infestation was evaluated according to the evaluation criteria for coating defect area described below. The results are shown in Table 1. The antifouling coating film of Comparative Example 1 completely disappeared after being placed in a dynamic immersion environment, making accurate evaluation impossible. For this reason, the evaluation was given as "-".

[0087] (Anti-fouling evaluation criteria based on barnacle adhesion area) 5: The total area where barnacles are attached is less than 1% of the entire anti-fouling coating film (100%). 4: The area where barnacles are attached is 1% or more but less than 10%. 3: The area where barnacles are attached is 10% or more but less than 30%. 2: The area where barnacles are attached is 30% or more but less than 70%. 1: The area where barnacles are attached is 70% or more.

[0088] (Evaluation criteria for the area of ​​defects in the coating) 5: The total area of ​​the defects in the antifouling coating is less than 1% of the total area of ​​the antifouling coating, which is 100%. 4: The area is 1% or more but less than 5%. 3: The area is 5% or more but less than 20%. 2: The area is 20% or more but less than 40%. 1: The area is 40% or more.

[0089]

[0090]

[0091] The content ratios of the rosin compound monomer and the rosin compound multimer (dimer) in "rosin compound 1" in Table 2 are peak area ratios measured by GPC under the following conditions. GPC conditions Apparatus: "HLC-8420GPC" (manufactured by Tosoh Corporation) Columns: "TSKgel guard column Super H-L" (manufactured by Tosoh Corporation, 4.6 mm (inner diameter), 3.5 cm (length)) x 1, "TSKgel Super H2000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)) x 1, "TSKgel Super H4000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)) x 2 Eluent: tetrahydrofuran (THF) Flow rate: 0.600 mL / min Detector: RI Column thermostat temperature: 40°C Standard material: polystyrene Sample preparation method: Rosin compound 1, the concentration of which was adjusted with THF to a solid content of 1.5% by mass, was filtered through a membrane filter (0.45 μm), and the resulting filtrate was used as a GPC measurement sample.

Claims

1. An underwater antifouling coating composition comprising a rosin compound (A) and a pigment (B), the rosin compound (A) comprises a rosin compound monomer (A1) and a rosin compound multimer (A2), the content of the multimer (A2) per 1 part by mass of the monomer (A1) is 0.1 to 5 parts by mass, and the content of xylene insoluble matter in the underwater antifouling coating composition is 50 to 90% by mass relative to 100% by mass of the solids content of the underwater antifouling coating composition.

2. The underwater antifouling coating composition according to claim 1, wherein the content of the multimer (A2) is 1 to 20 mass % relative to 100 mass % of the solids content of the underwater antifouling coating composition.

3. The underwater antifouling coating composition according to claim 1, wherein the content of the rosin compound (A) is 10 to 50 mass % relative to 100 mass % of the solids content of the underwater antifouling coating composition.

4. The underwater antifouling paint composition according to claim 1, wherein the pigment (B) comprises a flat pigment.

5. The underwater antifouling coating composition according to claim 1, wherein the pigment (B) comprises talc.

6. The underwater antifouling coating composition according to claim 1, further comprising an antifouling agent (C).

7. The underwater antifouling coating composition according to claim 6, wherein the antifouling agent (C) contains cuprous oxide, and the content of the cuprous oxide is 10 to 70 mass% relative to 100 mass% of the solids content of the underwater antifouling coating composition.

8. The underwater antifouling coating composition according to claim 6, wherein the total content of the pigment (B) and the antifouling agent (C) is 40 to 90 mass % relative to 100 mass % of the solids content of the underwater antifouling coating composition.

9. The underwater antifouling coating composition according to claim 1, further comprising a monocarboxylic acid compound (D) other than the rosin compound (A).

10. The underwater antifouling coating composition according to claim 9, wherein the monocarboxylic acid compound (D) contains a branched aliphatic carboxylic acid having 3 to 30 carbon atoms.

11. An antifouling coating film formed from the underwater antifouling coating composition according to any one of claims 1 to 10.

12. A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to claim 11.

13. A method for producing a substrate with an antifouling coating film, comprising the steps of applying the underwater antifouling coating composition according to any one of claims 1 to 10 to at least a part of the substrate, and then drying the composition.

14. A method for antifouling a substrate, comprising the step of forming the antifouling coating film according to claim 11 on at least a part of the substrate.

Images