Antifouling coating composition

Abstract

The present invention provides an antifouling paint composition capable of forming an antifouling coating film which is excellent in both general standing antifouling property and standing antifouling property after long-term dynamic immersion, and is also excellent in adhesion and peeling resistance to a base coating film and a middle coating film, and in adhesion to an old antifouling coating film. The antifouling paint composition of the present invention contains a hydrolyzable polymer (A) containing a metal ester group, which contains a structural unit derived from a metal ester group-containing monomer (a1) represented by the following formula (1) and / or a structural unit derived from a metal ester group-containing monomer (a2) represented by the following formula (2), metomidine (B), bromopyrollitryl cyanide (C), copper pyrithione (D), and a linear or branched alkyl carboxylic acid (E) having 4 to 30 carbon atoms. In formula (1), R 11 each independently represents a monovalent group containing a terminal olefinic unsaturated group, and M represents a copper atom or a zinc atom. In formula (2), R 21 represents a monovalent group containing a terminal olefinic unsaturated group, and R 22 represents a monovalent organic group having 1 to 30 carbon atoms which does not contain a terminal olefinic unsaturated group, and M represents a copper atom or a zinc atom.

Description

TECHNICAL FIELD

[0001] The present application relates to an antifouling coating composition, an antifouling coating film, a substrate with an antifouling coating film, a method for producing a substrate with an antifouling coating film, and an antifouling method for a substrate. More specifically, the present application relates to an antifouling coating composition, etc. containing a hydrolyzable polymer, an antifouling agent, etc. BACKGROUND

[0002] As a method for preventing the fouling of a substrate such as a ship by aquatic organisms, etc., a method of forming an antifouling coating film containing a hydrolyzable polymer on the surface of the substrate is widely used. As such an antifouling coating film, various studies have been made on an antifouling coating containing a polymer including a metal ester group.

[0003] For example, Patent Literature 1 discloses an antifouling coating composition containing a polymer including a metal ester group, and an antifouling agent containing at least Medetomidine and can further optionally contain Copper pyrithione, 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (alternative name: Tralopyril), etc. (Patent Claims, etc.), and describes that an "antifouling coating film having a stable coating film consumption degree and exerting excellent antifouling properties for a long period in a ship, a water structure, etc." can be formed from such an antifouling coating composition.

[0004] Patent Literature 2 discloses an antifouling coating composition containing a hydrolyzable polymer including a metal ester group, a tertiary carboxylic acid component including Versatic Acid, and an antifouling agent component such as 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (alternative name: bromopyrrole nitrile) (Patent Claims, etc.), and describes that an "antifouling coating film having a long-term excellent coating film consumption degree and antifouling properties, and excellent coating film properties such as weather resistance, etc., and being less likely to generate foaming (blistering) even when formed on a deteriorated coating film" can be formed from such an antifouling coating composition.

[0005] Patent Literature 3 discloses an antifouling coating composition containing a hydrolyzable polymer including a metal ester group, zinc oxide, and Medetomidine in specific amounts (Patent Claims, etc.), and describes that an "antifouling coating film maintaining a high antifouling property for a long period, and excellent in damage resistance" can be formed from such an antifouling coating composition.

[0006] Patent Literature 4 discloses an antifouling paint composition containing a resin having a specific metal carboxylate salt structure in each specific amount, and an antifouling agent containing at least metomidine and 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (alternative name: bromopyrol nitrile), and can further optionally contain copper pyrithione and the like (patent claims, etc.), and describes that a "coating film capable of ensuring long-term antifouling property even without using cuprous oxide" can be formed from such an antifouling paint composition.

[0007] Prior Art Documents

[0008] Patent Literature

[0009] Patent Literature 1: WO2011 / 118526

[0010] Patent Literature 2: WO2016 / 084769

[0011] Patent Literature 3: WO2018 / 003135

[0012] Patent Literature 4: Japanese Patent Application Publication No. 2020-100794 SUMMARY

[0013] PROBLEMS TO BE SOLVED BY THE INVENTION

[0014] In recent years, even the existing hydrolyzable antifouling coating film (for example, the hydrolyzable antifouling coating film containing metomidine described in Patent Literature 1) that is considered to have a certain level of antifouling performance as described in Patent Literatures 1 to 4 has been reported to confirm the attachment of animal species such as barnacles, bryozoans, and serpulid worms in low-speed / low-rotation in high-pollution sea areas, during mooring for waiting for berthing. Therefore, in particular, in the outfitting process at the time of building a new ship, a paint that has both standing antifouling property and antifouling property at the time of mooring after sailing (standing antifouling property after long-term dynamic immersion) is required. In addition, due to the influence of the global spread of COVID-19, not only ships that are long-term moored and ships that have a reduced operation rate have increased, but also the risk of fouling of ships has increased due to abnormal weather, changes in marine environments. In order to cope with such a risk of fouling of ships, there is a strong demand for the development of a paint composition that has excellent antifouling property even for a long-term moored ship, and even for a long-term ship that is moored after sailing.

[0015] On the other hand, in the construction of a new ship, the ship body is generally constructed by the ship body block construction method. In the installation process (the joining process of the ship body blocks) and the like, in the roughening of the coated film surface around the weld using a power tool, the existing antifouling coated film has a problem of peeling and scattering of the coated film pieces presumably due to the adhesion to the underlying anticorrosive coated film, the coated film properties (hardness) and the like. In addition, the antifouling coated film that has generally passed the service life is repaired (renovated) by being painted while the structure such as a ship is pulled onto land (example: a dock). However, in this repair painting, not only the ship cannot be used, but also the usage fee of the dock and the like is high, and thus it is strongly required in terms of economy to be completed in a short time. Therefore, not only is the adhesion to the underlying anticorrosive coated film or the like before use important, but also the excellent adhesion that enables direct painting to the deteriorated antifouling coated film (old antifouling coated film) of the repair object (i.e., without the need to remove the old antifouling coated film) is also important.

[0016] An object of the present application is to provide an antifouling paint composition that can form an antifouling coated film that is excellent in both (1) antifouling properties, which are the standing antifouling property generally required for an antifouling coated film and the long-term dynamic immersion and standing antifouling property required for a ship or the like (deteriorated, deteriorated or consumed antifouling coated film) at the time of parking after running, and (2) adhesion to a sound anticorrosive coated film or the like (underlying coated film or intermediate coated film) before use (before seawater immersion), peeling resistance of the coated film at the time of power tool processing, and adhesion to an old antifouling coated film after use (after seawater immersion).

[0017] Method for solving the problem

[0018] The present inventors and the like found that, by using, as essential components, a specific hydrolyzable polymer containing a metal ester group, specific three antifouling agents, i.e., metomidine, bromopyrol nitrile and copper pyrithione, and a specific alkyl carboxylic acid, such as tertiary carbonic acid, an antifouling paint composition that can solve the above problems can be prepared, and thus the present application was completed. Although these components are each or partially combined and used in the existing antifouling paint composition, the following is unexpected: by combining all of these components, an antifouling paint composition that can solve new problems while balancing various properties as described above is obtained; in particular, even if similar components are handled as equivalents or substitutes in the existing antifouling paint composition, by selecting specific components, effects that cannot be exerted when other components are selected can be achieved. Although the collection of the existing technologies can satisfy individual properties or several properties, the antifouling paint composition of the present application that can balance various properties while not impairing specific properties by combining specific components is not easily obtained by those skilled in the art other than the present inventors.

[0019] That is, the present application at least includes the following matters.

[0020] [Item 1]

[0021] An antifouling coating composition containing a hydrolyzable polymer (A) containing a metal ester group, metyridylol (B), bromopyrrole nitrile (C), copper pyrithione (D), and a linear or branched alkyl carboxylic acid (E) having a carbon number of 4 to 30,

[0022] The polymer (A) contains a structural unit derived from a metal ester group-containing monomer (a1) represented by the following formula (1) and / or a structural unit derived from a metal ester group-containing monomer (a2) represented by the following formula (2).

[0023]

[0024] (In formula (1), R 11 Each independently represents a monovalent group containing a terminal olefinic unsaturated group, and M represents a copper atom or a zinc atom.

[0025]

[0026] (In formula (2), R 21 represents a monovalent group containing a terminal olefinic unsaturated group, and R 22 represents a monovalent organic group having a carbon number of 1 to 30 not containing a terminal olefinic unsaturated group, and M represents a copper atom or a zinc atom.

[0027] [Item 2]

[0028] The antifouling coating composition according to item 1, wherein the polymer (A) contains a metal ester group-containing monomer (a1) represented by the following formula (1').

[0029]

[0030] (In formula (1'), R 12 Each independently represents a hydrogen atom or a methyl group, and M represents a copper atom or a zinc atom.

[0031] [Item 3]

[0032] The antifouling coating composition according to item 1 or 2, wherein the alkyl carboxylic acid (E) is a tertiary carbonic acid.

[0033] [Item 4]

[0034] The antifouling coating composition according to any one of items 1 to 3, wherein the content of the metyridylol (B) is 0.1 to 100 mass%, the content of the bromopyrrole nitrile (C) is 10 to 1700 mass%, and the content of the copper pyrithione (D) is 0.1 to 1000 mass% with respect to 100 mass% of the copper pyrithione (D).

[0035] The content of copper pyrithione (D) is 0.5 to 12 mass% relative to 100 mass% of the solid content of the antifouling coating composition.

[0036] [Item 5]

[0037] An antifouling coating film formed from the antifouling coating composition described in any one of Items 1 to 4.

[0038] [Item 6]

[0039] A substrate with an antifouling coating film having a substrate and the antifouling coating film described in Item 5.

[0040] [Item 7]

[0041] The substrate with an antifouling coating film according to Item 6, wherein the substrate is selected from the group consisting of a ship, a structure in water, and a fishing resource.

[0042] [Item 8]

[0043] A method for producing a substrate with an antifouling coating film, comprising:

[0044] a step (1) of applying or impregnating the antifouling coating composition described in any one of Items 1 to 4 to a substrate to obtain an applied body or an impregnated body; and

[0045] a step (2) of drying the applied body or the impregnated body.

[0046] [Item 9]

[0047] A method for preventing fouling of a substrate, comprising a step of forming the antifouling coating film described in Item 5 on at least a part of the substrate.

[0048] Effects of the Invention

[0049] With the antifouling coating composition of the present invention, it is possible to form an antifouling coating film that is not only excellent in general standing antifouling properties, but also excellent in standing antifouling properties after long-term dynamic immersion, and excellent in adhesion and peeling resistance to various base coating films and intermediate coating films, and in adhesion to various old antifouling coating films. Thus, it is also possible to cope with the new requirements for antifouling coating films for ships and the like that have become apparent due to environmental changes in recent years. DETAILED DESCRIPTION

[0050] In the present specification, "(meth)acrylic acid" refers to "acrylic acid or methacrylic acid" or "acrylic acid and methacrylic acid" depending on the context, and "(meth)acrylate" refers to "acrylate or methacrylate" or "acrylate and methacrylate" depending on the context.

[0051] The upper and lower limit values described in the present specification (for example, regarding the content of the components) can be arbitrarily combined to set a numerical range.

[0052] In the present specification (particularly, in the examples), "parts" as a unit added after a numerical value means "mass parts" unless otherwise specified.

[0053] - Antifouling coating composition -

[0054] The antifouling coating composition of the present application contains a hydrolyzable polymer (A) containing a metal ester group (sometimes also referred to as "polymer (A)" or "component (A)" in the present specification), metronidazole (B) (sometimes also referred to as "component (B)" in the present specification), brominated pyrrolidone (C) (sometimes also referred to as "component (C)" in the present specification), copper pyrithione (D) (sometimes also referred to as "component (D)" in the present specification), and a linear or branched alkyl carboxylic acid (E) having 4 to 30 carbon atoms (sometimes also referred to as "alkyl carboxylic acid (E)" or "component (E)" in the present specification).

[0055] <Polymer (A)>

[0056] The polymer (A) contains a structural unit derived from a metal ester group-containing monomer (a1) (sometimes also referred to as "monomer (a1)" in the present specification) and / or a structural unit derived from a metal ester group-containing monomer (a2) (sometimes also referred to as "monomer (a2)" in the present specification). The polymer (A) can use any one, or two or more kinds of structures, ratios, etc. of the structural unit derived from the monomer (a1) and / or the structural unit derived from the monomer (a2). The polymer (A) preferably contains at least a structural unit derived from the monomer (a1), that is, contains a structural unit derived from the monomer (a1), or both a structural unit derived from the monomer (a1) and a structural unit derived from the monomer (a2).

[0057] • Monomer (a1)

[0058] The metal ester group-containing monomer (a1) is a monomer represented by the following formula (1). The monomer (a1) can be any one, or two or more kinds.

[0059]

[0060] In formula (1), R 11 Each independently represents a monovalent group containing a terminal olefinic unsaturated group (CH2=C<), and M represents a copper atom or a zinc atom.

[0061] R 11The number of carbon atoms of the terminal ethylenically unsaturated group is preferably 2 to 50, more preferably 2 to 30, further preferably 2 to 10, and particularly preferably 2 to 6.

[0062] R 11 The ethylenically unsaturated group may be contained in addition to the terminal, but it is more preferable to contain the ethylenically unsaturated group only at the terminal.

[0063] R 11 Preferably, it is an organic group containing a terminal ethylenically unsaturated group (referred to as "terminal ethylenically unsaturated organic group" in this specification). As the terminal ethylenically unsaturated organic group, for example, an unsaturated aliphatic hydrocarbon group whose structure may be partially substituted by an ester bond, an amide bond, or an ether bond can be cited. Specific examples of such terminal ethylenically unsaturated organic groups include: groups obtained by removing a carboxyl group from an aliphatic unsaturated monocarboxylic acid containing a terminal ethylenically unsaturated group, such as acrylic acid (also known as 2-acrylic acid), methacrylic acid (also known as 2-methyl-2-acrylic acid), 3-butenoic acid, 4-pentenoic acid, 10-undecenoic acid, (meth)acryloyloxyalkylcarboxylic acid [e.g., 3-(meth)acryloyloxypropionic acid, 3-(meth)acryloyloxy-2-methylpropionic acid]; and groups obtained by removing one carboxyl group from an aliphatic unsaturated dicarboxylic acid having a terminal ethylenically unsaturated group, such as itaconic acid. As the terminal ethylenically unsaturated organic group, a group obtained by removing a carboxyl group from an aliphatic unsaturated monocarboxylic acid containing a terminal ethylenically unsaturated group is more preferred, a group obtained by removing a carboxyl group from acrylic acid, methacrylic acid or (meth)acryloyloxyalkylcarboxylic acid is further preferred, and a group obtained by removing a carboxyl group from acrylic acid or methacrylic acid is particularly preferred.

[0064] As the monomer (a1), a monomer represented by the following formula (1') is preferred (also referred to as "monomer (a1')" in this specification). Monomer (a1') corresponds to two R 11 The terminal ethylenically unsaturated organic groups are all groups obtained by removing a carboxyl group from acrylic acid or methacrylic acid.

[0065]

[0066] In formula (1'), R 12 Each independently represents a hydrogen atom or a methyl group, and M represents a copper atom or a zinc atom.

[0067] As the monomer (a1), for example, zinc diacrylate, zinc dimethacrylate, zinc methacrylate, zinc di(3-acryloyloxypropanoate), zinc di(3-methacryloyloxypropanoate), zinc di(3-(meth)acryloyloxy-2-methylpropanoate), copper diacrylate, copper dimethacrylate, copper methacrylate, copper di(3-acryloyloxypropanoate), copper di(3-methacryloyloxypropanoate), copper di(3-(meth)acryloyloxy-2-methylpropanoate) can be exemplified. Among these, from the viewpoint of being able to easily obtain an antifouling coating film or the like having sufficient antifouling properties, zinc diacrylate, zinc dimethacrylate, or zinc methacrylate is preferred. Note that zinc diacrylate, zinc dimethacrylate, zinc methacrylate, copper diacrylate, copper dimethacrylate, and copper methacrylate belong to the monomer (a1').

[0068] • Monomer (a2)

[0069] The metal-containing ester group-containing monomer (a2) is a monomer represented by the following formula (2). The monomer (a2) can be any one or two or more.

[0070]

[0071] In formula (2), R 21 represents a monovalent group containing a terminal ethylenically unsaturated group (CH2=C<), R 22 represents a monovalent organic group having 1 to 30 carbon atoms not containing a terminal ethylenically unsaturated group, and M represents a copper atom or a zinc atom.

[0072] As for technical matters related to the terminal ethylenically unsaturated group of R 21 , reference can be made directly to the technical matters related to the terminal ethylenically unsaturated group of R 11 described in relation to formula (1) in this specification.

[0073] As R 22 , for example, an aliphatic hydrocarbon group having 1 to 30 carbon atoms not containing a terminal ethylenically unsaturated group, a cycloaliphatic hydrocarbon group having 3 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and the like organic group (referred to as "non-terminal ethylenically unsaturated organic group" in this specification) can be exemplified. The non-terminal ethylenically unsaturated organic group can also contain a substituent (for example, a hydroxyl group).

[0074] The aliphatic hydrocarbon group in the non-terminal ethylenically unsaturated organic group can be either linear or branched, and can be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group (as long as it does not contain a terminal ethylenically unsaturated group). The aliphatic hydrocarbon group has 1 to 30 carbon atoms, preferably 1 to 28, more preferably 1 to 26, and further preferably 1 to 24. The aliphatic hydrocarbon group can be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

[0075] The alicyclic hydrocarbon group in the non-terminal ethylenically unsaturated organic group can be either a saturated alicyclic hydrocarbon group or an unsaturated alicyclic hydrocarbon group. The alicyclic hydrocarbon group has 3 to 30 carbon atoms, preferably 4 to 20, more preferably 5 to 16, and further preferably 6 to 12. The alicyclic hydrocarbon group can be substituted with an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0076] The aromatic hydrocarbon group in the non-terminal ethylenically unsaturated organic group has 6 to 30 carbon atoms, preferably 6 to 24, more preferably 6 to 18, and further preferably 6 to 10. The aromatic hydrocarbon group can be substituted with an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

[0077] R 22 The organic acid residue is preferably derived from a monobasic acid, and as specific examples, there can be mentioned groups obtained by removing a carboxyl group from organic acids such as versatic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, naphthenic acid, and the like, and among these, groups obtained by removing a carboxyl group from abietic acid, versatic acid, or naphthenic acid are preferred, and groups obtained by removing a carboxyl group from abietic acid or versatic acid are more preferred. Note that versatic acid is a general term for a mixture of branched carboxylic acids having 9 to 11 carbon atoms, mainly 10 carbon atoms.

[0078] As the monomer (a2), a monomer represented by the following formula (2') (hereinafter also referred to as "monomer (a2')" in the present specification) is preferred. The monomer (a2') corresponds to the terminal ethylenically unsaturated organic group of R 22 in the monomer (2). The monomer (a2') is a monomer in which the terminal ethylenically unsaturated organic group is a group obtained by removing a carboxyl group from acrylic acid or methacrylic acid.

[0079]

[0080] In formula (2'), R 23 represents a hydrogen atom or a methyl group, R 24 has the same meaning as R 22 in formula (2), and M represents a copper atom or a zinc atom.

[0081] As the monomer (a2), for example, 3-(meth)acryloyloxypropionic acid zinc abietate, 3-(meth)acryloyloxypropionic acid zinc versatate, (meth)acrylic acid zinc abietate, (meth)acrylic acid zinc versatate, (meth)acrylic acid zinc naphthenate, 3-(meth)acryloyloxypropionic acid copper abietate, 3-(meth)acryloyloxypropionic acid copper versatate, (meth)acrylic acid copper abietate, (meth)acrylic acid copper versatate, and (meth)acrylic acid copper naphthenate can be exemplified. Note that (meth)acrylic acid zinc abietate, (meth)acrylic acid zinc versatate, (meth)acrylic acid zinc naphthenate, (meth)acrylic acid copper abietate, (meth)acrylic acid copper versatate, and (meth)acrylic acid copper naphthenate belong to the monomer (a2').

[0082] • Other monomers

[0083] The polymer (A) can further contain, as needed, a monomer other than the monomer (a1) and the monomer (a2) that is copolymerizable with the monomer (a1) and / or the monomer (a2). As such an arbitrary monomer, a monomer that does not contain a metal ester group and has an ethylenically unsaturated group, for example, a silicone-oxane block-containing monomer (a3) (sometimes also referred to as "monomer (a3)" in the present specification); a (meth)acrylate or ester thereof (a4) (sometimes also referred to as "monomer (a4)" in the present specification); and a vinyl compound (a5) (sometimes also referred to as "monomer (a5)" in the present specification) can be exemplified.

[0084] • Monomer (a3)

[0085] The monomer (a3), i.e., the silicone-oxane block-containing monomer (a3), is a monomer represented by the following formula (3). The monomer (a3) can be any one or two or more.

[0086]

[0087] In formula (3), R 31 , R 32 , and R 33 each independently represent a monovalent hydrocarbon group, X each independently represents a (meth)acryloyloxyalkyl group or a mercaptoalkyl group, m is 1 or more, n is 0 or more, p and q each independently are 0 or 1, and n + p + q is 1 or more.

[0088] As the hydrocarbon group of R 31 , R 32 , and R 33 , for example, a linear, branched, or cyclic alkyl group, and an aryl group can be exemplified. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 8, and further preferably 1 to 4. The number of carbon atoms of the aryl group is preferably 6 to 14, and more preferably 6 to 10. From the viewpoint of easiness of polymerization, R 31 , R32 and R 33 each independently is an alkyl group such as a methyl group, a butyl group, and the like.

[0089] As X, for example, a (meth)acryloyloxyalkyl group such as a (meth)acryloyloxyethyl group, a (meth)acryloyloxypropyl group, a (meth)acryloyloxybutyl group, and the like; and a mercaptoalkyl group such as a mercaptomethyl group, a mercaptoethyl group, a mercaptopropyl group, a mercaptobutyl group, and the like can be exemplified. As X, from the viewpoint of performing uniform polymerization, a (meth)acryloyloxyalkyl group is preferred, and from the viewpoint of reducing the viscosity of the copolymer (A) and making the handling easy, a mercaptoalkyl group is preferred.

[0090] m and n each represent the average addition mole number of (SiR 32 2O), (SiXR 33 O). m + n is preferably 2 or more. That is, the organosiloxane block monomer (a3) is preferably a monomer containing a polyorganosiloxane block.

[0091] Note that, in the present specification, in the case where two or more different repeating units are juxtaposed between [ ] as shown in formula (3), it is meant that these repeating units can be repeated in any one of a random state, an alternating state, or a block state. That is, for example, in the case of formula -[Y3-Z3]- (here, Y and Z each represent a repeating unit), it can be in a random state such as -YYZYZZ-, it can be in an alternating state such as -YZYZYZ-, and it can be in a block state such as -YYYZZZ- or -ZZZYYY-.

[0092] As the first embodiment of the monomer (a3), a monomer (a31) in which n is 0, p is 1, and q is 0 can be exemplified. The copolymer (A) containing a structural unit derived from such a monomer (a31) is preferred because, for example, an antifouling coating composition easily forms an antifouling coating film excellent in antifouling properties. From the viewpoint of ease of polymerization and the like, m in the monomer (a31) is preferably 3 or more, more preferably 5 or more, and is preferably 200 or less, more preferably 70 or less.

[0093] As the monomer (a31), for example, the following commercially available products can be used: "FM-0711" (monoterminal methyl acryloyloxyalkyl-modified organopolysiloxane, number average molecular weight: 1000), "FM-0721" (monoterminal methyl acryloyloxyalkyl-modified organopolysiloxane, number average molecular weight: 5000), "FM-0725" (monoterminal methyl acryloyloxyalkyl-modified organopolysiloxane, number average molecular weight: 10000) manufactured by JNC Corporation; "X-22-174ASX" (monoterminal methyl acryloyloxyalkyl-modified organopolysiloxane, functional group equivalent: 900 g / mole), "KF-2012" (monoterminal methyl acryloyloxyalkyl-modified organopolysiloxane, functional group equivalent: 4600 g / mole), X-22-2426 (monoterminal methyl acryloyloxyalkyl-modified organopolysiloxane, functional group equivalent: 12000 g / mole) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0094] As the second embodiment of the monomer (a3), the monomer (a32) in which n is 0 and p and q are 1 can be exemplified. When the copolymer (A) contains a structural unit derived from such a monomer (a32), it is preferred because, for example, the antifouling coating composition is easily formed into an antifouling coating film which is excellent in repairability, i.e., adhesion to an old antifouling coating film after use (after seawater immersion). From the viewpoint of ease of polymerization and the like, m in the monomer (a32) is preferably 3 or more, more preferably 5 or more, and is preferably 200 or less, more preferably 70 or less.

[0095] As the monomer (a32), for example, the following can be used: "FM-7711" (both ends of which are modified with a methacryloxyalkyl group, number average molecular weight: 1000), "FM-7721" (both ends of which are modified with a methacryloxyalkyl group, number average molecular weight: 5000), "FM-7725" (both ends of which are modified with a methacryloxyalkyl group, number average molecular weight: 10000) manufactured by JNC Corporation; "X-22-164" (both ends of which are modified with a methacryloxyalkyl group, functional group equivalent: 190 g / mole), "X-22-164AS" (both ends of which are modified with a methacryloxyalkyl group, functional group equivalent: 450 g / mole), "X-22-164A" (both ends of which are modified with a methacryloxyalkyl group, functional group equivalent: 860 g / mole), "X-22-164B" (both ends of which are modified with a methacryloxyalkyl group, functional group equivalent: 1630 g / mole), "X-22-164C" (both ends of which are modified with a methacryloxyalkyl group, functional group equivalent: 2370 g / mole), "X-22-164E" (both ends of which are modified with a methacryloxyalkyl group, functional group equivalent: 3900 g / mole), "X-22-167B" (both ends of which are modified with a mercaptoalkyl group, functional group equivalent: 1670 g / mole) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0096] As the third embodiment of the monomer (a3), a monomer (a33) in which n is 1 or more can be exemplified. When the copolymer (A) contains a structural unit derived from such a monomer (a33), it is preferred because, for example, the viscosity of the antifouling coating composition is reduced, and the tendency for the operation to become easy is exhibited. In the monomer (a33), m is preferably from 50 to 1000, and n is preferably from 1 to 30.

[0097] As the monomer (a33), for example, the following can be used: "KF-2001" (side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent: 1900 g / mole), "KF-2004" (side chain mercaptoalkyl-modified organopolysiloxane, functional group equivalent: 30000 g / mole) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0098] • Monomer (a4)

[0099] The monomer (a4), that is, the (meth)acrylate or ester thereof (a4), is a compound represented by the following formula (4). The monomer (a4) can be any one, or two or more kinds.

[0100]

[0101] In formula (4), R41 represents a monovalent group containing an ethylenically unsaturated group, R 42 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyalkyl group, a hydroxyalkyl group, or a glycidyl group.

[0102] As a first embodiment of the monomer (a4), R 42 a monomer (a41) of which R is a hydrogen atom, for example, (meth)acrylic acid. In the case where the copolymer (A) contains such a monomer (a41), the obtained antifouling coating composition has a tendency to have excellent adhesion to an old antifouling coating film after use (after sea water immersion), low viscosity, excellent coating workability, and a tendency to have a higher degree of coating film consumption of the formed antifouling coating film.

[0103] As a second embodiment of the monomer (a4), R 42 a monomer (a42) of which R is an alkyl group or an aryl group. As the alkyl group of R 42 may have any of a linear, branched, or cyclic structure, and the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 12, and further preferably from 1 to 6. In the case where the copolymer (A) contains such a monomer (a42), the antifouling coating film formed from the obtained antifouling coating composition has a tendency to be able to suppress the degree of coating film consumption to an appropriate renewal rate without significantly impairing antifouling properties, and has a tendency to also have excellent damage resistance and / or crack resistance.

[0104] As specific examples of the monomer (a42), there can be mentioned methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, amyl (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, phenyl (meth)acrylate, and benzyl (meth)acrylate. For example, it is preferable to use at least one selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and cyclohexyl (meth)acrylate as the monomer (a42).

[0105] As a third embodiment of the monomer (a4), R 42 a monomer (a43) of which R is an alkoxyalkyl group. As the alkoxyalkyl group of R 42The alkoxyalkyl group of the monomer (a43) can have any of a linear, branched, or cyclic structure, and the number of carbon atoms (the total number of carbon atoms in the alkyl group of the alkoxy group and the alkyl group) is preferably from 1 to 20, more preferably from 1 to 12, and further preferably from 1 to 6. In the case where the copolymer (A) contains such a monomer (a43), the antifouling coating film formed from the resulting antifouling coating composition has a tendency to have a long-term appropriate degree of coating film consumption.

[0106] Specific examples of the monomer (a43) include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 3-methoxy-n-propyl (meth)acrylate, 2-propoxyethyl (meth)acrylate, 2-butoxyethyl (meth)acrylate, isobutoxybutyl diglycol (meth)acrylate, 2-phenoxyethyl (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, butoxy polyethylene glycol (meth)acrylate, and phenoxy polyethylene glycol (meth)acrylate. For example, 2-methoxyethyl (meth)acrylate is preferably used as the monomer (a43).

[0107] As the fourth embodiment of the monomer (a4), R 42 The monomer (a44) is a monomer in which R 42 The hydroxyalkyl group of the monomer (a44) can have any of a linear, branched, or cyclic structure, and the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 12, and further preferably from 1 to 6. In the case where the copolymer (A) contains such a monomer (a44), the antifouling coating film formed from the resulting antifouling coating composition has a tendency to have a higher degree of coating film consumption.

[0108] Specific examples of the monomer (a44) include hydroxymethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxy-3-phenoxypropyl (meth)acrylate.

[0109] As the fifth embodiment of the monomer (a4), R 42 The monomer (a45) is a monomer in which R

[0110] The polymer (A) preferably contains the monomer (a42) and / or the monomer (a43) among the above-mentioned monomers (a4), from the viewpoint that the antifouling coating film formed from the obtained antifouling coating composition can be appropriately adjusted in terms of coating film consumption, and has a tendency to be excellent in scratch resistance and / or crack resistance.

[0111] • Monomer (a5)

[0112] As the monomer (a5), i.e., the vinyl compound, there can be mentioned, for example, styrene, α-methylstyrene, vinyl acetate, vinyl benzoate, vinyltoluene, acrylonitrile, vinylpyridine, vinylpyrrolidone, vinyl chloride. The monomer (a5) can be any one of these, or two or more of these.

[0113] • Ratio of structural units

[0114] The kind and ratio of the structural units derived from the monomer (a1) and / or the monomer (a2) contained in the polymer (A) and the other monomers used as necessary can be appropriately adjusted in consideration of the effects of the present application, other technical matters, and the like.

[0115] For example, regarding the ratio of the structural unit derived from the monomer (a1) and / or the structural unit derived from the monomer (a2), relative to 100 mass% of the total constituting units in the copolymer (A), it is preferably 5 mass% or more, more preferably 7 mass% or more, and further preferably 9 mass% or more, and it is preferably 50 mass% or less, more preferably 40 mass% or less, and further preferably 30 mass% or less.

[0116] In addition, the polymer (A) preferably contains at least the structural unit derived from the (meth)acrylic acid ester or ester thereof (a4), and can further contain the structural unit derived from the organosiloxane block-containing monomer (a3), in addition to the structural unit derived from the monomer (a1) and / or the structural unit derived from the monomer (a2).

[0117] In the case where the polymer (A) contains the structural unit derived from the organosiloxane block-containing monomer (a3), regarding the ratio thereof, relative to 100 mass% of the total constituting units in the copolymer (A), it is preferably 5 mass% or more, more preferably 8 mass% or more, and it is preferably 20 mass% or less, more preferably 15 mass% or less.

[0118] In the case where the polymer (A) contains the structural unit derived from the (meth)acrylic acid ester or ester thereof (a4), regarding the ratio thereof, relative to 100 mass% of the total constituting units in the copolymer (A), it is preferably 3 mass% or more, more preferably 5 mass% or more, and it is preferably 95 mass% or less, more preferably 80 mass% or less, and particularly preferably 70 mass% or less.

[0119] In the case where the polymer (A) contains a structural unit derived from the vinyl compound (a4), the ratio thereof is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, particularly preferably 30% by mass or less, with respect to 100% by mass of the total constituting units in the copolymer (A).

[0120] Note that the ratio of each structural unit in the copolymer (A) can be determined by nuclear magnetic resonance spectroscopy (NMR), gas chromatography mass spectrometry (GC-MS), or the like according to a conventional method, or can be calculated from the amounts of use of each monomer used when the copolymer (A) is synthesized. In addition, the total constituting units in the copolymer (A) do not include structural units derived from a polymerization initiator and a chain transfer agent.

[0121] The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer (A) can be appropriately adjusted in a manner such that the effects of the present application are achieved to a desired extent, and in consideration of the viscosity, storage stability, coating film consumption (elution rate, renewability) of the obtained antifouling coating composition, and the like. The Mn of the polymer (A) is preferably 500 or more, more preferably 700 or more, and preferably 100,000 or less, more preferably 50,000 or less. The Mw of the copolymer (A) is preferably 1,000 or more, more preferably 1,200 or more, particularly preferably 1,500 or more, and preferably 150,000 or less, more preferably 10,000 or less, particularly preferably 7,000 or less.

[0122] Note that the Mn and the Mw can be determined by gel permeation chromatography according to a conventional method and converted using a standard polystyrene to be obtained. More specific determination methods, conditions, and the like of the Mn and the Mw can be referred to the Examples described later.

[0123] • Content of component (A)

[0124] The content of the polymer (A) can be appropriately adjusted in a manner such that the effects of the present application are achieved to a desired extent, and in consideration of the coating workability, other technical matters of the obtained antifouling coating composition, and the like, depending on the kind, properties, and the like of the component. The content of the polymer (A) is, for example, preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, with respect to 100% by mass of the solid components of the antifouling coating composition.

[0125] Note that in the present specification, the "solid content" of each component (for example, components (A) to (E), the oxidized polyethylene wax as the anti-blocking agent / settling preventing agent (G), the fatty acid amide wax, and the like) or the antifouling coating composition of the present application or each component contained therein refers to the component after removing the volatile component contained as a solvent in each component or the antifouling coating composition of the present application. Such a solid content can be calculated in the form of the ratio of the mass of the substance obtained by drying each component or the antifouling coating composition of the present application in a hot air drier at 108°C for 3 hours to the mass of each component or the antifouling coating composition of the present application. More specifically, according to JIS K 5601-1-2:2008, 1 ± 0.1 g of the measurement object is weighed into a flat-bottomed dish, spread uniformly on the bottom surface using a wire of known mass, dried at 108°C under 1 atmosphere for 3 hours, and the mass of the wire is subtracted from the obtained heated residue portion as the value of the mass percentage, whereby it is calculated. Note that as for the product of each component, in the case where the value in terms of the solid content is shown in the label, catalog, or the like, this value can be regarded as the solid content of the component. In addition, by the above measurement method, in the case where the formulation composition (the kind and amount of each component and the solid content of each component) of the antifouling coating composition of the present application is known, the value calculated based on the formulation composition can be regarded as the solid content of the antifouling coating composition of the present application.

[0126] <METAMIDOLE (B)>

[0127] Metamidole (B), the systematic name (+ / -) 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole, is a compound represented by the following structural formula. Note that metamidole (B) is a racemate (arbitrary ratio, for example, a mixture of approximately equal amounts) of (+) 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole and (-) 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole. Metamidole (B) has optical isomerism, and can be only one of them or a mixture in an arbitrary ratio. In addition, metamidole (B) can also use imidazole salt, an adduct with a metal or the like as a part or all thereof. In this case, as a raw material at the time of preparing the antifouling coating composition of the present application, imidazole salt, an adduct with a metal or the like as a part or all thereof. In this case, as a raw material at the time of preparing the antifouling coating composition of the present application, imidazole salt, an adduct with a metal or the like as a part or all thereof. In this case, as a raw material at the time of preparing the antifouling coating composition of the present application, imidazole

[0128] <BRONOPOLYACRYLONITRILE (C)>

[0129] Bromopyrrole nitrile (C), system name 4-bromo-2-(4-chlorophenyl)-5- (trifluoromethyl)-1H-pyrrole-3-carbonitrile, 2-(p-chlorophenyl)-3-cyano-4- bromo-5-trifluoromethylpyrrole is a compound represented by the following structural formula.

[0130]

[0131] Copper pyrithione (D)

[0132] Copper pyrithione (D), system name bis[1,2-dihydro-2-thioxopyridin-1-ol] copper (II) is a compound represented by the following structural formula.

[0133]

[0134] In formula (D), R 3 Each independently represents a hydrogen atom or an alkyl group, a cyclic alkyl group, an alkenyl group, an aryl group, an alkoxy group, or a haloalkyl group having 1 to 6 carbon atoms, and M is a copper atom. R 3 Preferably, it is a hydrogen atom.

[0135] Note that the antifouling coating composition of the present application contains at least metoclopramide (B), bromopyrrole nitrile (C), and copper pyrithione (D) as antifouling agents, and even if only these three antifouling agents are used, a certain level of excellent antifouling performance can be exhibited, and one or more other antifouling agents can be additionally used as needed. As antifouling agents other than metoclopramide (B), bromopyrrole nitrile (C), and copper pyrithione (D), for example, the following can be listed: cuprous oxide, pyrithione metal other than copper pyrithione (D) (for example, zinc pyrithione), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (alternative name: DCOIT), pyridine triphenylborane, 4-isopropylpyridine diphenylmethylborane, N,N-dimethyl-N'-(3,4-dichlorophenyl)urea (alternative name: Diuron), N-(2,4,6-trichlorophenyl)maleimide, 2,4,5,6-tetrachloroisophthalonitrile, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine (alternative name: Cybutryne), bisdimethyl dithiocarbamyl ethylene bisdithiocarbamic acid zinc (alternative name: Polycarbamate), chloromethyl n-octyl disulfide, N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio) sulfamide (alternative name: Dichlofluanid), tetraalkyl thiuram disulfide (alternative name: TMTD), zinc dimethyl dithiocarbamate (alternative name: Ziram), zinc ethylene bisdithiocarbamate, 2,3-dichloro-N-(2',6'-dimethylphenyl) maleimide, 2,3-dichloro-N-(2'-ethyl-6'-methylphenyl) maleimide, and the like.

[0136] However, cuprous oxide is a biocide that is high in environmental load, and the antifouling coating composition of the present application can exert excellent antifouling properties for a long period without using cuprous oxide. The content of cuprous oxide in the solid component of the antifouling coating composition of the present application is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 1% by mass or less, more further preferably 0.5% by mass or less, and particularly preferably substantially free of cuprous oxide. Note that substantially free of cuprous oxide means that cuprous oxide is not intentionally added, and does not exclude the case where a small amount of cuprous oxide is contained as an impurity.

[0137] • Contents of components (B), (C), and (D)

[0138] The contents of metomidine (B), bromopyrollitryl nitrile (C), and copper pyrithione (D) can be adjusted as appropriate in a manner such that the effects of the present application are achieved to a desired extent, and in consideration of the workability of the resulting antifouling coating composition, other technical matters.

[0139] For example, regarding the content of metomidine (B), relative to 100% by mass of copper pyrithione (D), it is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 100% by mass or less, more preferably 80% by mass or less, further preferably 50% by mass or less, and particularly preferably 10% by mass or less.

[0140] Regarding the content of bromopyrollitryl nitrile (C), relative to 100% by mass of copper pyrithione (D), it is preferably 10% by mass or more, more preferably 25% by mass or more, and preferably 1700% by mass or less, more preferably 1500% by mass or less, further preferably 1200% by mass or less, more further preferably 1000% by mass or less, and particularly preferably 100% by mass or less.

[0141] Regarding the content of copper pyrithione (D), relative to 100% by mass of the solid component of the antifouling coating composition, it is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 3.0% by mass or more, and preferably 12% by mass or less, more preferably 11% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less.

[0142] <Alkyl carboxylic acid (E)>

[0143] As the alkyl carboxylic acid (E) of 4 to 30 carbon atoms which is linear or branched, for example, versic acid, palmitic acid, stearic acid, and isostearic acid can be listed, among which, versic acid is preferred. Versic acid is a mixture of alkyl carboxylic acids having a branched chain of 5 to 15 carbon atoms, mainly 9 to 11 carbon atoms, and particularly 10 carbon atoms. The alkyl carboxylic acid (E) can be used only one kind, or two or more kinds can be used.

[0144] The alkyl carboxylic acid (E) can form a metal ester (example: copper ester). The metal ester can be formed in advance before the production of the antifouling coating composition, or can be formed at the time of the production of the antifouling coating composition by the reaction with other coating ingredients.

[0145] Note that rosin (rosin of gum rosin, wood rosin, tall oil rosin, and the like, rosin derivatives of hydrogenated rosin, disproportionated rosin, and the like) is a mixture of rosinic acid having three ring structures including a conjugated double bond and carboxyl groups and isomers thereof, and although it is a monocarboxylic acid, it does not belong to "alkyl carboxylic acid of 4 to 30 carbon atoms which is linear or branched". In addition, naphthenic acid, salicylic acid, and the like are also compounds having ring structures and carboxyl groups, and although they are monocarboxylic acids, they do not belong to "alkyl carboxylic acid of 4 to 30 carbon atoms which is linear or branched".

[0146] • Content of Component (E)

[0147] The content of the alkyl carboxylic acid (E) can be appropriately adjusted in consideration of the kind, properties, and the like of the component, and the effects of the present application, and the like. Regarding the content of the alkyl carboxylic acid (E), it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, relative to 100% by mass of the solid components of the antifouling coating composition.

[0148] <Optional Components>

[0149] The antifouling coating composition of the present application can further contain components other than the polymer (A), the metomidine (B), the bromopyrrole nitrile (C), the copper pyrithione (D), and the alkyl carboxylic acid (E) as necessary. As such optional components, for example, pigments (F), anti-sagging agents / anti-settling agents (G), solvents (H), plasticizers (I), binder components (J), and the like can be listed. Wetting dispersants, dehydrating agents, and the like can also be listed as optional components. These optional components are not essential to achieve the effects of the present application, but can be components which are naturally required or generally used at the time of implementation as an antifouling coating composition, components which can easily exert or enhance the effects of the present application, or components for exerting effects other than the present application.

[0150] <Pigments (F)>

[0151] The antifouling coating composition of the present application can contain a pigment (F) for the purpose of coloring the coating film, hiding the substrate, and / or for the purpose of adjusting the strength of the coating film to be appropriate. The pigment (F) can be used alone or two or more kinds can be used.

[0152] As the pigment (F), for example, the following can be listed: extender pigments such as zinc oxide, zinc phosphate, talc, mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate (e.g., precipitated barium sulfate), calcium sulfate (e.g., calcined gypsum), zinc sulfide, and the like; and coloring pigments such as red iron oxide (red ocher), titanium white (titanium oxide), yellow iron oxide, carbon black, naphthol red, phthalocyanine blue, and the like.

[0153] In the case where the antifouling coating composition of the present application contains the pigment (F), the content thereof can be appropriately adjusted depending on the purpose, the kind of the component, and the like, and for example, it is preferably 1 to 40 mass% with respect to 100 mass% of the solid components of the composition.

[0154] <Anti-sag agent / settling preventing agent (G)>

[0155] The antifouling coating composition of the present application can contain an anti-sag agent / settling preventing agent (G) for the purpose of adjusting the viscosity and the like of the composition. The anti-sag agent / settling preventing agent (G) can be used alone or two or more kinds can be used.

[0156] As the anti-sag agent / settling preventing agent (G), for example, the following can be listed: organic clay-based waxes (e.g., stearate salts of Al, Ca, Zn, lecithin salts, alkyl sulfonate salts), organic waxes (e.g., polyethylene wax, oxidized polyethylene wax, fatty acid amide wax, hydrogenated castor oil wax), mixtures of organic clay-based waxes and organic waxes, synthetic microfine silica. As such anti-sag agent / settling preventing agent (G), for example, the following commercially available products can be used: "Dispalon 305", "Dispalon 4200-20", "Dispalon A630-20X", "Dispalon 6900-20X" manufactured by Nankyo Chemical Process Co., Ltd.; "A-S-A D-120" manufactured by Itoh Oil & Fat Co., Ltd.; and the like.

[0157] In the case where the antifouling coating composition of the present application contains the anti-sag agent / settling preventing agent (G), the content thereof can be appropriately adjusted depending on the purpose, the kind of the component, and the like, and for example, it is preferably 0.01 mass% or more, more preferably 0.1 mass% or more, and preferably 10 mass% or less, more preferably 3 mass% or less, with respect to 100 mass% of the solid components of the composition.

[0158] <Solvent (H)>

[0159] The antifouling coating composition of the present application can contain a solvent (H) such as water or an organic solvent, for the purpose of adjusting the viscosity or the like of the composition. Note that the antifouling coating composition of the present application can be prepared using a liquid containing the copolymer (A) obtained at the time of synthesizing the copolymer (A), in which case the solvent contained in the liquid, a solvent or the like added additionally when mixing the copolymer (A) with the other necessary components (B) to (E) and the optional components as needed, corresponds to the solvent (H). The solvent (H) can be used as only one kind, or two or more kinds. As the solvent (H), an organic solvent is preferred.

[0160] As the organic solvent, for example, aromatic organic solvents such as xylene, toluene, ethylbenzene, and the like; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; aliphatic (carbon number 1 to 10, preferably about 2 to about 5) monohydric alcohols such as ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, propylene glycol monomethyl ether, and the like; ester solvents such as ethyl acetate, butyl acetate, and the like can be exemplified.

[0161] In the case where the antifouling coating composition of the present application contains the solvent (H), the content thereof can be adjusted as appropriate according to the purpose, the kind of the component, or the like, and for example, relative to 100% by mass of the composition, it is preferably 0 to 50% by mass.

[0162] <Plasticizer (I)>

[0163] The antifouling coating composition of the present application can contain a plasticizer (I) for the purpose of imparting plasticity or the like to the antifouling coating film formed. The plasticizer (I) can be used as only one kind, or two or more kinds.

[0164] As the plasticizer (I), for example, chlorinated paraffin, n-paraffin, tricresyl phosphate (TCP), dioctyl phthalate (DOP), diisodecyl phthalate (DIDP), and the like can be exemplified, with chlorinated paraffin and TCP being preferred.

[0165] The chlorinated paraffin can have either of a linear or branched molecular structure, and can be in a liquid state or in a solid state (for example, in a powder form) at room temperature (for example, 23°C).

[0166] The average number of carbon atoms in one molecule of the chlorinated paraffin is preferably 8 or more, more preferably 10 or more, and is preferably 30 or less, more preferably 26 or less. When the average number of carbon atoms is less than 8, sometimes the effect of suppressing the generation of cracks in the antifouling coating film formed is insufficient, on the other hand, when the average number of carbon atoms is more than 30, the hydrolyzability (coating film consumption, renewability, polishing cleanability) of the antifouling coating film formed becomes too small, and as a result, sometimes the antifouling property is poor.

[0167] The viscosity of the chlorinated paraffin (unit: poise, measurement temperature: 25°C) is preferably 1 or more, more preferably 1.2 or more. The specific gravity (25°C) is preferably 1.05 g / cm 3 or more, more preferably 1.10 g / cm 3 or more, and preferably 1.80 g / cm 3 or more, and preferably 1.80 g / cm 3 or more.

[0168] The chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 to 70 mass% when the chlorinated paraffin is set to 100 mass%, and is preferably 35 to 65 mass%.

[0169] In the case where the antifouling coating composition of the present application contains the plasticizer (I), the content thereof is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and preferably 10 mass% or less, more preferably 5 mass% or less, with respect to 100 mass% of the solid content of the antifouling coating composition of the present application, from the viewpoint of being able to favorably maintain the plasticity and the like of the antifouling coating film.

[0170] <Binder component (J)>

[0171] The antifouling coating composition of the present application can contain a binder component (J) for the purpose of imparting water resistance, crack resistance, strength, and the like to the formed antifouling coating film. Note that the binder component (J) refers to a component other than the polymer (A) in the binder component. The binder component (J) can be used alone or two or more kinds can be used.

[0172] As the binder component (J), for example, a polyester-based polymer, a (meth)acrylic-based polymer (copolymer), a vinyl-based polymer (copolymer), a terpene phenol resin, a petroleum resin, a ketone resin can be exemplified. Among these, a polyester-based polymer, a (meth)acrylic-based polymer (copolymer), a vinyl-based polymer (copolymer), a petroleum resin are preferred, and a polyester-based polymer, a petroleum resin are more preferred.

[0173] In the case where the antifouling coating composition of the present application contains the binder component (J), the content thereof can be appropriately adjusted depending on the purpose, the kind of the component, and the like, and is, for example, preferably 0.1 to 40 mass% with respect to 100 mass% of the solid content of the composition.

[0174] <Method for producing the antifouling coating composition>

[0175] The antifouling coating composition of the present application can be prepared by the same means (apparatus, method, conditions, etc.) as the usual antifouling coating composition using the components (A) to (E) and other optional components as needed. Specifically, it can be prepared by adding the resultant copolymer (A) (solution thereof), metyridylol (B), bromopyrrole nitrile (C), copper pyrithione (D), and alkyl carboxylic acid (E) and other optional components as needed, either all at once or sequentially, to a container after the synthesis of the copolymer (A), and stirring and mixing.

[0176] - Antifouling coating film -

[0177] The antifouling coating film of the present application is formed from the antifouling coating composition of the present application. As in the case of the existing antifouling coating film formed from the existing antifouling coating composition, the antifouling coating film of the present application is formed by drying the antifouling coating composition of the present application. However, the antifouling coating film of the present application is not limited to the antifouling coating film just formed from the antifouling coating composition of the present application, but also includes the antifouling coating film degraded due to use. As for the antifouling coating film of the present application, the antifouling coating film just formed contains the same substances as the antifouling coating composition of the present application except for the volatile components such as solvents lost due to drying or the like, and the antifouling coating film after use contains the same substances as the antifouling coating composition of the present application except for the volatile components and a part of the components lost (released) due to the volatilization of the antifouling properties.

[0178] The thickness of the antifouling coating film of the present application is not particularly limited, and can be set within an appropriate range according to the properties (e.g., coating film consumption rate) of the antifouling coating film of the present application, the use (kind of substrate, period of use, etc.), for example, preferably 30 to 1000 μm as the thickness in the state just after formation.

[0179] - Substrate with antifouling coating film -

[0180] The substrate with antifouling coating film of the present application has a substrate and the antifouling coating film of the present application. The antifouling coating film of the present application is usually formed on the substrate, and used as the substrate with antifouling coating film.

[0181] The substrate is not particularly limited as long as it is a substrate capable of forming the antifouling coating film of the present application and capable of functioning, and examples thereof include a ship (e.g., a hull outer plate of a large steel ship such as a container ship, an oil tanker, a bulk carrier, a fishing boat, an FRP ship, a wooden ship, a yacht, etc., a ship body of any one of a new ship or a repaired ship), a fishery or other marine resource (e.g., a rope, a fishing net, fishing tackle, a float, a buoy, a diving suit, diving goggles, an oxygen cylinder, swimwear, a torpedo), a structure in water (e.g., a structure such as an oil pipeline, a water guide pipe, a circulating water pipe, a water supply and drainage port of a thermal power plant and a nuclear power plant, an undersea cable, a sea water utilization equipment (a sea water pump, etc.), a giant float, a coastal road, an undersea tunnel, a harbor equipment, a canal and a waterway, etc., various structures for underwater civil engineering in the same), and the like. In view of the effects of the present application, as the substrate, a ship (a new ship or a ship after running) is preferable, and a large steel ship such as a container ship, an oil tanker, a bulk carrier, etc., which repeatedly performs long-distance navigation and berthing, is particularly preferable.

[0182] The substrate can be a substrate on which a coating film other than the antifouling coating film (non-antifouling coating film) such as a rust preventive, another treatment agent, a rust preventive coating film (e.g., zinc-rich paint), an anticorrosive coating film (e.g., an epoxy-based heavy-duty anticorrosive paint), an adhesive coating film, or the like is formed, or a substrate on which the antifouling coating film of the present application after deterioration, deterioration, or consumption, an antifouling coating film formed of another antifouling coating composition (old antifouling coating film). In the substrate with the antifouling coating film of the present application, the antifouling coating film does not necessarily have to be formed in direct contact with the surface of the substrate, and can be formed on the substrate with the treatment agent, another coating film, or the like interposed therebetween. Therefore, the substrate with the antifouling coating film of the present application can contain another treatment agent, a coating film, or the like, in addition to the substrate and the antifouling coating film of the present application. The antifouling coating film of the present application can be formed on various non-antifouling coating films, deteriorated antifouling coating films, or the like.

[0183] The "non-antifouling coating film" possessed by the substrate refers to a coating film other than the antifouling coating film, such as a base coating film, a middle coating film, or the like, which is formed on the substrate in advance before the antifouling coating film of the present application is formed, depending on the kind and use of the substrate. The kind of the non-antifouling coating film is not particularly limited, and examples thereof include a rust preventive coating film formed of a rust preventive paint, an anticorrosive coating film formed of an anticorrosive paint, an adhesive coating film formed of an adhesive paint, and the like. As the anticorrosive coating film, an anticorrosive coating film formed of an anticorrosive paint containing an epoxy-based resin can be cited, for example. As the adhesive coating film, an adhesive coating film formed of an adhesive paint containing one or two or more kinds of resins such as an epoxy-based resin, a vinyl-based resin, a (meth)acrylic-based resin, or the like can be cited, for example. Note that, when applied to a substrate such as a ship, there is no clear distinction between the anticorrosive coating film (base coating film) and the adhesive coating film (middle coating film), and a coating film serving both functions is sometimes used, but the "non-antifouling coating film" can also be an adhesive coating film having both the functions of such an anticorrosive coating film.

[0184] The "old antifouling coating film" possessed by the substrate means an antifouling coating film after use in contact with water (sea water) for a certain period (e.g., the service life of the antifouling coating film), and is an antifouling coating film in a state of deterioration, degeneration or consumption compared with the sound antifouling coating film before use (before sea water immersion). The degree of deterioration, degeneration or consumption of the antifouling coating film is not particularly limited, and is only required to be a degree in which it is considered necessary or preferable to form the antifouling coating film of the present application. The kind of the antifouling coating film is not particularly limited, and can be the antifouling coating film of the present application or another antifouling coating film. As the antifouling coating film, for example, a hydrolytic type (e.g., a coating film formed from a silyl ester resin-based antifouling paint), a hydration decomposition type (e.g., a coating film formed from a chloroethylene-isobutyl vinyl ether resin-based antifouling paint) can be exemplified.

[0185] - Method for producing a substrate with an antifouling coating film -

[0186] The method for producing a substrate with an antifouling coating film of the present application comprises the following steps (1) and (2):

[0187] (1) a step of applying the antifouling coating material composition of the present application to a substrate or impregnating the substrate with the antifouling coating material composition to obtain an applied body or an impregnated body;

[0188] (2) a step of drying the applied body or the impregnated body.

[0189] The application in the step (1) can be performed according to a general method, and for example, a method of applying the antifouling coating material composition to the substrate using an airless sprayer, an air sprayer, a brush, a roller or the like can be used. The impregnation in the step (1) can also be performed according to a general method, and for example, a method of immersing the substrate in the antifouling coating material composition can be used.

[0190] The conditions of the application or the impregnation can also be adjusted in consideration of the drying conditions in the step (2) so as to enable the formation of an antifouling coating film having a target thickness. For example, an appropriate amount of the antifouling coating material composition can be applied or impregnated to the substrate per unit area in such a manner that the thickness of the dried coating film after the step (2) becomes 10 to 300 μm, preferably 30 to 200 μm.

[0191] The drying in the step (2) can be performed according to a general method at an appropriate temperature, other environment for an appropriate time. For example, a method of leaving the applied body or the impregnated body obtained by the step (1) at ordinary temperature (e.g., 25°C) for preferably 0.5 to 14 days, more preferably 1 to 7 days can be exemplified. The drying in this step can be performed with heating or while air blowing.

[0192] The processes (1) and (2) can be repeated as necessary. For example, in the case where the antifouling coating film of the desired thickness cannot be formed by performing the processes (1) and (2) only once, the processes (1) and (2) can be performed a second time after the first processes (1) and (2), and the processes (1) and (2) can be further performed as necessary.

[0193] In one embodiment of the present application, the method for producing the substrate with an antifouling coating film of the present application includes, as the process (1), a process of applying the antifouling coating material composition of the present application to a substrate having an old antifouling coating film or impregnating the antifouling coating material composition into a substrate having an old antifouling coating film to obtain an applied body or an impregnated body. In this embodiment, a process necessary before the process (1) can also be included, for example, a process of removing dirt on the surface of the old antifouling coating film by water washing or the like and drying. Note that, in the case of using an existing antifouling coating material composition, a process of removing the old antifouling coating film is sometimes necessary because of poor adhesion to the old antifouling coating film, but since the antifouling coating material composition of the present application has excellent adhesion to various old antifouling coating films, such a removal process can be omitted.

[0194] -Method for preventing fouling of a substrate-

[0195] The method for preventing fouling of a substrate of the present application includes a process of forming the antifouling coating film of the present application on at least a part of the substrate.

[0196] In the substrate, the part on which the antifouling coating film of the present application is formed is not particularly limited and can be appropriately selected depending on the use. For example, in the case where the substrate is a ship, the bottom portion (permanent immersion portion) exposed to a biological fouling environment and the waterline portion (wet-dry portion) can be set as the part (a part of the substrate) on which the antifouling coating film of the present application is formed.

[0197] The process of forming an antifouling coating film in the method for preventing fouling of a substrate is basically the same as the above-described processes (1) and (2) in the method for producing a substrate with an antifouling coating film. That is, the method for preventing fouling of a substrate of the present application includes, in other words, (1') a process of applying the antifouling coating material composition of the present application to at least a part of a substrate or impregnating the antifouling coating material composition into at least a part of a substrate to obtain an applied body or an impregnated body; and (2') a process of drying the above-mentioned applied body or impregnated body.

[0198] Further, in the present specification, the technical matters described with respect to the method for producing a substrate with an antifouling coating film can be appropriately replaced with technical matters with respect to the method for preventing fouling of a substrate. For example, in correspondence with the embodiment in which the substrate is a substrate having a deteriorated antifouling coating film, the method for preventing fouling of a substrate of the present application can be replaced with a method for repairing a substrate with a deteriorated antifouling coating film.

[0199] Examples

[0200] (1) Production Example of the synthesis of the metal ester group-containing monomer

[0201] [Production Example M1] Production of metal ester group-containing monomer mixture solution (M-1)

[0202] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer, PGM 85.4 parts and zinc oxide 40.7 parts were charged, and while stirring, the temperature was raised to 75°C. Next, a mixture containing methacrylic acid 43.1 parts, acrylic acid 36.1 parts, and water 5 parts was added at a constant rate from the dropping funnel over 3 hours. Further stirring was performed for 2 hours, and then PGM 36 parts was added to obtain a transparent metal ester group-containing monomer mixture solution (M-1). The solid content in this solution (M-1) was 44.8 mass%. Note that this solution (M-1) contains zinc diacrylate, zinc dimethacrylate, and zinc methacrylate which belong to compound (1') as a mixture of metal ester group-containing monomers (al).

[0203] [Production Example M2] Production of metal ester group-containing monomer mixture solution (M-2)

[0204] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer, PGM 72.4 parts and zinc oxide 40.7 parts were charged, and while stirring, the temperature was raised to 75°C. Next, a mixture containing methacrylic acid 30.1 parts, acrylic acid 25.2 parts, and tertiary carbonic acid 51.6 mass parts was added at a constant rate from the dropping funnel over 3 hours. Further stirring was performed for 2 hours, and then PGM 11 parts was added to obtain a transparent metal ester group-containing monomer mixture solution (M-2). The solid content in this solution (M-2) was 59.6 mass%. Note that this solution (M-2) contains zinc diacrylate, zinc dimethacrylate, and zinc methacrylate which belong to compound (1') and zinc (meth)acrylate tertiary carbonic acid which belongs to monomer (2') as a mixture of metal ester group-containing monomers (al) and (a2).

[0205] [Production Example M3] Production of metal ester group-containing monomer mixture solution (M-3)

[0206] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, PGM 59.9 parts and zinc oxide 40.7 parts were charged, and while stirring, the temperature was raised to 75°C. Next, a mixture containing methacrylic acid 43 parts, acrylic acid 36 parts and water 5 parts was added dropwise at a constant rate from the dropping funnel over 3 hours. Further stirring was conducted for 2 hours, and then PGM 29.4 parts was added to obtain a transparent ester group-containing monomer mixture solution (M-3) containing metal. The solid content of this solution (M-3) was 55.1 mass%. Note that this solution (M-3) contains zinc diacrylate, zinc dimethacrylate and zinc methacrylate which are compounds (1') as the ester group-containing monomer mixture (al) containing metal.

[0207] (2) Production Example of the Synthesis of the Ester Group-Containing Hydrolyzable Copolymer

[0208] [Production Example Al] Production of Hydrolyzable Copolymer Solution (A-1)

[0209] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, PGM 59.9 parts and zinc oxide 40.7 parts were charged, and while stirring, the temperature was raised to 75°C. Next, a mixture containing methacrylic acid 43 parts, acrylic acid 36 parts and water 5 parts was added dropwise at a constant rate from the dropping funnel over 3 hours. Further stirring was conducted for 2 hours, and then PGM 29.4 parts was added to obtain a transparent ester group-containing monomer mixture solution (M-3) containing metal. The solid content of this solution (M-3) was 55.1 mass%. Note that this solution (M-3) contains zinc diacrylate, zinc dimethacrylate and zinc methacrylate which are compounds (1') as the ester group-containing monomer mixture (al) containing metal.

[0210] [Production Example Al] Production of Hydrolyzable Copolymer Solution (A-1)

[0211] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 10 parts of PGM, 63 parts of xylene and 3 parts of ethyl acrylate (EA) were charged, and while stirring, the temperature was raised to 100 ± 5°C. While maintaining the temperature, 50.3 parts of the above-mentioned metal ester group-containing monomer mixture solution (M-2), 9 parts of methyl methacrylate (MMA), 58 parts of ethyl acrylate (EA), 5 parts of 2,2'-azobis(2-methylbutyronitrile) (AMBN) and 10 parts of PGM were added dropwise over 4 hours using the dropping funnel. After the dropwise addition was completed, 0.5 part of a polymerization initiator, t-butyl peroctoate, and 7 parts of xylene were added dropwise over 30 minutes, and further stirring was carried out for 1 hour and 30 minutes, and then 12 parts of xylene was added to obtain a light yellow transparent hydrolyzable copolymer solution (A-2).

[0212] [Production Example A3] Production of Hydrolyzable Copolymer Solution (A-3)

[0213] Into a pressurizable polymerization autoclave equipped with a cooler, a thermometer, a dropping tank and a stirrer, 10 parts of PGM, 35 parts of xylene and 4 parts of ethyl acrylate (EA) were charged, and while stirring, the temperature was raised to 135°C under pressurization to 350 kPa. Next, 15 parts of methyl methacrylate (MMA), 48 parts of ethyl acrylate (EA), 15 parts of n-butyl acrylate (n-BA), 40 parts of the above-mentioned metal ester group-containing monomer mixture solution (M-3), 10 parts of xylene, 1.8 parts of "Nofmer MSD", 4 parts of 2,2'-azobisisobutyronitrile (AIBN) and 2 parts of 2,2'-azobis(2-methylbutyronitrile) (AMBN) were added dropwise at a constant rate from the dropping tank over 2.5 hours. After the dropwise addition was completed, the temperature was lowered to 110°C over 30 minutes, 0.5 part of t-butyl peroctoate and 5 parts of xylene were added dropwise over 30 minutes, and further stirring was carried out for 1 hour and 30 minutes, and then 3 parts of xylene was added. The obtained mixture was filtered with a 300-mesh screen, whereby a hydrolyzable copolymer solution (A-3) was obtained as a light yellow transparent filtrate having no undissolved matter.

[0214] [Production Example A4] Production of Hydrolyzable Copolymer Solution (A-4)

[0215] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 15 parts of n-butanol, 56 parts of xylene and 4 parts of ethyl acrylate (EA) were charged, and while stirring, the temperature was raised to 100°C. Next, from the dropping funnel, 12.5 parts of n-butyl acrylate (BA), 30.2 parts of methyl methacrylate (MMA), 23.2 parts of ethyl acrylate, 6 parts of 2-methoxyethyl acrylate (2-MEA), 10 parts of "X-22-174ASX" (product name, manufactured by Shin-etsu Chemical Co., Ltd.), 31.3 parts of the above-mentioned solution of metal ester group-containing monomer mixture (M-l), 10 parts of xylene, 0.8 part of "Nofmer MSD", 1 part of 2,2'-azobisisobutylonitrile (AIBN) and 8 parts of 2,2'-azobis(2-methylbutylonitrile) (AMBN) were added dropwise at a constant rate over 6 hours. After the completion of the dropwise addition, 2 parts of t-butyl peroctoate (TBPO) and 7 parts of xylene were added dropwise over 90 minutes, and further stirring was carried out for 60 minutes, and then 7.5 parts of xylene was added to obtain a colorless transparent hydrolyzable copolymer solution (A-4).

[0216] [Production Example A5] Production of Hydrolyzable Copolymer Solution (A-5)

[0217] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 15 parts of n-butanol, 56 parts of xylene and 4 parts of ethyl acrylate (EA) were charged, and while stirring, the temperature was raised to 100°C. Next, from the dropping funnel, 12.5 parts of n-butyl acrylate (BA), 30.2 parts of methyl methacrylate (MMA), 23.2 parts of ethyl acrylate, 6 parts of 2-methoxyethyl acrylate (2-MEA), 10 parts of "X-22-174ASX" (product name, manufactured by Shin-etsu Chemical Co., Ltd.), 31.3 parts of the above-mentioned solution of metal ester group-containing monomer mixture (M-l), 10 parts of xylene, 0.8 part of "Nofmer MSD", 1 part of 2,2'-azobisisobutylonitrile (AIBN) and 8 parts of 2,2'-azobis(2-methylbutylonitrile) (AMBN) were added dropwise at a constant rate over 6 hours. After the completion of the dropwise addition, 2 parts of t-butyl peroctoate (TBPO) and 7 parts of xylene were added dropwise over 90 minutes, and further stirring was carried out for 60 minutes, and then 7.5 parts of xylene was added to obtain a colorless transparent hydrolyzable copolymer solution (A-4).

[0218] [Production Example A6] Production of Hydrolyzable Copolymer Solution (A-6)

[0219] Into a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, 15 parts of n-butanol, 36 parts of xylene and 4 parts of ethyl acrylate (EA) were charged, and while being stirred, the temperature was raised to 100°C. Next, 7.5 parts of n-butyl acrylate (n-BA), 21 parts of methyl methacrylate (MMA), 30.9 parts of ethyl acrylate (EA), 12.5 parts of cyclohexyl methacrylate (CHMA), 10 parts of "X-22-174ASX", 31.3 parts of the above-mentioned solution of the metal-containing ester group-containing monomer mixture (M-1), 0.8 part of "Nofmer MSD", 1 part of 2,2'-azobisisobutyronitrile (AIBN) and 10 parts of 2,2'-azobis(2-methylbutyronitrile) (AMBN) were uniformly dropped from the dropping funnel over 6 hours. After the dropping was completed, 2 parts of t-butyl peroctoate (TBPO) and 7 parts of xylene were dropped over 90 minutes, and further stirred for 60 minutes, and then 13.5 parts of xylene was added to obtain a colorless transparent hydrolyzable copolymer solution (A-6).

[0220] Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw) of copolymer

[0221] The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the copolymer contained in the hydrolyzable copolymer solutions (A-1) to (A-6) were measured by gel permeation chromatography (GPC) based on the following conditions.

[0222] Apparatus: "HLC-8320GPC" (manufactured by Tosoh Corporation)

[0223] Column: "TSKgel G4000HXL G2000HXL" (manufactured by Tosoh Corporation, size 7.8 mm ID x 30 cm L)

[0224] Eluent: THF (1 mmol of citric acid)

[0225] Flow rate: 1.000 ml / minute

[0226] Detector: RI

[0227] Column oven temperature: 40°C

[0228] Standard substance: Polystyrene

[0229] Sample preparation method: To the copolymer solution prepared in each production example, 1 mmol of THF (tetrahydrofuran) with citric acid was added, and diluted so that the solid content concentration of the copolymer would be 0.4% by weight, and then filtered with a membrane filter, and the obtained filtrate was used as a GPC measurement sample.

[0230] Information (monomers and properties) on the hydrolyzable copolymer solutions (A-1) to (A-6) is shown in Table 1.

[0231]

[0232] (3) Preparation of the antifouling coating composition of Examples 1 to 23 and Comparative Examples 1 to 6

[0233] In a plastic container, 6.5 parts of xylene as a solvent, 3 parts of "propylene glycol monomethyl ether" (product name, propylene glycol monomethyl ether), 0.5 parts of tertiary carbonic acid, 1 part of chlorinated paraffin, and 35 parts of the hydrolyzable polymer solution (A-3) were added, and mixed using a shaker until each component was uniformly dispersed or dissolved. Then, further, 10 parts of talc, 25 parts of zinc oxide, 2 parts of red iron oxide, 5 parts of precipitated barium sulfate, 2 parts of calcined gypsum, 5 parts of copper pyrithione, 0.5 parts of metomidine, 2.5 parts of bromopyrollnitrile, and 1 part of an oxidized polyethylene wax were added to the plastic container, and the components were dispersed by stirring for 1 hour using a shaker. After the dispersion, 1 part of a fatty acid amide wax was further added, and stirred for 20 minutes using a shaker, and then the mixture was filtered using a filter screen (pore size: 80 mesh) to remove the residue, thereby obtaining the metal ester-based antifouling coating composition of Example 1 as a filtrate.

[0234] The metal ester-based antifouling coating compositions of Examples 2 to 23 and Comparative Examples 1 to 6 were obtained by the same preparation method as described above, except that the blending amounts of each component were changed as described in Table 2.

[0235] Note that the blending amounts of each component described in Table 2 represent the blending amounts in wet weight. For example, the fatty acid amide wax in Example 1 has a blending amount of 1 part in wet weight (as a whole), and the solid content is 20% by mass, so the blending amount of the fatty acid amide wax is 0.2 parts.

[0236] (4) Evaluation test

[0237] (4-1) Static antifouling performance after sailing (dynamic immersion)

[0238] A sandblasted steel plate (length 170 mm x width 70 mm x thickness 2.3 mm) prepared for bending processing was made capable of being installed on the side surface of a rotating drum provided on a test raft moored in the Hiroshima Bay. An epoxy anticorrosive paint (manufactured by China Paint Co., Ltd., "Banno 500") was applied to the sandblasted steel plate in a dry film thickness of 150 μm, and then dried at room temperature for 1 day to form a coating film. An epoxy adhesive paint (manufactured by China Paint Co., Ltd., "Banno 500N") was applied to the surface of the anticorrosive coating film in a dry film thickness of 100 μm, and dried at room temperature for 1 day. Further, each antifouling paint composition prepared in the examples and comparative examples was applied to the coating film in a dry film thickness of 100 μm, and dried at room temperature for 7 days to produce a test plate 1 with an antifouling coating film.

[0239] First, the above test plate 1 with an antifouling coating film was installed on the rotating drum, assuming the sailing of an actual ship, and continuously rotated at a circumferential speed of 10 kt for 6 months to dynamically immerse the test plate as a whole in seawater according to the dynamic antifouling property test. Next, the test plate 1 with an antifouling coating film after dynamic immersion was set on the test raft in the Hiroshima Bay so as to immerse the test plate as a whole in seawater, and the static antifouling property test was carried out for 6 months and 12 months. The area of attachment of aquatic organisms on each antifouling coating film after 6 months and 12 months was measured, and the static antifouling property of the antifouling coating film after sailing (dynamic immersion) was evaluated according to the following evaluation criteria of antifouling performance.

[0240] (4-2) Static antifouling performance of wet-dry cycle portion

[0241] An epoxy anticorrosive paint (manufactured by China Paint Co., Ltd., "Banno 500") was applied to a sandblasted steel plate (length 300 mm x width 100 mm x thickness 2.3 mm) in a dry film thickness of 150 μm, and then dried at room temperature for 1 day to form a coating film. An epoxy adhesive paint (manufactured by China Paint Co., Ltd., "Banno 500N") was applied to the surface of the anticorrosive coating film in a dry film thickness of 100 μm, and dried at room temperature for 1 day. Further, each antifouling paint composition prepared in the examples and comparative examples was applied to the coating film in a dry film thickness of 100 μm, and dried at room temperature for 7 days to produce a test plate 2 with an antifouling coating film.

[0242] The above test plate 2 with an antifouling coating film was set on the test raft in the Hiroshima Bay so as to immerse half of the test plate in seawater, and the static antifouling property test was carried out for 6 months and 12 months. The area of attachment of aquatic organisms on each antifouling coating film after 6 months and 12 months was measured, and the static antifouling property of the antifouling coating film of the wet-dry cycle portion was evaluated according to the following evaluation criteria of antifouling performance.

[0243] <Evaluation criteria for antifouling performance / 0, 1, and 2 points are considered passing scores>

[0244] 0: No marine organisms attached

[0245] 1: The attachment area of ​​marine organisms is less than 1% of the total

[0246] 2: The attachment area of ​​marine organisms is more than 1% and less than 10% of the total area

[0247] 3: The attachment area of ​​marine organisms is more than 10% and less than 30% of the total area

[0248] 4: The attachment area of ​​marine organisms is more than 30% and less than 70% of the total area

[0249] 5: The attachment area of ​​marine organisms is more than 70% of the total

[0250] (4-3) Adhesion performance on adhesive coating (60°C × 2 days drying)

[0251] An epoxy anticorrosion coating ("Banno 500," manufactured by China Paint Co., Ltd.) was applied to a sandblasted steel plate (150 mm long, 70 mm wide, and 2.3 mm thick) to a dry film thickness of 150 μm, followed by drying at room temperature for one day to form a coating film. An epoxy adhesive coating ("Banno 500N," manufactured by China Paint Co., Ltd.) was applied to the surface of this anticorrosion coating film to a dry film thickness of 100 μm, followed by drying at 40°C for one day. Furthermore, each of the antifouling coating compositions prepared in the Examples and Comparative Examples was applied to this coating film to a dry film thickness of 100 μm, followed by drying at 60°C for two days to produce a test plate 3 with an antifouling coating film.

[0252] According to JIS K 5600-5-3:1999, 6. DuPont formula, a 1000 g weight was dropped from a height of 50 cm onto the antifouling coating-coated test plate 3. The coating surface after the weight was dropped was visually evaluated for cracking according to the following adhesion performance evaluation criteria.

[0253] <Evaluation criteria for adhesion performance / 0, 1, and 2 points are considered passing scores>

[0254] 0: No cracking or peeling on the coating surface

[0255] 1: Peeling occurs on the coating surface, and the maximum length of peeling measured at the center point of a falling weight is less than 10 mm

[0256] 2: Peeling occurs on the coating surface, with the maximum length being 10 mm or more and less than 20 mm

[0257] 3: Peeling occurs on the coated surface, and the maximum length is 20 mm or more and less than 30 mm

[0258] 4: Peeling occurs on the coated surface, and the maximum length is 30 mm or more and less than 40 mm

[0259] 5: Peeling occurs on the coated surface, and the maximum length is 40 mm or more

[0260] (4-4) Adhesion to the adhesive substrate (immersion in natural seawater at 40°C for 3 months)

[0261] The test plate 2 with the antifouling coating film was immersed in natural seawater at 40°C for 3 months, and then cut at intervals of 5 mm by a method based on JIS K 5600-5-6: 1999, and evaluated according to the following evaluation criteria for adhesion.

[0262] < Evaluation Criteria for Adhesion / 0, 1, 2 Points are Pass>

[0263] 0: No peeling

[0264] 1: Peeling area is less than 5% of the whole

[0265] 2: Peeling area is 5% or more and less than 10% of the whole

[0266] 3: Peeling area is 10% or more and less than 30% of the whole

[0267] 4: Peeling area is 30% or more and less than 70% of the whole

[0268] 5: Peeling area is 70% or more of the whole

[0269] (4-5) Adhesion to deteriorated coating film

[0270] An epoxy-based anticorrosive paint (manufactured by China Coatings Co., Ltd., "Banno 500") was applied to a sandblasted steel plate (length 300 mm x width 100 mm x thickness 2.3 mm) so as to have a dry film thickness of 150 μm, and then allowed to stand at room temperature for 1 day to form a coating film. An epoxy-based adhesive paint (manufactured by China Coatings Co., Ltd., "Banno 500N") was applied to the surface of the anticorrosive coating film so as to have a dry film thickness of 100 μm, and allowed to dry at room temperature for 1 day. Further, each of the silyl ester resin-based antifouling paint composition, the vinyl chloride-isobutyl vinyl ether resin-based antifouling paint composition, and the antifouling paint composition prepared in the examples and comparative examples was applied to the coating film so as to have a dry film thickness of 100 μm, and allowed to dry at room temperature for 7 days, and then immersed in natural seawater at 40°C for 3 months to produce test plates 1 to 3 with deteriorated coating films.

[0271] The test panels 1 to 3 with the deteriorated coating films were subjected to water washing at a pressure of 80 kgf / cm 2

[0272]

[0273] 0: no peeling

[0274] 1: peeling area less than 5% of the whole

[0275] 2: peeling area 5% or more but less than 10% of the whole

[0276] 3: peeling area 10% or more but less than 30% of the whole

[0277] 4: peeling area 30% or more but less than 70% of the whole

[0278] 5: peeling area 70% or more of the whole

[0279] Note that the above silyl ester resin-based antifouling coating composition was prepared according to the following Production Example X, and the above vinyl chloride-isobutyl vinyl ether resin-based antifouling coating composition was prepared according to the following Production Example Y. The test panel 1 with the deteriorated coating film refers to a test panel on which a silyl ester resin-based antifouling coating film was formed, the test panel 2 with the deteriorated coating film refers to a test panel on which a vinyl chloride-isobutyl vinyl ether resin-based antifouling coating film was formed, and the test panel 3 with the deteriorated coating film refers to a test panel on which an antifouling coating film described in the examples and comparative examples was formed.

[0280] [Production Example X] Silyl ester resin-based antifouling coating composition

[0281] ​​The following reaction was carried out under normal pressure under a nitrogen atmosphere. Into a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel were charged 428.6 parts of xylene and 100 parts of triisopropylsilyl methacrylate (TIPSMA), and while stirring with the stirrer, the liquid was heated to 80°C. While maintaining the liquid temperature in the reaction vessel at 80 ± 5°C, a mixture containing 500 parts of triisopropylsilyl methacrylate (TIPSMA), 250 parts of 2-methoxyethyl methacrylate (MEMA), 100 parts of methyl methacrylate (MMA), 50 parts of butyl acrylate (BA), and 13 parts of 2,2'-azobisisobutyronitrile (AIBN) was added dropwise from the dropping funnel into the reaction vessel over 2 hours. After the dropwise addition was completed, the reaction liquid was stirred at 80°C for 1 hour and at 80 to 95°C for 1 hour and 30 minutes. Then, while maintaining 95°C, 1 part of AIBN was added to the reaction liquid every 30 minutes for a total of 4 times, the liquid temperature was raised to 105°C, and the polymerization reaction was completed. Next, 238 parts of xylene was added to the reaction vessel, and the liquid was stirred until it became uniform, to obtain a copolymer solution (X1) having a solid content of 61.1 mass% and a viscosity of 1498 mPa-s. The Mw of the copolymer contained in this copolymer solution (X1) was 31213.

[0282] Into a plastic container were added 8.5 parts of xylene as a solvent, 1 part of an aromatic hydrocarbon solvent (Solvesso No. 100, manufactured by Exxon Mobil Corporation), 2.5 parts of rosin, 0.5 part of an alkoxysilane (Ethyl Silicate 28, manufactured by Colcoat Corporation), and 21 parts of the copolymer solution (X1), and these were mixed using a paint shaker until the respective components were uniformly dispersed or dissolved. Then, 4 parts of talc, 4 parts of zinc oxide, 50 parts of cuprous oxide (NC-301), 1.5 parts of red iron oxide, 2.5 parts of titanium oxide (Tipaque PFC105, manufactured by Seido Chemical Industry Co., Ltd.), 2 parts of copper pyrithione, and 1 part of oxidized polyethylene wax were further added to the plastic container, and these components were dispersed by stirring using a paint shaker for 1 hour. After the dispersion, 1.5 parts of a fatty acid amide wax was further added, and stirring was performed using a paint shaker for 20 minutes, and then the mixture was filtered using a filter screen (pore size: 80 mesh) to remove the residue, to obtain a silyl ester-based antifouling coating composition as a filtrate.

[0283] [Manufacturing Example Y] Vinyl chloride-isobutyl vinyl ether resin-based antifouling coating composition

[0284] To a plastic container were added xylene 13 parts as solvent, 2-heptanone 3 parts, rosin 9 parts, triphenyl phosphate (TCP, manufactured by Kyowa Fermentation Industries, Ltd.) 3 parts, chloroethylene-isobutyl vinyl ether copolymer (Laroflex MP25, manufactured by BASF) 5 parts, and mixing was performed using a paint shaker until each component was uniformly dispersed or dissolved. Then, talc 10 parts, zinc oxide 3 parts, cuprous oxide (Red Copp 97N Premium, manufactured by American Chemet Corp) 42 parts, titanium oxide 4 parts, and DCOIT (SEANINE 211N, manufactured by Rohm and Haas Japan KK, solid content 30%) 5 parts were further added to the plastic container, and these components were dispersed by stirring using a paint shaker for 1 hour. After dispersion, fatty acid amide wax 3 parts was further added, and stirring was performed using a paint shaker for 20 minutes, and then the mixture was filtered using a filter screen (pore size: 80 mesh) to remove the residue, and a chloroethylene-isobutyl vinyl ether-based antifouling paint composition was obtained as a filtrate.

[0285] Information on the antifouling paint compositions of Examples 1 to 23 and Comparative Examples 1 to 6 (composition and evaluation test results) is shown in Table 2. In addition, detailed contents of the components (products) described in Table 2 used in the preparation of these antifouling paint compositions are shown in Table 3.

[0286]

[0287]

[0288]

[0289]

[0290]

[0291] By comparing the evaluation test results of the examples and comparative examples described in Table 2, the following results can be obtained, for example.

[0292] (1) From the comparison of Comparative Example 1 containing bromopyrrole nitrile (C) and copper pyrithione (D) as antifouling agents but not containing metomidine (B) with Examples 1, 2 and 4 containing all of metomidine (B), bromopyrrole nitrile (C) and copper pyrithione (D) and being identical with Comparative Example 1 except for the components, it is known that the antifouling coating composition of the present application having the constituting means of the latter can form an antifouling coating film which is particularly excellent in the standing antifouling property after long-term dynamic immersion without impairing the properties in other evaluation tests, and is also excellent in the standing antifouling property in the wet-dry cycle section. In addition, the antifouling coating film of the latter is also excellent in the adhesion to the chloroethylene-isobutyl vinyl ether resin-based deteriorated antifouling coating film compared with the antifouling coating film of the former.

[0293] (2) From the comparison of Comparative Example 4 containing metomidine (B) and copper pyrithione (D) as antifouling agents but not containing bromopyrrole nitrile (C) with Examples 2, 5 and 6 containing all of metomidine (B), bromopyrrole nitrile (C) and copper pyrithione (D) and being identical with Comparative Example 4 except for the components, it is known that the antifouling coating composition of the present application having the constituting means of the latter can form an antifouling coating film which is excellent in the standing antifouling property after long-term dynamic immersion and the standing antifouling property in the wet-dry cycle section without impairing the properties in other evaluation tests. In addition, the antifouling coating film of the latter is also excellent in the adhesion to the chloroethylene-isobutyl vinyl ether resin-based deteriorated antifouling coating film compared with the antifouling coating film of the former.

[0294] (3) From the comparison of Comparative Example 5 not containing the straight-chain or branched-chain alkyl carboxylic acid (E) having 4 to 30 carbon atoms (tertiary carbonic acid as a representative example) with Examples 2, 9 and 10 containing the alkyl carboxylic acid (E) and being identical with Comparative Example 9 except for the components, it is known that the antifouling coating composition of the present application having the constituting means of the latter can form an antifouling coating film which is excellent in the adhesion to the silyl ester resin-based deteriorated antifouling coating film, the chloroethylene-isobutyl vinyl ether resin-based deteriorated antifouling coating film (i.e. the old antifouling coating film other than the same antifouling coating film) and the epoxy-based adhesive coating film without impairing the properties in other evaluation tests compared with the antifouling coating composition of the former.

[0295] (4) From the comparison between Comparative Example 3 containing no copper pyrithione (D) and zinc pyrithione and Example 2 containing zinc pyrithione but containing no copper pyrithione (D) and having the same components as those of Comparative Example 3 except for this, it is known that the antifouling coating composition of the present application having the configuration of the latter is capable of forming an antifouling coating film which is excellent in adhesion to epoxy adhesive coating film and to chlorovinyl-isobutyl vinyl ether resin-based deteriorated antifouling coating film (i.e., old antifouling coating film other than the same antifouling coating film) without impairing the properties in other evaluation tests, compared with the conventional antifouling coating composition like the former.

[0296] (5) From the comparison between Comparative Example 6 containing no straight-chain or branched-chain alkyl carboxylic acid (E) having 4 to 30 carbon atoms (tertiary carbonic acid as a representative example thereof) and rosin and Example 2 containing straight-chain or branched-chain alkyl carboxylic acid (E) having 4 to 30 carbon atoms (tertiary carbonic acid as a representative example thereof) but containing no rosin and having the same components as those of Comparative Example 6 except for this, it is known that the antifouling coating composition of the present application having the configuration of the latter is capable of forming an antifouling coating film which is significantly excellent in adhesion to the same deteriorated antifouling coating film, in addition to being significantly excellent in adhesion to chlorovinyl-isobutyl vinyl ether resin-based deteriorated antifouling coating film (i.e., old antifouling coating film other than the same antifouling coating film) without impairing the properties in other evaluation tests, compared with the conventional antifouling coating composition like the former.

Claims

1. An antifouling coating composition comprising a hydrolyzable polymer containing a metal ester group (A), medetomidine (B), bromopyrrole carbonitrile (C), copper pyrithione (D), and a linear or branched alkyl carboxylic acid having 4 to 30 carbon atoms (E). The polymer (A) contains a structural unit derived from a metal ester group-containing monomer (a1) represented by the following formula (1), In formula (1), R 11 Each independently represents a monovalent group containing a terminal ethylenically unsaturated group, and M represents a copper atom or a zinc atom.

2. The antifouling coating composition according to claim 1, wherein The polymer (A) comprises a structural unit derived from a metal ester group-containing monomer (a1) represented by the following formula (1'), In formula (1'), R 12 Each independently represents a hydrogen atom or a methyl group, and M represents a copper atom or a zinc atom.

3. The antifouling coating composition according to claim 1 or 2, wherein The alkyl carboxylic acid (E) is versatic acid.

4. The antifouling coating composition according to claim 1 or 2, wherein With respect to 100% by mass of the copper pyrithione (D), the content of the medetomidine (B) is 0.1 to 100% by mass, and the content of the bromopyrrole carbonitrile (C) is 10 to 1700% by mass, and The content of copper pyrithione (D) is 0.5 to 12% by mass relative to 100% by mass of the solid content of the antifouling coating composition. 5 . An antifouling coating film formed from the antifouling coating composition according to claim 1 . A substrate with an antifouling coating film, comprising a substrate and the antifouling coating film according to claim 5.

7. The substrate with an antifouling coating according to claim 6, wherein The substrate is selected from the group consisting of ships, underwater structures and fishery materials.

8. A method for producing a substrate with an antifouling coating, comprising: A step (1) of applying the antifouling coating composition according to claim 1 or 2 onto a substrate or impregnating the substrate to obtain a coated body or an impregnated body; and A step (2) of drying the coated or impregnated body.

9. An antifouling method for a substrate, comprising the step of forming the antifouling coating film according to claim 5 on at least a portion of a substrate.

Images