Antifouling coating composition

Abstract

The purpose of the present invention is to provide an antifouling coating composition which has excellent dispersibility while exhibiting excellent antifouling properties and excellent production workability of an antifouling coating film obtained therefrom, is capable of suppressing the generation of aggregates even after storage, is capable of maintaining high anti-sagging properties even after storage, has excellent storage stability, and is also capable of providing an antifouling coating film that can be formed from the antifouling coating composition. Also provided are a method for producing the antifouling coating composition, an antifouling coating film obtained from the antifouling coating composition, a substrate with an antifouling coating film having the antifouling coating film, and a method for producing the substrate. This antifouling coating composition contains a curable polyorganosiloxane (A), a pyrithione metal salt (B), and an oxidized polyethylene wax (C), and satisfies at least one of the following conditions (A) and (B). Condition A: The median diameter (D50) of the pyrithione metal salt (B) in the antifouling coating composition is 5.0 [mu] m or less. Condition B: the median diameter (D50) of the pyrithione metal salt (B) as the starting material is 3.0 [mu] m or less.

Description

TECHNICAL FIELD

[0001] The present application relates to an antifouling coating composition and a method for producing the same, an antifouling coating film using the antifouling coating composition, and a substrate having the antifouling coating film and a method for producing the same. BACKGROUND

[0002] Polyorganosiloxane-based antifouling coating films have a low environmental burden compared to conventional water and decomposition type, hydrolysis type, and the like, and are therefore widely used to prevent the attachment of aquatic organisms to ships, underwater structures, fishing materials, and the like. In addition, from the viewpoint of improving antifouling properties against microorganism species, they are used containing an antifouling agent (particularly, a pyrithione metal salt).

[0003] Patent Literature 1 discloses an antifouling coating composition characterized by containing (A) a diorganopolysiloxane having at least two silanol groups in one molecule, (B) an organosilane having at least two hydrolyzable groups in one molecule and / or a partial hydrolytic condensate thereof, and (C) a pyrithione metal salt, with the aim of providing an antifouling coating composition capable of forming a coating film having high antifouling properties against slime (slime resistance), and excellent strength, rubber properties, and the like, having a suitable viscosity (atomizability at the time of spray work and coating film surface leveling property) and anti-sagging properties, and in which deterioration of these properties is inhibited, and which has high storage stability.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT LITERATURE

[0006] Patent Literature 1: International Publication No. 2014 / 077205 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] Regarding pyrithione metal salts, in recent years, small-particle-size products of around 3 pm or less have gradually become mainstream, and in conjunction therewith, there have been cases in which a decrease in dispersibility, an increase in the viscosity of the antifouling coating, a decrease in storage stability, and the like have occurred, and in order to apply small-particle-size pyrithione metal salts to antifouling coating compositions containing curable polyorganosiloxanes, it is required to improve the dispersibility. However, in Patent Literature 1, a decrease in dispersibility in conjunction with the small-particle-size of the pyrithione metal salt was not investigated.

[0009] An object of the present application is to provide an antifouling coating composition, an antifouling coating film obtained from the same, a substrate having the antifouling coating film, and a method for producing the same, which have excellent antifouling properties, excellent workability, excellent dispersibility, and excellent storage stability, and which can suppress the generation of agglomerates even after storage, and can maintain high anti-sagging properties even after storage.

[0010] Means for solving the problems

[0011] The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the above problems can be solved by using an oxidized polyethylene wax in a polyorganosiloxane-based antifouling coating containing a small-particle-size pyrithione metal salt, thereby completing the present application.

[0012] The present application relates to the following [1] to

[14] .

[0013] [1] An antifouling coating composition comprising a curable polyorganosiloxane (A), a pyrithione metal salt (B), and an oxidized polyethylene wax (C),

[0014] The above antifouling coating composition satisfies at least one of the following conditions A and B.

[0015] Condition A: the median diameter (D50) of the pyrithione metal salt (B) in the antifouling coating composition is 5.0 μm or less

[0016] Condition B: the median diameter (D50) of the pyrithione metal salt (B) as a raw material is 3.0 μm or less

[0017] [2] The antifouling coating composition as recited in [1], wherein the above pyrithione metal salt (B) is copper pyrithione.

[0018] [3] The antifouling coating composition as recited in [1] or [2], which further contains a slip agent (D).

[0019] [4] The antifouling coating composition as recited in any one of [1] to [3], which further contains a coloring pigment (E).

[0020] [5] The antifouling coating composition as recited in [4], wherein the above coloring pigment (E) contains an organic pigment.

[0021] [6] The antifouling coating composition as recited in any one of [1] to [5], wherein the curable polyorganosiloxane (A) is a compound represented by the following formula (Al).

[0022] [Chemical Formula 1]

[0023]

[0024] (in formula (Al), R 11 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, or a halogenated alkyl group, R 12 each independently represent a hydroxyl group or a hydrolyzable group, and r represents an integer of 1 to 3, and p represents 10 to 10,000.)

[0025] [7] The antifouling coating composition according to any one of [1] to [6], wherein the content of the curable polyorganosiloxane (A) in the solid components of the antifouling coating composition is 45 mass% or more and 85 mass% or less.

[0026] [8] The antifouling coating composition according to any one of [1] to [7], wherein the content of the pyrithione metal salt (B) in the solid components of the antifouling coating composition is 0.5 mass% or more and 15 mass% or less.

[0027] [9] The antifouling coating composition according to any one of [1] to [8], wherein the content of the oxidized polyethylene wax (C) in the solid components of the antifouling coating composition is 0.1 mass% or more and 3.0 mass% or less.

[0028]

[10] An antifouling coated film formed from the antifouling coating composition according to any one of [1] to [9].

[0029]

[11] A substrate with an antifouling coated film, which has a substrate and the antifouling coated film according to

[10] provided on the surface of the substrate.

[0030]

[12] A method for producing a substrate with an antifouling coated film, which has the following (1-1) and (1-2) or the following (2-1) and (2-2).

[0031] (1-1) a step of coating or impregnating the antifouling coating composition according to any one of [1] to [9] on the surface of a substrate to obtain a coated or impregnated article

[0032] (1-2) a step of drying the coated or impregnated article obtained in the step (1-1) to form an antifouling coated film

[0033] (2-1) a step of drying the antifouling coating composition according to any one of [1] to [9] to form an antifouling coated film

[0034] (2-2) a step of attaching the antifouling coated film obtained in the step (2-1) to a substrate

[0035] The method for producing the antifouling coating composition according to any one of [1] to [9], the method comprising steps a and b in this order.

[0036] Step a: a step of obtaining a mixture A containing a pyrithione metal salt (B) and an oxidized polyethylene wax (C)

[0037] Step b: a step of mixing the mixture A obtained in step a and a curable polyorganosiloxane (A) to obtain the antifouling coating composition

[0038]

[14] The method for producing the antifouling coating composition according to

[13] , wherein in the above step a, the median diameter (D50) of the pyrithione metal salt (B) as a raw material is 3.0 μm or less.

[0039] Effects of the Invention

[0040] According to the present application, it is possible to provide an antifouling coating composition, an antifouling coating film obtained therefrom, which is excellent in antifouling property, excellent in workability, excellent in dispersibility, can suppress the generation of agglomerates even after storage, can maintain high anti-sagging property even after storage, and excellent in storage stability, a substrate having the antifouling coating film, and a method for producing the same. Furthermore, according to the present application, it is possible to provide an antifouling coating film obtained from the above-described antifouling coating composition, a substrate having the antifouling coating film, and a method for producing the same. DETAILED DESCRIPTION

[0041] Hereinafter, the antifouling coating composition and the method for producing the same, the antifouling coating film using the above-described antifouling coating composition, and the substrate having the antifouling coating film and the method for producing the same according to the present application will be described in detail.

[0042] [Antifouling Coating Composition]

[0043] The antifouling coating composition according to the present application contains a curable polyorganosiloxane (A), a pyrithione metal salt (B), and an oxidized polyethylene wax (C), and satisfies at least one of the following conditions A and B.

[0044] Condition A: the median diameter (D50) of the pyrithione metal salt (B) in the antifouling coating composition is 5.0 μm or less

[0045] Condition B: the median diameter (D50) of the pyrithione metal salt (B) as a raw material is 3.0 μm or less

[0046] The antifouling coating composition according to the present application can provide an antifouling coating composition, an antifouling coating film obtained therefrom, which is excellent in antifouling property, excellent in workability, excellent in dispersibility, can suppress generation of agglomerates even after storage, and can maintain high anti-sagging property even after storage, and is excellent in storage stability.

[0047] Although the detailed reason why the above effects can be obtained is not clear, it is considered that the antifouling coating composition becomes an antifouling coating composition excellent in antifouling property because it contains the curable polyorganosiloxane (A) and the pyrithione metal salt (B).

[0048] It is also considered that the viscosity can be suppressed from increasing, the workability at the time of coating preparation is excellent, the dispersibility is excellent, generation of agglomerates can be suppressed even after storage, and the high anti-sagging property can be maintained even after storage because the pyrithione metal salt (B) in the antifouling coating composition and / or the pyrithione metal salt (B) as a raw material is small in particle diameter, due to the presence of the oxidized polyethylene wax (C). Note that the above effects are effects that are first exhibited in the combination of the curable polyorganosiloxane (A), the pyrithione metal salt (B), and the oxidized polyethylene wax (C).

[0049] Hereinafter, each component contained in the antifouling coating composition will be described.

[0050] 〔Curable polyorganosiloxane (A)〕

[0051] The antifouling coating composition of the present embodiment contains a curable polyorganosiloxane (A) with the aim of improving the antifouling property of an antifouling coating film.

[0052] As the curable polyorganosiloxane (A) used in the present embodiment, an organopolysiloxane having a main chain having a polyorganosiloxane structure and a reactive group, which reacts with each other or reacts with a reactive group of an organosilicon crosslinking agent (I) described later, thereby forming a three-dimensional crosslinked structure to cure, can be given, for example. In addition, it can also react with a silane coupling agent described later.

[0053] As the polyorganosiloxane structure, a polydimethylsiloxane structure, a polymethylphenylsiloxane structure, or the like can be given, of which a polydimethylsiloxane structure is preferable, and an alkylene group, a polyoxyalkylene group, or the like can be present in a block form.

[0054] In addition, as the linking site of the main chain and the reactive group, an alkylene group, a polyoxyalkylene group, or the like can be present, for example.

[0055] The above-mentioned reactive group is an addition reactive group or a condensation reactive group, and from the viewpoint of less influence from a curing hindering substance and obtaining a stable reaction rate in a curing reaction, a condensation reactive group is preferable.

[0056] As the above-mentioned condensation reactive group, a silanol group, an oximatosilyl group, an acyloxysilyl group, an alkoxysilyl group, an enoxy silyl group, an aminosilyl group, an amidosilyl group, and the like can be given, and a silanol group, an oximatosilyl group, an acyloxysilyl group, an alkoxysilyl group, an enoxysilyl group are preferable, a silanol group, an oximatosilyl group, an alkoxysilyl group, an enoxysilyl group are more preferable, a silanol group, an oximatosilyl group, an alkoxysilyl group, an enoxysilyl group are further preferable, and a silanol group, an oximatosilyl group are more further preferable.

[0057] As the oximato group, an oximato group having a carbon number of 1 to 10 is preferable, and a dimethylketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, and a methyl isobutyl ketoxime group are more preferable, and a dimethylketoxime group and a methyl isobutyl ketoxime group are further preferable.

[0058] As the alkoxyl group, an alkoxyl group having a carbon number of 1 to 6 is preferable, and a methoxyl group, an ethoxyl group, a propoxyl group, a butoxyl group are more preferable, a methoxyl group and an ethoxyl group are further preferable, and a methoxyl group is more further preferable.

[0059] The oximato group and the alkoxyl group are preferably two or more oximato groups or alkoxyl groups bonded to one silicon atom as the above-mentioned condensation reactive group.

[0060] As the position of the above-mentioned reactive group, direct bonding to a silicon atom of a main chain, in a side chain, both ends of a main chain, one end of a main chain, and the like can be given, and both ends of a main chain are preferable.

[0061] The curable polyorganosiloxane (A) is preferably a curable polyorganosiloxane having a reactive group. As a specific example thereof, a silicone containing a silanol group, a silicone containing an oximatosilyl group, a silicone containing an alkoxyl group, a silicone containing an enol silyl ether group, and the like can be given, and a silicone containing a silanol group, a silicone containing an oximatosilyl group, a silicone containing an alkoxyl group are preferable, and a silicone containing a silanol group, a silicone containing an oximatosilyl group are more preferable.

[0062] As the curable polyorganosiloxane (A) having the above-mentioned reactive group, a polyorganosiloxane forming a silicone rubber at the time of curing is preferable, and for example, a compound represented by the following formula (A1) is preferable.

[0063] [Chemical Formula 2]

[0064]

[0065] (In formula (A1), R 11 and R13 each independently represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, or a haloalkyl group, R 12 each independently represents a hydroxyl group or a hydrolyzable group. In addition, r represents an integer of 1 to 3, and p represents 10 to 10,000.

[0066] In formula (A1), R 11 and R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, or a haloalkyl group.

[0067] R 11 and R 13 The alkyl group in R

[0068] R 11 and R 13 The alkenyl group in R

[0069] R 11 and R 13 The aryl group in R

[0070] R 11 and R 13 The aralkyl group in R

[0071] R 11 and R 13 The haloalkyl group in R

[0072] Among them, R 11 is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, more preferably a methyl group, an ethyl group, a vinyl group, or a phenyl group, and further preferably a methyl group or a vinyl group.

[0073] In addition, R 13 is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, more preferably a methyl group, an ethyl group, a vinyl group, or a phenyl group, and further preferably a methyl group, an ethyl group, or a phenyl group, and more further preferably a methyl group or a phenyl group.

[0074] Note that the plurality of R 13 may be the same or different. In addition, the plurality of R 11 may be the same or different.

[0075] In formula (Al), R 12 each independently represents a hydroxyl group or a hydrolyzable group.

[0076] As the hydrolyzable group in R 12 , for example, an oxime group, an acyloxy group, an alkoxy group, an alkenyloxy group, an amino group, an amido group, and an aminooxy group, etc. can be given.

[0077] As the oxime group in R 12 , an oxime group having a total of 1 to 10 carbon atoms is preferred, and for example, a dimethylketoxime group, a methylethylketoxime group, a diethylketoxime group, a methylisopropylketoxime group, a methylisobutylketoxime group, etc. can be given.

[0078] As the acyloxy group (RC(=0)0-) in R 12 , an aliphatic acyloxy group having a total of 1 to 10 carbon atoms or an aromatic acyloxy group having a total of 7 to 12 carbon atoms is preferred, and for example, an acetyloxy group, a propionyloxy group, a butyryloxy group, a benzoyloxy group, etc. can be given.

[0079] As the alkoxy group in R 12 , an alkoxy group having a total of 1 to 10 carbon atoms is preferred. Note that in the alkoxy group in R 12 , one or more oxygen atoms can be present between one or more carbon atoms.

[0080] As the alkoxy group in R 12 , specific examples can be given of a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a methoxyethoxy group, an ethoxyethoxy group, etc.

[0081] As the alkenyloxy group in R 12 , an alkenyloxy group having a total of 3 to 10 carbon atoms is preferred, and for example, an isopropenyl group, an isobutenyl group, a 1-ethyl-2-methylethenyl group, etc. can be given.

[0082] As the amino group in R 12 , an amino group having a total of 1 to 10 carbon atoms is preferred, and for example, an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-butylamino group, an N,N-dimethylamino group, an N,N-diethylamino group, a cyclohexylamino group, etc. can be given.

[0083] As the aminooxy group in R 12The amido group in the formula (A1) is preferably an amido group having a total of 2 to 10 carbon atoms, and examples thereof include an N-methylacetamido group, an N-ethylacetamido group, and an N-methylbenzamido group.

[0084] The amino group in the formula (A1) is preferably an amino group having a total of 2 to 10 carbon atoms, and examples thereof include an N,N-dimethylamino group and an N,N-diethylamino group. 12 The amino group in the formula (A1) is preferably an amino group having a total of 2 to 10 carbon atoms, and examples thereof include an N,N-dimethylamino group and an N,N-diethylamino group.

[0085] Among them, from the viewpoint of excellent curing properties and antifouling properties of the antifouling coating film formed, R 12 The hydroxyl group, the oximato group, and the alkoxy group are preferred, and the hydroxyl group and the oximato group are more preferred, and the hydroxyl group, the methyl ethyl ketoxime group, and the methyl isobutyl ketoxime group are further preferred.

[0086] Note that there are a plurality of R 12 Each of them can be the same or different.

[0087] In the formula (A1), r represents an integer of 1 to 3.

[0088] In the case where R 12 is a hydroxyl group, r is preferably 1, and in the case where R 12 is a substituent other than a hydroxyl group, r is preferably 2.

[0089] In the formula (A1), p represents 10 to 10,000, and is preferably 100 to 1,000, and can be appropriately adjusted so as to satisfy the following weight average molecular weight.

[0090] Note that p means the average number of repetitions of - (SiR 13 2-O) -.

[0091] The weight average molecular weight (Mw) of the curable polyorganosiloxane (A) is preferably 500 or more, more preferably 5,000 or more, further preferably 10,000 or more, and more further preferably 15,000 or more, and more further preferably 20,000 or more, from the viewpoint of improving the handling properties of the antifouling coating composition at the time of production, improving the coating handling properties, the curability, and the strength of the coating film formed, and is preferably 1,000,000 or less, more preferably 100,000 or less, further preferably 50,000 or less, and more further preferably 40,000 or less.

[0092] In the present embodiment, the "weight average molecular weight (Mw)" and the "number average molecular weight (Mn)" described later are measured using GPC (gel permeation chromatography) and are calculated by converting using a standard polystyrene having a known molecular weight.

[0093] Further, the viscosity at 25°C of the curable polyorganosiloxane (A) is preferably 20 mPa-s or more, more preferably 100 mPa-s or more, further preferably 500 mPa-s or more, and still further preferably 1000 mPa-s or more, and is preferably 100,000 mPa-s or less, more preferably 10,000 mPa-s or less, further preferably 5,000 mPa-s or less, and still further preferably 3,000 mPa-s or less, from the viewpoint of improving the handling properties of the antifouling coating composition at the time of production, improving the coating properties, curability, and strength of the coating film formed.

[0094] Note that the viscosity at 25°C of the curable polyorganosiloxane (A) in the present specification is a viscosity measured using a B-type rotational viscometer (for example, Model BM, Tokimec Co., Ltd.).

[0095] The content of the curable polyorganosiloxane (A) in the antifouling coating composition is preferably 25% by mass or more, more preferably 30% by mass or more, and further preferably 35% by mass or more, and is preferably 90% by mass or less, more preferably 70% by mass or less, and further preferably 60% by mass or less, from the viewpoint of improving the antifouling properties and strength of the antifouling coating film formed.

[0096] Further, the content of the curable polyorganosiloxane (A) in the solid components of the antifouling coating composition is preferably 45% by mass or more, more preferably 50% by mass or more, and further preferably 55% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.

[0097] Note that the "solid components of the antifouling coating composition" in the present specification means components after removal of the organic solvent (F) and volatile components contained as a solvent in each component, and the content in the solid components of the antifouling coating composition can be calculated as the content in the solid components obtained by drying the antifouling coating composition in a hot air drier at 125°C for 1 hour.

[0098] As the curable polyorganosiloxane (A), commercially available polyorganosiloxanes can be used. As commercially available products, for example, "DMS-S35" manufactured by GELEST Co., Ltd. and "KE-445" manufactured by Shin-Etsu Chemical Co., Ltd. can be mentioned. Further, as the curable polyorganosiloxane (A), the polyorganosiloxane described in Japanese Patent Application Publication No. 2001-139816 can also be used.

[0099] 〔Pyridinethione Metal Salt (B)〕

[0100] The antifouling coating composition of the present embodiment contains a pyrithione metal salt (B) for the purpose of improving the antifouling property of the antifouling coating film.

[0101] As the pyrithione metal salt (B), copper pyrithione and zinc pyrithione can be exemplified, among which, from the viewpoint of the antifouling property of the antifouling coating film, copper pyrithione is preferred.

[0102] The antifouling coating composition of the present embodiment satisfies at least one of the following Condition A and Condition B.

[0103] Condition A: the median diameter (D50) of the pyrithione metal salt (B) in the antifouling coating composition is 5.0 μm or less

[0104] Condition B: the median diameter (D50) of the pyrithione metal salt (B) as a raw material is 3.0 μm or less

[0105] In the case where at least one of Condition A and Condition B is satisfied, the viscosity of the mixture A containing the pyrithione metal salt (B) prepared at the time of production becomes high, and there is a problem that the manufacturing workability is reduced. In addition, after storage, agglomerates considered to be derived from the pyrithione metal salt (B) are generated, as a result, the sag resistance is reduced, that is, the film thickness before drying at which sag does not occur (sag limit wet film thickness) is reduced, and there is a problem that the manufacturing workability of the antifouling coating film is also poor. In addition, as a result of the generation of the agglomerates, there is a problem that the coating film appearance of the obtained antifouling coating film is also poor.

[0106] In the present embodiment, from the viewpoint of solving the above problems, at least one of Condition A and Condition B is satisfied, preferably at least Condition A is satisfied, and more preferably both Condition A and Condition B are satisfied.

[0107] The antifouling coating composition of the present embodiment is an antifouling coating composition that solves the above problems.

[0108] With respect to Condition A, the lower limit of the median diameter of the pyrithione metal salt (B) in the coating composition is not particularly limited, however, from the viewpoint of further suppressing the occurrence of the above problems, it is preferably 1.0 μm or more, more preferably 1.5 μm or more, and further preferably 2.0 μm or more. In addition, if the upper limit of the median diameter is 5.0 μm or less, the above problems are significant, if it is 4.8 μm or less, they are more significant, and if it is 4.5 μm or less, they are further significant.

[0109] As for the condition B, the lower limit of the median diameter of the pyrithione metal salt (B) as a raw material is not particularly limited, however, from the viewpoint of further suppressing the occurrence of the above-mentioned problems, it is preferably 0.5 μm or more, more preferably 1.0 μm or more, and further preferably 1.5 μm or more. In addition, if the upper limit of the median diameter is 3.0 μm, the above-mentioned problems are remarkable, if it is 2.5 μm or less, they are more remarkable, and if it is 2.0 μm or less, they are further remarkable.

[0110] The median diameter of the pyrithione metal salt (B) is measured by the method described in the Examples.

[0111] As for the content of the pyrithione metal salt (B) in the solid component of the antifouling coating composition, from the viewpoint of obtaining an antifouling coating film excellent in antifouling property, it is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and further preferably 3.0 mass% or more, and more further preferably 5.0 mass% or more, and, from the viewpoints of manufacturing workability, dispersibility, storage stability, and the like, it is preferably 15 mass% or less, more preferably 13 mass% or less, and further preferably 10 mass% or less.

[0112] 〔Oxidized polyethylene wax (C)〕

[0113] The antifouling coating composition of the present embodiment contains the oxidized polyethylene wax (C). By containing the oxidized polyethylene wax (C), even if a pyrithione metal salt (B) having a small particle diameter, i.e., a median diameter of 3.0 μm or less is used, it is possible to produce an antifouling coating composition excellent in dispersibility and storage stability, while being excellent in manufacturing workability.

[0114] As the oxidized polyethylene wax (C), for example, a resin obtained by subjecting polyethylene to an oxidation treatment and introducing a polar group can be mentioned.

[0115] Such an oxidized polyethylene wax (C) can be synthesized by a method known in the art, or can be a commercially available product.

[0116] As commercially available products, "DISPARLON 4200-20" manufactured by Nippon Shokubai Co., Ltd., "ASA D-120" manufactured by Itoh Oil, Inc., and the like can be mentioned.

[0117] The above-mentioned oxidized polyethylene wax (C) can be used alone or in combination with two or more kinds.

[0118] The acid value of the oxidized polyethylene wax (C) is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and is preferably 40 mgKOH / g or less, more preferably 35 mgKOH / g or less. If the acid value of the oxidized polyethylene wax (C) is within the above range, an antifouling coating composition that is excellent in ease of production, dispersibility, and storage stability can be obtained, and thus is preferred.

[0119] The content of the oxidized polyethylene wax (C) (nonvolatile component) in the solid components of the antifouling coating composition is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and further preferably 0.25 mass% or more, and is preferably 3.0 mass% or less, more preferably 2.2 mass% or less, further preferably 1.5 mass% or less, and more further preferably 1.0 mass% or less. If the content of the oxidized polyethylene wax (C) in the solid components of the antifouling coating composition is within the above range, an antifouling coating composition that is excellent in ease of production, dispersibility, and storage stability can be obtained, and thus is preferred.

[0120] In addition, the content of the oxidized polyethylene wax (C) (nonvolatile component) with respect to 100 parts by mass of the pyrithione metal salt (B) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, further preferably 1.0 parts by mass or more, and more further preferably 1.5 parts by mass or more, and is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and further preferably 30 parts by mass or less, from the same reasons.

[0121] As to the presence or absence of the oxidized polyethylene wax (C) in the antifouling coating composition, a sample from which the pigment has been removed by solvent fractionation from the xylene insoluble of the antifouling coating composition is subjected to methyl esterification, and the obtained sample is measured using high temperature gel permeation chromatography (high temperature GPC), whereby it can be confirmed.

[0122] The antifouling coating composition of the present embodiment preferably contains other components in addition to the above (A) to (C).

[0123] As the other components, a slip agent (D), a coloring pigment (E), an organic solvent (F), a silica particle (G), a curing catalyst (H), a silicone crosslinking agent (I), a silane coupling agent (J), a biorepellent other than the pyrithione metal salt (B) (K), a pigment other than the coloring pigment (E) and the silica particle (G), a dehydrating agent other than the silicone crosslinking agent (I), an anti-sagging-anti-settling agent other than the oxidized polyethylene wax (C), a wet dispersing agent other than the oxidized polyethylene wax (C), an enzyme, a flame retardant, and a thermal conductivity modifier can be given.

[0124] The antifouling coating composition of the present embodiment preferably contains a slip agent (D), a coloring pigment (E), an organic solvent (F), a silica particle (G), a curing catalyst (H), and a silicone crosslinking agent (I) within a range that does not hinder the effects of the present application.

[0125] 〔Slip agent (D)〕

[0126] The antifouling coating composition of the present application contains a slip agent (D) from the viewpoint of the application properties of the antifouling coating composition and antifouling properties.

[0127] The slip agent (D) imparts slipperiness to the formed antifouling coating film, whereby the adhesion hindering properties (antifouling properties) against aquatic organisms can be improved.

[0128] The slip agent (D) preferably has fluidity at 25°C, and more preferably is in a liquid state. It is considered that by imparting fluidity to the slip agent, the mobility within the antifouling coating film is high, and the effect of imparting slipperiness to the surface can be improved. In addition, the viscosity of the antifouling coating composition can be reduced, and the application properties can be made good.

[0129] As the slip agent (D), one or more selected from oils and polymers having a hydrophilic group are preferable.

[0130] As the oils, silicone oil, paraffin oil, and fats and oils can be given, and silicone oil is preferable.

[0131] As the paraffin oil, liquid paraffin and the like can be given.

[0132] As the fats and oils, esters of fatty acids and glycerin can be given, and animal fats and oils, vegetable fats and oils, and the like can be given.

[0133] As the polymers having a hydrophilic group, an acrylic polymer having a hydrophilic group, a polyglycerin ester, a polyalkylene glycol, and the like can be given, and an acrylic polymer having a hydrophilic group is preferable.

[0134] As the polyglycerin ester, a polyglycerin fatty acid ester is preferable. The polyglycerin fatty acid ester is an ester of polyglycerin and a fatty acid, and as the fatty acid, a saturated or unsaturated fatty acid having a carbon number of 8 or more and 24 or less is preferable, and caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, and the like can be given as examples. The average repetition number of glycerin in the polyglycerin ester is preferably 3 or more and 100 or less, and more preferably 5 or more and 30 or less. In addition, the glycerin ester can be a monoester having one ester group, a diester having two ester groups, or a polyester having three or more ester groups. As the polyglycerin fatty acid ester, S Face series manufactured by Shakuhan Yakuhin Kogyo Co., Ltd. can be given as examples.

[0135] As the polyalkylene glycol, polyethylene glycol, polypropylene glycol, a copolymer of ethylene glycol and propylene glycol, and alkyl ethers thereof can be mentioned.

[0136] That is, the slip agent (D) is preferably one or more selected from the group consisting of silicone oil, paraffin oil, oil and fat, acrylic polymer having a hydrophilic group, polyglycerol ester, and polyalkylene glycol, more preferably one or more selected from the group consisting of silicone oil and acrylic polymer having a hydrophilic group, further preferably silicone oil. In addition, from the viewpoint of the workability in the production of the antifouling coating composition and the antifouling property of the antifouling coating film formed, it is preferable to contain the acrylic polymer having a hydrophilic group, more preferably to contain both the silicone oil and the acrylic polymer having a hydrophilic group.

[0137] The silicone oil (D1), the acrylic polymer having a hydrophilic group (D2), and the paraffin oil (D3) as the suitable slip agent (D) are described in detail below.

[0138] < Silicone oil (D1 ) >

[0139] As the silicone oil (D1) used in the antifouling coating composition of the present application, dimethyl silicone (polydimethylsiloxane, unmodified silicone), modified silicone can be mentioned. The modified silicone is a silicone in which a methyl group of a part of dimethyl silicone is replaced with an organic group other than methyl, and can have a reactive group at one terminal.

[0140] The silicone oil is easy to move on the surface of the antifouling coating film because of the low surface tension and the property not easily changing in a low temperature environment or the like, and can efficiently improve the antifouling property against aquatic organisms and the damage resistance.

[0141] In the case where the silicone oil (D1) has a reactive group at one terminal, as the reactive group, silanol group, oximato silyl group, acyloxy silyl group, alkoxy silyl group, alkenyloxy silyl group, aminosilyl group, amidosilyl group, and the like can be mentioned, preferably silanol group, oximato silyl group, acyloxy silyl group, alkoxy silyl group, alkenyloxy silyl group, more preferably silanol group, oximato silyl group, alkoxy silyl group, alkenyloxy silyl group, further preferably silanol group, oximato silyl group, alkenyloxy silyl group, more further preferably silanol group, oximato silyl group.

[0142] As the oximato group, an oximato group having 1 or more and 10 or less carbon atoms is preferable, more preferably dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, methyl isopropyl ketoxime group, methyl isobutyl ketoxime group, further preferably methyl isobutyl ketoxime group.

[0143] As the alkoxy group, an alkoxy group having 1 or more and 6 or less carbon atoms is preferable, more preferably methoxy group, ethoxy group, propoxy group, butoxy group, further preferably methoxy group, ethoxy group, more further preferably methoxy group.

[0144] Two or more oxime groups or alkoxy groups may be bonded to one silicon atom. Preferably, two or more oxime groups or alkoxy groups are bonded to one silicon atom, and more preferably, two oxime groups are bonded to one silicon atom.

[0145] The viscosity of the silicone oil (D1) at 25°C is preferably 10 mPa·s or higher, more preferably 20 mPa·s or higher, even more preferably 40 mPa·s or higher, even more preferably 60 mPa·s or higher, even more preferably 80 mPa·s or higher, and is preferably 10,000 mPa·s or lower, more preferably 5,000 mPa·s or lower, and even more preferably 4,000 mPa·s or lower, from the viewpoint of imparting lubricity to aquatic organisms, improving antifouling properties, and improving the coating properties of the antifouling coating composition.

[0146] In addition, in this specification, the viscosity of the silicone oil (D1) at 25° C. refers to the viscosity measured by a Brookfield type rotational viscometer.

[0147] The kinematic viscosity of the silicone oil (D1) at 25°C is preferably 10 mm / s from the viewpoint of improving the sliding property to aquatic organisms, improving the antifouling property, and improving the coating property of the antifouling coating composition. 2 / s or more, more preferably 30mm 2 / s or more, more preferably 50mm 2 / s or more, and preferably 5000mm 2 / s or less, more preferably 4000mm 2 / s or less, more preferably 3500mm 2 / s or less.

[0148] Examples of modified silicones include phenyl-modified silicones, polyether-modified silicones, long-chain alkyl-modified silicones, higher fatty acid ester-modified silicones, fluoroalkyl-modified silicones, carbinol-modified silicones, carboxyl-modified silicones, amino-modified silicones, epoxy-modified silicones, methacrylic-modified silicones, mercapto-modified silicones, and phenol-modified silicones.

[0149] Among such modified silicones, the silicone oil (D1) is preferably at least one selected from phenyl-modified silicones and polyether-modified silicones from the viewpoint of improving antifouling properties, imparting appropriate thixotropy to the antifouling coating composition, and improving coating properties.

[0150] Examples of the structure of the modified silicone include a side chain modified type, a double terminal modified type, a single terminal modified type, a block type, a side chain and single terminal modified type, and a side chain and double terminal modified type.

[0151] As a commercially available product of the above-described dimethyl silicone, "KF-96-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 100 mm 2 / s), "KF-96-1000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 1000 mm 2 / s), and the like can be given.

[0152] Regarding the phenyl modification ratio of the phenyl-modified silicone, from the viewpoints of antifouling property and easiness in forming an antifouling coating film, it is preferably 3% or more and 50% or less, more preferably 3% or more and 20% or less, and further preferably 4% or more and 10% or less. The phenyl modification ratio is a value expressed in percentage of the number of phenyl groups with respect to the total number of phenyl groups and methyl groups bonded to silicon.

[0153] Regarding the kinematic viscosity at 25°C of the phenyl-modified silicone, from the viewpoints of antifouling property of the formed antifouling coating film and coatability of the antifouling coating composition, it is preferably 10 mm 2 / s or more and 5000 mm 2 / s or less, more preferably 50 mm 2 / s or more and 4000 mm 2 / s or less, further preferably 80 mm 2 / s or more and 3500 mm 2 / s or less.

[0154] As a commercially available product of the phenyl-modified silicone, "KF-50-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification ratio = 5%, kinematic viscosity (25°C): 100 mm 2 / s), "KF-50-1000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification ratio = 5%, kinematic viscosity (25°C): 1000 mm 2 / s), "KF-50-3000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification ratio = 5%, kinematic viscosity (25°C): 3000 mm 2 / s), and the like can be given.

[0155] In addition, as a commercially available product of the mono-terminal methyl ethyl ketoxime-side chain phenyl-modified silicone, "BCA-011" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification ratio = 5%, kinematic viscosity (25°C): 100 mm 2 / s) can be given.

[0156] In the case where the antifouling coating composition of the present application contains a phenyl-modified silicone, the content in the solid components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more, and more further preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less, from the viewpoints of antifouling properties of the formed antifouling coating film, and easiness of formation of the antifouling coating film.

[0157] As the structure of the polyether-modified silicone, a side chain-modified type, a double-end-modified type, a single-end-modified type, a block type, a side chain- and single-end-modified type, a side chain- and double-end-modified type, a side chain-modified type, and a double-end-modified type are exemplified, and the side chain-modified type and the double-end-modified type are preferred, and the double-end-modified type is more preferred.

[0158] The polyether (polyalkylene glycol) constituting the polyether group (polyalkylene glycol group) of the polyether-modified silicone can be exemplified by polyethylene glycol, polypropylene glycol, and a copolymer of ethylene glycol and propylene glycol, and the copolymer of polyethylene glycol and polypropylene glycol is preferred.

[0159] From the viewpoints of antifouling properties of the formed antifouling coating film, and easiness of formation of the antifouling coating film, the proportion of the polyether moiety structure in the structure of the polyether-modified silicone is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 50% by mass or less, and further preferably 20% by mass or more and 50% by mass or less.

[0160] In the case where the antifouling coating composition of the present application contains a polyether-modified silicone, the content in the solid components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, and is preferably 20% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less, from the viewpoints of improvement of antifouling properties of the formed antifouling coating film, easiness of formation of the antifouling coating film, and the like.

[0161] In the polyether-modified silicone, in the case where the polyether group has an ethylene oxide (EO) group and a propylene oxide (PO) group, the molar ratio of the ethylene oxide (EO) group to the propylene oxide (PO) group in the polyether group [EO / PO] is preferably 0.5 or more, and is preferably 9.0 or less, more preferably 5.0 or less, further preferably 4.0 or less, and more further preferably 3.5 or less, from the viewpoint of obtaining a composition having excellent long-term antifouling properties.

[0162] The molar ratio of the EO group to the PO group in the polyether-modified silicone can be determined, for example, by H NMR measurement. 1 H NMR measurement.

[0163] (Calculation of the molar ratio [EO / PO] in the polyether-modified silicone)

[0164] The molar ratio [EO / PO] in the polyether-modified silicone is based on 1 The integral value of the methyl group of PO at about 0.8 to 1.2 ppm and the non-methyl group portion of EO and PO at about 3 to 4 ppm in1H NMR is calculated using the following equation.

[0165] EO / PO = { ([integral value at about 3 to 4 ppm] - [integral value at about 0.8 to 1.2 ppm]) / 4} / { [integral value at about 0.8 to 1.2 ppm] / 3}.

[0166] In the case where the antifouling coating composition of the present application contains the polyether-modified silicone containing an ethylene oxide (-OC2H4-) structural unit, from the viewpoint of imparting good antifouling properties to the formed antifouling coating film, the total mass of the ethylene oxide (-OC2H4-) partial structure is preferably 0.1 mass part or more and 10 mass parts or less, more preferably 0.3 mass part or more and 5 mass parts or less, with respect to 100 mass parts of the dimethylsiloxane partial structure ((CH3)2Si-O-) of the silicone.

[0167] Regarding the kinematic viscosity at 25°C of the above-described polyether-modified silicone, from the viewpoints of antifouling properties and coatability of the antifouling coating composition, etc., it is preferably 10 mm 2 / s or more and 5000 mm 2 / s or less, more preferably 50 mm 2 / s or more and 2000 mm 2 / s or less, further preferably 100 mm 2 / s or more and 500 mm 2 / s or less.

[0168] As the commercially available product of the above-described polyether-modified silicone, "X-22-4272" (manufactured by Shin-Etsu Chemical Co., Ltd., double-end type, kinematic viscosity (25°C): 270 mm 2 / s), "KF-6020" (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type, kinematic viscosity (25°C): 180 mm 2 / s), "FZ-2203" (manufactured by Toray Dow Corning Co., Ltd., block type), etc. can be given.

[0169] Regarding the content of the silicone oil (D1) in the solid component of the antifouling coating composition, from the viewpoints of improving the antifouling properties of the formed antifouling coating film, facilitating the formation of the antifouling coating film, etc., it is preferably 1 mass% or more, more preferably 3 mass% or more, further preferably 5 mass% or more, and, on the other hand, it is preferably 50 mass% or less, more preferably 40 mass% or less, further preferably 30 mass% or less, and more further preferably 20 mass% or less.

[0170] <Acrylic polymer having a hydrophilic group (D2)>

[0171] As the acrylic polymer having a hydrophilic group (D2) used in the antifouling coating composition of the present application, it is preferable to contain a constitutional unit derived from a monomer having a hydrophilic group, more preferable to contain a constitutional unit derived from a monomer having a hydrophilic group and a constitutional unit derived from a hydrophobic monomer, and further preferable to be composed of a constitutional unit derived from a monomer having a hydrophilic group and a constitutional unit derived from a hydrophobic monomer.

[0172] The content of the constitutional unit derived from a monomer having a hydrophilic group in the acrylic polymer having a hydrophilic group (D2) is preferably 1% by mass or more and 100% by mass or less, more preferably 3% by mass or more and 80% by mass or less, further preferably 5% by mass or more and 70% by mass or less, and more further preferably 10% by mass or more and 60% by mass or less.

[0173] It is considered that by having the acrylic polymer having a hydrophilic group, the hydrophilic site of the acrylic polymer in the antifouling coating film is dissolved or swelled, and slowly transferred to the surface of the antifouling coating film, whereby the attachment of aquatic organisms can be efficiently prevented. In addition, since it has an acrylic structure, hydrolysis occurs slowly, and the affinity to water changes, whereby the antifouling property can be maintained for a long time.

[0174] As the hydrophilic group of the above-mentioned monomer having a hydrophilic group, from the viewpoint of antifouling property, an ether group, a hydroxyl group are preferable, and an ether group is more preferable.

[0175] In addition, the content of the constitutional unit derived from a hydrophobic monomer in the acrylic polymer having a hydrophilic group (D2) is preferably 99% by mass or less, more preferably 97% by mass or less, further preferably 95% by mass or less, and more further preferably 90% by mass or less, and on the other hand, 20% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more.

[0176] It is considered that by having a hydrophobic monomer, high affinity with a silicone crosslinking body or the like, which is another component of the antifouling coating film, can be obtained, and a slip effect can be uniformly exhibited on the surface of the antifouling coating film.

[0177] As the monomer having a hydrophilic group mentioned above, from the viewpoint of antifouling property, a monomer having a polyalkylene glycol group, a monomer having a hydroxyl group, and a monomer having an alkoxyalkyl group are preferable, and a monomer having a polyalkylene glycol group is more preferable.

[0178] Specifically, from the viewpoint of improving the antifouling property, one or more selected from the group consisting of polyalkylene glycol (meth)acrylate, hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloylmorpholine, and vinylpyrrolidone is preferred, one or more selected from the group consisting of polyalkylene glycol (meth)acrylate and hydroxyalkyl (meth)acrylate is more preferred, and polyalkylene glycol (meth)acrylate is further preferred.

[0179] Note that "(meth)acrylate" means "acrylate or methacrylate".

[0180] As the polyalkylene glycol (meth)acrylate, polyalkylene glycol (meth)acrylate in which one end of polyalkylene glycol is directly bonded to (meth)acrylic acid via an ester bond or via a linking group, and the other end is a hydroxyl group or an alkoxy group can be given, and polyalkylene glycol (meth)acrylate in which the other end is an alkoxy group is preferred.

[0181] Among them, polyalkylene glycol (meth)acrylate in which one end of polyalkylene glycol is directly bonded to (meth)acrylic acid via an ester bond is preferred, and polyalkylene glycol (meth)acrylate in which the other end is an alkoxy group is more preferred.

[0182] The (meth)acrylic acid at the end is preferably acrylic acid and methacrylic acid, and acrylic acid is more preferred.

[0183] The alkoxy group at the end can be given as methoxy group, phenoxy group, octyloxy group, and the like, and methoxy group and phenoxy group are preferred, and methoxy group is more preferred.

[0184] The polyalkylene glycol constituting the polyalkylene glycol (meth)acrylate is preferably polyethylene glycol, polypropylene glycol, and a copolymer of ethylene glycol and propylene glycol, and polyethylene glycol is more preferred.

[0185] The average alkylene glycol unit number of the polyalkylene glycol constituting the polyalkylene glycol (meth)acrylate described above is preferably 2 or more and 25 or less, more preferably 3 or more and 15 or less, and further preferably 5 or more and 12 or less.

[0186] As specific examples of the above polyalkylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-butylene glycol) mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, allyloxy poly (ethylene glycol-propylene glycol) mono (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol methacrylate, octyloxy poly (ethylene glycol-propylene glycol) mono (meth) acrylate, dodecyloxy polyethylene glycol mono (meth) acrylate, stearyloxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol acrylate, and the like can be given, with methoxypolyethylene glycol mono (meth) acrylate being preferred.

[0187] As specific examples of the above polyalkylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-butylene glycol) mono (meth) acrylate, methoxypolyethylene glycol mono (meth) acrylate, allyloxy poly (ethylene glycol-propylene glycol) mono (meth) acrylate, phenoxy polyethylene glycol-polypropylene glycol methacrylate, octyloxy poly (ethylene glycol-propylene glycol) mono (meth) acrylate, dodecyloxy polyethylene glycol mono (meth) acrylate, stearyloxy polyethylene glycol mono (meth) acrylate, nonylphenoxy polypropylene glycol acrylate, and the like can be given, with methoxypolyethylene glycol mono (meth) acrylate being preferred.

[0188] As the above (meth) acrylic acid hydroxyalkyl ester, (meth) acrylic acid hydroxyethyl ester, (meth) acrylic acid hydroxypropyl ester can be given.

[0189] As the commercially available product of the above-mentioned (meth)acrylic acid hydroxyalkyl ester, LIGHT ESTER HOA (N) (2-hydroxyethyl (meth)acrylate), LIGHT ESTER HO-250 (N) (2-hydroxyethyl (meth)acrylate), LIGHT ESTER HOP (N) (2-hydroxypropyl (meth)acrylate), and the like manufactured by NOF Corporation can be given.

[0190] As the above-mentioned (meth)acrylic acid alkoxyalkyl ester, (meth)acrylic acid methoxyethyl ester, and the like can be given.

[0191] As the above-mentioned (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid tetrahydrofurfuryl ester is preferred, and acrylic acid tetrahydrofurfuryl ester is more preferred.

[0192] As the above-mentioned 4-(meth)acryloylmorpholine, 4-acryloylmorpholine, 4-methacryloylmorpholine are preferred, and 4-acryloylmorpholine is more preferred.

[0193] As the above-mentioned vinylpyrrolidone, 1-vinyl-2-pyrrolidone, 3-acetyl-1-vinylpyrrolidin-2-one, 3-benzoyl-1-vinylpyrrolidin-2-one, and the like can be given, and 1-vinyl-2-pyrrolidone is preferred.

[0194] As the above-mentioned hydrophobic monomer, (meth)acrylic acid alkyl ester having an alkyl group of 1 or more and 30 or less in the number of carbon, (meth)acrylic acid aryl ester having an aromatic group of 6 or more and 10 or less in the number of carbon, and silicone containing a (meth)acrylic acid group can be given, and (meth)acrylic acid alkyl ester and silicone containing a (meth)acrylic acid group are preferred, and (meth)acrylic acid alkyl ester is more preferred.

[0195] The number of carbon of the alkyl group of the above-mentioned alkyl (meth)acrylate is preferably 1 or more and 30 or less, more preferably 4 or more and 18 or less, further preferably 4 or more and 8 or less, and more further preferably 4 or more and 6 or less.

[0196] In addition, the above-mentioned alkyl group is branched, linear, or cyclic, and is preferably branched or linear, and more preferably branched.

[0197] As specific examples of the above-mentioned alkyl (meth)acrylate, there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, phenyl (meth)acrylate, and benzyl (meth)acrylate, etc., among which n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred.

[0198] The number of carbon atoms of the aromatic group of the above-mentioned aryl (meth)acrylate is preferably 6 or more and 10 or less, more preferably 6 or more and 7 or less.

[0199] As specific examples of the above-mentioned aryl (meth)acrylate, there can be mentioned phenyl (meth)acrylate and benzyl (meth)acrylate, etc.

[0200] As the above-mentioned (meth)acryl group-containing silicone, there can be mentioned a silicone having a methacryl group and a silicone having an acryl group, with preference given to a silicone having a methacryl group.

[0201] The above-mentioned (meth)acryl group-containing silicone is preferably a silicone in which a (meth)acryl group is bonded to one end of a silicone main chain via a linking group and a silicone in which a (meth)acryl group is directly bonded to one end of a silicone main chain, with preference given to a silicone in which a (meth)acryl group is bonded to one end of a silicone main chain via a linking group.

[0202] The above-mentioned linking group is preferably trimethylene.

[0203] The above-mentioned silicone main chain is preferably composed of a linear or branched dimethyl silicone (polydimethylsiloxane), more preferably composed of a linear dimethyl silicone.

[0204] Further, it is more preferable that an alkyl group having a number of carbon atoms of 1 or more and 6 or less be present at the end on the side opposite to the (meth)acryl group, with preference given to a butyl group.

[0205] As commercially available products of the above-mentioned (meth)acryl group-containing silicone, Silaplane TM-0701T (trimethylsilyloxy) methylsilyl propyl methacrylate), Silaplane FM-0711 (dimethylpolysiloxane containing a methacryl group, number average molecular weight 1000), and Silaplane FM-0721 (dimethylpolysiloxane containing a methacryl group, number average molecular weight 5000), etc. manufactured by JNC Corporation can be mentioned.

[0206] By containing the above-mentioned (meth)acryl group-containing silicone, the antifouling property of the formed antifouling coating film can be improved.

[0207] In the case where the antifouling coating composition contains the acrylic polymer having a hydrophilic group (D2) having an ethylene oxide (-OC2H4-) partial structure, from the viewpoint of imparting a good antifouling property to the formed antifouling coating film, the total mass of the ethylene oxide (-OC2H4-) partial structure is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the dimethylsiloxane partial structure ((CH3)2Si-O-) of the silicone.

[0208] The weight average molecular weight (Mw) of the acrylic polymer having a hydrophilic group (D2) is preferably 1000 or more, more preferably 3000 or more, further preferably 5000 or more, and still further preferably 7000 or more, and is preferably 150000 or less, more preferably 100000 or less, further preferably 50000 or less, and still further preferably 30000 or less, from the viewpoints of the antifouling property and the viscosity of the antifouling coating composition.

[0209] If the weight average molecular weight (Mw) of the acrylic polymer having a hydrophilic group (D2) is within the above-mentioned range, it is preferred from the viewpoint of being able to impart a good antifouling property to the antifouling coating film.

[0210] In the case where the antifouling coating composition of the present application contains the acrylic polymer having a hydrophilic group (D2), the content of the acrylic polymer having a hydrophilic group (D2) in the solid content of the antifouling coating composition is preferably 0.2% by mass or more, more preferably 0.8% by mass or more, further preferably 2% by mass or more, and still further preferably 4% by mass or more, and is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less, from the viewpoint of balancing the antifouling property and the manufacturing operability.

[0211] <Paraffin oil (D3)>

[0212] The paraffin oil (D3) is not particularly limited, and a paraffin oil having a kinematic viscosity described later can be appropriately selected from publicly known paraffin oils.

[0213] As the paraffin oil, a liquid paraffin is preferred.

[0214] The kinematic viscosity of the paraffin oil (D3) at 25°C is preferably 10 mm 2 / s or more, more preferably 50 mm 2 / s or more, further preferably 100 mm 2 / s or more, and preferably 5000 mm 2 / s or less, more preferably 2000 mm 2 / s or less, further preferably 500 mm 2 / s or less.

[0215] The content of the paraffin oil (D3) in the solid component of the antifouling coating composition of the present application is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, from the viewpoint of improving the antifouling property of the antifouling coating film formed, facilitating the formation of the antifouling coating film, and the like.

[0216] The total content of the slip agent (D) in the solid component of the antifouling coating composition of the present application is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, and more further preferably 10% by mass or more, and preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 25% by mass or less, and more further preferably 20% by mass or less, from the viewpoint of improving the antifouling property of the antifouling coating film formed, facilitating the formation of the antifouling coating film, and the like.

[0217] 〔Coloring pigment (E)〕

[0218] The antifouling coating composition of the present application preferably further contains a coloring pigment (E).

[0219] By including the coloring pigment (E) in the antifouling coating composition of the present application, the strength of the coating film can be improved.

[0220] The coloring pigment (E) is not particularly limited, and examples thereof include inorganic pigments such as iron oxide, titanium oxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate; and organic pigments such as naphthol red and phthalocyanine blue. From the viewpoints of the workability in the production of the antifouling coating composition, the coatability, the storage stability, and the antifouling property of the antifouling coating film formed, the antifouling coating composition preferably contains at least an inorganic pigment, and more preferably contains one or more selected from the group consisting of iron oxide, titanium oxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate, even more preferably one or more selected from the group consisting of iron oxide, titanium oxide, and carbon black, and still more preferably one or more selected from the group consisting of iron oxide and titanium oxide.

[0221] Examples of the iron oxide include red iron oxide, yellow iron oxide, and black iron oxide.

[0222] Examples of the titanium oxide include rutile, anatase, and brookite. From the viewpoints of the stability of the antifouling coating film and the antifouling coating composition and the easy availability, the rutile is preferably used.

[0223] The coloring pigment (E) can be used alone or in combination with two or more kinds.

[0224] The present inventors have found that if the antifouling coating composition contains an organic pigment as the coloring pigment (E) in addition to the pyrithione metal salt (B), the antifouling coating composition is likely to cause aggregation due to storage. The occurrence of the aggregation due to storage and the reduction in the anti-striation property accompanying the occurrence of the aggregation can be efficiently suppressed by the addition of the oxidized polyethylene wax (C).

[0225] Thus, the antifouling coating composition of the present embodiment is particularly effective when the antifouling coating composition contains an organic pigment as the coloring pigment (E).

[0226] Examples of the organic pigment include phthalocyanine blue, phthalocyanine green, naphthol red, and diketopyrrolopyrrole red, and one or more selected from the group consisting of phthalocyanine blue and naphthol red is preferable.

[0227] In the case where the antifouling coating composition of the present application contains the coloring pigment (E), the content of the coloring pigment (E) in the solid components of the antifouling coating composition is preferably 0.01% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and still more preferably 3% by mass or more and 12% by mass or less, from the viewpoints of the antifouling property of the antifouling coating film formed and the workability in the production, the coatability, and the storage stability of the antifouling coating composition.

[0228] In the case where the antifouling coating composition of the present application contains an organic pigment as the coloring pigment (E), the content of the organic pigment in the solid components of the antifouling coating composition is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.1% by mass or more and 9% by mass or less, and further preferably 0.2% by mass or more and 8% by mass or less, from the viewpoints of the workability in the production of the antifouling coating composition, the workability in the coating, and the storage stability.

[0229] [Organic solvent (F)]

[0230] The antifouling coating composition of the present application can contain an organic solvent (F) in order to keep the viscosity of the coating composition low and improve the workability in the coating.

[0231] As the organic solvent (F), for example, aromatic hydrocarbon-based organic solvents, aliphatic hydrocarbon-based organic solvents, alicyclic hydrocarbon-based organic solvents, ketone-based organic solvents, alcohol-based organic solvents, and ester-based organic solvents, and the like can be given, with aromatic hydrocarbon-based organic solvents and ketone-based organic solvents being preferred, and aromatic hydrocarbon-based organic solvents being more preferred.

[0232] As the aromatic hydrocarbon-based organic solvent described above, toluene, xylene, mesitylene, and the like can be given, with xylene being preferred.

[0233] As the aliphatic hydrocarbon-based organic solvent described above, pentane, hexane, heptane, octane, and the like can be given.

[0234] As the alicyclic hydrocarbon-based organic solvent described above, cyclohexane, methylcyclohexane, ethylcyclohexane, and the like can be given.

[0235] As the ketone-based organic solvent described above, acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl carbonate, and the like can be given, with acetylacetone being preferred.

[0236] As the alcohol-based organic solvent described above, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, and the like can be given.

[0237] As the ester-based organic solvent described above, ethyl acetate, propyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and the like can be given.

[0238] The organic solvent (F) can be used alone or in combination with two or more.

[0239] In the case where the antifouling coating composition of the present application contains the organic solvent (F), the content of the organic solvent (F) in the coating composition is preferably 3% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more from the viewpoint of improving the coatability, and is preferably 45% by mass or less, more preferably 40% by mass or less, and further preferably 35% by mass or less from the viewpoint of suppressing sagging at the time of coating and reducing the environmental burden.

[0240] [Silica particles (G)]

[0241] The antifouling coating composition of the present application preferably contains the silica particles (G) from the viewpoint of the hardness, softness, and strength of the formed antifouling coating film, and as the silica particles (G), hydrophobic silica particles (G1) and hydrophilic silica particles (G2) can be exemplified.

[0242] The silica particles (G) not only improve the properties of the formed antifouling coating film but also make the flowability and thixotropy of the antifouling coating composition good.

[0243] The antifouling coating composition preferably contains at least one selected from the group consisting of the hydrophobic silica particles (G1) and the hydrophilic silica particles (G2), preferably contains at least the hydrophobic silica particles (G1), and more preferably contains both the hydrophobic silica particles (G1) and the hydrophilic silica particles (G2).

[0244] Note that the hydrophobic silica particles (G1) are preferably added from the viewpoint of the hardness, softness, and strength of the formed antifouling coating film and the improvement of the flowability and thixotropy of the antifouling coating composition. In addition, the hydrophilic silica particles (G2) have a function of improving the antifouling properties of the formed antifouling coating film although there is a tendency to reduce the viscosity by the addition thereof.

[0245] As the silica particles (G), dry-process silica and wet-process silica are preferable, and dry-process silica is more preferable.

[0246] The hydrophobic silica particles (G1) are hydrophobically treated silica (silica whose surface has been subjected to hydrophobic treatment), and can be obtained by treating hydroxyl groups (silanol groups) bonded to silicon atoms on the surface of silica with a hydrophobic treatment agent, and examples include aqueous wet-process silica and hydrophobic fumed silica.

[0247] Examples of the hydrophobizing agent include organodisilazane, organoalkoxysilane, organochlorosilane, cyclic organopolysilazane, and linear organopolysiloxane. Among these, organodisilazane, organoalkoxysilane, and organochlorosilane are preferred. More specifically, hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, 1,3-diethyl-1,1,3,3-tetramethyldisilazane, 1,3-dimethyl-1,1,3,3-tetraethyldisilazane, 1,3-divinyltetramethyldisilazane, 1,3-diallyltetramethyldisilazane, 1,3-dibutenyltetramethyldisilazane, 1,3-dipentenyltetramethyldisilazane, 1,3-dihexenyltetramethyldisilazane, 1,3-diheptenyltetramethyldisilazane, 1,3-dioctenyltetramethyldisilazane, 1,3-dinonenyltetramethyldisilazane, Silazane compounds such as tetramethyldisilazane, 1,3-didecenyltetramethyldisilazane, 1,3-divinyltetraethyldisilazane, and 1,3-dimethyltetravinyldisilazane; alkoxysilane compounds such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, and butenyltrimethoxysilane; and chlorosilane compounds such as trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dimethylvinylchlorosilane, and allyldimethylchlorosilane. From the perspectives of operability, reactivity with silanol groups on the silica surface, etc., it is preferred to use silazane compounds or chlorosilane compounds, more preferably methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and 1,3-divinyltetramethyldisilazane, and even more preferably hexamethyldisilazane, 1,3-divinyltetramethyldisilazane, and dimethyldichlorosilane.

[0248] Examples of commercially available hydrophobic silica include "AEROSILR974" and "AEROSILRX200" manufactured by Nippon Aerosil Co., Ltd.

[0249] The hydrophilic silica particles (G2) are untreated silica (surface-untreated silica), and examples thereof include dry-process silica (fumed silica, anhydrous silica) and wet-process silica (water and silica). Dry-process silica is preferred, and fumed silica is more preferred.

[0250] Examples of commercially available hydrophilic silica include "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd.

[0251] In the case where the antifouling coating composition of the present application contains the silica particles (G), the content of the silica particles (G) in the solid components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more, from the viewpoint of improving the strength and hardness of the antifouling coating film formed, and is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0252] The content of the silica particles (G) with respect to 100 parts by mass of the curable polyorganosiloxane (A) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more, from the viewpoint of improving the strength and hardness of the antifouling coating film formed, and is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15 parts by mass or less.

[0253] In addition, in the case where the hydrophobic silica particles (G1) and the hydrophilic silica particles (G2) are used in combination as the silica particles (G), the ratio (G1 / G2) of the content of the hydrophobic silica particles (G1) to the content of the hydrophilic silica (G2) in the antifouling coating composition is preferably 5 / 95 or more and 90 / 10 or less, more preferably 10 / 80 or more and 80 / 20 or less, further preferably 15 / 85 or more and 70 / 30 or less, more further preferably 20 / 80 or more and 60 / 40 or less, and more further preferably 20 / 80 or more and 40 / 60 or less.

[0254] 〔Curing Catalyst (H)〕

[0255] The antifouling coating composition of the present embodiment preferably contains a curing catalyst (H) in order to improve the curing speed and the film strength of the antifouling coating film.

[0256] As the curing catalyst (H), a tin compound, a titanium compound, a metal salt of a fatty acid, and an amine compound are preferred, and a tin compound, an alkali metal salt of a fatty acid, and an amine compound are more preferred. Furthermore, from the viewpoint of improving the curing speed in a low-temperature high-humidity environment, a combination of a metal salt of a fatty acid and an amine compound is preferred, and a combination of an alkali metal salt of a fatty acid and an amine compound is more preferred.

[0257] As the above tin compound, dibutyltin diacetate, dibutyltin acetylacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctanoate, dibutyltin dineopentanoate, dioctyltin dineopentanoate, bis (dibutyltin laurate) oxide, bis (triethoxysilyloxy) dibutyltin, bis (dibutyltin acetate) oxide, bis (ethylmalonate) dibutyltin, bis (ethylmalonate) dioctyltin, tin naphthenate, tin oleate, and the like can be given, with dibutyltin diacetate, dibutyltin acetylacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctanoate, dibutyltin dineopentanoate being preferred, and dibutyltin dilaurate being more preferred.

[0258] As a commercial product of the above tin compound, "NEOSTANN U-100" manufactured by Nitto Kasei Co., Ltd., "Gleck TL" manufactured by DIC Corporation, and the like can be given.

[0259] As the above titanium compound, tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra (2-ethylhexyloxy) titanium, dipropoxybis (acetylacetonato) titanium, isopropoxyoctylglycol titanium, and the like can be given.

[0260] As the above organic metal compound other than the above tin compound and titanium compound, zinc naphthenate, zinc stearate, zinc 2-ethyloctanoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, cobalt naphthenate, alkoxyaluminum compounds, and the like can be given.

[0261] As the above fatty acid constituting the metal salt of the fatty acid, acetic acid, 2-ethylhexanoic acid, octanoic acid, decanoic acid, neodecanoic acid, naphthenic acid, versatic acid, oxalic acid, and the like can be given.

[0262] As the metal forming the metal salt, alkali metals such as lithium, sodium, and potassium, magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, bismuth, aluminum, and the like can be given. Among them, alkali metals and metals of Groups 10 to 12 such as nickel, copper, and zinc are preferred, and alkali metals and zinc are more preferred.

[0263] As the above amine compound, N,N,N,N-tetramethyl-1,6-hexanediamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,2-dimethylimidazole, and the like can be given. Among them, 2,4,6-tris (dimethylaminomethyl) phenol is preferred.

[0264] The curing catalyst (H) can be used alone or in combination of two or more.

[0265] In the case where the antifouling coating composition of the present application contains the curing catalyst (H), the content of the curing catalyst (H) in the solid components of the antifouling coating composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more, from the viewpoint of improving the curing speed, and is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less.

[0266] In the case where the antifouling coating composition of the present application contains the curing catalyst (H), the content of the curing catalyst (H) in the antifouling coating composition is preferably 0.03 parts by mass or more and 30 parts by mass or less, more preferably 0.3 parts by mass or more and 10 parts by mass or less, and further preferably 0.5 parts by mass or more and 5 parts by mass or less, with respect to 100 parts by mass of the curable polyorganosiloxane (A).

[0267] [Organosilicon crosslinking agent (I)]

[0268] The antifouling coating composition of the present application preferably contains the organosilicon crosslinking agent (I) in order to improve the curing speed, the strength of the antifouling coating film, and the adhesion to the substrate. Note that the organosilicon crosslinking agent is not limited to one that is intended to have these functions, and can be incorporated for the purpose of functioning as a wetting agent for the coloring pigment (E), for example.

[0269] The organosilicon crosslinking agent (I) has 3 or 4 hydrolyzable groups at a silicon atom, and in the case of having 3 hydrolyzable groups, is an organosilane further having 1 hydrocarbon group, and also includes a partial condensate thereof.

[0270] The above hydrolyzable group is 3 or 4 with respect to 1 silicon atom.

[0271] As the above hydrolyzable group, an alkoxy group is preferable.

[0272] As the above alkoxy group, a methoxy group and an ethoxy group are preferable.

[0273] As the above hydrocarbon group, a hydrocarbon group having a carbon number of 1 or more and 6 or less is preferable, and a methyl group, an ethyl group, a propyl group are more preferable, and a methyl group and an ethyl group are further preferable.

[0274] As the organosilicon crosslinking agent (I), tetraethyl orthosilicate, a partial hydrolysis condensate of tetraethyl orthosilicate, an alkyltrialkoxysilane, and an oxime-based silane can be given, and tetraethyl orthosilicate and a partial hydrolysis condensate of tetraethyl orthosilicate are preferable.

[0275] As the above commercially available product of tetraethyl orthosilicate, "Ethyl Silicate 28" manufactured by Colcoat Co., Ltd., and "Ethyl Orthosilicate" manufactured by Tomy Chemical Industry Co., Ltd., and the like can be given.

[0276] As a commercially available product of the partial hydrolytic condensate of tetraethyl orthosilicate, "Silicate 40" manufactured by DOW CORNING TORAY SILICONE CO., LTD. and "WACKER SILICATE TES 40 WN" manufactured by WACKER SILICONE CO., LTD. can be given.

[0277] As a commercially available product of the above-mentioned alkyltrialkoxysilane, "KBM-13" manufactured by SHIN-ETSU CHEMICAL CO., LTD. can be given.

[0278] As a commercially available product of the above-mentioned oxime-based silane, "MTO (MOS)" (methyltris(methylethylketoxime)silane), "VTO (VOS)" (vinyltris(methylethylketoxime)silane) manufactured by Toray Industries, Inc. can be given.

[0279] The organosilicon crosslinking agent (I) can be used alone or in combination of two or more.

[0280] In the case where the antifouling coating composition of the present application contains the organosilicon crosslinking agent (I), the content of the organosilicon crosslinking agent (I) in the solid components of the antifouling coating composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.3% by mass or more, and is preferably 15% by mass or less, more preferably 12% by mass or less, and further preferably 9% by mass or less.

[0281] In the case where the antifouling coating composition of the present application contains the organosilicon crosslinking agent (I), the content of the organosilicon crosslinking agent (I) in the antifouling coating composition is 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.5 parts by mass or more, relative to 100 parts by mass of the curable polyorganosiloxane (A), and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.

[0282] [Silane Coupling Agent (J)]

[0283] The antifouling coating composition of the present embodiment can contain a silane coupling agent (J) for the purpose of improving the curing speed, the curability of the antifouling coating film, and the adhesiveness to the substrate.

[0284] The silane coupling agent (J) is an organoalkoxysilane in which a silicon atom has at least one alkoxy group and at least one organic reactive group.

[0285] As the above-mentioned alkoxy group, a methoxy group, an ethoxy group are preferred, and a methoxy group is more preferred.

[0286] One to three alkoxy groups are bonded to the silicon atom, preferably two to three, and more preferably three.

[0287] As the above organic reactive group, amino group, mercapto group, epoxy group, isocyanate group, urea group, vinyl group, acrylic acid group, methacrylic acid group, styryl group can be given, preferably amino group, mercapto group, epoxy group, isocyanate group, urea group, more preferably amino group, mercapto group, epoxy group, further preferably amino group.

[0288] As the specific organic reactive group containing amino group, 2- (aminoethyl) -3-aminopropyl group, 3-aminopropyl group are preferred.

[0289] As the silane coupling agent (J), 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2- (2-aminoethylamino) ethylamino) propyltrimethoxysilane, 3- glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3- mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and the like can be given, preferably 3- (2-aminoethylamino) propyltrimethoxysilane, 3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, more preferably 3- (2- aminoethylamino) propyltrimethoxysilane.

[0290] As the silane coupling agent (J), condensates of the above compounds can be used. The silane coupling agent (J) can be used alone, or two or more can be used in combination.

[0291] In the case where the antifouling coating composition of the present application contains the silane coupling agent (J), the content of the silane coupling agent (J) in the solid component of the antifouling coating composition is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and, on the other hand, is preferably 3% by mass or less, more preferably 1% by mass or less.

[0292] The content of the silane coupling agent (J) in the above antifouling coating composition is preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the curable polyorganosiloxane (A), and, on the other hand, is preferably 3 parts by mass or less, more preferably 1 part by mass or less.

[0293] The antifouling coating composition of the present application preferably contains the organosilicon crosslinking agent (I) and / or the silane coupling agent (J) for the purpose of improving the curability, strength and adhesion to the substrate of the antifouling coating film.

[0294] Biorepellent (K) other than pyrithione metal salt (B)

[0295] The antifouling coating composition of the present application preferably contains the biorepellent (K) other than pyrithione metal salt (B) (hereinafter also simply referred to as biorepellent (K)) for the purpose of improving the antifouling property of the formed antifouling coating film.

[0296] The bio-repellent (K) is a substance that is dissolved from the antifouling coating film in water, and has an effect of inhibiting the attachment of aquatic organisms to the surface of the antifouling coating film, and improving the antifouling property.

[0297] As the bio-repellent (K), a substance having a repellent effect on aquatic organisms and having a certain dissolution rate in water is preferred, and one or more selected from the group consisting of 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (alias: tralopyril) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (alias: DCOIT) is preferred. The bio-repellent (K) can be used alone or in combination with two or more.

[0298] In the case where the antifouling coating composition of the present application contains the bio-repellent (K), the content of the bio-repellent (K) in the solid components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 5% by mass or more, from the viewpoint of the strength and the antifouling property of the antifouling coating film and the coatability of the antifouling coating composition, and is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

[0299] [Other Optional Components]

[0300] As pigments other than the coloring pigments (E) and the silica particles (G), talc, mica, calcium carbonate, barium carbonate, potassium feldspar, kaolin, and glass short fibers, etc. can be given, and these inorganic fillers can be used alone or in combination with two or more.

[0301] As dehydrating agents other than the silicone crosslinking agent (I), zeolite, porous alumina, and ortho esters such as alkyl orthoformate, orthoboric acid, isocyanate compounds, etc. can be given.

[0302] As anti-sagging-anti-settling agents other than the oxidized polyethylene wax (C), organic clay-based waxes (stearate salts of Al, Ca, Zn, lecithin salts, alkyl sulfonate salts, etc.), organic waxes (polyethylene wax, amide wax, polyamide wax, hydrogenated castor oil wax, etc.), and mixtures of organic clay-based waxes and organic waxes, etc. can be given.

[0303] As wet dispersing agents other than the oxidized polyethylene wax (C), publicly known wet dispersing agents of the organic or inorganic type can be used, and for example, wet dispersing agents having a silicone main chain, etc. can be given. As commercially available products, "KP-578", "KF-6106", etc. manufactured by Shin-Etsu Chemical Co., Ltd. can be given.

[0304] As the enzyme, for example, serine protease, cysteine protease, metalloprotease, cellulase, hemicellulase, pectinase, and glycosidase, etc. can be exemplified.

[0305] As the above-mentioned flame retardant, antimony oxide, and oxidized paraffin, etc. can be exemplified.

[0306] As the above-mentioned thermal conductivity modifier, boron nitride, and aluminum oxide, etc. can be exemplified.

[0307] [Form of the antifouling coating composition]

[0308] The antifouling coating composition of the present application can be a one-liquid type antifouling coating composition in which the above-mentioned components are made into one composition, or a multi-liquid type antifouling coating composition in which the above-mentioned components are made into two or more compositions, and mixed before coating. From the aspect of preventing deterioration during storage, the multi-liquid type antifouling coating composition is preferred, and from the aspect of coating operability, the one-liquid type antifouling coating composition is preferred.

[0309] As the above-mentioned multi-liquid type antifouling coating composition, a two-liquid type antifouling coating composition, a three-liquid or more multi-liquid type antifouling coating composition can be exemplified. From the aspect of coating operability, the two-liquid type antifouling coating composition is preferred, and from the aspect of preventing deterioration during storage, the three-liquid or more multi-liquid type antifouling coating composition is preferred.

[0310] In the case where the antifouling coating composition of the present application is a multi-liquid type antifouling coating composition, it is preferred that the curable polyorganosiloxane (A) and the curing catalyst (H), the silicone crosslinking agent (I), and the silane coupling agent (J) are contained in different liquids.

[0311] The pyrithione metal salt (B), the oxidized polyethylene wax (C), the silica particles (G), the coloring pigment (E), and the biorepellent (K) other than the pyrithione metal salt (B) are preferably contained in the same liquid as the curable polyorganosiloxane (A).

[0312] Note that the content of each component in the antifouling coating composition of the present embodiment is the content relative to the total amount of the entire composition, even in the case of a multi-liquid type antifouling coating composition.

[0313] [Method for producing the antifouling coating composition]

[0314] The above-mentioned antifouling coating composition is preferably produced as shown below.

[0315] First, it is preferred to have a step of kneading the curable polyorganosiloxane (A) and the silica particles (G). In addition, heating can be performed at the time of kneading or after kneading. By kneading them in advance, the affinity of the two components is improved, and the aggregation of silica and the increase in the viscosity of the coating composition can be suppressed.

[0316] The conditions at the time of heating are preferably 100°C or higher, more preferably 100°C or higher and 300°C or lower, and further preferably 140°C or higher and 200°C or lower. The pressure is preferably normal pressure or reduced pressure, and the treatment time is preferably 3 hours or longer and 30 hours or shorter.

[0317] Further, the production method of the antifouling coating composition of the present embodiment preferably has the process a and the process b in this order.

[0318] Process a: process of obtaining a mixture A containing the pyrithione metal salt (B) and the oxidized polyethylene wax (C)

[0319] Process b: process of obtaining the antifouling coating composition by mixing the mixture A obtained in the process a and the curable polyorganosiloxane (A)

[0320] If the curable polyorganosiloxane (A) or the like having a silicone chain is incorporated into the mixture A, the water repellency becomes high, and a shrinkage hole is generated, and therefore it is preferable to prepare the mixture A with the components other than the curable polyorganosiloxane (A) or the like having a silicone chain, and then incorporate the curable polyorganosiloxane (A) or the like having a silicone chain.

[0321] Note that in the process a, the grind base A preferably contains a part of the organic solvent (F), and further preferably contains a part of the organic solvent (F) and other components (for example, the coloring pigment (E) or the like) in addition to the pyrithione metal salt (A) and the polyethylene wax (B).

[0322] On the other hand, in the process b, it is preferable to mix the remaining organic solvent (F) in addition to the mixture A and the curable polyorganosiloxane (A), and obtain the antifouling coating composition.

[0323] Even in the case where the antifouling coating composition of the present application is a one-liquid type antifouling coating composition, it is preferable to premix the curable polyorganosiloxane (A) and the silica particles (G) as described above.

[0324] Further, if a compound having a silicone chain such as the curable polyorganosiloxane (A) and the silicone oil (D1) is added, there is a tendency that the water repellency of the antifouling coating composition becomes higher, and therefore, in the case of a one-pack type antifouling coating composition, it is preferable that, in the step a, a mixture A is prepared by mixing and stirring the pyrithione metal salt (B), the oxidized polyethylene wax (C), a part of the organic solvent (F), and other components, except for a compound having a silicone chain such as the curable polyorganosiloxane (A) and the silicone oil (D1), and then, in the step b, a compound having a silicone chain such as the curable polyorganosiloxane (A) and the silicone oil (D1) and the remaining organic solvent (F) are added and mixed and stirred, thereby preparing the antifouling coating composition. Note that, in the case of having a step of mixing the silica particles (G) with the curable polyorganosiloxane (A), it is preferable that the silica particles (G) are added to the mixture A together with the curable polyorganosiloxane (A) in the step 2.

[0325] Even in the case where the antifouling coating composition of the present application is a multi-pack type antifouling coating composition, it is preferable that the curable polyorganosiloxane (A) and the silica particles (G) are mixed in advance as described above.

[0326] Further, it is preferable that a compound having a silicone chain other than the curable polyorganosiloxane (A) is contained in the base agent. Thus, it is preferable that the base agent contains only the curable polyorganosiloxane (A) as the compound having a silicone chain. Note that, in the case where a compound having a silicone chain such as the silicone oil (D1) is contained in the base agent in addition to the curable polyorganosiloxane (A), it is preferable that it is added in the step b.

[0327] In the preparation of the base agent of the multi-pack type antifouling coating composition, it is preferable that, in the step a, a mixture A is prepared by mixing and stirring the pyrithione metal salt (B), the oxidized polyethylene wax (B), a part of the organic solvent (F), and other components, except for the curable polyorganosiloxane (A) having a silicone chain, and then, in the step b, a compound having a silicone chain such as the curable polyorganosiloxane (A) and the remaining organic solvent (F) are added and mixed and stirred, thereby preparing the antifouling coating composition. Note that, in the case of having a step of mixing the silica particles (G) with the curable polyorganosiloxane (A), it is preferable that the silica particles (G) are added to the mixture A together with the curable polyorganosiloxane (A) in the step b.

[0328] The mixing and stirring is preferably performed at 0°C or higher and 50°C or lower.

[0329] [Antifouling coating film]

[0330] The antifouling coating film of the present application is an antifouling coating film formed from the antifouling coating composition described above. The antifouling coating film can be formed by coating or impregnating the antifouling coating composition of the present application on a substrate, and then drying and curing it.

[0331] In addition, the antifouling coating film is preferably an antifouling coating film used for the purpose of preventing fouling of a substrate by aquatic organisms in water.

[0332] [Substrate with antifouling coating film and method for producing the same]

[0333] The substrate with antifouling coating film of the present application has a substrate and an antifouling coating film provided on the surface of the substrate.

[0334] The method for producing the substrate with antifouling coating film described above preferably has a step (coating step) of coating the antifouling coating composition of the present application on a substrate or a step of impregnating a substrate in the antifouling coating composition of the present application, and further preferably has a step of drying and curing the antifouling coating composition.

[0335] <Coating step>

[0336] As a method for coating the antifouling coating composition of the present application, known methods such as brushing, roll coating, spraying, roll coater coating, flow coater coating, slit coater coating, gravure coater coating, spin coater coating, curtain coater coating, electrostatic coating, dip coating, screen printing, and spin coating can be mentioned.

[0337] The thickness of the coating film formed from the antifouling coating composition of the present application is set so that the antifouling coating film finally formed has the thickness described later. The coating film can be formed by one coating, or can be formed by two or more coatings (coating two or more times).

[0338] The thickness of the antifouling coating film of the present application is not particularly limited, and is preferably 5 μm or more, more preferably 10 μm or more, and further preferably 50 μm or more, and is preferably 1000 μm or less, more preferably 500 μm or less, and further preferably 300 μm or less. If the antifouling coating film is in this form, it becomes an antifouling coating film excellent in long-term antifouling properties.

[0339] <Drying and curing step>

[0340] The antifouling coating composition of the present application coated by the method described above is, for example, preferably left to stand for 0.5 days or more and 14 days or less, and more preferably for 1 day or more and 10 days or less, at 23°C, whereby it is dried and cured to obtain an antifouling coating film.

[0341] Note that the drying and curing of the antifouling coating composition of the present application can be performed with heating and / or while blowing air.

[0342] Here, the substrate is not particularly limited, but is preferably a substrate that comes into contact with seawater or fresh water, more preferably at least one selected from the group consisting of a ship, a water structure, a fishing material, a water supply and drainage pipe, and a device used on or in water, further preferably a ship and a water structure, and particularly preferably a ship. Specifically, examples include a ship (for example, a ship body outer plate of a large steel ship such as a container ship or a tanker, a fishing boat, an FRP ship, a wooden ship, a yacht, and the like, particularly from a waterline portion to a bottom portion, and also including any kind of a manufacturing ship or a repair ship), a water structure (for example, a structure for various water civil engineering works in an oil pipeline, a water guide pipe, a circulating water pipe, a water supply and drainage port of a factory and a thermal power plant, a nuclear power plant, a submarine cable, a seawater utilization device (seawater pump and the like), an ultra-large floating offshore structure, a coastal road of a gulf, a submarine tunnel, a harbor device, a canal, a water channel, and the like), a fishing material (for example, a rope, a fishing net, fishing tackle, a fishing float or a buoy, and the like), a water supply and drainage pipe for seawater and the like in a factory and a thermal power plant, a nuclear power plant, and the like, a device used on or in water (a solar power generation panel, a measuring instrument, an observation window of a device, a camera lens, an underwater light, an underwater sensor, and the like), a monitoring window of a submarine, and the like.

[0343] The material of the substrate is not particularly limited, but examples include steel, aluminum, wood, FRP, glass, plastic, and the like, particularly for a ship, and glass, plastic, and the like, particularly for a device used on or in water.

[0344] In addition, the substrate can be treated with another treatment agent such as an antirust agent, can have a coating film such as a primer formed on the surface in advance, can have the present composition applied thereto, and can be an old antifouling coating film that has deteriorated over the years after formation of the present coating film or another antifouling coating film, and is not particularly limited.

[0345] Examples

[0346] Hereinafter, the present application will be further specifically described based on examples, but the present application is not limited to these examples.

[0347] (1) Mixture of curable silicone (A) and silica particles (G)

[0348] The curable silicone (A) and the silica particles (G) shown in Table 1 were mixed at the proportions described in Table 1 to obtain a mixture. The viscosities in Table 1 are values at 25°C and were measured using a B-type rotational viscometer in accordance with JIS K 6249:2003. In addition, the weight average molecular weight was measured in the same manner as the average molecular weight of the polymers described later.

[0349]

[0350] (2) Components of the antifouling coating composition

[0351] The components used in the antifouling coating composition are shown in Table 2. The kinematic viscosity in Table 2 is the value at 25°C, measured in accordance with JIS Z 8803:2011.

[0352]

[0353] (3) Synthesis Example 1 (acrylic resin having a hydrophilic group (d-4))

[0354] The reaction was performed under normal pressure in a nitrogen atmosphere. To a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel, 42.86 parts by mass of methyl amyl ketone was added, and heated to 100°C while stirring until the methyl amyl ketone reached 100°C. While maintaining the temperature of the reaction mixture at 100 ± 5°C, a mixture containing 40.0 parts by mass of NKEster AM-90G (methoxypolyethylene glycol acrylate, average number of polyethylene glycol units 9, manufactured by Shin-Nakamura Chemical Co., Ltd.), 60.0 parts by mass of isobutyl acrylate, and 4.0 parts by mass of 2,2'-azobis(2-methylbutyronitrile) was added dropwise to the reaction vessel over 4 hours. Thereafter, while maintaining 100 ± 5°C, stirring was performed for 2 hours to obtain a solution of the polymer (d-4). The solid content of the obtained solution was 70.3 mass%, the viscosity was 109 mPa-s, and the weight average molecular weight (Mw) of the polymer (d-4) was 9100.

[0355] The physical properties of the polymer (d-4) were measured as shown below.

[0356] 〔Solid content of polymer solution〕

[0357] The polymer solution was dried at 108°C under 1 atmosphere for 3 hours, and the solid content (mass%) was obtained by dividing the mass of the obtained solid content by the mass of the polymer solution before drying.

[0358] 〔Viscosity of polymer solution〕

[0359] The viscosity (mPa-s) of the polymer solution at a liquid temperature of 25°C was measured using a viscometer (TV-25, manufactured by Tokimec, Inc.).

[0360] 〔Average molecular weight of polymer〕

[0361] The weight average molecular weight (Mw) of the polymer was measured using gel permeation chromatography (GPC) under the following conditions.

[0362] <GPC Conditions>

[0363] Apparatus: "HLC-8420GPC" (manufactured by Tosoh Corporation)

[0364] Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" (manufactured by Tosoh Corporation, 6 mm (inner diameter), 15 cm (length)) were connected.

[0365] Eluent: Tetrahydrofuran (THF)

[0366] Flow rate: 0.600 mL / min

[0367] Detector: RI

[0368] Column oven temperature: 40°C

[0369] Standard substance: Polystyrene

[0370] Sample preparation method: A sample for GPC measurement was obtained by adding THF to a polymer solution and filtering with a membrane filter.

[0371] [Examples 1 to 25, Comparative Examples 1 to 3, Reference Examples 1 to 2]

[0372] (1) Preparation of Antifouling Coating Composition

[0373] Each component was mixed and stirred in accordance with the compounding amounts (parts by mass) described in Table 3, and a three-component coating composition or a one-component coating composition including a main agent component, a curing agent component, and an additive component was prepared. In the case of applying the three-component coating composition, the components of each component were mixed and stirred uniformly using a disperser.

[0374] More specifically, for the main agent of the three-component coating composition, each component except for the kneaded product of the curable polyorganosiloxane (A) and the curable polyorganosiloxane (A) and the silica particles (G) was mixed and stirred with 10 parts by mass of xylene, a mixture A was prepared, and the curable polyorganosiloxane (A), the kneaded product of the curable polyorganosiloxane (A) and the silica particles (G), and the remaining xylene were mixed and stirred, and an antifouling coating composition was prepared.

[0375] In addition, for the one-component coating composition, each component except for the curable polyorganosiloxane (A), the kneaded product of the curable polyorganosiloxane (A) and the silica particles (G), and the slip agent (D) was mixed and stirred with 10 parts by mass of xylene, a mixture A was prepared, and the curable polyorganosiloxane (A), the kneaded product of the curable polyorganosiloxane (A) and the silica particles (G), and the slip agent (D) and the remaining xylene were mixed and stirred, and an antifouling coating composition was prepared.

[0376] (2) Production of Substrate (Test Body) with Coating Film

[0377] A sandblasted plate coated with an epoxy-based anticorrosive paint ("BANNOH 500" manufactured by Nippon Paint Co., Ltd.) was coated with a paint ("CMP BIOCLEAN TIE-COAT" manufactured by Nippon Paint Co., Ltd.) so that the thickness after drying (curing) was 100 μm, and after drying for 24 hours at ordinary temperature, the paint composition of the examples, comparative examples, and reference examples was coated at ordinary temperature so that the thickness after drying (curing) was 200 μm. After one week at ordinary temperature, test plates with a coating film were prepared.

[0378] (3) Evaluation method

[0379] [Median diameter (D50) of pyrithione metal salt in paint composition]

[0380] A coating film of each paint composition was prepared, and measurement was performed using a table-type SEM device (device name: Miniscope (registered trademark) TM3030 Plus (Hitachi High-Tech Corporation)).

[0381] (Preparation of coating film)

[0382] A tinplate was coated with the paint composition of the examples, comparative examples, and reference examples so that the thickness after drying (curing) was 200 μm, and after drying for 1 day at ordinary temperature, a coating film was prepared.

[0383] (Measurement method)

[0384] The prepared coating film was cut using a single blade specified in JIS K 5600-5-6, and the surface or cross section of the coating film was observed at 1000 times magnification using a table-type SEM device. The maximum particle diameters of 50 pyrithione metal salts that could be confirmed in the field of view were measured, and the average of the measured maximum particle diameters was set as the median diameter of the pyrithione metal salt in the paint composition.

[0385] [Median diameter (D50) of pyrithione metal salt of raw material]

[0386] Measurement was performed using a laser diffraction / scattering type particle diameter distribution measuring device (MT3300EX II manufactured by Microtrac Bel Corporation).

[0387] (Measurement method)

[0388] A few drops of a dispersing medium (0.2% sodium hexametaphosphate aqueous solution) were added dropwise to water, a pyrithione metal salt was added, and ultrasonic dispersion was performed for about 5 minutes, and further, measurement of the median diameter was performed after dispersion in the device for about 10 minutes.

[0389] [Viscosity]

[0390] The mixture A of each composition was measured at 23°C using a Stormer viscometer (manufacturer: Tokushu Kinzoku Co., Ltd., product name Stormer viscometer, model number: 691).

[0391] The lower the Stormer viscosity, the more excellent the manufacturing workability.

[0392] [Storage stability]

[0393] The main agent component was prepared in the case of a multi-liquid kit, and the coating composition was prepared in the case of a one-liquid type, and then after storage for 30 days at a temperature of 50°C, the following properties were confirmed and the storage stability of the coating was evaluated.

[0394] <Anti-sag property>

[0395] Each composition was coated on a tinplate using a sag tester of a box type shown in JIS K 5400 (1990) 6.4 on a horizontal platform, the film thickness was measured using a wet film thickness gauge, and then immediately after, the test plate was vertically erected in such a manner that the track line of the sag tester was horizontal, and the anti-sag property of the film was measured.

[0396] The coating layer in which the amount of the sample flowing out in the space between the coating layers was less than 1 / 2 of the space was set as a pass, and the anti-sag limit film thickness of each composition was calculated.

[0397] <Coating film appearance>

[0398] The state of the coating film appearance of the test plate on which the anti-sag property was measured was evaluated by visual observation immediately after preparation and after storage for 30 days at a temperature of 50°C.

[0399] 3: No agglomerates were observed, and the coating film surface was maintained in good condition

[0400] 2: Although agglomerates were observed, the state of the coating film surface was not changed

[0401] 1: While agglomerates were observed, the state of the coating film surface was also observed to be abnormal

[0402] [Evaluation of dynamic antifouling property]

[0403] The above test plate provided on the side surface of a rotating rotor was immersed in real seawater in Hiroshima Prefecture, and was rotated at a speed of about 15 knots. The test plate was provided in such a manner that sunlight was sufficiently irradiated to the test surface, and was set in a condition in which the formation of slime was likely to occur. The ratio of the area of the region to which slime was attached in the antifouling film surface of the test plate to the total area of the test plate was evaluated by visual observation after 6 months. The dynamic antifouling property was evaluated using the score shown below.

[0404] (Benchmark of antifouling property)

[0405] 5: No adhesion of slime

[0406] 4: Adhesion area of slime is 20% or more and less than 40% of the entire test surface

[0407] 3: Adhesion area of slime is 40% or more and less than 60% of the entire test surface

[0408] 2: Adhesion area of slime is 60% or more and less than 80% of the entire test surface

[0409] 1: Adhesion area of slime is 80% or more of the entire test surface

[0410]

[0411]

[0412] According to the embodiment, an antifouling coating film having excellent antifouling properties is obtained from the antifouling coating composition containing the curable polyorganosiloxane (A), the pyrithione metal salt (B), and the oxidized polyethylene wax (C), and satisfying at least one of the above-described Condition A and Condition B. In addition, the Staudinger viscosity of the grind vehicle is low, and the manufacturing workability is excellent. Furthermore, even after storage, the anti-sagging properties can be maintained, and in addition, the aggregation of the coating is inhibited, as a result, an antifouling coating composition having excellent storage stability, from which an antifouling coating film having excellent appearance can be obtained, is obtained.

[0413] On the other hand, in the antifouling coating composition in which the pyrithione metal salt (B) satisfying at least one of Condition A and Condition B is used, and the oxidized polyethylene wax (C) is not contained, as shown in Comparative Examples 1 to 3, although an antifouling coating film having excellent antifouling properties is obtained, the Staudinger viscosity of the grind vehicle is high, and the manufacturing workability is poor. In addition, the anti-sagging properties are reduced after storage, and as aggregation is generated in the antifouling coating composition, the appearance of the coating film is also reduced.

Claims

1. An antifouling coating composition comprising a curable polyorganosiloxane A, a pyridinethione metal salt B, and an oxidized polyethylene wax C, The antifouling coating composition satisfies at least one of the following conditions A and B: Condition A: The median diameter D50 of the pyridinethione metal salt B in the antifouling coating composition is 5.0 μm or less; Condition B: The median diameter D50 of the pyridinethione metal salt B as a raw material is 3.0 μm or less.

2. The antifouling coating composition according to claim 1, wherein The pyrithione metal salt B is copper pyrithione. The antifouling coating composition according to claim 1 , further comprising a slip agent D. The antifouling coating composition according to claim 1 , further comprising a coloring pigment E.

5. The antifouling coating composition according to claim 4, wherein The coloring pigment E contains an organic pigment.

6. The antifouling coating composition according to claim 1, wherein The curable polyorganosiloxane A is a compound represented by the following formula (A1): In formula (A1), R 11 and R 13 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group or a halogenated alkyl group having 1 to 16 carbon atoms, and R 12 Each independently represents a hydroxyl group or a hydrolyzable group, r represents an integer of 1 to 3, and p represents 10 to 10,000.

7. The antifouling coating composition according to claim 1, wherein The content of the curable polyorganosiloxane A in the solid content of the antifouling coating composition is 45% by mass or more and 85% by mass or less.

8. The antifouling coating composition according to claim 1, wherein The content of the pyridinethione metal salt B in the solid content of the antifouling coating composition is 0.5% by mass or more and 15% by mass or less.

9. The antifouling coating composition according to claim 1, wherein The content of the oxidized polyethylene wax C in the solid content of the antifouling coating composition is 0.1% by mass or more and 3.0% by mass or less. 10 . An antifouling coating film formed from the antifouling coating composition according to claim 1 .

11. A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to claim 10 provided on a surface of the substrate.

12. A method for producing a substrate with an antifouling coating film, the method comprising the following (1-1) and (1-2) or the following (2-1) and (2-2): (1-1) a step of coating or impregnating the surface of a substrate with the antifouling coating composition according to any one of claims 1 to 9 to obtain a coated or impregnated product; (1-2) a step of drying the coated or impregnated product obtained in step (1-1) to form an antifouling coating film; (2-1) a step of drying the antifouling coating composition according to any one of claims 1 to 9 to form an antifouling coating film; (2-2) A step of attaching the antifouling coating film obtained in step (2-1) to a substrate.

13. The method for producing the antifouling coating composition according to any one of claims 1 to 9, comprising the steps a and b in this order: Step a: a step of obtaining a mixture A containing a pyridinethione metal salt B and an oxidized polyethylene wax C; Step b: A step of mixing the mixture A obtained in step a and the curable polyorganosiloxane A to obtain an antifouling coating composition.

14. The method for producing an antifouling coating composition according to claim 13, wherein: In the step a, the median diameter D50 of the pyridinethione metal salt B as a raw material is 3.0 μm or less.

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