Substrate with laminated coating film

Abstract

One embodiment of the present invention relates to a substrate with a laminated coating film or a method for producing a substrate with a laminated coating film, wherein the substrate with a laminated coating film comprises, in this order: a substrate; an antifouling coating film A1 containing a silyl ester polymer (a1) having a structural unit derived from trialkylsilyl methacrylate (a11); and an epoxy resin-based coating film S1.

Description

Substrate with a laminated coating film

[0001] One embodiment of the present invention relates to a substrate with a laminated coating film or a method for manufacturing the same.

[0002] On the surface of substrates that are exposed (for a long time) in water (such as the ocean, rivers, lakes, etc.), such as ships, underwater structures, and fishing nets, various aquatic organisms such as barnacles, mussels, barnacles, etc., plants such as seaweeds, and bacteria are likely to adhere and reproduce. When these aquatic organisms adhere and reproduce on the substrate surface, various problems occur. For example, when the substrate is a ship, the surface roughness increases from the ship's waterline to the bottom of the ship, and as a result, the ship's speed may decrease and fuel consumption may increase. Also, when the substrate is an underwater structure, the anticorrosive coating film applied to the substrate surface may be damaged, resulting in damage such as a decrease in the strength and function of the anticorrosive coating film and a significant shortening of its lifespan. Further, when the substrate is a fishing net such as an aquaculture net or a fixed net, the mesh may be blocked by aquatic organisms, leading to serious problems such as oxygen deficiency and death of cultured organisms or caught organisms. Additionally, when the substrate is a seawater supply and drainage pipe of a thermal power plant or a nuclear power plant, etc., the seawater (cooling water) supply and drainage pipe may be blocked or the flow rate may decrease, causing problems in the circulation system.

[0003] In order to suppress the problems caused by the adhesion and reproduction of such various aquatic organisms, various antifouling paints are applied to various substrates to form an antifouling coating film. Examples of the antifouling paint include a hydrolyzable silyl ester copolymer-based antifouling paint and a hydrolyzable crosslinked metal salt copolymer-based antifouling paint. In order for the antifouling coating film to suppress the adhesion and reproduction of various aquatic organisms, the antifouling coating film is usually formed on the outermost surface of the substrate (the outermost surface opposite to the substrate).

[0004] Incidentally, when an antifouling coating is used for a long period of time, it will wear out, deteriorate, be damaged, or peel off. Therefore, in order to maintain its antifouling performance, it is necessary to periodically repair or repaint the antifouling coating. If the worn or deteriorated antifouling coating (hereinafter also referred to as "old antifouling coating") on the substrate surface is removed beforehand prior to such repair or repainting, it will take extra time and expense. Therefore, from the standpoint of economy and work efficiency, it is desirable to directly apply a new antifouling coating on top of the old antifouling coating. On the other hand, when applying a new antifouling coating on the surface of such an old antifouling coating, adhesion between the newly applied antifouling coating (new antifouling coating) and the old antifouling coating is often a problem. For this reason, an epoxy resin coating is sometimes formed on the old antifouling coating before applying a new antifouling coating on top of it (e.g., Patent Document 1).

[0005] International Publication No. 2006 / 109600

[0006] In recent years, when applying organopolysiloxane-based antifouling paint to newly built ships, the surface of the old antifouling coating applied before launching is roughened in the final dock using a power tool equipped with nonwoven abrasive material, and then an epoxy resin-based coating is formed (hereinafter this method is also referred to as the "epoxy coating system"). However, conventionally, this epoxy coating system has generally been applied when the old antifouling coating is an antifouling coating formed from a cross-linked metal salt copolymer-based antifouling paint.

[0007] On the other hand, in recent years, it has become clear that there is a need to improve the epoxy coating system due to factors such as the increasing demand for silicone-based antifouling coatings, the need for antifouling performance when the period from launching to final docking becomes longer due to changes in the marine environment, and the increasing demand in rivers (freshwater environments) where cross-linked metal salt copolymer-based antifouling coatings cannot be applied. Furthermore, since the surface roughening process is time-consuming and costly, from the standpoint of economy and work efficiency, it is desirable to be able to form a laminated coating film with excellent adhesion between the old antifouling coating film and the epoxy resin-based coating film without surface roughening.

[0008] One embodiment of the present invention provides a substrate with a laminated coating that exhibits excellent adhesion between the antifouling coating and the epoxy resin-based coating formed thereon, even without roughening the surface of the antifouling coating.

[0009] As a result of diligent research by the inventors, we have found that the above-mentioned problems can be solved by the following configuration example, and have completed the present invention. The configuration example of the present invention is as follows.

[0010] In this specification, "A to B" indicating a numerical range means A or greater and B or less. In this specification, "(co)polymer having constituent units derived from compound X" means a (co)polymer obtained using compound X as a raw material, and refers to a (co)polymer that contains a structure based on compound X through polymerization reactions, etc. Furthermore, in the following description, "(meth)acrylate," "(meth)acryloyl," and "(meth)acrylic acid" mean "acrylate and / or methacrylate," "acryloyl and / or methacryloyl," and "acrylic acid and / or methacrylic acid," respectively.

[0011] [1] A substrate with a laminated coating, comprising in this order a base material, an antifouling coating A1 containing a silyl ester polymer (a1) having constituent units derived from trialkylsilyl methacrylate (a11), and an epoxy resin coating S1.

[0012] [2] A substrate with a laminated coating according to [1], comprising, in this order, a substrate, an antifouling coating A1 containing a silyl ester polymer (a1) having structural units derived from trialkylsilyl methacrylate (a11), an epoxy resin coating S1, and an organopolysiloxane antifouling coating A2.

[0013] [3] A laminated coated substrate according to [2], comprising a silicone tie coat T1 between the epoxy resin coating film S1 and the organopolysiloxane antifouling coating film A2.

[0014] [4] A laminated coated substrate according to any one of [1] to [3], wherein the antifouling coating A1 further comprises copper or a copper compound (a2). [5] A laminated coated substrate according to any one of [1] to [4], wherein the content of the silyl ester polymer (a1) in the antifouling coating A1 is 5 to 50% by mass. [6] A laminated coated substrate according to any one of [1] to [5], wherein the content of the constituent units derived from trialkylsilyl methacrylate (a11) in the antifouling coating A1 is 3 to 15% by mass.

[0015] [7] The laminated coated substrate according to any one of [1] to [6], wherein the epoxy resin coating film S1 is a coating film formed from a composition S1 comprising an epoxy resin, an amine-based curing agent, and a pigment.

[0016] [8] The laminated coated substrate according to [2] or [3], wherein the organopolysiloxane-based antifouling coating A2 is a coating film formed from composition A2 containing a curable polyorganosiloxane and a lubricant. [9] The laminated coated substrate according to [8], wherein the lubricant is one or more selected from the group consisting of silicone oil, paraffin oil, oils and fats, (meth)acrylic polymers having hydrophilic groups, polyglycerin esters and polyalkylene glycols.

[0017]

[10] A method for manufacturing a substrate with a laminated coating, comprising the steps of: (i) cleaning the antifouling coating R1 of a substrate with an antifouling coating R1 that is to be repaired or repainted; and (ii) forming an epoxy resin coating S1 on the antifouling coating R1 after step (i), wherein the antifouling coating R1 is an antifouling coating formed from a composition containing a silyl ester polymer having constituent units derived from triisopropylsilyl methacrylate.

[0018]

[11] A method for manufacturing a substrate with a laminated coating according to

[10] , comprising the step (iii) of forming an organopolysiloxane-based antifouling coating A2 on the side of the epoxy resin-based coating S1 formed in step (ii) that is opposite to the substrate.

[0019]

[12] A method for manufacturing a substrate with a laminated coating according to

[10] or

[11] , comprising the steps of: (iv) forming a silicone tie coat T1 on the side of the epoxy resin coating film S1 formed in step (ii) that is opposite to the substrate; and (v) forming an organopolysiloxane antifouling coating film A2 on the side of the silicone tie coat T1 formed in step (iv) that is opposite to the epoxy resin coating film S1.

[0020]

[13] A method for manufacturing a substrate with a laminated coating according to any one of

[10] to

[12] , wherein the step between step (i) and step (ii) is to roughen the surface of the antifouling coating R1 after step (i).

[0021] According to one embodiment of the present invention, it is possible to provide a substrate with a laminated coating that exhibits excellent adhesion between the antifouling coating and the epoxy resin coating formed thereon, even without roughening the surface of the antifouling coating. In particular, according to one embodiment of the present invention, even if the antifouling coating is an existing antifouling coating, it is possible to provide a substrate with a laminated coating that exhibits excellent adhesion even without roughening the surface of the existing antifouling coating. Furthermore, according to one embodiment of the present invention, it is possible to provide a substrate with a laminated coating that exhibits excellent adhesion between all layers of the laminated coating, including the antifouling coating that may be formed on the epoxy resin coating. Thus, according to one embodiment of the present invention, it is possible to provide a substrate with a laminated coating that exhibits excellent adhesion between each layer, even without roughening the surface of the antifouling coating, and thus a desired substrate with a laminated coating can be obtained in a way that is superior in terms of economy and work efficiency.

[0022] <Laminated Coating Substrate> A laminated coating substrate according to one embodiment of the present invention (hereinafter also referred to as "this laminated coating substrate") comprises, in this order, a substrate, an antifouling coating A1 containing a silyl ester polymer (a1) having constituent units derived from trialkylsilyl methacrylate (a11), and an epoxy resin coating S1. As a result of diligent research by the present inventors, although the reason is not clear, it has been found that, for the first time when the antifouling coating A1 contains a silyl ester polymer (a1) having constituent units derived from trialkylsilyl methacrylate (a11), rather than a silyl ester polymer having constituent units derived from trialkylsilyl methacrylate (a11), it is possible to obtain a laminated coating substrate with excellent adhesion between the antifouling coating A1 and the epoxy resin coating S1 formed thereon, without roughening the surface of the antifouling coating A1. Furthermore, it has been found that a laminated coating substrate with excellent adhesion between the antifouling coating A1 and the epoxy resin coating S1 formed thereon can be obtained regardless of the type of epoxy resin coating S1. Moreover, it has been found that a laminated coating substrate with excellent adhesion between all layers of the laminated coating, including the tie coat T1 and antifouling coating A2 that can be formed on the epoxy resin coating S1, can be obtained.

[0023] The laminated coating substrate is not particularly limited as long as it includes the substrate, antifouling coating A1, and coating S1 in this order, but it is preferable that the antifouling coating A1 and coating S1 are in contact with each other, in order to better exhibit the effects of the present invention. The laminated coating substrate preferably includes the substrate, antifouling coating A1, coating S1, and organopolysiloxane-based antifouling coating A2 in this order. It is even more preferable to include a silicone-based tie coat T1 between the coating S1 and the antifouling coating A2, that is, the substrate, antifouling coating A1, coating S1, tie coat T1, and antifouling coating A2 in this order, in order to easily obtain a laminated coating substrate with superior adhesion between coating S1 and antifouling coating A2. In this case, it is preferable that coating S1 and tie coat T1 are in contact, and it is preferable that tie coat T1 and antifouling coating A2 are in contact. This laminated coated substrate may include two or more layers of antifouling coating A1, two or more layers of coating S1, two or more layers of tie-coat T1, and / or two or more layers of antifouling coating A2, but typically there is one layer each of antifouling coating A1, coating S1, tie-coat T1, and antifouling coating A2. This laminated coated substrate may also include films (layers) other than antifouling coating A1, coating S1, tie-coat T1, and antifouling coating A2.

[0024] <Anti-fouling coating A1> The anti-fouling coating A1 contains a silyl ester polymer (a1) having a constituent unit derived from trialkylsilyl methacrylate (a11), and is preferably formed from the anti-fouling paint composition A1 described below.

[0025] The aforementioned antifouling coating A1 may be an old antifouling coating that has been worn down or deteriorated due to exposure to water (ocean, river, lake, etc.) for a certain period of time and is subject to repair or repainting. In other words, it is preferable that the coating be an old antifouling coating, as this allows the effects of the present invention to be better demonstrated. Such an old antifouling coating may be referred to as "old antifouling coating A1" and / or "antifouling coating R1" below. Furthermore, the description of "antifouling coating A1" in this specification also applies to "old antifouling coating A1" and "antifouling coating R1".

[0026] Examples of the aforementioned old antifouling coating include antifouling coatings that have expired after a predetermined service life. Antifouling coatings formed from antifouling paint applied to the bottom of ships, etc., generally have a service life determined according to the type of operation, and are usually repainted after the service life has expired. Specifically, the service life is 3 to 6 months for small vessels such as fishing boats and pleasure boats. For large vessels such as crude oil tankers and container ships, it is 12 to 90 months. Thus, the service life varies widely depending on the type of operation, such as the route the ship takes, and is not particularly limited.

[0027] The thickness of the antifouling coating A1 can be arbitrarily selected depending on the renewal rate of the antifouling coating A1 and the period of use, but for example, it is preferably about 30 to 1,000 μm, more preferably about 40 to 850 μm, and even more preferably about 50 to 700 μm.

[0028] [Anti-fouling paint composition A1] The anti-fouling paint composition A1 comprises a silyl ester polymer (a1) having a constituent unit derived from trialkylsilyl methacrylate (a11).

[0029] [Silyl ester polymer (a1)] The silyl ester polymer (a1) is not particularly limited as long as it has constituent units derived from trialkylsilyl methacrylate (a11), and may be a (co)polymer consisting of (only) one or more constituent units derived from trialkylsilyl methacrylate (a11), or it may be a copolymer (a11-12) having constituent units derived from trialkylsilyl methacrylate (a11) and constituent units derived from an ethylenically unsaturated monomer other than trialkylsilyl methacrylate (a11) (a12), but the copolymer (a11-12) is preferred. The polymer (a1) used in composition A1 may be one type or two or more types.

[0030] <Trialkylsilyl methacrylate (a11)> Examples of the trialkylsilyl methacrylate (a11) include trimethylsilyl methacrylate, triethylsilyl methacrylate, tripropylsilyl methacrylate, triisopropylsilyl methacrylate, tributylsilyl methacrylate, triisobutylsilyl methacrylate, tri-sec-butylsilyl methacrylate, tri-2-ethylhexylsilyl methacrylate, and butyldiisopropylsilyl methacrylate. Among these, trialkylsilyl methacrylate having a branched alkyl group is preferred, and triisopropylsilyl methacrylate is particularly preferred, from the viewpoint that it can easily form an antifouling coating film A1 that has a good balance of long-term antifouling properties and crack resistance. One type or two or more types of (a11) may be used in the synthesis of the copolymer.

[0031] The content of constituent units derived from (a11) relative to 100% by mass of all constituent units of the copolymer (a11-12) is preferably 35 to 75% by mass, more preferably 40 to 70% by mass, and even more preferably 45 to 70% by mass, in order to easily obtain an antifouling coating A1 that has good water resistance and antifouling properties over a long period of time. In particular, when the content of constituent units derived from (a11) is 45 to 70% by mass, an antifouling coating A1 with superior water resistance and superior crack resistance can be easily formed.

[0032] The content of constituent units derived from (a11) in the antifouling coating A1 is preferably 3 to 15% by mass, more preferably 4 to 13% by mass, and even more preferably 5 to 10% by mass, in order to easily obtain a laminated coating substrate with superior adhesion between the antifouling coating A1 and the coating film S1 formed thereon, and to easily form an antifouling coating A1 with superior coating strength. If the content of constituent units derived from (a11) in the antifouling coating A1 is less than the lower limit, the coating strength of the antifouling coating A1 may decrease, and the adhesion of the antifouling coating A1 to the coating film S1 may decrease. Therefore, it is preferable that the content of constituent units derived from (a11) in the antifouling coating A1 is greater than or equal to the lower limit, in order to easily form an antifouling coating A1 with superior coating strength and to easily obtain a laminated coating substrate with superior adhesion between the antifouling coating A1 and the coating film S1. Furthermore, if the content of constituent units derived from (a11) in the antifouling coating A1 exceeds the upper limit, the antifouling properties of the antifouling coating A1 may decrease. Therefore, it is preferable that the content of constituent units derived from (a11) in the antifouling coating A1 be less than or equal to the upper limit, as this allows for the easy formation of an antifouling coating A1 with superior antifouling properties. The content of constituent units derived from (a11) in the antifouling coating A1 can be calculated by multiplying the content (mass%) of polymer (a1) in the antifouling coating A1 by the content (mass%) of constituent units derived from (a11) in the polymer (a1) / 100.

[0033] Furthermore, the copolymer (a11-12) may have structures derived from the polymerization initiator at its ends. However, the content of constituent units derived from (a11) can be approximated by the proportion (mass ratio) of (a11) in the total monomer components used when synthesizing the copolymer (a11-12), and the same applies to the content of other constituent units.

[0034] <Monomer (a12)> The monomer (a12) is not particularly limited as long as it is an ethylenically unsaturated monomer other than trialkylsilyl methacrylate (a11), but it is preferable that it contains 2-methoxyethyl (meth)acrylate (a12-1), and more preferably that it contains (a12-1) and other ethylenically unsaturated monomers other than these (a12-2).

[0035] - The copolymer (a11-12) of 2-methoxyethyl (meth)acrylate (a12-1) is preferably composed of constituent units derived from (a12-1) because it can easily form an antifouling coating film A1 with superior antifouling properties. When (a12-1) is used in the synthesis of the copolymer (a11-12), 2-methoxyethyl acrylate may be used, 2-methoxyethyl methacrylate may be used, or 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate may be used.

[0036] The content of constituent units derived from (a12-1) relative to 100% by mass of all constituent units of copolymer (a11-12) is preferably 15 to 35% by mass, more preferably 20 to 35% by mass, and even more preferably 20 to 30% by mass, from the viewpoint that a stable wear-resistant and antifouling coating film A1 can be easily formed. In particular, when the content of constituent units derived from (a12-1) is 20 to 30% by mass, it has appropriate hydrophilicity, so an antifouling coating film A1 that can achieve both antifouling and crack resistance can be easily formed. Furthermore, 2-methoxyethyl methacrylate is preferred from the viewpoint of similar effects.

[0037] The total content of constituent units derived from (a11) and (a12-1) relative to 100% by mass of all constituent units of copolymer (a11-12) is preferably 60 to 99% by mass, more preferably 70 to 98% by mass, even more preferably 75 to 95% by mass, and particularly preferably 75 to 90% by mass, from the viewpoint that an antifouling coating film A1 with excellent antifouling properties and physical properties can be easily formed.

[0038] - Other ethylenically unsaturated monomers (a12-2) There are no particular restrictions on (a12-2) as long as it is an ethylenically unsaturated monomer other than (a11) and (a12-1) mentioned above, except for oligomers and polymers described later. When (a12-2) is used in the synthesis of copolymer (a11-12), one type of (a12-2) may be used, or two or more types may be used.

[0039] Examples of (a12-2) include unsaturated carboxylic acids such as (meth)acrylic acid, (meth)acryloyloxyalkyl succinic acid, (meth)acryloyloxyalkyl phthalic acid, (meth)acryloyloxyalkyl hexahydrophthalic acid, itaconic acid, and maleic acid; (Meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, and other alkyl (meth)acrylates; cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, and other (meth)acrylic acid esters; Examples include silyl acrylates such as trimethylsilyl acrylate, triethylsilyl acrylate, and triisopropylsilyl acrylate; vinyl compounds such as vinyl acetate, vinyl propionate, vinyl sulfonic acid, and vinylphosphonic acid; and styrenes such as styrene and ammonium styrenesulfonate.

[0040] Among these, unsaturated carboxylic acids, alkyl (meth)acrylates, and vinyl compounds are preferred, (meth)acrylic acid, alkyl (meth)acrylates having an alkyl group with 1 to 4 carbon atoms, and vinyl sulfonic acid are more preferred, and methyl methacrylate, butyl acrylate, (meth)acrylic acid, and vinyl sulfonic acid are particularly preferred.

[0041] The content of constituent units derived from (a12-2) relative to 100% by mass of all constituent units of copolymer (a11-12) is preferably 1 to 40% by mass, more preferably 2 to 30% by mass, even more preferably 5 to 25% by mass, and particularly preferably 10 to 25% by mass, from the viewpoint that the physical properties of the antifouling coating film A1 can be easily adjusted.

[0042] <Other components besides (a11), (a12-1), and (a12-2)> The copolymer (a11-12) may have a structure derived from other components besides (a11), (a12-1), and (a12-2). When the other components are used in the synthesis of the copolymer (a11-12), one or more of these other components may be used.

[0043] Other components include, for example, oligomers or polymers that have polymerizable ethylenically unsaturated groups at the ends of their molecular chains and are incorporated into the structure of the copolymer (a11-12). The number average molecular weight of these oligomers or polymers is usually 500 to 30,000, preferably 1,000 to 20,000.

[0044] Examples of the oligomers or polymers include macromonomers such as AA-6 (trade name, manufactured by Toagosei Co., Ltd., terminal methacryloyl group polymethyl methacrylate) and AS-6 (trade name, manufactured by Toagosei Co., Ltd., terminal methacryloyl group polystyrene); silicones such as Cylaprene FM-0711 (trade name, manufactured by JNC Corporation, one-terminated methacryloxy group polydimethyl silicone) and KF-2012 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., one-terminated methacryloxy group polydimethyl silicone); and polymers such as alkyd resins having unsaturated groups.

[0045] <Solid Acid Value of Polymer (a1)> The solid acid value of polymer (a1) is preferably 0 to 10 mg KOH / g, more preferably 0.5 to 9 mg KOH / g, and even more preferably 1 to 8 mg KOH / g, in order to easily obtain an antifouling coating composition A1 that is easy to apply and to easily form an antifouling coating film A1 that has excellent long-term antifouling properties. "Acid value" is the number of mg of potassium hydroxide required to neutralize the free acid present in 1 g of the sample, and is expressed in units of "mg KOH / g". Specifically, the solid acid value can be measured by the method described in the examples.

[0046] The acid group that gives polymer (a1) the aforementioned acid value is not particularly limited, but examples include carboxyl groups, sulfonic acid groups, and phosphate groups, with carboxyl groups being preferred.

[0047] Methods for introducing the acid group into the polymer (a1) include, for example, copolymerizing monomers having an acid group, or using a polymerization initiator having an acid group. Examples of monomers having an acid group include unsaturated carboxylic acids, vinyl sulfonic acid, and vinyl phosphonic acid, among which unsaturated carboxylic acids and vinyl sulfonic acid are preferred, (meth)acrylic acid and vinyl sulfonic acid are more preferred, and (meth)acrylic acid is particularly preferred. One type of monomer having an acid group may be used, or two or more types may be used.

[0048] The content of monomers having acid groups is preferably adjusted so that the solid content acid value falls within the aforementioned range, and the content of constituent units derived from monomers having acid groups relative to 100% by mass of all constituent units of polymer (a1) is preferably 0.01 to 5% by mass.

[0049] <Weight-average molecular weight (Mw) of polymer (a1)> The Mw of polymer (a1) is preferably 60,000 or less, more preferably 40,000 or less. An antifouling coating film A1 formed from an antifouling coating composition A1 containing polymer (a1) with an Mw in the above range has good hydrolysis resistance, good abrasion resistance (coating film wear resistance), further improved antifouling properties, and tends to exhibit excellent long-term durability. The Mw of polymer (a1) is preferably 12,000 or more, more preferably 13,000 or more, from the viewpoint that it is possible to easily form an antifouling coating film A1 with excellent strength, long-term durability, etc. The Mw of polymer (a1) can be measured by gel permeation chromatography (GPC), and the value obtained by GPC is a value (polystyrene equivalent value) obtained using a calibration curve prepared with polystyrene as the standard substance.

[0050] <Content of polymer (a1)> In order to easily form an antifouling coating A1 that has excellent adhesion to the coating film S1 and excellent water resistance and various physical properties (crack resistance of the coating film, coating film strength, antifouling properties) over a long period of time, the solid content of polymer (a1) is preferably 5 to 50% by mass, more preferably 7 to 20% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1. The solid content of polymer (a1) can also be said to be the content of polymer (a1) in the antifouling coating A1.

[0051] Furthermore, the "solid content" in antifouling paint composition A1 and each raw material used in said antifouling paint composition A1 refers to the mass excluding volatile components, and is the residue after drying antifouling paint composition A1 and each raw material containing volatile components such as solvents in a hot air dryer at 105°C for 3 hours to allow the volatile components such as solvents to evaporate.

[0052] [Optional Components] Antifouling coating composition A1 may contain optional components other than the polymer (a1) as long as they do not impair the effects of the present invention. Examples of such optional components include copper or copper compounds (a2), rosins and / or monocarboxylic acid compounds, organic antifouling agents, other binder components, coloring pigments, extender pigments, (pigment) dispersants, plasticizers, anti-sagging agents, anti-settlement agents, dehydrating agents, and solvents.

[0053] <Copper or copper compound (a2)> The antifouling coating composition A1 may contain copper or a copper compound (a2) (excluding copper pyrithione) in order to further improve the antifouling properties of the antifouling coating film A1 that is formed. One type of copper or copper compound (a2) may be used, or two or more types may be used.

[0054] The copper compound may be either an organic or inorganic copper compound. Examples of copper or copper compound (a2) include powdered copper, cuprous oxide, copper thiocyanate (copper rhodane), and cupronickel. Among the copper or copper compound (a2), it is more preferable to include cuprous oxide, as it allows for the easy formation of an antifouling coating A1 with excellent antifouling properties, particularly against aquatic organisms including animals, and water resistance.

[0055] The cuprous oxide preferably contains cuprous oxide with an average particle size of about 1 to 30 μm, and more preferably contains cuprous oxide with an average particle size of 2 to 10 μm, as this allows for the easy formation of an antifouling coating A1 with excellent antifouling and water resistance properties.

[0056] As the aforementioned cuprous oxide, cuprous oxide surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, or mineral oil is preferred in terms of its antifouling properties and long-term stability during storage.

[0057] Commercially available products can be used as the aforementioned cuprous oxide, including, for example, "NC-301" (average particle size: 2-4 μm) and "NC-803" (average particle size: 6-10 μm) manufactured by NC Tech Co., Ltd., "NORDOX" manufactured by Nordox Industries AS, "Red Copp97N Premium" manufactured by AMERICAN CHEMET Co., Ltd., "Purple Copp" manufactured by AMERICAN CHEMET Co., Ltd., and "LoLoTint97" manufactured by AMERICAN CHEMET Co., Ltd.

[0058] When the antifouling coating composition A1 contains copper or a copper compound (a2), the amount is preferably 20 to 80% by mass, more preferably 40 to 75% by mass, and even more preferably 40 to 70% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1, in order to easily form an antifouling coating film A1 with excellent antifouling performance and water resistance.

[0059] <Rosins and / or Monocarboxylic Acid Compounds> The antifouling coating composition A1 can further improve the antifouling properties of the antifouling coating film A1 that is formed, and it is preferable that it contains rosins and / or monocarboxylic acid compounds, in particular for improving static antifouling properties. Furthermore, by using rosins and / or monocarboxylic acid compounds, the renewal of the antifouling coating film A1 from the surface in water is promoted, and if the antifouling coating film A1 contains an antifouling agent, the release of the antifouling agent into water is promoted, thereby improving the antifouling properties of the antifouling coating film A1, and it is also possible to impart appropriate water resistance to the antifouling coating film A1. One type of rosin and / or monocarboxylic acid compound may be used, or two or more types may be used.

[0060] Preferred rosins and / or monocarboxylic acid compounds include, for example, compounds in which one carboxyl group is substituted on a saturated or unsaturated aliphatic hydrocarbon having 10 to 40 carbon atoms, compounds in which one carboxyl group is substituted on a saturated or unsaturated alicyclic hydrocarbon having 3 to 40 carbon atoms, and compounds in which one carboxyl group is substituted on a modified aliphatic or alicyclic hydrocarbon. Among these, abietic acid, neoabietic acid, dehydroabietic acid, palastic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexenecarboxylic acid, versatic acid, stearic acid, naphthenic acid, etc. are preferred. Rosins mainly composed of abietic acid, palastic acid, isopimaric acid, etc. are also preferred. Examples of rosins include gum rosin, wood rosin, tall oil rosin, and other rosins; hydrogenated rosin, disproportionated rosin, rosin metal salts and other rosin derivatives; modified rosins and rosin derivatives (e.g., modified with acid anhydrides such as maleic anhydride, esterified products); and pine tar.

[0061] Examples of the trimethylisobutenylcyclohexenecarboxylic acid include the reaction product of 2,6-dimethylocta-2,4,6-triene and methacrylic acid. The reaction product mainly consists of 1,2,3-trimethyl-5-(2-methylpropa-1-en-1-yl)cyclohexa-3-en-1-carboxylic acid and 1,4,5-trimethyl-2-(2-methylpropa-1-en-1-yl)cyclohexa-3-en-1-carboxylic acid (85% by mass or more).

[0062] If the antifouling coating composition A1 contains rosins and / or monocarboxylic acid compounds, the content is preferably 1 to 50% by mass, more preferably 2 to 20% by mass, and even more preferably 3 to 10% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1. Furthermore, from the viewpoint of easily forming an antifouling coating A1 with good antifouling properties and physical properties (e.g., crack resistance, coating gloss (aesthetics)), the content is preferably 5 to 170 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 15 to 100 parts by mass, based on 100 parts by mass of the solid content of the polymer (a1).

[0063] <Organic Antifouling Agent> Antifouling paint composition A1 may contain an organic antifouling agent (excluding copper or copper compounds (a2)). One type of organic antifouling agent may be used, or two or more types may be used.

[0064] Examples of organic antifouling agents include copper pyrithione, zinc pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (also known as tralopyril), 4,5-dimethyl-1H-imidazole, (+ / -)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (also known as medetomidine), borane-nitrogen-based base adducts (pyridinetriphenylborane, 4-isopropylpyridinediphenylmethylborane, etc.), N,N-dimethyl-N'-(3,4-dichlorophenyl)urea, N-(2,4,6-trichlorophenyl Examples include maleimide, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-1,3,5-triazine, 2,4,5,6-tetrachloroisophthalonitrile, bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate, chloromethyl-n-octyl disulfide, N',N'-dimethyl-N-phenyl-(N-fluorodichloromethylthio)sulfamide, tetraalkylthiuram disulfide, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, 2,3-dichloro-N-(2',6'-diethylphenyl)maleimide, and 2,3-dichloro-N-(2'-ethyl-6'-methylphenyl)maleimide. Among these, copper pyrithione, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, and (+ / -)-4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole are preferred, with copper pyrithione being particularly preferred.

[0065] When the antifouling coating composition A1 contains an organic antifouling agent, the amount of the organic antifouling agent is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, relative to 100% by mass of the solid content of the antifouling coating composition A1, in order to easily obtain an antifouling coating composition A1 with excellent paintability and to easily form an antifouling coating film A1 with excellent antifouling performance and water resistance.

[0066] <Other Binder Components> The antifouling coating composition A1 may contain other binder components in addition to the polymer (a1) in order to impart static antifouling properties, water resistance, crack resistance, strength, etc., to the antifouling coating film A1 that is formed. Examples of such other binder components include acrylic (co)polymers (acrylic resins), vinyl polymers, n-paraffins, and terpene phenols. One type of other binder component may be used, or two or more types may be used.

[0067] The acrylic (co)polymer preferably contains at least one constituent unit selected from the group consisting of (meth)acrylic acid esters and metal ester group-containing unsaturated monomers, for example, in order to easily form an antifouling coating film A1 with excellent static antifouling properties. The (meth)acrylic acid ester may be used by one type or by two or more types.

[0068] The aforementioned metal ester group-containing unsaturated monomer refers to a monomer containing a metal ester group formed by the bonding of a metal and a carboxylic acid. A polyvalent metal ester group is preferred as the metal ester group, and a divalent metal ester group is more preferred. The polyvalent metal ester group or divalent metal ester group refers to a group formed by the bonding of a polyvalent metal or divalent metal and a carboxylic acid.

[0069] Examples of metals constituting the metal ester group include magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, and aluminum. Among these, metals of groups 10 to 12 such as nickel, copper, and zinc are preferred, metals selected from the group consisting of copper and zinc are more preferred, and zinc is even more preferred.

[0070] Examples of the metal ester group-containing unsaturated monomers include zinc di(meth)acrylate, copper di(meth)acrylate, zinc acrylate (methacrylic acid), copper acrylate (methacrylic acid), zinc di(3-(meth)acryloyloxypropionic acid), copper di(3-(meth)acryloyloxypropionic acid), zinc (meth)acrylate (naphthenate), and copper (meth)acrylate (naphthenate). One metal ester group-containing unsaturated monomer may be used, or two or more may be used.

[0071] The acrylic (co)polymer may contain constituent units derived from vinyl compounds other than the (meth)acrylic acid esters and metal ester group-containing unsaturated monomers. Examples of such other vinyl compounds include styrene, α-methylstyrene, vinyl acetate, vinyl benzoate, vinyltoluene, acrylonitrile, methacrylonitrile, vinylpyridine, vinylpyrrolidone, and vinyl chloride. One or more of these other vinyl compounds may be used.

[0072] Other binder components may be commercially available products, for example, "Dianal BR-106" (acrylic polymer) manufactured by Mitsubishi Chemical Corporation, and an acid group-containing polymer obtained by reacting a polymer containing two or more acid groups (e.g., polyester polymer or acrylic polymer) with the rosins and / or monocarboxylic acid compounds and a metal compound, as described in International Publication No. 2014 / 010702.

[0073] If the antifouling coating composition A1 contains other binder components, the amount thereof is preferably 1 to 20% by mass relative to 100% by mass of the solid content of the antifouling coating composition A1.

[0074] <Coloring Pigments> The antifouling coating composition A1 may contain coloring pigments for purposes such as adjusting the color tone of the formed antifouling coating film A1 or imparting an arbitrary color tone to the formed antifouling coating film A1. One type of coloring pigment may be used, or two or more types may be used.

[0075] Examples of coloring pigments include various known organic and inorganic coloring pigments. Examples of organic coloring pigments include carbon black (e.g., Pigment Black 7), naphthol red (e.g., Pigment Red 170), and phthalocyanine blue (e.g., Pigment Blue 15). Examples of inorganic coloring pigments include red iron oxide (red iron oxide) (Fe ２ O ３ ), black iron oxide (Fe ３ O ４ ), titanium oxide (titanium white / TiO ２ Examples include yellow iron oxide. Furthermore, the antifouling paint composition A1 may contain a coloring agent other than a coloring pigment, such as a dye, together with the coloring pigment, or in place of the coloring pigment.

[0076] If the antifouling coating composition A1 contains a coloring pigment, the preferred amount is determined by the desired viscosity according to the required opacity of the antifouling coating film A1 formed and the application method of the antifouling coating composition A1, but is preferably 0.5 to 10% by mass relative to 100% by mass of the solid content of the antifouling coating composition A1.

[0077] <Extender Pigments> Antifouling coating composition A1 may contain extender pigments because it can easily form an antifouling coating film A1 with excellent coating film properties such as crack resistance. One type of extender pigment may be used, or two or more types may be used.

[0078] Examples of extender pigments include pigments other than the inorganic dehydrating agents listed below, such as talc, zinc oxide, zinc phosphate, silica (diatomaceous earth, acid clay, etc.), mica, clay, potassium feldspar, calcium carbonate, kaolin, alumina white, white carbon, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, and zinc sulfide. Among these, talc, zinc oxide, zinc phosphate, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, and potassium feldspar are preferred.

[0079] If the antifouling coating composition A1 contains an extender pigment, the preferred amount is determined by the desired viscosity according to the required opacity of the antifouling coating film A1 formed and the application method of the antifouling coating composition A1, but is preferably 1 to 50% by mass relative to 100% by mass of the solid content of the antifouling coating composition A1.

[0080] <(Pigment) Dispersant> If the antifouling paint composition A1 contains coloring pigments, extender pigments, etc., the antifouling paint composition A1 may contain a (pigment) dispersant to improve the dispersibility of the coloring pigments, extender pigments, etc. One type of (pigment) dispersant may be used, or two or more types may be used.

[0081] Examples of pigment dispersants include various known organic or inorganic pigment dispersants, with specific examples including aliphatic amines, organic acids, and "Disperbyk-101" manufactured by BYK Corporation.

[0082] <Plasticizer> The antifouling coating composition A1 may contain a plasticizer to improve the crack resistance of the antifouling coating film A1 that is formed. One type of plasticizer may be used, or two or more types may be used.

[0083] Examples of plasticizers include tricresyl phosphate (TCP), chlorinated paraffin, petroleum resins, ketone resins, polyvinyl ethyl ether, and dialkyl phthalates. Among these, chlorinated paraffin, petroleum resins, and ketone resins are preferred because they can easily form an antifouling coating A1 with excellent water resistance and hydrolysis resistance (abrasion resistance).

[0084] Specific examples of chlorinated paraffins include "Toyopalux A-40 / A-50 / A-70 / A-145 / A-150" manufactured by Tosoh Corporation. Examples of petroleum resins include C5 series, C9 series, styrene series, dichloropentadiene series, and hydrogenated versions thereof, with a specific example being "Quinton 1500 / 1700" manufactured by Nippon Zeon Corporation.

[0085] If the antifouling coating composition A1 contains a plasticizer, the amount is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1, in order to maintain good plasticity of the formed antifouling coating film A1.

[0086] <Anti-slip agent> Antifouling paint composition A1 may contain an anti-slip agent (run-stopping agent) in order to reduce the occurrence of sagging when composition A1 is applied to a substrate. One type of anti-slip agent may be used, or two or more types may be used.

[0087] Examples of anti-slip agents include amide waxes (such as fatty acid amides), hydrogenated castor oil waxes, mixtures thereof, and synthetic fine silica (such as Aerosil®), among which amide waxes or synthetic fine silica are preferred.

[0088] Using amide wax or synthetic fine silica as a sagging inhibitor makes it easy to obtain an antifouling coating composition A1 with excellent storage stability, and it is preferable because it can easily suppress a decrease in adhesion (interlayer adhesion, recoating ability) between the antifouling coating A1 and the coating S1.

[0089] Commercially available anti-dripping agents include "Disparon A630-20X" and "Disparon 4200-20" manufactured by Kusumoto Kasei Co., Ltd., and "A-S-A T-250F" manufactured by Ito Seiyu Co., Ltd.

[0090] If the antifouling coating composition A1 contains an anti-slip agent, its content is preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.2 to 2% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1.

[0091] <Settling Inhibitor> Antifouling paint composition A1 may contain a settling inhibitor, which can suppress the formation of precipitates and improve agitation during storage of composition A1. One type of settling inhibitor may be used, or two or more types may be used.

[0092] Examples of anti-settling agents include organic clay waxes such as stearate salts, lecithin salts, and alkyl sulfonates of Al, Ca, or Zn, polyethylene wax, and oxidized polyethylene wax. Among these, oxidized polyethylene wax is preferred. A commercially available example of oxidized polyethylene wax is "Disparon 4200-20X" manufactured by Kusumoto Kasei Co., Ltd.

[0093] If the antifouling coating composition A1 contains a settling inhibitor, its content is preferably 0.01 to 10% by mass, more preferably 0.05 to 3% by mass, and even more preferably 0.1 to 2% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1.

[0094] <Dehydrating Agent> Antifouling coating composition A1 has excellent storage stability because it contains a polymer (a1) with good storage stability. However, by adding a dehydrating agent as needed, an antifouling coating composition A1 with even better long-term storage stability can be easily obtained. One type of dehydrating agent may be used, or two or more types may be used.

[0095] Examples of dehydrating agents include inorganic and organic dehydrating agents. Preferred inorganic dehydrating agents are synthetic zeolites, anhydrous gypsum, and hemihydrate gypsum. Preferred organic dehydrating agents include alkoxy or aryloxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraphenoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, and trimethylethoxysilane, polyalkoxysilanes which are partial hydrolysis condensates thereof, and alkyl orthoformate esters such as methyl orthoformate and ethyl orthoformate. Among these, tetraethoxysilane, which is an alkoxysilane, is preferred.

[0096] If the antifouling coating composition A1 contains a dehydrating agent, the amount of the dehydrating agent is preferably 0.01 to 10% by mass, more preferably 0.1 to 3% by mass, and even more preferably 0.15 to 1% by mass, based on 100% by mass of the solid content of the antifouling coating composition A1, in order to easily obtain an antifouling coating composition A1 with excellent storage stability.

[0097] <Solvent> The antifouling coating composition A1 may contain a solvent as needed, in order to improve the dispersibility of the polymer (a1), maintain a low viscosity of composition A1, and improve spray atomization. The solvent may be the solvent used when synthesizing the polymer (a1), or a solvent added separately when mixing the polymer (a1) with any optional components as needed. One type of solvent may be used, or two or more types may be used.

[0098] As solvents, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, and alcohols can be used, with aromatic hydrocarbons being preferred. Examples of aromatic hydrocarbons include toluene, xylene, and mesitylene. Examples of aliphatic hydrocarbons include pentane, hexane, heptane, and octane. Examples of alicyclic hydrocarbons include cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of ketones include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate. Examples of esters include propylene glycol monomethyl ether acetate. Examples of alcohols include isopropanol, n-butanol, and propylene glycol monomethyl ether.

[0099] If the antifouling coating composition A1 contains a solvent, the amount of solvent is determined by the desired viscosity and anti-sagging properties depending on the application method of the antifouling coating composition A1, but is preferably 50% by mass or less, more preferably 10 to 40% by mass, and even more preferably 15 to 35% by mass, relative to 100% by mass of the antifouling coating composition A1.

[0100] <Epoxy resin coating film S1> The coating film S1 is not particularly limited as long as it is an epoxy resin coating film, but it is preferably a coating film formed from a composition S1 containing an epoxy resin, an amine-based curing agent, and a pigment. The substrate with this laminated coating film has a specific antifouling coating film A1, and the coating film S1 is formed on thereon, so the adhesion between the antifouling coating film A1 and the coating film S1 is excellent, and the type of coating film S1 is not particularly limited as long as it is epoxy resin-based, and it has excellent adhesion to the antifouling coating film A1. In one embodiment of the present invention, the coating film S1 can also be called an "epoxy sealer coat".

[0101] The thickness of the coating film S1 can be adjusted as appropriate depending on the desired application, but is preferably 30 to 300 μm, and more preferably 50 to 200 μm.

[0102] [Composition S1] Composition S1 preferably contains an epoxy resin, an amine-based curing agent, and a pigment. Such a composition S1 may be a one-component composition, but is usually a two-component composition consisting of a main component containing an epoxy resin and a curing agent component containing an amine-based curing agent. If necessary, composition S1 may also be a three-component or more composition containing other components other than the main component and the curing agent component. These main component, curing agent component, and other components are usually stored, transported, etc., in separate containers and mixed immediately before use of composition S1.

[0103] [Epoxy Resin] The epoxy resin is preferred because it exhibits adhesive strength to the coating film it comes into contact with, has excellent mechanical properties, and hardens easily when an amine-based curing agent, as described later, is used. One type of epoxy resin may be used, or two or more types may be used.

[0104] The epoxy resin is not particularly limited as long as it does not impair the effects of the present invention, but examples include bisphenol-type epoxy resins, glycidyl ester-based epoxy resins, glycidylamine-based epoxy resins, novolac-type epoxy resins (e.g., phenol novolac-type epoxy resins, cresol novolac-type epoxy resins), dimer acid-modified epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and epoxidized oil-based epoxy resins.

[0105] Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolac type epoxy resin are preferred due to their excellent adhesion to the antifouling coating A1 and corrosion resistance. Furthermore, in order to improve curability and quickly obtain a coating film S1 with practical strength, the bisphenol A type and bisphenol F type epoxy resins are preferably semi-solid resins at 25°C. In addition, in order to easily form a coating film S1 with sufficient strength without the coating film strength (hardness) being too high, it is particularly preferable to use them in combination with novolac type epoxy resin rather than using them alone.

[0106] A semi-solid epoxy resin at 25°C refers to a highly viscous epoxy resin whose viscosity at 25°C, when the epoxy resin is considered to have 100% solid content, is preferably 1,000 cPs or more, more preferably 10,000 cPs or more.

[0107] Commercially available epoxy resins can be used. Examples of commercially available liquid epoxy at room temperature (5-35°C, JIS Z 8703; the same applies hereafter) include "Epotote YD-128" (product name, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent 184-194, viscosity 12,000-15,000 cPs / 25°C), "jER828" (product name, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 180-190, viscosity 12,000-15,000 cPs / 25°C), "Epotote YDF-170" (product name, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent 160-180, viscosity 2,000-5,000 cPs / 25°C), and "Frep 60" (product name, manufactured by Toray Thiocol Co., Ltd., epoxy equivalent approximately 280, viscosity approximately 17,000 cPs / 25°C).

[0108] Examples of commercially available semi-solid products at room temperature include "E-834-85X(T)" (product name, manufactured by Ohtake Meishin Chemical Co., Ltd., epoxy equivalent 230-270), "jER834" (product name, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent 230-270), "Epotote YD134" (product name, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent 230-270), "Epotote YD-172" (product name, manufactured by Nippon Steel & Sumitomo Metal Corporation, epoxy equivalent 600-700), and "Epiclon-5300-70" (product name, manufactured by DIC Corporation, epoxy equivalent 450-500).

[0109] Examples of commercially available solid products at room temperature include "jER1001-75X" (product name, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight 450-500).

[0110] The epoxy equivalent of the epoxy resin is preferably 160 to 700, more preferably 160 to 500. The viscosity of the epoxy resin is preferably 500 to 20,000 cPs / 25°C, more preferably 500 to 18,000 cPs / 25°C. When the epoxy equivalent and viscosity of the epoxy resin are within the above ranges, a composition S1 with excellent workability can be easily obtained, and a coating film S1 with excellent strength and adhesion to the antifouling coating film A1 can be easily formed, which is preferable.

[0111] When forming a tie coat T1 or an antifouling coating A2 on a coating film S1, it has been found that the adhesion between the coating film S1 and the tie coat T1 or antifouling coating A2 tends to decrease as the epoxy equivalent of the epoxy resin used in composition S1 increases. For this reason, when forming a tie coat T1 or an antifouling coating A2 on a coating film S1, the epoxy equivalent of the epoxy resin is preferably 500 or less, more preferably 160 to 490, and even more preferably 170 to 480. The epoxy equivalent is calculated based on JIS K 7236:2001. Note that when two or more epoxy resins are blended in composition S1, the epoxy equivalent of the epoxy resin is the epoxy equivalent of the two or more epoxy resins as a whole. Specifically, when combining epoxy resin e1 with a solid epoxy equivalent of a in mass of y parts (solids) and epoxy resin e2 with a solid epoxy equivalent of b in mass of z parts (solids), the epoxy equivalent of the epoxy resin is calculated as a × y / (y + z) + b × z / (y + z).

[0112] The solid content of the epoxy resin is preferably 0.1 to 50% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass, based on 100% by mass of the solid content of composition S1. When the epoxy resin content is within the above range, a composition S1 with excellent paintability can be easily obtained, and a coating film S1 with excellent leveling properties, adhesion to the antifouling coating film A1, toughness, and flexibility can be easily formed.

[0113] Furthermore, the "solid content" of composition S1 and each raw material used in composition S1 refers to the mass excluding volatile components. For raw materials containing volatile components such as solvents, the solid content refers to the residue after drying in a hot air dryer at 105°C for 3 hours to evaporate the volatile components. In addition, the solid content of composition S1 is calculated according to JIS K 5601-1-2:2008 by weighing 1 ± 0.1 g of this composition (in the case of the two-component type composition, the composition immediately after mixing the main component and the curing agent component) onto a flat-bottomed dish, spreading it uniformly using a wire of known mass, leaving it at 23°C for 24 hours, drying it at 110°C for 1 hour under normal pressure, and then weighing the heat residue and the mass of the wire.

[0114] Also, as described above, when (i) bisphenol A type and / or bisphenol F type epoxy resin and (ii) novolac type epoxy resin are used in combination, from the viewpoint that the coating film strength (hardness) is not too high and a coating film S1 having sufficient strength can be easily formed, the usage ratio ((i):(ii)) is a mass ratio, preferably 500:100 to 100:300, more preferably 400:100 to 100:200, and even more preferably 300:100 to 100:150.

[0115] [Amine curing agent] The amine curing agent is not particularly limited as long as it is an amine compound other than a tertiary amine (an amine compound having only a tertiary amino group as an amino group). For example, an amine compound containing two or more amino groups in one molecule can be mentioned. Specific examples include aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, araliphatic amine curing agents, and heterocyclic amine curing agents. The amine curing agent may be used alone or in combination of two or more.

[0116] Examples of the aliphatic amine curing agent include alkyl monoamines, alkylene polyamines, polyalkylene polyamines, and alkylaminoalkylamines.

[0117] The alkylene polyamine is, for example, a compound represented by the formula: "H ２ N-R １ -NH ２ " (R １ is a divalent hydrocarbon group having 1 to 12 carbon atoms.). Specific examples include methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, and trimethylhexamethylenediamine.

[0118] Examples of the polyalkylene polyamine include the formula: "H ２ N-(C ｍ H ２ｍ NH) ｎCompounds represented by (H) (where m is an integer from 1 to 10, and n is an integer from 2 to 10, preferably from 2 to 6) are examples, and specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, and triethylene-bis(trimethylene)hexamine.

[0119] Examples of the alkylaminoalkylamine include formula: ２ ２ N-(CH ２ ) ｐ -NH ２ (R ２ These are independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (wherein at least one R ２ A is an alkyl group having 1 to 8 carbon atoms, and p is an integer from 1 to 6. Examples of compounds represented by ) include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0120] Other aliphatic amine-based curing agents include, for example, tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, 2,2'-[ethylenebis(iminotrimethyleneimino)]bis(ethaneamine), tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, and polyoxyalkylene polyamines (especially diethylene glycol bis(3-aminopropyl) ether).

[0121] Examples of the alicyclic amine-based curing agents include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebiscyclohexylamine), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine, 2,4-di(4-aminocyclohexylmethyl)aniline, bis(aminomethyl)cyclohexane, isophoronediamine, and mensendiamine (MDA).

[0122] Examples of aromatic amine-based curing agents include aromatic polyamine compounds having two or more primary amino groups bonded to aromatic rings such as benzene rings or naphthalene rings. Specific examples of these aromatic amine-based curing agents include phenylenediamine, naphthalenediamine, diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, and 3,3'-dimethoxy-4,4'-diaminobiphenyl.

[0123] Examples of aromatic aliphatic amine-based curing agents include bis(aminoalkyl)benzene and bis(aminoalkyl)naphthalene. Specific examples of these aromatic aliphatic amine-based curing agents include o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, bis(aminomethyl)naphthalene, and bis(aminoethyl)naphthalene.

[0124] Examples of heterocyclic amine-based curing agents include N-methylpiperazine, morpholine, 1,4-bis-(3-aminopropyl)piperazine, 1,4-diazacycloheptane, 1-(2'-aminoethylpiperazine), 1,4-bis(3-aminopropyl)piperazine, 1-[2'-(2''-aminoethylamino)ethyl]piperazine, 1,11-diazacycloeicosane, and 1,15-diazacyclooctacosane.

[0125] Examples of amine-based curing agents include amines (amine compounds) described in Japanese Patent Publication No. 49-48480, polyetherdiamines, modified products of the aforementioned amine compounds, such as fatty acid modified products such as polyamidoamines, amine adducts with epoxy compounds, Mannich-modified amines (e.g., Mannich-modified amines having a phenol-derived skeleton (phenalkamine, phenalkamide, etc.)), Michael adducts, ketimines, aldimines, urethane-modified products, and the like.

[0126] Among these, as an amine-based curing agent, it is preferable to use a Mannich-modified amine, and more preferably MXDA Mannich-modified amine, because it is possible to easily obtain a composition S1 that is excellent in curing speed, especially at low temperatures (5°C or below), and to easily form a coating film S1 that is excellent in a good balance of adhesion to the antifouling coating film A1 and strength.

[0127] As the MXDA Mannich-modified amine, for example, a Mannich-modified amine obtained by Mannich condensation using phenols, aldehydes, and m-xylylenediamine (MXDA) is preferred.

[0128] Examples of the phenols include phenols containing unsaturated substituents and phenols containing saturated substituents, and one type may be used, or two or more types may be used.

[0129] Examples of the unsaturated substituent-containing phenol include compounds that contain at least one monohydroxyphenyl group in the molecule, and in which some of the hydrogen atoms in the phenyl group, i.e., 1 to 5 hydrogen atoms bonded to the phenyl group, are substituted with an unsaturated hydrocarbon group. Examples of the unsaturated hydrocarbon group include alkylene groups having about 1 to 10 carbon atoms, and phenyl groups containing alkylene groups having about 1 to 10 carbon atoms. Specific examples of such unsaturated substituent-containing phenols include cardanol, isopropenylphenol, diisopropenylphenol, butenylphenol, isobutenylphenol, cyclohexenylphenol, monostyrenated phenol (C6H5-CH=CH-C6H4-OH), and distyrenated phenol ((C6H5-CH=CH)2-C6H3-OH).

[0130] The saturated substituent-containing phenol may be monovalent or polyvalent, and may be mononuclear or polynuclear. Specific examples include monovalent mononuclear phenols such as phenol; divalent mononuclear phenols such as resorcinol and hydroquinone; divalent polynuclear phenols such as 1,5-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene; alkylphenols such as methylphenol (o,m,p-cresol), ethylphenol, butylphenol, t-butylphenol, octylphenol, nonylphenol, dodecylphenol, and dinonylphenol (number of carbon atoms in the alkyl group: 1 to 10, preferably 1 to 5); halogenated phenols such as chlorophenol; alkoxyphenols such as methoxyphenol (number of carbon atoms in the alkoxy group: 1 to 10, preferably 1 to 5); and bisphenol A and bisphenol F. Among these, monovalent mononuclear phenols are preferred.

[0131] Examples of the aforementioned aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, etc., and one or more of these may be used.

[0132] In the Mannich condensation described above, theoretically equimolar amounts of phenols, aldehydes, and MXDA can be used, but typically, 0.5 to 2.5 moles of aldehydes and 0.5 to 2.5 moles of MXDA are used per mole of phenols, and the reaction is carried out by heating at a temperature of about 50 to 180°C for about 3 to 12 hours. After the reaction is complete, the reaction product may be heated under reduced pressure to remove water and unreacted substances.

[0133] Among the MXDA-mannig modified amines obtained by reacting the aforementioned phenols, aldehydes, and MXDA in a mannig condensation reaction, the mannig modified amine obtained by reacting cardanol, formaldehyde, and MXDA is preferred.

[0134] The amine value of the amine-based curing agent is preferably 100 to 500 mg KOH / g, more preferably 200 to 500 mg KOH / g, because it allows for easy acquisition of a composition S1 with excellent curability and facilitates the formation of a coating film S1 with a good balance of coating film strength and adhesion to the anti-fouling coating film A1. For similar reasons, the active hydrogen equivalent of the amine-based curing agent is preferably 50 to 500, more preferably 80 to 400.

[0135] As the amine-based curing agent, commercially available products may be used. Examples of such commercially available products include Laccamide V6-221 (MXDA Mannich-modified amine, liquid, solid content 100% by mass, amine value 420 mg KOH / g) manufactured by DIC Corporation, and MAD-204(A) (MXDA Mannich-modified amine, solid, solid content 65% by mass, amine value 250 mg KOH / g) manufactured by Otake Meishin Chemical Co., Ltd.

[0136] Although it cannot be determined definitively due to factors such as the coating and curing conditions of composition S1, the viscosity of an amine-based curing agent measured with an E-type viscometer (rotation speed: 60 rpm) when the solid content is normally adjusted to 50 to 100% by mass is preferably 100 to 100,000 cPs / 25°C, and more preferably 500 to 10,000 cPs / 25°C, in order to easily obtain a composition S1 with excellent handling and coating properties.

[0137] It is preferable to use an amine-based curing agent in an amount such that the reaction ratio calculated by the following formula is preferably 0.3 to 1.0, more preferably 0.5 to 1.0, because it is possible to easily obtain a composition S1 with excellent curability, and to easily form a coating film S1 that has a good balance of coating film strength and adhesion to the antifouling coating film A1 and the topcoat coating film (Tiecoat T1 and antifouling coating film A2). Reaction ratio = {(Amount of solid content of amine curing agent (B) / Active hydrogen equivalent of solid content of amine curing agent (B)) + (Amount of solid content of component reactive with epoxy resin (A) / Functional group equivalent of solid content of component reactive with epoxy resin (A))} / {(Amount of solid content of epoxy resin (A) / Epoxy equivalent of solid content of epoxy resin (A)) + (Amount of solid content of component reactive with amine curing agent (B) / Functional group equivalent of solid content of component reactive with amine curing agent (B))}

[0138] Here, the "component that reacts with epoxy resin (A)" in the above formula can be a compound having a primary or secondary amino group, and a specific example thereof is the silane coupling agent listed below. Furthermore, the "component that reacts with amine curing agent (B)" can be a compound having an epoxy group or a (meth)acryloyl group, and a specific example thereof is the silane coupling agent, reactive diluent, and (meth)acrylic acid ester listed below. As the silane coupling agent, a silane coupling agent having an amino group or an epoxy group as the reactive group can be used, so it is necessary to determine whether the silane coupling agent reacts with epoxy resin (A) or amine curing agent (B) depending on the type of reactive group, and calculate the reaction ratio. For example, when two or more epoxy resins are blended into composition S1, specifically, when y parts by mass (solids) of epoxy resin e1 having an epoxy equivalent of a solid content and z parts by mass (solids) of epoxy resin e2 having an epoxy equivalent of b solid content, the above-mentioned "(amount of solids of epoxy resin (A) blended / epoxy equivalent of solids of epoxy resin (A))" is calculated as y / a + z / b. The same applies to other components.

[0139] The "functional group equivalent" of each component refers to the mass (g) per 1 mol of functional group obtained by dividing the mass of 1 mol of these components by the number of mol of functional groups contained within them.

[0140] [Pigments] The aforementioned pigments are not particularly limited as long as they are pigments other than gypsum listed below. Examples include extender pigments, coloring pigments, and rust-preventive pigments, and they may be organic or inorganic. One type of pigment may be used, or two or more types may be used.

[0141] The extender pigment is a pigment with a low refractive index that is transparent and does not obscure the coated surface when mixed with oil or varnish. Composition S1 containing the extender pigment is preferable because it allows for the easy formation of a coating film S1 with excellent properties such as crack resistance. One extender pigment may be used, or two or more extender pigments may be used.

[0142] Examples of the extender pigments include zinc oxide, talc, silica, mica, clay, potassium feldspar, glass flakes, calcium carbonate (also used as a settling inhibitor), kaolin, alumina white, white carbon (also used as a matting agent), aluminum hydroxide, magnesium carbonate, barium carbonate, and barium sulfate (e.g., barite powder). Among these, at least one pigment selected from the group consisting of talc, silica, mica, clay, calcium carbonate, kaolin, barium sulfate, and potassium feldspar is preferred.

[0143] Composition S1 preferably contains flattened pigments such as talc, mica, and glass flakes as extender pigments, in terms of easing internal stress in the formed coating film S1 and improving adhesion to the antifouling coating film A1. As the flattened pigments, talc and mica are preferred because they are inexpensive, readily available, and allow for the easy formation of a coating film S1 with even better effects.

[0144] If composition S1 contains an extender pigment, its content is preferably such that the PVC is within the following ranges, specifically, preferably 0.1 to 500 parts by mass, more preferably 50 to 400 parts by mass, per 100 parts by mass of epoxy resin. Furthermore, if composition S1 contains a flattened pigment, its content is preferably 0.1 to 300 parts by mass, more preferably 10 to 200 parts by mass, per 100 parts by mass of epoxy resin, from the viewpoint that it is possible to easily form a coating film S1 that has excellent adhesion to the antifouling coating film A1.

[0145] As the coloring pigment, various conventionally known organic and inorganic coloring pigments can be used. Examples of organic pigments include naphthol red and phthalocyanine blue. Examples of inorganic pigments include carbon black, red iron oxide, titanium white, yellow iron oxide, and aluminum powder. One coloring pigment may be used, or two or more may be used.

[0146] If composition S1 contains a coloring pigment, the amount is preferably such that the PVC is within the following ranges, specifically, preferably 0.01 to 100 parts by mass, more preferably 0.01 to 70 parts by mass, per 100 parts by mass of epoxy resin.

[0147] Examples of the aforementioned rust-preventive pigments include molybdate-based, phosphoric acid-based, boric acid-based, ferrite-based, and lead acid-based rust-preventive pigments. One type of rust-preventive pigment may be used, or two or more types may be used.

[0148] The pigment volume concentration (PVC) in composition S1 is preferably 25 to 50%, more preferably 30 to 48%. When the PVC is within this range, composition S1 with excellent film-forming properties and paintability can be easily obtained, and a coating film S1 with excellent adhesion to the antifouling coating film A1 due to stress relaxation can be easily formed, suppressing blistering and cracking.

[0149] The PVC in composition S1 refers to the total volume concentration of pigments and gypsum in composition S1 relative to the volume of solids in composition S1. Specifically, the PVC can be calculated using the following formula: PVC in composition S1 [%] = Total volume of all pigments and gypsum in composition S1 × 100 / Volume of solids in composition S1

[0150] The volume of the solid content of composition S1 can be calculated from the mass and true density of the solid content of composition S1. The mass and true density of the solid content may be measured values ​​or values ​​calculated from the raw materials used. The volume of the pigment and gypsum can be calculated from the mass and true density of the pigment and gypsum used. The mass and true density of the pigment and gypsum may be measured values ​​or values ​​calculated from the raw materials used. For example, this can be calculated by separating the pigment and gypsum from the other components from the solid content of composition S1 and measuring the mass and true density of the separated pigment and gypsum.

[0151] [Optional Components] Composition S1 may contain optional components other than the epoxy resin, amine-based curing agent, and pigment, to the extent that they do not impair the effects of the present invention. Examples of such optional components include gypsum; curing accelerators; plasticizers; (pigment) dispersants; anti-sagging agents; anti-settlement agents; solvents; reactive diluents; adhesion enhancers such as silane coupling agents; thermoplastic resins (e.g., vinyl-based (co)polymers [including vinyl chloride resin], excluding petroleum resins); dehydrating agents (stabilizers); antifouling agents; cement; fibrous fillers such as rock wool and glass fibers; other film-forming components; and dyes.

[0152] <Gypsum> By including gypsum in composition S1, a coating film S1 with excellent water resistance, saltwater resistance, and corrosion resistance can be easily formed. One type of gypsum may be used, or two or more types may be used.

[0153] Examples of the gypsum include crystalline gypsum (CaSO4・2H2O), hemihydrate gypsum (CaSO4・0.5H2O), and anhydrous gypsum (CaSO4), with hemihydrate gypsum and / or anhydrous gypsum being preferred. These may be natural or artificial products. There are no particular restrictions on the shape, but it is preferable that it be in powder form.

[0154] Anhydrous gypsum and hemihydrate gypsum have the property of hardening when they adsorb moisture and also retain moisture. Therefore, it is thought that the coating film S1 containing anhydrous gypsum or hemihydrate gypsum retains moisture and relieves internal stress in the coating film through its plasticizing effect, thereby improving adhesion to the antifouling coating film A1.

[0155] Hemihydrate gypsum comes in α-type and β-type, but the β-type is preferred in terms of the strength of the formed coating film S1. An example of hemihydrate gypsum is "FT-2" (average particle size 15 μm) manufactured by Noritake Co., Ltd.

[0156] Furthermore, anhydrous gypsum comes in three types: Type I, Type II, and Type III, but is not particularly limited. An example of anhydrous gypsum is "AS Gypsum" manufactured by San-Es Gypsum Co., Ltd.

[0157] If composition S1 contains gypsum, the amount is preferably such that the PVC is within the aforementioned range, and it is possible to easily form a coating S1 with excellent adhesion to the antifouling coating A1 and suppressed cracking. Specifically, the amount is preferably 5 to 100 parts by mass, more preferably 5 to 80 parts by mass, per 100 parts by mass of epoxy resin.

[0158] <Curing Accelerator> Composition S1 preferably contains a curing accelerator in order to further improve the curing speed and low-temperature curing properties. One type of curing accelerator may be used, or two or more types may be used.

[0159] As the curing accelerator, any conventionally known curing accelerator used in paints may be used, but tertiary amines and (meth)acrylic acid esters are preferred because they allow for easy acquisition of composition S1, which has excellent curing speed and low-temperature (below 5°C) curing properties.

[0160] The tertiary amine is not particularly limited, but for example, triethanolamine, dialkylaminoethanol {[CH ３ (CH ２ ) ｎ ] ２ NCH ２ CH ２Examples include OH, triethylenediamine [1,4-diazacyclo(2,2,2)octane], and 2,4,6-tri(dimethylaminomethyl)phenol (e.g., trade name "Versamin EH30", manufactured by BASF Japan Co., Ltd., trade name "Ankamin K-54" (manufactured by Air Products Japan Co., Ltd.)). Among these, 2,4,6-tri(dimethylaminomethyl)phenol is preferred.

[0161] The (meth)acrylic acid ester is not particularly limited, but a polyfunctional (meth)acrylic acid ester is preferred. A commercially available example of such a ester is a polyfunctional (meth)acrylic acid ester (trade name "M-Cure 400", manufactured by Sartomer).

[0162] If composition S1 contains a curing accelerator, the amount is preferably 0.01 to 30 parts by mass, more preferably 0.01 to 15 parts by mass, per 100 parts by mass of epoxy resin, in order to easily obtain composition S1 with excellent curing speed and low-temperature curing properties.

[0163] <Plasticizer> It is preferable that composition S1 contains a plasticizer, as it allows for easy adjustment of the viscosity of composition S1, has the effect of relieving internal stress in the formed coating film S1, and allows for the easy formation of a coating film S1 with excellent adhesion to the antifouling coating film A1 and coating film strength. One type of plasticizer may be used, or two or more types may be used.

[0164] Examples of plasticizers include phosphate esters (e.g., tricresyl phosphate [TCP]), chlorinated paraffins (chlorinated paraffins), petroleum resins, ketone resins, polyvinyl ethyl ethers, and dialkyl phthalates. Among these, phosphate esters are preferred.

[0165] If composition S1 contains a plasticizer, its content is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of epoxy resin, in order to easily form a coating film S1 that has excellent adhesion to the antifouling coating film A1.

[0166] <(Pigment) Dispersant> As the (pigment) dispersant, various conventionally known organic and inorganic dispersants can be used. Examples of organic dispersants include aliphatic amines or organic acids (e.g., "Duomin TDO" manufactured by LION Co., Ltd., "DisperBYK101" manufactured by BYK CHEMIE Co., Ltd.). One (pigment) dispersant may be used, or two or more may be used.

[0167] If composition S1 contains a (pigment) dispersant, its content is preferably 0.01 to 20 parts by mass, and more preferably 0.01 to 10 parts by mass, per 100 parts by mass of epoxy resin.

[0168] <Anti-sagging agent> It is preferable that composition S1 contains an anti-sagging agent, as this allows for adjustment of the anti-sagging properties during painting. One type of anti-sagging agent may be used, or two or more types may be used.

[0169] Examples of anti-slip agents include amide wax compounds, hydrogenated castor oil wax compounds, polyamide wax compounds, inorganic bentonite compounds, synthetic fine silica, and mixtures thereof, with polyamide wax and synthetic fine silica being preferred. Commercially available anti-slip agents may also be used, such as "Disparon 6650" and "Disparon A630-20XC" manufactured by Kusumoto Chemicals Co., Ltd., "ASAT-250F" manufactured by Ito Oil Co., Ltd., and "Benton 27" manufactured by Elementis Specialties, Inc.

[0170] If composition S1 contains an anti-sagging agent, its content is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of epoxy resin.

[0171] <Settling Inhibitor> It is preferable that composition S1 contains a settling inhibitor, as this can reduce the amount of sediment that may occur during storage of composition S1 and improve the agitability of composition S1. One type of settling inhibitor may be used, or two or more types may be used.

[0172] Examples of the aforementioned settling inhibitors include organic clay-based Al, Ca, or Zn amine salts, polyethylene wax, and polyethylene oxide wax, with polyethylene oxide wax being preferred among these. Commercially available products may also be used as settling inhibitors, such as "Disparon 4200-20X" manufactured by Kusumoto Kasei Co., Ltd.

[0173] If composition S1 contains a settling inhibitor, its content is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of epoxy resin.

[0174] <Solvent> As the solvent, conventionally known solvents with a wide range of boiling points can be used. Specifically, examples include aliphatic solvents such as turpentine; aromatic solvents such as toluene and xylene; alcoholic solvents such as isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol; esteric solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; etheric or ether esteric solvents such as ethylene glycol monomethyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monomethyl ether (PGM), and propylene glycol monomethyl ether acetate; and preferably xylene, n-butyl alcohol, methyl isobutyl ketone, and propylene glycol monomethyl ether. One solvent may be used, or two or more may be used.

[0175] If composition S1 contains a solvent, its content is not particularly limited, but considering coating properties, it is usually preferably 0.1 to 80% by mass, and more preferably 0.1 to 60% by mass, relative to 100% by mass of composition S1.

[0176] <Silane Coupling Agent> By using a silane coupling agent, it is possible to further improve the adhesion of the formed coating film S1 to the antifouling coating film A1, as well as to improve the corrosion resistance of the formed coating film S1. Therefore, it is preferable that composition S1 contains a silane coupling agent. One type of silane coupling agent may be used, or two or more types may be used.

[0177] The silane coupling agent is not particularly limited, and conventionally known compounds can be used. However, it is preferable that the compound has at least two functional groups within the same molecule and can contribute to improving adhesion to the antifouling coating A1, reducing the viscosity of composition S1, etc.

[0178] Silane coupling agents include, for example, formula: "X-SiMe ｎ Y ３－ｎ It is preferable that the compound is represented by "[n is 0 or 1, X represents a functional group that can react with organic matter (e.g., amino group, vinyl group, epoxy group, mercapto group, halogeno group, a group in which part of a hydrocarbon group is substituted with these groups, or a group in which part of a hydrocarbon group is substituted with an ether bond, etc., and part of that group is substituted with these groups), Me is a methyl group, and Y represents a hydrolyzable group (e.g., alkoxy groups such as methoxy group and ethoxy group)].

[0179] Among the silane coupling agents, it is preferable that the X is an epoxy group-containing silane coupling agent in which X is an epoxy group, a group in which part of a hydrocarbon group is substituted with an epoxy group, or a group in which part of a hydrocarbon group is substituted with an ether bond or the like and part of it is substituted with an epoxy group.

[0180] Commercially available silane coupling agents may be used, and examples of such commercially available products include "KBM-403" (manufactured by Shin-Etsu Chemical Co., Ltd.), which is 3-glycidoxypropyltrimethoxysilane, and "Sylace S-510" (manufactured by JNC Corporation).

[0181] When composition S1 contains a silane coupling agent, the amount is preferably 0.1 to 10% by mass, more preferably 0.3 to 5% by mass, relative to 100% by mass of the solid content of composition S1, in order to reduce the viscosity of composition S1, improve paintability, and easily form a coating S1 with excellent adhesion to the antifouling coating A1.

[0182] <Substrate> This laminated coating substrate can maintain the antifouling properties of substrates exposed to water (ocean, rivers, lakes, etc.) for extended periods in a wide range of industrial fields such as ships, fisheries, and underwater structures. Examples of such substrates include ships (large steel ships such as container ships and tankers, fishing boats, FRP ships, wooden ships, yachts, etc., especially the hull plating from the waterline to the bottom, and newly built or repaired ships of these types), fishing materials (ropes, fishing nets, fishing gear, floats, buoys, etc.), underwater structures (oil pipelines, water intake pipes, circulating water pipes, water supply and drainage pipes for factories and thermal and nuclear power plants, submarine cables, seawater utilization equipment (seawater pumps, etc.), mega-floats, coastal roads, underwater tunnels, port facilities, and various underwater civil engineering structures in canals and waterways, etc.), items used underwater and on the water (underwater lights, underwater sensors, oxygen cylinders, etc.), and torpedoes. Among these, a base material selected from the group consisting of ships, underwater structures, and fishing materials is preferred, a base material selected from the group consisting of ships and underwater structures is more preferred, and a ship is even more preferred.

[0183] The material of the base material is not particularly limited. When the base material is a ship or the like, examples include iron and steel (iron, steel, ferroalloy, carbon steel, mild steel, alloy steel, etc.), non-ferrous metals (zinc, aluminum, copper, brass, galvanized steel, zinc sprayed steel, etc.), stainless steel (SUS304, SUS410, etc.), wood, and FRP. When the base material is a fishing net or the like, examples include natural or synthetic fibers. When the base material is a float, buoy, etc., examples include synthetic resin.

[0184] The substrate on which the antifouling coating A1 of this laminated coating substrate is formed is preferably a substrate that has been treated with other treatment agents such as rust inhibitors, or a substrate on which an undercoat coating (e.g., primer coating, anticorrosion coating) has been formed.

[0185] Examples of compositions for forming the aforementioned undercoat include zinc-based pepper primers, epoxy resin-based zinc-rich primers, and epoxy resin-based anticorrosive paints, with epoxy resin-based anticorrosive paints being preferred. The epoxy resin-based anticorrosive paint typically contains an epoxy resin component and an amine-based curing agent for epoxy resins, and may also contain, as necessary, thermoplastic resins (e.g., vinyl copolymers), rosins, plasticizers, extender pigments, coloring pigments, rust-preventive pigments, solvents, curing accelerators, coupling agents, anti-sagging agents, and anti-settlement agents. Furthermore, composition S1 may be used as the composition for forming the aforementioned undercoat.

[0186] Furthermore, in order to improve the adhesion between the substrate and the undercoat, the substrate surface may be treated beforehand by methods such as sandblasting, friction, or degreasing to remove oil and dust before forming the undercoat.

[0187] <Organopolysiloxane-based antifouling coating A2> In order to suppress the attachment and reproduction of various aquatic organisms, it is preferable that the substrate with this laminated coating has an organopolysiloxane-based antifouling coating A2 on the outermost surface of the substrate (the outermost surface opposite the substrate). The antifouling coating A2 can also be called a new antifouling coating, as it is formed from an antifouling paint that is newly applied to the antifouling coating A1 (old antifouling coating A1).

[0188] The antifouling coating A2 is preferably a coating formed from a composition containing a curable polyorganosiloxane and a lubricant.

[0189] The thickness of the antifouling coating A2 is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, preferably 1,000 μm or less, more preferably 500 μm or less, and even more preferably 300 μm or less, from the viewpoint that an antifouling coating with excellent long-term antifouling properties can be easily formed.

[0190] [Composition A2] Composition A2 preferably contains a curable polyorganosiloxane and a lubricant. Alternatively, the antifouling coating composition A1 may be used as composition A2.

[0191] [Curable Polyorganosiloxane] When composition A2 contains a curable polyorganosiloxane, an antifouling coating A2 with excellent antifouling properties can be easily formed. One type of curable polyorganosiloxane may be used, or two or more types may be used.

[0192] Examples of curable polyorganosiloxanes include compounds having a main chain with a polyorganosiloxane structure and reactive groups, which harden by forming a three-dimensional crosslinked structure through the reaction of these reactive groups with each other or with the reactive groups of the organosilicon crosslinking agent described later. They may also react with the silane coupling agent described later.

[0193] Examples of polyorganosiloxane structures include polydimethylsiloxane and polymethylphenylsiloxane structures, with polydimethylsiloxane being preferred, and alkylene groups, polyoxyalkylene groups, etc., may be present in block form or other configurations. Furthermore, alkylene groups, polyoxyalkylene groups, etc., may be present as linkage sites between the main chain and reactive groups.

[0194] Specific examples of the reactive group include addition-reactive groups and condensation-reactive groups. In the curing reaction, condensation-reactive groups are preferred because they have less influence from curing inhibitors and allow for a stable reaction rate. Examples of the condensation-reactive groups include silanol groups, oximesilyl groups, acyloxysilyl groups, alkoxysilyl groups, alkenyloxysilyl groups, aminosilyl groups, and amidesilyl groups. Silanol groups, oximesilyl groups, acyloxysilyl groups, and alkoxysilyl groups are preferred, silanol groups, oximesilyl groups, and alkoxysilyl groups are more preferred, and silanol groups and oximesilyl groups are even more preferred.

[0195] As the oximesilyl group, a carbon-1 to carbon-10 oximesilyl group is preferred, dimethylketooximesilyl group, methylethylketooximesilyl group, diethylketooximesilyl group, methylisopropylketooximesilyl group, and methylisobutylketooximesilyl group are more preferred, and methylethylketooximesilyl group and methylisobutylketooximesilyl group are even more preferred.

[0196] As for the alkoxysilyl group, an alkoxysilyl group having 1 to 10 carbon atoms is preferred, a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group are more preferred, a methoxysilyl group and an ethoxysilyl group are even more preferred, and a methoxysilyl group is particularly preferred.

[0197] In the case of oxime groups and alkoxy groups, it is preferable that two or more oxime groups or alkoxy groups are bonded to one silicon atom as the condensation reactive group.

[0198] Possible locations for the reactive group include being directly bonded to a silicon atom of the main chain, being in the side chain, being at both ends of the main chain, or being at one end of the main chain, with both ends of the main chain being preferred.

[0199] The curable polyorganosiloxane is preferably a curable polyorganosiloxane having a reactive group. Specific examples include silanol group-containing polyorganosiloxane, oximesilyl group-containing polyorganosiloxane, alkoxy group-containing polyorganosiloxane, and enolsilyl ether group-containing polyorganosiloxane. Silanol group-containing polyorganosiloxane, oximesilyl group-containing polyorganosiloxane, and alkoxy group-containing polyorganosiloxane are preferred, and silanol group-containing polyorganosiloxane and oximesilyl group-containing polyorganosiloxane are more preferred.

[0200] As the curable polyorganosiloxane having the reactive group, those that form silicone rubber upon curing are preferred, and for example, compounds represented by the following formula (A1) are preferred.

[0201] [In formula (A1), R １１ and R １３Each of these independently represents a hydrogen atom, a C1-C16 alkyl group, a C2-C16 alkenyl group, a C6-C16 aryl group, a C7-C16 aralkyl group, or a C1-C16 halogenated alkyl group, R １２ Each of these independently represents either a hydroxyl group or a hydrolyzable group. Note that there are multiple R groups. １１ ~R １３ These can be the same or different. Also, r represents an integer from 1 to 3, and p represents an integer from 10 to 10,000.

[0202] R １１ and R １３ The alkyl group in this context is a group having 1 to 16 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, and heptyl group.

[0203] R １１ and R １３ The alkenyl group in this context is a group having 2 to 16 carbon atoms, and examples include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, and cyclohexenyl groups.

[0204] R １１ and R １３ The aryl group in this formula is a group having 6 to 16 carbon atoms and may have substituents such as alkyl groups on the aromatic ring. Examples include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), and a naphthyl group.

[0205] R １１ and R １３ The aralkyl group in this context is a group having 7 to 16 carbon atoms, such as the benzyl group, 2-phenylethyl group, 2-naphthylethyl group, and diphenylmethyl group.

[0206] R １１ and R １３ The halogenated alkyl group in this context is a group having 1 to 16 carbon atoms, and examples include a group in which some or all of the hydrogen atoms in the alkyl group are replaced by halogen atoms such as fluorine, chlorine, bromine, or iodine atoms.

[0207] Among these, R １１ The group is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, more preferably a methyl group, an ethyl group, a vinyl group, or a phenyl group, and even more preferably a methyl group or a vinyl group.

[0208] Also, R １３ The group is preferably a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group; more preferably a methyl group, an ethyl group, a vinyl group, or a phenyl group; even more preferably a methyl group, an ethyl group, or a phenyl group; and particularly preferably a methyl group or a phenyl group.

[0209] R １２ Examples of hydrolyzable groups in this context include oxime groups, acyloxy groups, alkoxy groups, alkenyloxy groups, amino groups, amide groups, and aminooxy groups.

[0210] R １２ The oxime group in is preferably an oxime group having a total of 1 to 10 carbon atoms, such as a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, or a methyl isobutyl ketoxime group.

[0211] R １２ The acyloxy group (RC(=O)O-) in this is preferably an aliphatic acyloxy group with a total of 2 to 10 carbon atoms or an aromatic acyloxy group with a total of 7 to 12 carbon atoms, for example, an acetoxy group, a propionyloxy group, a butyryloxy group, or a benzoyloxy group.

[0212] R １２ The alkoxy group in is preferably an alkoxy group having a total of 1 to 10 carbon atoms. １２ In the alkoxy group in R, one or more oxygen atoms may be present between one or more carbon atoms. １２ Specific examples of alkoxy groups in this context include methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, and ethoxyethoxy groups.

[0213] R １２The alkenyloxy group in is preferably an alkenyloxy group having 3 to 10 carbon atoms, such as isopropenyloxy, isobutenyloxy, and 1-ethyl-2-methylvinyloxy groups.

[0214] R １２ The amino group in is preferably an amino group having 1 to 10 carbon atoms, such as N-methylamino group, N-ethylamino group, N-propylamino group, N-butylamino group, N,N-dimethylamino group, N,N-diethylamino group, and cyclohexylamino group.

[0215] R １２ The amide group in this is preferably an amide group having a total of 2 to 10 carbon atoms, for example, an N-methylacetamide group, an N-ethylacetamide group, or an N-methylbenzamide group.

[0216] R １２ The aminooxy group in is preferably an aminooxy group having a total of 2 to 10 carbon atoms, for example, an N,N-dimethylaminooxy group and an N,N-diethylaminooxy group.

[0217] Among these, R １２ The group is preferably a hydroxyl group, an oxime group, or an alkoxy group; more preferably a hydroxyl group or an oxime group; and even more preferably a hydroxyl group, a methyl ethyl ketoxime group, or a methyl isobutyl ketoxime group.

[0218] R １２ When is a hydroxyl group, r is preferably 1, R １２ If the group is not a hydroxyl group, r is preferably 2.

[0219] p is preferably 100 to 1,000, and is preferably adjusted as appropriate to satisfy the following weight-average molecular weight. Note that p is -(SiR １３ ２ This refers to the average number of repetitions of -O)-.

[0220] The weight-average molecular weight (Mw) of the curable polyorganosiloxane is preferably 500 or more, more preferably 5,000 or more, even more preferably 10,000 or more, even more preferably 15,000 or more, particularly preferably 20,000 or more, preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, particularly preferably 40,000 or less, from the viewpoint of improving workability during the manufacture of composition A2, and improving the coating properties, curability, and strength of the antifouling coating film A2 formed. The "weight-average molecular weight (Mw)" and the "number-average molecular weight (Mn)" of each raw material used in composition A2 are measured using GPC and calculated by converting them to standard polystyrene with known molecular weight.

[0221] The viscosity of the curable polyorganosiloxane at 25°C is preferably 20 mPa·s or more, more preferably 100 mPa·s or more, even more preferably 500 mPa·s or more, particularly preferably 1,000 mPa·s or more, preferably 100,000 mPa·s or less, more preferably 10,000 mPa·s or less, even more preferably 5,000 mPa·s or less, particularly preferably 3,000 mPa·s or less, from the viewpoint of improving workability during the manufacture of composition A2, and improving the coating properties, curability, and strength of the antifouling coating film A2 formed.

[0222] Commercially available curable polyorganosiloxanes may be used, such as "DMS-S35" manufactured by GELEST Corporation and "KE-445" manufactured by Shin-Etsu Chemical Co., Ltd. Furthermore, compounds described in Japanese Patent Publication No. 2001-139816, etc., can also be used as curable polyorganosiloxanes.

[0223] The content of curable polyorganosiloxane in composition A2 is preferably 25% by mass or more, more preferably 30% by mass or more, even more preferably 35% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, from the viewpoint that it is possible to easily form an antifouling coating film A2 that has excellent antifouling properties and strength. For similar reasons, the content of curable polyorganosiloxane in 100% by mass of solids in composition A2 is preferably 45% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, preferably 85% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less.

[0224] In addition, the "solid content" of each raw material used in composition A2 refers to the components excluding the organic solvent and volatile components contained in each raw material, as described later, and the "solid content of composition A2" refers to the solid content obtained by drying composition A2 in a hot air dryer at 125°C for 1 hour.

[0225] <Lubricant> Composition A2 may contain a lubricant, as it allows for easy acquisition of a composition A2 with excellent coating properties and antifouling properties. Furthermore, composition A2 containing a lubricant can impart slipperiness to the formed antifouling coating A2, thereby improving the ability to inhibit the adhesion of aquatic organisms (antifouling properties). One type of lubricant may be used, or two or more types may be used.

[0226] The lubricant is preferably fluid at 25°C, and more preferably liquid. Using a fluid lubricant is thought to enhance its mobility within the antifouling coating A2, thereby improving the effect of providing slipperiness to the surface of the antifouling coating A2. Furthermore, using a fluid lubricant can reduce the viscosity of the resulting composition A2, resulting in improved coatability.

[0227] When composition A2 contains a lubricant, the solid content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, particularly preferably 10% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent formability and antifouling properties.

[0228] As a lubricant, one or more selected from oils and polymers having hydrophilic groups are preferred. Examples of oils include silicone oil, paraffin oil, and fats and oils, with silicone oil being preferred among these. Examples of polymers having hydrophilic groups include (meth)acrylic polymers having hydrophilic groups, polyglycerin esters, and polyalkylene glycols, with (meth)acrylic polymers having hydrophilic groups being preferred.

[0229] The lubricant is preferably one or more selected from the group consisting of silicone oil, paraffin oil, oils and fats, hydrophilic (meth)acrylic polymers, polyglycerin esters, and polyalkylene glycols, more preferably one or more selected from silicone oil and hydrophilic (meth)acrylic polymers, and even more preferably silicone oil. Furthermore, from the viewpoint of ease of preparation of composition A2 and the antifouling properties of the antifouling coating film A2 formed, it is preferable to include a hydrophilic (meth)acrylic polymer, and more preferably to include both silicone oil and a hydrophilic (meth)acrylic polymer.

[0230] - Silicone oil The silicone oil has low interfacial tension and its properties do not easily change even in low-temperature environments, so it easily moves to the surface of the antifouling coating A2, and can efficiently form an antifouling coating A2 that has excellent antifouling properties (prevention of aquatic organism adhesion) and damage resistance. One type of silicone oil may be used, or two or more types may be used.

[0231] The viscosity of the silicone oil at 25°C is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, even more preferably 40 mPa·s or more, even more preferably 60 mPa·s or more, particularly preferably 80 mPa·s or more, preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, and even more preferably 4,000 mPa·s or less, from the viewpoint that it can improve the applicability of the resulting composition A2, impart slipperiness to the formed antifouling coating film A2 for aquatic organisms, and improve antifouling properties.

[0232] The kinematic viscosity of the silicone oil at 25°C is preferably 10 mm, as this improves the applicability of the resulting composition A2, imparts slipperiness to the formed antifouling coating A2 for aquatic organisms, and enhances its antifouling properties. ２ / s or more, more preferably 30 mm ２ / s or more, more preferably 50 mm ２ The value is 1 / s or more, preferably 5,000 mm ２ / s or less, more preferably 4,000 mm ２ / s or less, more preferably 3,500 mm ２ The value is less than or equal to / s. Note that the kinematic viscosity of the silicone oil at 25°C was measured in accordance with JIS Z 8803:2011.

[0233] When composition A2 contains silicone oil, the solid content is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent formability and antifouling properties.

[0234] Examples of silicone oils include dimethyl silicone (polydimethylsiloxane, unmodified silicone) and modified silicone. Preferably, the silicone oil is one that does not contain reactive groups. Examples of such reactive groups include those described in the section on curable polyorganosiloxanes.

[0235] A commercially available product may be used as the dimethyl silicone, and an example of such a product is "KF-96-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 100 mm²). ２ / s), "KF-96-1,000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 1,000 mm) ２ Examples include / s).

[0236] Examples of the modified silicones include compounds in which some of the methyl groups of dimethyl silicone are replaced with organic groups other than methyl groups. Specific examples include phenyl-modified silicones, polyether-modified silicones, long-chain alkyl-modified silicones, higher fatty acid ester-modified silicones, and alkyl fluoride-modified silicones.

[0237] Examples of modified silicone structures include side-chain modified type, both-end modified type, one-end modified type, block type, side-chain and one-end modified type, and side-chain and both-end modified type.

[0238] Among the modified silicones mentioned above, one or more selected from phenyl-modified silicones and polyether-modified silicones are preferred because they impart appropriate vibrational modification to composition A2, improve its coating properties, and allow for the easy formation of an antifouling coating film A2 with excellent antifouling properties.

[0239] The phenyl modification rate of the phenyl-modified silicone is preferably 3 to 50%, more preferably 3 to 20%, and even more preferably 4 to 10%, from the viewpoint of easily forming an antifouling coating A2 with excellent formability and antifouling properties. The phenyl modification rate is expressed as a percentage of the number of phenyl groups relative to the total number of phenyl and methyl groups bonded to silicon.

[0240] The kinematic viscosity of the phenyl-modified silicone at 25°C is preferably 10 to 5,000 mm, considering the coating properties of the resulting composition A2 and the antifouling properties of the formed antifouling coating film A2. ２ / s, more preferably 50 to 4,000 mm ２ / s, more preferably 80 to 3,500 mm ２ It is / s.

[0241] A commercially available product may be used as the phenyl-modified silicone. For example, "KF-50-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25°C): 100 mm) is a commercially available product. ２ / s), "KF-50-1,000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25℃): 1,000 mm) ２ / s), "KF-50-3,000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25℃): 3,000 mm) ２ Examples include / s).

[0242] When composition A2 contains phenyl-modified silicone, the solid content is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, particularly preferably 5% by mass or more, preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent formability and antifouling properties.

[0243] Examples of polyether-modified silicone structures include side-chain modified type, both-end modified type, one-end modified type, block type, side-chain and one-end modified type, and side-chain and both-end modified type. The side-chain modified type and both-end modified type are preferred, and the both-end modified type is even more preferred.

[0244] Examples of polyethers (polyalkylene glycols) that constitute the polyether group (polyalkylene glycol group) of polyether-modified silicone include polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, and copolymers of polyethylene glycol and polypropylene glycol, with the copolymer of polyethylene glycol and polypropylene glycol being preferred.

[0245] Polyether-modified silicone can easily form an antifouling coating A2 with excellent formability and antifouling properties, and therefore, the proportion of polyether substructure in its structure is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, and even more preferably 20 to 50% by mass.

[0246] In polyether-modified silicones, when the polyether group has both an ethyleneoxy (EO) group and a propyleneoxy (PO) group, the molar ratio [EO / PO] of the ethyleneoxy (EO) group to the propyleneoxy (PO) group in the polyether group is preferably 0.3 or higher, preferably 9.0 or lower, more preferably 5.0 or lower, even more preferably 4.0 or lower, and particularly preferably 3.5 or lower, from the viewpoint that it is possible to easily form an antifouling coating A2 with excellent long-term antifouling properties.

[0247] The molar ratio of EO groups to PO groups in the polyether-modified silicone is, for example, １ It can be measured by H-NMR measurement. Specifically, １ Based on the integral values ​​of the methyl group of the PO group (approximately 0.8–1.2 ppm) and the EO group and the nonmethyl group portion of the PO group (approximately 3–4 ppm) as measured by 1H-NMR, the following formula can be used to calculate EO / PO = {([integral value of approximately 3–4 ppm] - [integral value of approximately 0.8–1.2 ppm]) / 4} / {[integral value of approximately 0.8–1.2 ppm] / 3}

[0248] Composition A2 has an ethylene oxy partial structure (-OC ２ H ４When a polyether-modified silicone containing a dimethylsiloxane substructure (-Si(CH)) is included, it is possible to impart good antifouling properties to the formed antifouling coating film A2, and from this point of view, the dimethylsiloxane substructure of the silicone (-Si(CH)) is used. ３ ) ２ The total content of the ethyleneoxy substructure per 100 parts by mass of -O- is preferably 0.1 to 20 parts by mass, more preferably 0.3 to 15 parts by mass.

[0249] The kinematic viscosity of the polyether-modified silicone at 25°C is preferably 10 to 5,000 mm, considering the coating properties of the resulting composition A2 and the antifouling properties of the formed antifouling coating film A2. ２ / s, more preferably 50 to 2,000 mm ２ / s, more preferably 100 to 500 mm ２ It is / s.

[0250] A commercially available product may be used as the polyether-modified silicone. For example, "X-22-4272" (manufactured by Shin-Etsu Chemical Co., Ltd., double-ended type, kinematic viscosity (25°C): 270 mm) is one such commercially available product. ２ / s), "KF-6020" (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type, kinematic viscosity (25°C): 180 mm) ２ Examples include the "FZ-2203" (manufactured by Toray Dow Corning Co., Ltd., block type).

[0251] When composition A2 contains polyether-modified silicone, the solid content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent formability and antifouling properties.

[0252] • Paraffin oil The paraffin oil is not particularly limited, but liquid paraffin is preferred. One type of paraffin oil may be used, or two or more types may be used.

[0253] The kinematic viscosity of the paraffin oil at 25°C is preferably 10 mm ２ / s or more, more preferably 50 mm ２ / s or more, still more preferably 100 mm ２ / s or more, and preferably 5,000 mm ２ / s or less, more preferably 2,000 mm ２ / s or less, still more preferably 500 mm ２ / s or less.

[0254] When the composition A2 contains paraffin oil, the solid content thereof is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, based on 100% by mass of the solid content of the composition A2, from the viewpoints such as being able to easily form an antifouling coating film A2 excellent in formability and antifouling property.

[0255] - Oil and fat Examples of the oil and fat include esters obtained using fatty acids and glycerin, such as animal fats and vegetable oils. The oil and fat may be used alone or in combination of two or more.

[0256] - (Meth)acrylic polymer having a hydrophilic group The (meth)acrylic polymer having a hydrophilic group preferably contains a structural unit derived from a monomer having a hydrophilic group, more preferably contains a structural unit derived from a monomer having a hydrophilic group and a structural unit derived from a hydrophobic monomer, and still more preferably consists of a structural unit derived from a monomer having a hydrophilic group and a structural unit derived from a hydrophobic monomer. However, it contains a structural unit derived from a (meth)acrylic monomer. The (meth)acrylic polymer having a hydrophilic group may be used alone or in combination of two or more.

[0257] Because the (meth)acrylic polymer has hydrophilic groups, the hydrophilic portions of the (meth)acrylic polymer in the formed antifouling coating A2 dissolve or swell and gradually migrate to the surface of the antifouling coating A2, thereby efficiently suppressing the adhesion of aquatic organisms. Furthermore, because it has a (meth)acrylic structure, it is thought that it can maintain its antifouling properties over a long period of time by undergoing gradual hydrolysis and changing its affinity for water.

[0258] The content of constituent units derived from monomers having hydrophilic groups in the (meth)acrylic polymer having hydrophilic groups is preferably 1 to 100% by mass, more preferably 3 to 80% by mass, even more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass.

[0259] As the hydrophilic group, ether groups and hydroxyl groups are preferred from the viewpoint of antifouling properties, and ether groups are more preferred.

[0260] As the monomer having the hydrophilic group, monomers having a polyalkylene glycol group, monomers having a hydroxyl group, and monomers having an alkoxyalkyl group are preferred from the viewpoint of antifouling properties, and monomers having a polyalkylene glycol group are more preferred.

[0261] Specific examples of monomers having hydrophilic groups include one or more selected from polyalkylene glycol (meth)acrylate, hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloylmorpholine, and vinylpyrrolidone, which can further improve the antifouling properties of the formed antifouling coating film A2. One or more selected from polyalkylene glycol (meth)acrylate and hydroxyalkyl (meth)acrylate are more preferred, and polyalkylene glycol (meth)acrylate is even more preferred.

[0262] Examples of polyalkylene glycol (meth)acrylates include compounds in which one end of the polyalkylene glycol is directly esterified with (meth)acrylic acid or linked via a linking group, and the other end is a hydroxyl group or an alkoxy group, with compounds in which the other end is an alkoxy group being preferred. Among these, compounds in which one end of the polyalkylene glycol is directly esterified with (meth)acrylic acid are preferred, and compounds in which the other end is an alkoxy group are more preferred.

[0263] The (meth)acrylic acid is preferably acrylic acid and methacrylic acid, with acrylic acid being more preferred. The terminal alkoxy group may be, for example, a methoxy group, a phenoxy group, or an octoxy group, with methoxy and phenoxy groups being preferred, and methoxy groups being more preferred.

[0264] The polyalkylene glycol constituting the polyalkylene glycol (meth)acrylate is preferably polyethylene glycol, polypropylene glycol, or a copolymer of ethylene glycol and propylene glycol, with polyethylene glycol being more preferred.

[0265] The average number of alkylene glycol units constituting the polyalkylene glycol in the polyalkylene glycol (meth)acrylate is preferably 2 to 25, more preferably 3 to 15, and even more preferably 5 to 12.

[0266] Specific examples of the polyalkylene glycol (meth)acrylate include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-butylene glycol) mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol (meth)acrylate, octoxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, dodecyloxypolyethylene glycol mono(meth)acrylate, octadecyloxypolyethylene glycol mono(meth)acrylate, and nonylphenoxypolypropylene glycol (meth)acrylate, with methoxypolyethylene glycol mono(meth)acrylate being preferred.

[0267] The polyalkylene glycol (meth)acrylate may be a commercially available product, such as NK Ester AM-90G (methoxypolyethylene glycol #400 acrylate), NK Ester AM-130G (methoxypolyethylene glycol #550 acrylate), NK Ester M-90G (methoxypolyethylene glycol #400 methacrylate), and NK Ester, all manufactured by Shin Nakamura Chemical Industry Co., Ltd. Examples include M-230G (methoxy polyethylene glycol #1000 methacrylate); Light Acrylate MTG-A (methoxy-triethylene glycol acrylate), Light Acrylate EC-A (ethoxy-diethylene glycol acrylate), Light Acrylate EHDG-AT (2-ethylhexyloxy-diethylene glycol acrylate), and Light Ester 041MA (methoxy polyethylene glycol methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.; Bremmer ANP-300 (nonylphenoxy polypropylene glycol acrylate), Bremmer AP-400 (polypropylene glycol monoacrylate), Bremmer 70PEP-350B (polyethylene glycol polypropylene glycol monomethacrylate), Bremmer 55PET-800 (polyethylene glycol tetramethylene glycol monomethacrylate), and Bremmer 50POEP-800B (octoxy polyethylene glycol polypropylene glycol methacrylate) manufactured by NOF Corporation; and Viscoat #MTG (methoxy polyethylene glycol acrylate) manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0268] Examples of the hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Commercially available hydroxyalkyl (meth)acrylates may also be used, such as Light Ester HOA(N) (2-hydroxyethyl acrylate), Light Ester HO-250(N) (2-hydroxyethyl methacrylate), and Light Ester HOP(N) (2-hydroxypropyl methacrylate) manufactured by Kyoeisha Chemical Co., Ltd.

[0269] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate.

[0270] Tetrahydrofurfuryl acrylate is more preferred as the tetrahydrofurfuryl (meth)acrylate.

[0271] As the 4-(meth)acryloylmorpholine, 4-acryloylmorpholine is more preferred.

[0272] Examples of the vinylpyrrolidone include 1-vinyl-2-pyrrolidone (N-vinyl-2-pyrrolidone), 3-acetyl-1-vinylpyrrolidine-2-one, and 3-benzoyl-1-vinylpyrrolidine-2-one, with 1-vinyl-2-pyrrolidone being preferred.

[0273] The content of constituent units derived from hydrophobic monomers in the (meth)acrylic polymer having hydrophilic groups is preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 95% by mass or less, particularly preferably 90% by mass or less, preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more.

[0274] It is believed that the (meth)acrylic polymer having hydrophilic groups has constituent units derived from hydrophobic monomers, which gives it high affinity to other components of the formed antifouling coating A2, such as silicone crosslinks, and allows for a uniform sliding effect to be exerted on the surface of the antifouling coating A2.

[0275] Examples of the hydrophobic monomers include alkyl (meth)acrylates having branched, linear, or cyclic alkyl groups having 1 to 30 carbon atoms, aryl (meth)acrylates having aromatic groups having 6 to 10 carbon atoms, and (meth)acrylic group-containing silicones. Alkyl (meth)acrylates and (meth)acrylic group-containing silicones are preferred, and alkyl (meth)acrylates are more preferred.

[0276] The number of carbon atoms in the alkyl(meth)acrylate is preferably 4 to 18, more preferably 4 to 8, and particularly preferably 4 to 6. Furthermore, the alkyl group is preferably branched or linear, and more preferably branched.

[0277] Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 3,5,5-trimethylhexyl (meth)acrylate, lauryl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate. Among these, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate are preferred.

[0278] The number of carbon atoms in the aryl group of the aryl (meth)acrylate is preferably 6 to 7. Specific examples of aryl (meth)acrylates include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0279] As the (meth)acrylic group-containing silicone, a methacrylic group-containing silicone is preferred. As the (meth)acrylic group-containing silicone, a compound in which the (meth)acrylic group is bonded to one end of the silicone main chain via a linking group is preferred, a compound in which the (meth)acrylic group is directly bonded to one end of the silicone main chain is preferred, and a compound in which the (meth)acrylic group is bonded to one end of the silicone main chain via a linking group is preferred. The linking group is preferably a trimethylene group. Furthermore, it is more preferable that an alkyl group having 1 to 6 carbon atoms is present at the end opposite to the (meth)acrylic group, and it is preferable that a butyl group is present.

[0280] The silicone main chain is preferably composed of a linear or branched dimethylsilicone (polydimethylsiloxane), and more preferably of a linear dimethylsilicone.

[0281] Commercially available silicones containing (meth)acrylic groups may be used, and examples of such commercially available products include Cylaprene™-0701T (tris(trimethylsiloxy)silylpropyl methacrylate), Cylaprene FM-0711 (methacrylic group-containing dimethylpolysiloxane, number average molecular weight 1,000), and Cylaprene FM-0721 (methacrylic group-containing dimethylpolysiloxane, number average molecular weight 5,000), all manufactured by JNC Corporation.

[0282] The weight-average molecular weight (Mw) of the (meth)acrylic polymer having hydrophilic groups is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, particularly preferably 7,000 or more, preferably 150,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and particularly preferably 30,000 or less, from the viewpoint of the viscosity of the resulting composition A2 and the antifouling properties of the formed antifouling coating film A2.

[0283] When composition A2 contains a (meth)acrylic polymer having hydrophilic groups, the solid content is preferably 0.2% by mass or more, more preferably 0.8% by mass or more, even more preferably 2% by mass or more, particularly preferably 4% by mass or more, preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent formability and antifouling properties.

[0284] Polyglycerol esters are preferred as polyglycerol fatty acid esters. One type of polyglycerol ester may be used, or two or more types may be used.

[0285] Polyglycerol fatty acid esters are, for example, esters obtained using polyglycerol and fatty acids. The fatty acids are preferably saturated or unsaturated fatty acids having 8 to 24 carbon atoms. Specific examples include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, linoleic acid, and linolenic acid. The average number of glycerol repeats in the polyglycerol ester is preferably 3 to 100, more preferably 5 to 30. Furthermore, the polyglycerol ester may be a monoester having one ester group, a diester having two ester groups, or a polyester having three or more ester groups. An example of a polyglycerol fatty acid ester is the S-Face series manufactured by Sakamoto Pharmaceutical Co., Ltd.

[0286] Polyalkylene glycol Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, and alkyl ethers thereof. One type of polyalkylene glycol may be used, or two or more types may be used.

[0287] [Optional Components] Composition A2 may contain optional components other than curable polyorganosiloxane and lubricants. Examples of such optional components include at least one component selected from the group consisting of silica particles, pyrithione metal salts, polyethylene oxide wax, coloring pigments, organic solvents, curing catalysts, organosilicon crosslinking agents, silane coupling agents, biological repellents other than pyrithione metal salts, pigments other than silica particles and coloring pigments, dehydrating agents other than organosilicon crosslinking agents, anti-sagging and anti-settling agents other than polyethylene oxide wax, wetting and dispersing agents other than polyethylene oxide wax, enzymes, flame retardants, and heat conduction improvers.

[0288] [Silica Particles] Composition A2 preferably contains silica particles because it can improve the fluidity and thixotropy of composition A2, and can easily form an antifouling coating A2 with excellent hardness, flexibility, and strength. One type of silica particle may be used, or two or more types may be used.

[0289] Dry-processed silica particles and wet-processed silica particles are preferred as silica particles, with dry-processed silica particles being more preferred.

[0290] The silica particles preferably contain at least one selected from the group consisting of hydrophobic silica particles and hydrophilic silica particles, and it is preferable that at least hydrophobic silica particles are included. Hydrophobic silica particles are preferable to be added from the viewpoint of improving the fluidity and thixotropy of composition A2, and from the viewpoint of the hardness, flexibility, and strength of the antifouling coating film A2 that is formed. Hydrophilic silica particles are preferable to be added from the viewpoint of reducing the viscosity of composition A2 and improving the antifouling properties of the antifouling coating film A2 that is formed.

[0291] Hydrophobic silica particles are hydrophobic treated silica (silica whose surface has been hydrophobicized), and can be obtained, for example, by treating the hydroxyl groups (silanol groups) bonded to the silicon atoms on the silica surface with a hydrophobic treatment agent. Examples include aqueous wet silica and hydrophobic fumed silica.

[0292] Examples of the hydrophobic treatment agents include organodisilazane, organoalkoxysilane, organochlorosilane, cyclic organopolysilazane, and organopolysiloxane, among which organodisilazane, organoalkoxysilane, organochlorosilane, and organopolysiloxane are preferred. Specific examples of these include hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, 1,3-diethyl-1,1,3,3-tetramethyldisilazane, 1,3-dimethyl-1,1,3,3-tetraethyldisilazane, 1,3-divinyltetramethyldisilazane, 1,3-diallyltetramethyldisilazane, 1,3-dibutenyltetramethyldisilazane, 1,3-dipentenyltetramethyldisilazane, 1,3-dihexenyltetramethyldisilazane, 1,3-diheptenyltetramethyldisilazane, 1,3-dioctenyltetramethyldisilazane, 1,3-dinonenyltetramethyldisilazane, 1,3-didekenyltetramethyldisilazane, and 1,3-divinyltetramethyldisilazane. Examples include silazane compounds such as laethyldisilazane and 1,3-dimethyltetravinyldisilazane; alkoxysilane compounds such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, and butenyltrimethoxysilane; chlorosilane compounds such as methyltrichlorosilane, trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dimethylvinylchlorosilane, and allyldimethylchlorosilane; and siloxane compounds such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane. From the viewpoint of workability and reactivity with silanol groups on the silica surface, silazane compounds, chlorosilane compounds, and siloxane compounds are preferred, hexamethyldisilazane, 1,3-divinyltetramethyldisilazane, methyltrichlorosilane, dimethyldichlorosilane, hexamethylcyclotrisiloxane, and octamethylcyclotetrasiloxane are more preferred, and hexamethyldisilazane, 1,3-divinyltetramethyldisilazane, and dimethyldichlorosilane are even more preferred.

[0293] Commercially available hydrophobic silica particles may be used, and examples of such commercially available products include "AEROSIL R974" and "AEROSIL RX200" manufactured by Nippon Aerosil Co., Ltd.

[0294] Examples of hydrophilic silica particles include untreated silica particles (surface-untreated silica particles), and specific examples include dry-process silica particles (fumed silica, anhydrous silica) and wet-process silica particles (hydrated silica), with dry-process silica particles being preferred and fumed silica being more preferred. Commercially available hydrophilic silica particles may also be used, and an example of such a commercial product is "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd.

[0295] When composition A2 contains silica particles, the amount is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent strength and hardness.

[0296] When composition A2 contains silica particles, the amount is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, even more preferably 3 parts by mass or more, preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less, per 100 parts by mass of curable polyorganosiloxane, in order to easily form an antifouling coating A2 with excellent strength and hardness.

[0297] <Pyrithione Metal Salt> Composition A2 may contain a pyrithione metal salt for purposes such as enhancing the antifouling properties of the antifouling coating film A2 that is formed. Examples of pyrithione metal salts include copper pyrithione and zinc pyrithione, and among these, copper pyrithione is preferred because it can easily form an antifouling coating film A2 with excellent antifouling properties. One type of pyrithione metal salt may be used, or two or more types may be used.

[0298] When composition A2 contains a pyrithione metal salt, the content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, even more preferably 3.0% by mass or more, and particularly preferably 5.0% by mass or more, based on 100% by mass of the solid content of composition A2, in order to easily form an antifouling coating A2 with excellent antifouling properties. Furthermore, the content is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less, in order to easily obtain a composition A2 with excellent ease of preparation, dispersibility, and storage stability.

[0299] <Oxidized Polyethylene Wax> Composition A2 may contain oxided polyethylene wax because it is easy to prepare, has excellent dispersibility, and allows for easy acquisition of composition A2 with excellent storage stability. One type of oxided polyethylene wax may be used, or two or more types may be used.

[0300] Examples of oxidized polyethylene waxes include resins obtained by oxidizing polyethylene and introducing polar groups. Such oxidized polyethylene waxes may be synthesized by conventionally known methods or may be commercially available. Examples of such commercially available products include "Disparon 4200-20" manufactured by Kusumoto Chemical Co., Ltd. and "ASA-D-120" manufactured by Ito Oil Co., Ltd.

[0301] The acid value (solid acid value) of the oxidized polyethylene wax is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or more, more preferably 40 mg KOH / g or less, and more preferably 35 mg KOH / g or less, from the viewpoint that composition A2, which is excellent in ease of preparation, excellent in dispersibility, and excellent in storage stability, can be easily obtained.

[0302] When composition A2 contains oxidized polyethylene wax, the solid content is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, preferably 3.0% by mass or less, more preferably 2.2% by mass or less, even more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily obtain composition A2 which is excellent in ease of preparation, dispersibility, and storage stability.

[0303] Furthermore, when composition A2 contains a pyrithione metal salt and polyethylene oxide wax, the solid content of polyethylene oxide wax relative to 100 parts by mass of pyrithione metal salt is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1.0 part by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less, for similar reasons.

[0304] <Coloring Pigments> It is preferable that composition A2 contains coloring pigments. By including coloring pigments in composition A2, the coating strength of the antifouling coating A2 that is formed can be increased. One type of coloring pigment may be used, or two or more types may be used.

[0305] The coloring pigments are not particularly limited, but examples include inorganic pigments such as iron oxide, titanium dioxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate; and organic pigments such as naphthol red, phthalocyanine blue, phthalocyanine green, and diketopyrrolopyrrole red. Among these, it is preferable that the composition A2 contains at least an inorganic pigment, from the viewpoint of ease of preparation, coating properties, storage stability, and the antifouling properties of the antifouling coating film A2 formed. It is more preferable that it contains one or more selected from iron oxide, titanium dioxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate, even more preferable that it contains one or more selected from iron oxide, titanium dioxide, and carbon black, and particularly preferable that it contains one or more selected from iron oxide and titanium dioxide.

[0306] Examples of the iron oxide include red iron oxide, yellow iron oxide, and black iron oxide. As for the titanium oxide, any of the rutile, anatase, or brookite types can be used, but the rutile type is preferred from the viewpoint of the stability and availability of composition A2 and the antifouling coating A2.

[0307] When composition A2 contains an inorganic pigment as a coloring pigment, the amount of the inorganic pigment is preferably 0.01 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 3 to 12% by mass, relative to 100% by mass of the solid content of composition A2, in order to easily obtain composition A2 which is excellent in ease of preparation, coating properties and storage stability, and to easily form an antifouling coating film A2 which is excellent in antifouling properties.

[0308] On the other hand, when composition A2 contains an organic pigment, the amount is preferably 0.01 to 10% by mass, more preferably 0.1 to 9% by mass, and even more preferably 0.2 to 8% by mass, based on 100% by mass of the solid content of composition A2, in order to easily obtain composition A2 which is excellent in terms of ease of preparation, coating properties, and storage stability.

[0309] <Organic Solvents> Composition A2 may contain organic solvents, for example, to keep its viscosity low and improve its coating properties. One type of organic solvent may be used, or two or more types may be used.

[0310] Examples of organic solvents include aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents, alicyclic hydrocarbon organic solvents, ketone organic solvents, alcohol organic solvents, and ester organic solvents. Aromatic hydrocarbon organic solvents and ketone organic solvents are preferred, and aromatic hydrocarbon organic solvents are more preferred.

[0311] Examples of aromatic hydrocarbon organic solvents include toluene, xylene, and mesitylene, with xylene being preferred. Examples of aliphatic hydrocarbon organic solvents include pentane, hexane, heptane, and octane. Examples of alicyclic hydrocarbon organic solvents include cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of ketone organic solvents include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate, with acetylacetone being preferred. Examples of alcohol organic solvents include ethanol, n-propanol, isopropyl alcohol, n-butanol, and isobutanol. Examples of ester organic solvents include ethyl acetate, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.

[0312] If composition A2 contains an organic solvent, the amount is preferably 3% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to 100% by mass of composition A2, in order to easily obtain composition A2 with excellent coating properties, and preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less, in order to suppress sagging during coating of composition A2 and reduce environmental impact.

[0313] <Curing Catalyst> Composition A2 preferably contains a curing catalyst, as it can improve the curing speed and the film strength of the antifouling coating A2. One type of curing catalyst may be used, or two or more types may be used.

[0314] Preferred curing catalysts include tin compounds, titanium compounds, organometallic compounds other than tin and titanium compounds, metal salts of fatty acids, and amine compounds, with tin compounds, alkali metal salts of fatty acids, and amine compounds being more preferred. Furthermore, from the viewpoint of improving the curing rate in low-temperature and high-humidity environments, it is preferable to use metal salts of fatty acids and amine compounds, and more preferable to use alkali metal salts of fatty acids and amine compounds.

[0315] Examples of the tin compounds include dibutyltin diacetate, dibutyltin acetoacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, bis(dibutyltin laurate) oxide, dibutylbis(triethoxysiloxy)tin, and bis(dibutyltin acetate). Examples include dibutyltin oxide, dibutyltin bis(ethyl maleate), dioctyl tin bis(ethyl maleate), tin naphthenate, and tin oleate. Dibutyltin diacetate, dibutyltin acetoacetonate, dibutyltin dilaurate, dibutyltin dioleate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, and dibutyltin dineodecanoate are preferred, with dibutyltin dilaurate being more preferred.

[0316] Commercially available products may be used as the tin compound, and examples of such commercial products include "NEOSTANN U-100" manufactured by Nitto Chemical Co., Ltd. and "Glex TL" manufactured by DIC Corporation.

[0317] Examples of the aforementioned titanium compounds include tetraisopropoxytitanium, tetra-N-butoxytitanium, tetrakis(2-ethylhexyl) orthotitanate, dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctyl glycol.

[0318] Examples of organometallic compounds other than the tin and titanium compounds mentioned above include zinc naphthenate, zinc stearate, zinc-2-ethyl octoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, and alkoxyaluminum compounds.

[0319] Examples of fatty acids that constitute the metal salts of the aforementioned fatty acids include acetic acid, 2-ethylhexanoic acid, octanoic acid, decanoic acid, neodecanoic acid, naphthenic acid, versatic acid, and oxalic acid.

[0320] Examples of metals that form the metal salts of the fatty acids include alkali metals such as lithium, sodium, and potassium, magnesium, calcium, neodymium, titanium, zirconium, iron, ruthenium, cobalt, nickel, copper, zinc, bismuth, and aluminum. Among these, metals of groups 10 to 12 such as alkali metals, nickel, copper, and zinc are preferred, and alkali metals and zinc are more preferred.

[0321] Examples of the amine compounds include 1,6-hexanediamine-N,N,N,N-tetramethyl, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,2-dimethylimidazole. Among these, 2,4,6-tris(dimethylaminomethyl)phenol is preferred.

[0322] When composition A2 contains a curing catalyst, the amount thereof is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily obtain composition A2 with excellent curing speed.

[0323] If composition A2 contains a curing catalyst, its content is preferably 0.03 to 30 parts by mass, more preferably 0.3 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of solid content of the curable polyorganosiloxane.

[0324] <Organosilicon Crosslinking Agent> Composition A2 preferably contains an organosilicon crosslinking agent because it can improve the curing speed, the strength of the formed antifouling coating A2, and the adhesion to the coating S1 and tie coat T1. The organosilicon crosslinking agent is not limited to those intended for these functions, and may also be included for purposes such as functioning as a wetting agent for colored pigments, etc. One type of organosilicon crosslinking agent may be used, or two or more types may be used.

[0325] Examples of organosilicon crosslinking agents include organosilanes in which three or four hydrolyzable groups are bonded to a silicon atom, and their partial condensates are also included. In addition, an example of an organosilane in which three hydrolyzable groups are bonded to a silicon atom is an organosilane in which one more hydrocarbon group is bonded to a silicon atom. The hydrolyzable groups are preferably alkoxy groups, more preferably methoxy groups and ethoxy groups. The hydrocarbon groups are preferably hydrocarbon groups having 1 to 6 carbon atoms, more preferably methyl groups, ethyl groups and propyl groups, and even more preferably methyl groups and ethyl groups.

[0326] Examples of organosilicon crosslinking agents include tetraethyl orthosilicate, partially hydrolyzed condensates of tetraethyl orthosilicate, alkyltrialkoxysilane, and oximesilane, with tetraethyl orthosilicate and partially hydrolyzed condensates of tetraethyl orthosilicate being preferred.

[0327] Commercially available products may be used as the tetraethyl orthosilicate, such as "Ethyl Silicate 28" manufactured by Colcoat Co., Ltd. and "Ethyl Orthosilicate" manufactured by Tama Chemical Industry Co., Ltd. Commercially available products may be used as the partial hydrolysis condensate of the tetraethyl orthosilicate, such as "Silicate 40" manufactured by Tama Chemical Industry Co., Ltd. and "WACKER SILICATE TES 40 WN" manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Commercially available products may be used as the alkyltrialkoxysilane, such as "KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd. Commercially available oximesilanes may be used, and examples of such commercial products include "X-93-4096" (vinylmethyltris(methylisobutylketoxime)silane) manufactured by Shin-Etsu Chemical Co., Ltd., "MTO (MOS)" (methyltris(methylethylketoxime)silane) and "VTO (VOS)" (vinyltris(methylethylketoxime)silane) manufactured by Toray Industries, Inc.

[0328] If composition A2 contains an organosilicon crosslinking agent, its content is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 9% by mass or less, based on 100% by mass of the solid content of composition A2. If composition A2 contains an organosilicon crosslinking agent, its content is preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.5 parts by mass or more, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and even more preferably 10 parts by mass or less, based on 100 parts by mass of the solid content of the curable polyorganosiloxane.

[0329] <Silane Coupling Agent> Composition A2 may contain a silane coupling agent, as it can improve the curing speed, the curability of the formed antifouling coating A2, and the adhesion to the coating S1 and tie coat T1. It is preferable that composition A2 contains an organosilicon crosslinking agent and / or a silane coupling agent for the purpose of improving the curability, strength, and adhesion of the formed antifouling coating A2 to the coating S1 and tie coat T1. One type of silane coupling agent may be used, or two or more types may be used.

[0330] Examples of silane coupling agents include organic alkoxysilanes having at least one alkoxy group and at least one organic reactive group.

[0331] The alkoxy group is preferably a methoxy group or an ethoxy group, with the methoxy group being more preferred. One to three alkoxy groups are bonded to a silicon atom, preferably two to three, and more preferably three.

[0332] Examples of the aforementioned organic reactive groups include amino groups, mercapto groups, epoxy groups, isocyanate groups, ureido groups, vinyl groups, (meth)acrylic groups, and styryl groups, with amino groups, mercapto groups, epoxy groups, isocyanate groups, and ureido groups being preferred, amino groups, mercapto groups, and epoxy groups being more preferred, and amino groups being even more preferred.

[0333] Specific organic reactive groups containing an amino group include the 2-(aminoethyl)-3-aminopropyl group and the 3-aminopropyl group.

[0334] Examples of silane coupling agents include 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-(2-(2-aminoethylamino)ethylamino)propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane, with 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane being preferred, and 3-(2-aminoethylamino)propyltrimethoxysilane being more preferred. Condensed products of the above compounds may also be used as silane coupling agents.

[0335] If composition A2 contains a silane coupling agent, the solid content is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, preferably 3% by mass or less, and more preferably 1% by mass or less, based on 100% by mass of the solid content of composition A2.

[0336] If composition A2 contains a silane coupling agent, the solid content is preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, preferably 3 parts by mass or less, and more preferably 1 part by mass or less, per 100 parts by mass of curable polyorganosiloxane.

[0337] <Biological repellents other than pyrithione metal salts> Composition A2 preferably contains biological repellents other than pyrithione metal salts (hereinafter also simply referred to as "biological repellents") for the purpose of improving the antifouling properties of the antifouling coating A2 that is formed. Biological repellents can suppress the adhesion of aquatic organisms to the surface of the antifouling coating A2 and improve its antifouling properties. One type of biological repellent may be used, or two or more types may be used.

[0338] As a biological repellent, it is preferable to have a repellent effect on aquatic organisms and a constant elution rate into water, and one or more selected from 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (also known as tralopyril) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (also known as DCOIT) are preferred.

[0339] When composition A2 contains a biological repellent, the solid content is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, based on 100% by mass of the solid content of composition A2, in order to easily obtain composition A2 with excellent coating properties and to easily form an antifouling coating A2 with excellent strength and antifouling properties.

[0340] <Pigments other than silica particles and coloring pigments> Examples of pigments other than silica particles and coloring pigments include talc, mica, calcium carbonate, barium carbonate, potassium feldspar, kaolin, and glass short fibers. One type of pigment other than silica particles and coloring pigments may be used, or two or more types may be used.

[0341] <Dehydrating agents other than organosilicon crosslinking agents> Examples of dehydrating agents other than the organosilicon crosslinking agents include zeolites, porous alumina, orthoesters such as alkyl orthoformate, orthoboric acid, and isocyanate compounds. One type of dehydrating agent other than the organosilicon crosslinking agent may be used, or two or more types may be used.

[0342] <Anti-sagging and anti-settling agents other than polyethylene oxide wax> Examples of anti-sagging and anti-settling agents other than polyethylene oxide wax include organic clay waxes (stearate salts, lecithin salts, alkyl sulfonates, etc. of Al, Ca, and Zn), organic waxes (polyethylene wax, amide wax, polyamide wax, hydrogenated castor oil wax, etc.), and mixtures of organic clay wax and organic wax. One type of anti-sagging and anti-settling agent other than polyethylene oxide wax may be used, or two or more types may be used.

[0343] <Wetting and dispersing agents other than polyethylene oxide wax> Examples of wetting and dispersing agents other than polyethylene oxide wax include known organic or inorganic wetting and dispersing agents, such as wetting and dispersing agents having a silicone main chain. Commercially available products may be used as wetting and dispersing agents other than polyethylene oxide wax, such as "KP-578" and "KF-6106" manufactured by Shin-Etsu Chemical Co., Ltd. One type of wetting and dispersing agent other than polyethylene oxide wax may be used, or two or more types may be used.

[0344] <Enzymes> Examples of the enzymes include serine proteases, cysteine ​​proteases, metalloproteinases, cellulases, hemicellulases, pectinases, and glycosidases. One type of enzyme may be used, or two or more types may be used.

[0345] <Flame retardant> Examples of the flame retardant include antimony oxide and paraffin oxide. One flame retardant may be used, or two or more may be used.

[0346] <Thermal Conductivity Improver> Examples of the thermal conductivity improver include boron nitride and aluminum oxide. One thermal conductivity improver may be used, or two or more may be used.

[0347] [Aspects of Composition A2] Composition A2 may be a one-component antifouling paint composition in which each of the raw materials constituting Composition A2 is made into one composition, or it may be a two-component or more type antifouling paint composition in which each of the raw materials constituting Composition A2 is made into two or more agents, and the two or more agents are mixed before application of Composition A2. However, a two-component or more type antifouling paint composition is preferred in terms of being able to suppress deterioration during storage, and a one-component antifouling paint composition is preferred in terms of coatability. Examples of the two-component antifouling paint composition include a two-component antifouling paint composition and a three-component or more type antifouling paint composition. A two-component antifouling paint composition is preferred in terms of coatability, and a three-component or more type antifouling paint composition is preferred in terms of suppressing deterioration during storage.

[0348] When composition A2 contains at least one selected from a curing catalyst, an organosilicon crosslinking agent, and a silane coupling agent, and composition A2 is a two-component or more type composition, it is preferable that the curable polyorganosiloxane and at least one selected from the curing catalyst, organosilicon crosslinking agent, and silane coupling agent are contained in different agents. When composition A2 contains at least one selected from silica particles, a pyrithione metal salt, an oxidized polyethylene wax, a coloring pigment, and a biological repellent, it is preferable that the silica particles, the pyrithione metal salt, the oxidized polyethylene wax, the coloring pigment, and the biological repellent are contained in the same agent as the curable polyorganosiloxane.

[0349] [Method for Manufacturing Composition A2] Composition A2 containing silica particles is preferably manufactured as follows. First, it is preferable to have a step of kneading a curable polyorganosiloxane and silica particles. Heating may also be done during or after kneading. By kneading them in advance, the affinity between the two components is improved, and aggregation of silica particles and an increase in the viscosity of composition A2 can be suppressed. The heating conditions are preferably 100°C or higher, more preferably 100 to 300°C, and even more preferably 140 to 200°C. The pressure at this time is preferably at normal pressure or under reduced pressure, and the processing time is preferably 3 to 30 hours. When the optional component is to be added to composition A2, composition A2 can be manufactured by mixing the resulting kneaded product with the optional component.

[0350] <Silicone-based tie coat T1> It is preferable to provide a silicone-based tie coat T1 between the coating film S1 and the antifouling coating film A2, as this allows for easy acquisition of a laminated coating substrate with superior adhesion between the coating film S1 and the antifouling coating film A2. The tie coat T1 is preferably a coating film formed from a composition T1 containing a curable polyorganosiloxane and a lubricant.

[0351] The film thickness of Tiecoat T1 can be adjusted as appropriate depending on the desired application, but is preferably 50 to 200 μm, and more preferably 75 to 150 μm.

[0352] [Composition T1] Composition T1 preferably contains a curable polyorganosiloxane and a lubricant. For example, composition T1 may be the same as composition A2. That is, composition A2 can be used to form tie coat T1 and antifouling coating A2, and in some cases there may be no significant difference in composition between tie coat T1 and antifouling coating A2. However, in this laminated coating substrate, the antifouling coating formed on the outermost surface of the substrate (the outermost surface opposite to the substrate) is called the antifouling coating A2, and the coating provided between the coating S1 and the antifouling coating A2 is called tie coat T1. When forming tie coat T1 and antifouling coating A2 on coating S1, composition T1 for forming tie coat T1 and composition A2 for forming antifouling coating A2 may be the same composition, but it is preferable that they be compositions with different types and amounts of raw materials used.

[0353] <<Method for Manufacturing a Laminated Coating Substrate>> This laminated coating substrate, comprising a substrate, an antifouling coating A1, and a coating S1 in this order, can be manufactured, for example, by a method including the steps of: (I) applying or impregnating the substrate with the antifouling paint composition A1 to obtain a coated body or impregnated body; (II) drying (curing) the coated body or impregnated body to form an antifouling coating A1; and (III) applying the composition S1 on the antifouling coating A1 formed in step (II) (on the side of the antifouling coating A1 opposite to the substrate), and drying (curing) the applied composition S1 to form a coating S1. The laminated coated substrate, comprising a substrate, an antifouling coating A1, a coating S1, and an antifouling coating A2 in this order, can be manufactured, for example, by a method including step (IV) of applying composition A2 onto the coating S1 formed in step (III) (on the side of the coating S1 opposite to the substrate side), and drying (curing) the applied composition A2 to form the antifouling coating A2. A laminated coated substrate comprising a substrate, an antifouling coating A1, a coating S1, a tie coat T1, and an antifouling coating A2 in this order can be manufactured, for example, by a method including the steps of: (V) applying composition T1 onto the coating S1 formed in step (III) (on the side of the coating S1 opposite to the substrate side), drying (curing) the applied composition T1 to form a tie coat T1; and (VI) applying composition A2 onto the tie coat T1 formed in step (V) (on the side of the tie coat T1 opposite to the substrate side), and drying (curing) the applied composition A2 to form an antifouling coating A2.

[0354] When applying or impregnating, it is preferable to apply or impregnate in such a way that the thickness of the resulting coating or tie coat falls within the specified range. In this case, the coating or tie coat of the desired thickness may be formed in a single application or impregnation, or it may be formed in two or more applications or impregnations.

[0355] Examples of the application method include using coating means such as air spray, airless spray, brush, or roller. The drying (curing) method can be appropriately selected depending on the composition used, but for example, it may be air drying (at room temperature) or drying using drying means such as a heater.

[0356] The antifouling coating A1 may be an antifouling coating R1 (old antifouling coating) that has been worn down or deteriorated due to exposure to water (ocean, river, lake, etc.) for a certain period of time and is subject to repair painting or repainting. However, it is preferable that the antifouling coating R1 (old antifouling coating) is present in order to better demonstrate the effects of the present invention. A substrate with this laminated coating containing such an antifouling coating R1 can be manufactured, for example, by a method including a step (i) of cleaning the antifouling coating R1 of the substrate with the antifouling coating R1, and a step (ii) of forming a coating S1 on the antifouling coating R1 after step (i). Here, the antifouling coating R1 is an antifouling coating formed from a composition containing a silyl ester polymer having constituent units derived from triisopropylsilyl methacrylate, and it is preferable that the antifouling coating is formed from the antifouling paint composition A1. The laminated coated substrate including the antifouling coating R1 may include a step (iiii) of forming an antifouling coating A2 on the coating S1 formed in step (ii) (on the side of the coating S1 opposite to the substrate), a step (iv) of forming a tie coat T1 on the coating S1 formed in step (ii) (on the side of the coating S1 opposite to the substrate), and a step (v) of forming an antifouling coating A2 on the tie coat T1 formed in step (iv) (on the side of the tie coat T1 opposite to the coating S1). These steps (ii) to (v) correspond to steps (III) to (VI), respectively.

[0357] The aforementioned step (i) is a step of removing foreign matter (e.g., various aquatic organisms, oil, dust) adhering to the antifouling coating R1, and is a step of roughening the surface as described below. Specifically, there are no particular restrictions as long as it is a step other than roughening with a power tool, but for example, a step of washing the antifouling coating R1 with water is included. For example, the washing may be done with water at a pressure of about 5 to 10 MPa, and the washing time is not particularly limited as long as the foreign matter adhering to the antifouling coating R1 is removed, but for example, it is 1 to 10 seconds.

[0358] Conventionally, when forming an epoxy resin coating on an existing antifouling coating, a step of roughening the surface of the existing antifouling coating using a power tool equipped with a nonwoven abrasive material was performed between step (i) and step (ii) to improve adhesion between the coatings. On the other hand, according to the present invention, since a specific antifouling coating R1 is used, a substrate with a laminated coating that has excellent adhesion between the antifouling coating R1 and the coating S1 can be obtained without performing a step of roughening the surface of the antifouling coating R1 using a power tool. For this reason, it is preferable that the effects of the present invention are more fully realized, and from the viewpoint of economy and work efficiency, the step of roughening the surface of the antifouling coating R1 after step (i), specifically the step of roughening the surface of the antifouling coating R1 after step (i) using a power tool is not included between step (i) and step (ii).

[0359] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0360] <Production Example a1-1> Preparation of Copolymer Solution (a1-1) The following reaction was carried out under atmospheric pressure and a nitrogen atmosphere. In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel, 428.6 parts by mass of xylene and 100 parts by mass of triisopropylsilyl methacrylate (TIPSMA) were charged, and the mixture was heated with stirring until the liquid temperature reached 80°C. While maintaining the liquid temperature in the reaction vessel at 80±5°C, a mixture consisting of 500 parts by mass of TIPSMA, 250 parts by mass of 2-methoxyethyl methacrylate (MEMA), 100 parts by mass of methyl methacrylate (MMA), 50 parts by mass of butyl acrylate (BA), and 13 parts by mass of 2,2'-azobisisobutyronitrile (AIBN) was added dropwise to the reaction vessel over 2 hours using a dropping funnel. After the dropwise addition was complete, the reaction mixture was stirred at 80°C for 1 hour and then at 80-95°C for 1 hour and 30 minutes. Subsequently, while maintaining a temperature of 95°C, 1 part by mass of AIBN was added to the reaction mixture four times at 30-minute intervals, raising the liquid temperature to 105°C to complete the polymerization reaction. Next, 238 parts by mass of xylene were added to the reaction vessel and the mixture was stirred until the liquid was homogeneous to obtain copolymer solution (a1-1).

[0361] <Production Examples a1-2 and ca1-1 to ca1-2> Production of copolymer solution (a1-2), copolymer solution (ca1-1), and copolymer solution (ca1-2) Instead of the monomer mixture used in production example a1-1, the monomers of the types and amounts (parts by mass) shown in Table 1 were used, and the reaction was carried out in the same manner as in production example a1-1, while appropriately adjusting the reaction temperature, dropping time, initiator amount, etc., to obtain copolymer solution (a1-2), copolymer solution (ca1-1), and copolymer solution (ca1-2), respectively. In Table 1, "MAAc" is an abbreviation for methacrylic acid, and "TIPSA" is an abbreviation for triisopropylsilyl acrylate.

[0362] The obtained copolymer solutions (a1-1) to (a1-2) and copolymer solutions (ca1-1) to (ca1-2) were used to measure various physical properties as follows. The results are shown in Table 1.

[0363] <Method for measuring the solid content (heating residue) in copolymer solutions> Copolymer solutions (a1-1) to (a1-2) and copolymer solutions (ca1-1) to (ca1-2) were weighed into metal test dishes of known mass. The solutions were spread on the bottom of the test dishes and heated in a constant temperature bath maintained at 105°C for 3 hours. After that, the test dishes were removed from the constant temperature bath and allowed to cool to room temperature, and then weighed again to measure the mass of the heating residue in the metal test dishes. The solid content (mass %) in the copolymer solutions was calculated using the following formula: Solid content (mass %) in copolymer solutions = Mass of heating residue (g) × 100 / Mass of weighed copolymer solution (g)

[0364] <Method for measuring the viscosity of copolymer solutions> The viscosity (unit: mPa·s) of copolymer solutions (a1-1) to (a1-2) and copolymer solutions (ca1-1) to (ca1-2) was measured using an E-type viscometer under the following conditions. Viscosity measurement conditions Equipment: "TVE-25 type viscometer TV-25" (manufactured by Toki Sangyo Co., Ltd.) Rotor used: Standard rotor (1°34' × R24) Measurement temperature: 25℃ Rotation speed: 60 rpm

[0365] <Method for measuring the weight-average molecular weight (Mw) of copolymers> The weight-average molecular weight (Mw) of copolymers in copolymer solutions (a1-1) to (a1-2) and copolymer solutions (ca1-1) to (ca1-2) was measured using gel permeation chromatography (GPC) under the following conditions. • GPC measurement conditions: Equipment: "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: "TSKgel guardcolumn SuperMP(HZ)-M + TSKgel SuperMultiporeHZ-M + TSKgel SuperMultiporeHZ-M" (manufactured by Tosoh Corporation) Eluent: Tetrahydrofuran (THF) Flow rate: 0.35 mL / min Detector: RI Column constant temperature bath temperature: 40°C Calibration curve: Standard polystyrene and styrene monomer sample preparation method: After diluting each copolymer solution with THF, the filtrate obtained by filtering through a membrane filter was used as the GPC measurement sample.

[0366] <Method for Measuring the Solid Acid Value of Copolymer Solutions> Copolymer solutions (a1-1) to (a1-2) and copolymer solutions (ca1-1) to (ca1-2) were each weighed into a 2.0 g beaker. Next, 60 mL of the diluent shown below was measured into this beaker, and each copolymer solution was diluted. Then, using the apparatus and titration solution shown below, potentiometric titration was performed on each diluted copolymer solution, and the point of maximum slope of the titration curve was taken as the endpoint. A blank measurement was performed using the same procedure except that a copolymer solution was not used, and the solid acid value of the copolymer solution was calculated according to the following formula.

[0367] Diluent: Toluene:Ethanol:Urpure water = 100:95:5 (volume ratio) Solution apparatus: "Automatic titrator CPM-1750" (manufactured by Hiranuma Sangyo Co., Ltd.) Titration solution: Ethanol-based potassium hydroxide solution (manufactured by Junsei Kagaku Co., Ltd.) (s = 0.1 mol / L, f = 1.001, or s = 0.01 mol / L, f = 1.005)

[0368] Solid content acid value (mgKOH / g) = {(q-r) × s × 56.11 × f} / (p × solid content in copolymer solution / 100) f: factor of potassium hydroxide solution p: weight of copolymer solution weighed into a beaker (unit: g) q: titration volume to the point of maximum slope of the titration curve when using the copolymer solution (unit: mL) r: titration volume to the point of maximum slope of the titration curve in the blank measurement (unit: mL) s: molar concentration of the titration solution (unit: mol / L)

[0369] <Production of Metal Ester Group-Containing Monomers> In a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket, 85.4 parts by mass of propylene glycol monomethyl ether and 40.7 parts by mass of zinc oxide were charged and the temperature was raised to 75°C while stirring. Subsequently, a mixture consisting of 43.1 parts by mass of methacrylic acid, 36.1 parts by mass of acrylic acid, and 5.0 parts by mass of water was added dropwise from the dropping device at a constant rate over 3 hours. After the addition was complete, the mixture was stirred for a further 2 hours, and then 36.0 parts by mass of propylene glycol monomethyl ether was added to obtain a reaction solution containing metal ester group-containing monomers.

[0370] <Production Example ca1-3> Preparation of copolymer solution (ca1-3) In a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket, 15.0 parts by mass of propylene glycol monomethyl ether, 57.0 parts by mass of xylene, and 4.0 parts by mass of ethyl acrylate (EA) were charged, and the mixture was heated to 100 ± 5°C while stirring. While maintaining the same temperature, 52.0 parts by mass of the reaction solution containing the metal ester group-containing monomer obtained above (amount of metal ester group-containing monomer used: 23.4 parts by mass), 1.0 part by mass of MMA, 66.2 parts by mass of EA, 5.4 parts by mass of 2-methoxyethyl acrylate (MEA), 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, 7.0 parts by mass of polymerization initiator 2,2'-azobis(2-methylbutyronitrile), 1.0 part by mass of chain transfer agent "Nofmer MSD" (manufactured by NOF Corporation), and 10.0 parts by mass of xylene were added dropwise from a dropping device to the reaction vessel over a period of 6 hours. After the dropwise addition was complete, 0.5 parts by mass of the polymerization initiator tert-butyl peroctoate (TBPO) and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and the mixture was stirred for a further 1 hour and 30 minutes. Then, 4.4 parts by mass of xylene were added to obtain a pale yellow transparent copolymer solution (ca1-3) containing a hydrolyzable polymer (metal ester group-containing copolymer).

[0371] <Production Example ca1-4> Preparation of copolymer solution (ca1-4) In a reaction vessel equipped with a stirrer, condenser, thermometer, dropping device, nitrogen inlet tube, and heating / cooling jacket, 15.0 parts by mass of propylene glycol monomethyl ether, 60.0 parts by mass of xylene, and 4.0 parts by mass of EA were charged, and the mixture was heated to 100 ± 5°C while stirring. While maintaining the same temperature, 40.2 parts by mass of the reaction solution containing the metal ester group-containing monomer obtained above (amount of metal ester group-containing monomer used: 18.1 parts by mass), 15.0 parts by mass of MMA, 48.0 parts by mass of EA, 15.0 parts by mass of BA, 2.5 parts by mass of polymerization initiator 2,2'-azobisisobutyronitrile, 6.5 parts by mass of polymerization initiator 2,2'-azobis(2-methylbutyronitrile), 1.2 parts by mass of chain transfer agent "Nofmer MSD", and 10.0 parts by mass of xylene were added dropwise from a dropping device to the reaction vessel over a period of 6 hours. After the dropwise addition was complete, 0.5 parts by mass of the polymerization initiator tert-butyl peroctoate and 7.0 parts by mass of xylene were added dropwise over 30 minutes, and the mixture was stirred for a further 1 hour and 30 minutes. Then, 8.0 parts by mass of xylene were added to obtain a pale yellow, transparent copolymer solution (ca1-4) containing a hydrolyzable polymer (metal ester group-containing copolymer).

[0372] The obtained copolymer solutions (ca1-3) and (ca1-4) were used to measure various physical properties as follows. The results are shown in Table 1.

[0373] <Method for measuring the solid content (heat residue) in copolymer solutions> The heat residue was measured after drying copolymer solutions (ca1-3) and (ca1-4) in a hot air dryer at 105°C for 3 hours to volatilize the solvent, etc. The solid content (mass%) in the copolymer solution was calculated using the following formula: Solid content (mass%) in copolymer solution = Heat residue (g) × 100 / Mass of copolymer solution placed in the hot air dryer (g)

[0374] <Method for measuring the viscosity of copolymer solutions> The viscosity of copolymer solutions (ca1-3) and (ca1-4) at 25°C was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 60 rpm.

[0375] <Method for measuring the weight-average molecular weight (Mw) of copolymers> The Mw of copolymers in copolymer solutions (ca1-3) and (ca1-4) was measured using GPC under the following conditions. ・GPC measurement conditions Apparatus: "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: Two "TSKgel SuperAWM-H" columns and one "TSKgel SuperAW2500" column linked together (both manufactured by Tosoh Corporation, inner diameter 6 mm / length 15 cm) Eluent: N,N-dimethylformamide (DMF) (with 20 mM lithium bromide added) Flow rate: 0.600 ml / min Detector: RI Column constant temperature bath temperature: 40°C Standard substance: Polystyrene Sample preparation method: After adding a small amount of calcium chloride to each copolymer solution to dehydrate it, the filtrate obtained by filtering through a membrane filter was used as the GPC measurement sample.

[0376]

[0377] <Production Example A1-1> In a polyethylene container for the production of antifouling paint composition A1-1, 8.5 parts by mass of xylene, 1.0 part by mass of Solvesso No. 100, 2.5 parts by mass of rosin, 0.5 parts by mass of ethyl silicate, and 21.0 parts by mass of the copolymer solution (a1-1) obtained in Production Example a1-1 were added and mixed using a paint shaker until each component was uniformly dispersed or dissolved. Then, 4.0 parts by mass of talc, 4.0 parts by mass of zinc oxide, 50.0 parts by mass of cuprous oxide, 1.5 parts by mass of red iron oxide, 2.5 parts by mass of titanium dioxide, 2.0 parts by mass of copper pyrithione, and 1.0 part by mass of a settling inhibitor were added to the polyethylene container and stirred using a paint shaker for 1 hour to disperse these components. After dispersion, 1.5 parts by mass of an anti-slip agent was added, and the mixture was stirred for 20 minutes using a paint shaker. The resulting mixture was filtered through a filter mesh (mesh size: 80 mesh) to remove the residue and obtain the filtrate (anti-fouling paint composition A1-1).

[0378] <Manufacturing Examples A1-2 to A1-8 and Manufacturing Examples cA1-1 to cA1-5> Antifouling coating compositions A1-2 to A1-6 and antifouling coating compositions cA1-1 to cA1-5 were manufactured in the same manner as in Manufacturing Example A1-1, except that the types and amounts (numerical values, parts by mass) of raw materials used were changed as shown in Table 2. Details of each raw material listed in Table 2 are shown in Table 3.

[0379]

[0380]

[0381] <Manufacturing Example S1-1> Manufacturing of epoxy resin-based paint composition S1-1 In a 1000 mL poly container, 120.0 parts by mass of epoxy resin, 2.5 parts by mass of vinyl chloride resin, 2.5 parts by mass of plasticizer, 21.0 parts by mass of talc, 11.0 parts by mass of barium sulfate, 7.0 parts by mass of aluminum paste, 1.5 parts by mass of titanium white, 0.2 parts by mass of carbon black, 11.0 parts by mass of anti-sagging agent, 11.3 parts by mass of xylene, 3.0 parts by mass of PGM, and 3.0 parts by mass of methyl isobutyl ketone were blended, and 200 parts by mass of glass beads were added thereto, and the mixture was dispersed in a paint shaker for 1 hour. The resulting dispersion was filtered through a 60-mesh filter to prepare the main component (filtrate). Furthermore, 14.5 parts by mass of amine curing agent, 0.3 parts by mass of tertiary amine, 0.6 parts by mass of xylene, 0.5 parts by mass of n-butyl alcohol, and 0.1 parts by mass of silane coupling agent were mixed in a 250 mL poly container and dispersed in a paint shaker for 10 minutes until uniform. The resulting dispersion was filtered through a 60-mesh filter to prepare the curing agent component (filtrate). By mixing the prepared main component and curing agent component, epoxy resin coating composition S1-1 was obtained.

[0382] <Manufacturing Examples S1-2 to S1-9> Except for changing the types and amounts (numerical values, parts by mass) of raw materials used in the manufacture of epoxy resin-based paint compositions S1-2 to S1-9 as shown in Table 4, the main component and curing agent component were prepared in the same manner as in Manufacturing Example S1-1 to obtain epoxy resin-based paint compositions. Details of each raw material listed in Table 4 are shown in Table 5.

[0383]

[0384]

[0385] <Preparation of Compounds of Curable Silicone and Silica Particles (Compounds 1 to 5)> The curable silicone and silica particles shown in Table 6 were kneaded in the amounts indicated in Table 6 to obtain compound products. The viscosity values ​​in Table 6 are all values ​​at 25°C and were measured using a Type B rotational viscometer at a rotation speed of 60 rpm in accordance with JIS K 6249:2003. The weight-average molecular weight (Mw) in Table 6 was measured using the same method as described later.

[0386]

[0387] <Synthesis of (meth)acrylic polymers having hydrophilic groups> The reaction was carried out under atmospheric pressure and a nitrogen atmosphere. 42.86 parts by mass of methyl amyl ketone were charged into a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube, and dropping funnel, and heated with stirring until the methyl amyl ketone reached 100°C. While maintaining the temperature of the reaction mixture at 100±5°C, a mixture consisting of 40.0 parts by mass of NK ester AM-90G (methoxypolyethylene glycol acrylate, average polyethylene glycol unit count 9, manufactured by Shin Nakamura Chemical Industry Co., Ltd.), 60.0 parts by mass of isobutyl acrylate, and 4.0 parts by mass of 2,2'-azobis(2-methylbutyronitrile) was added dropwise to the reaction vessel over 4 hours. The mixture was then stirred for 2 hours while maintaining the temperature at 100±5°C to obtain a solution of (meth)acrylic polymers having hydrophilic groups.

[0388] [Solid Content] The solid content (mass%) was determined by dividing the mass of the solid obtained from drying the solution of the hydrophilic (meth)acrylic polymer at 105°C and 1 atm for 3 hours by the mass of the solution before drying. The solid content was 70.3% by mass.

[0389] [Viscosity] The viscosity (mPa·s) of the obtained hydrophilic (meth)acrylic polymer solution was measured at a liquid temperature of 25°C using an E-type viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd., rotation speed: 60 rpm). The viscosity was 109 mPa·s.

[0390] [Weight-average molecular weight (Mw)] The Mw of the hydrophilic (meth)acrylic polymer was measured using gel permeation chromatography (GPC) under the following conditions. The Mw was 9,100. • GPC conditions: Apparatus: "HLC-8420GPC" (Tosoh Corporation) Column: "TSKgel SuperH2000" and "TSKgel SuperH4000" (both Tosoh Corporation, 6 mm inner diameter, 15 cm length) linked together Eluent: Tetrahydrofuran (THF) Flow rate: 0.600 mL / min Detector: RI Column temperature: 40°C Standard substance: Polystyrene Sample preparation method: THF was added to the obtained polymer solution and filtered through a membrane filter to obtain a sample for GPC measurement.

[0391] <Manufacturing Examples A2-1 to A2-3> According to the mixing amounts (numerical values, parts by mass) listed in Table 7 for organopolysiloxane-based antifouling coating compositions A2-1 to A2-3, the raw materials listed in Table 7 were mixed and stirred to prepare three-component organopolysiloxane-based antifouling coating compositions (organopolysiloxane-based antifouling coating compositions A2-1 to A2-3) consisting of a main component, a curing agent component, and an additive component. For the main component, the components other than curable polyorganosiloxane 1 and compound-1 listed in Table 7 were mixed and stirred with 10 parts by mass of xylene to prepare a mixture, and then curable polyorganosiloxane 1, compound-1, and the remaining xylene were stirred and mixed to prepare the main component. Furthermore, when applying each composition A2-1 to A2-3, each component (main component, hardener component, and additive component) was thoroughly stirred and mixed using a disperser to ensure uniformity before use. Details of each raw material listed in Table 7 are shown in Table 9.

[0392] <Manufacturing Examples A2-4 to A2-7 and T1-1 to T1-3> One-component organopolysiloxane-based antifouling coating compositions (organopolysiloxane-based antifouling coating compositions A2-4 to A2-7 and silicone-based tie-coat compositions T1-1 to T1-3) were prepared by mixing and stirring each of the raw materials listed in Table 8 according to the blending amounts (numerical values, parts by mass) listed in Table 8. Note that the compositions listed in Table 8 were prepared by mixing and stirring each of the components except the kneaded material and lubricant with 10 parts by mass of xylene to prepare a mixture, and then stirring and mixing the kneaded material, lubricant and the remaining xylene into it. Details of each raw material listed in Table 8 are shown in Table 9.

[0393] <Sagging Resistance> Using a box-type sag tester described in JIS K 5400 (1990) 6.4, each composition was applied to a tin plate, and the film thickness (wet film thickness) was measured with a wet film gauge. Immediately afterward, the tin plate was placed vertically so that the sag tester's track line was horizontal, and the sagging resistance of the applied composition was measured. A pass was defined as when the amount of composition that flowed into the space between the applied compositions was 1 / 2 or less of the space. The coating film thickness (wet film thickness) was gradually increased, and the limit of the wet film thickness (μm) at which this pass could be maintained was measured. The sagging resistance was tested using the compositions obtained in Production Examples A2-1 to A2-7 and T1-1 to T1-3 immediately after preparation, and the compositions after being stored for 30 days under a temperature of 50°C. The results are shown in Tables 7 and 8.

[0394] <Appearance of the coating film> The appearance of the coating film on each tinplate sheet, for which the anti-sagging properties were measured, was evaluated visually according to the following evaluation criteria. The results are shown in Tables 7 and 8.

[0395] • Evaluation Criteria 3: No aggregates are observed, and the coating surface is in good condition. 2: Aggregates are observed, but no abnormalities are observed in the condition of the coating surface (unevenness or wrinkles in the coating, etc.). 1: Aggregates are observed, and abnormalities are also observed in the condition of the coating surface (unevenness or wrinkles in the coating, etc.).

[0396] <Dynamic antifouling property> On a sandblasted plate coated with an epoxy-based anticorrosive paint ("Banno 500" manufactured by China Paint Co., Ltd.), an intermediate paint ("CMP Bioclin Taikoat" manufactured by China Paint Co., Ltd.) was applied so that the thickness after drying (curing) would be 100 μm, dried at room temperature for 24 hours, and then each composition obtained in Production Examples A2-1 to A2-7 and T1-1 to T1-3 was painted at room temperature so that the thickness after drying (curing) would be 200 μm. After allowing one week to pass at room temperature, a test plate with an antifouling coating film was produced.

[0397] The test plate with an antifouling coating film installed on the side surface of the rotating rotor was immersed in the actual sea off Kure, Hiroshima Prefecture and rotated at a speed of about 15 knots. The test plate was installed so that sunlight sufficiently hit the antifouling coating film surface, creating conditions where slime formation was likely to occur. The ratio of the area of the region where slime adhered to the entire surface of the antifouling coating film of the test plate 6 months and 12 months after immersion in the sea was calculated by visual observation and evaluated according to the following evaluation criteria. The results are shown in Tables 7 and 8.

[0398] - Evaluation criteria: 5: No slime adhesion; 4: The slime adhesion area is 20% or more and less than 40% of the entire antifouling coating film surface; 3: The slime adhesion area is 40% or more and less than 60% of the entire antifouling coating film surface; 2: The slime adhesion area is 60% or more and less than 80% of the entire antifouling coating film surface; 1: The slime adhesion area is 80% or more of the entire antifouling coating film surface.

[0399]

[0400]

[0401]

[0402] Note that the kinematic viscosities in Table 9 are all values at 25°C and are values measured in accordance with JIS Z 8803:2011.

[0403] [Examples 1-54, Examples z1-z2 and Comparative Examples 1-45] An epoxy-based anticorrosive coating ("Banno 500", manufactured by Chugoku Marine Paints Ltd.) was applied to a sandblasted steel plate (300 mm long x 100 mm wide x 2.3 mm thick) to a dry film thickness of 150 μm, and then dried at room temperature for one day to form an anticorrosive coating. On the formed anticorrosive coating, an epoxy-based binder coating ("Banno 500N", manufactured by Chugoku Marine Paints Ltd.) was applied to a dry film thickness of 100 μm, and dried at room temperature for one day to form a laminated primer coating. On the formed laminated primer coating, each antifouling coating composition listed in Table 2 was applied to a dry film thickness of 100 μm, and dried at room temperature for seven days to form an antifouling coating A1, and test plates with antifouling coating A1 were prepared. The prepared test plates were immersed in the Seto Inland Sea for three months to create test plates with the old antifouling coating A1.

[0404] The surface of the prepared test plate with the old antifouling coating A1 was washed with water at a water pressure of 5 to 7 MPa for 5 to 7 seconds, and then dried for one day. After that, each epoxy resin coating composition listed in Table 4 was applied onto the old antifouling coating A1 to a dry film thickness of 100 μm, and dried at room temperature for one week to form the epoxy resin coating S1, thereby preparing the test plate 1 with the epoxy resin coating S1. Tables 10 and 11 show the symbols of the manufacturing examples (compositions) used to form the antifouling coating A1 and the epoxy resin coating S1 in each example and comparative example.

[0405] <Adhesion> The surface of the epoxy resin coating S1 was washed with water at a water pressure of 10 MPa for 3 to 5 seconds from a distance of 10 cm from the surface of the test plate 1 with the prepared epoxy resin coating S1. The degree of peeling of the epoxy resin coating S1 from the old antifouling coating A1 (adhesion) was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 10 and 11.

[0406] • Evaluation Criteria 5: No peeling observed at all 4: Peeling observed with a length of 1 mm or less 3: Peeling observed with a length exceeding 1 mm but not exceeding 5 mm 2: Peeling observed with a length exceeding 5 mm but not exceeding 1 cm 1: Peeling observed with a length exceeding 1 cm

[0407]

[0408]

[0409] [Examples 55-198] Test plates with the old antifouling coating A1 were prepared in the same manner as in Example 1. The coating surface of the prepared test plate with the old antifouling coating A1 was washed with water at a water pressure of 5-7 MPa for 5-7 seconds, and then dried for 1 day. Thereafter, each epoxy resin coating composition listed in Table 4 was applied onto the old antifouling coating A1 to a dry film thickness of 100 μm, and dried at room temperature for 1 day to form an epoxy resin coating S1, thereby preparing a test plate with epoxy resin coating S1. Each composition listed in Table 8 was applied onto the epoxy resin coating S1 of the prepared test plate with epoxy resin coating S1 to a dry film thickness of 200 μm, and dried at room temperature for 1 day to form an antifouling coating A2, thereby preparing a test plate 2 with antifouling coating A2. Tables 12 and 13 show the reference numerals of the manufacturing examples (compositions) used to form the antifouling coating A1, epoxy resin coating S1, and antifouling coating A2 in each example.

[0410] <Delamination> A single cut was made on the surface of the antifouling coating A2 of the prepared test plate 2 with antifouling coating A2, reaching the epoxy resin coating S1, using a single blade specified in JIS J5600-5-6. The surface was then rubbed 20 times perpendicular to the cut using a paper cloth. The degree of delamination between the epoxy resin coating S1 and the antifouling coating A2 was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 12 and 13. This delamination observation was performed on the test plate 2 the day after it was prepared (hereinafter referred to as "initial delamination") and on the test plate 2 after it had been immersed in fresh water at 23°C for 3 months (hereinafter referred to as "accelerated delamination").

[0411] • Evaluation Criteria 5: No damage is observed to the antifouling coating A2 except for the cut. 4: Delamination occurred within a range of less than 1 mm from the cut. 3: Delamination occurred between 1 mm and less than 3 mm from the cut. 2: Delamination occurred between 3 mm and less than 10 mm from the cut. 1: Delamination occurred within a range of 10 mm or more from the cut.

[0412]

[0413]

[0414] [Examples 199-702] Test plates with epoxy resin coating S1 were prepared in the same manner as in Example 55, etc. On the epoxy resin coating S1 of the prepared test plate, the silicone tie-coat composition described in Table 8 was applied to a dry film thickness of 100 μm, and dried at room temperature for one day to form tie-coat T1, thereby preparing a test plate with tie-coat T1. On the tie-coat T1 of the prepared test plate with tie-coat T1, each of the antifouling paint compositions described in Table 7 or 8 was applied to a dry film thickness of 200 μm, and dried at room temperature for one day to form antifouling coating A2, thereby preparing a test plate 3 with antifouling coating A2. Tables 14-17 show the symbols of the manufacturing examples (compositions) used to form the antifouling coating A1, epoxy resin coating S1, tie-coat T1, and antifouling coating A2 in each example.

[0415] <Delamination> A single cut was made on the surface of the antifouling coating A2 of the test plate 3 with the prepared antifouling coating A2, reaching the epoxy resin coating S1, using a single blade specified in JIS J5600-5-6. The surface was then rubbed 20 times perpendicular to the cut using a paper cloth. At this time, the degree of delamination between the epoxy resin coating S1 and the antifouling coating A2 was visually observed and evaluated using the same evaluation criteria as for delamination in Example 55, etc. The results are shown in Tables 14 to 17. This observation of delamination was performed using the test plate 3 the day after the test plate 3 with the antifouling coating A2 was prepared (hereinafter referred to as "initial delamination") and using the test plate 3 after the prepared test plate 3 with the antifouling coating A2 was immersed in fresh water at 23°C for 3 months (hereinafter referred to as "accelerated delamination").

[0416]

[0417]

[0418]

Claims

1. A substrate with a laminated coating, comprising, in this order, a base material, an antifouling coating A1 containing a silyl ester polymer (a1) having constituent units derived from trialkylsilyl methacrylate (a11), and an epoxy resin coating S1.

2. A substrate with a laminated coating according to claim 1, comprising, in this order, a substrate, an antifouling coating A1 containing a silyl ester polymer (a1) having structural units derived from trialkylsilyl methacrylate (a11), an epoxy resin coating S1, and an organopolysiloxane antifouling coating A2.

3. A laminated coated substrate according to claim 2, wherein a silicone tie coat T1 is provided between the epoxy resin coating film S1 and the organopolysiloxane antifouling coating film A2.

4. The laminated coated substrate according to claim 1, wherein the antifouling coating A1 further comprises copper or a copper compound (a2).

5. The laminated coated substrate according to claim 1, wherein the content of the silyl ester polymer (a1) in the antifouling coating A1 is 5 to 50% by mass.

6. The laminated coated substrate according to claim 1, wherein the content of constituent units derived from trialkylsilyl methacrylate (a11) in the antifouling coating A1 is 3 to 15% by mass.

7. The laminated coated substrate according to claim 1, wherein the epoxy resin coating film S1 is a coating film formed from a composition S1 comprising an epoxy resin, an amine-based curing agent, and a pigment.

8. The laminated substrate with a coating film according to claim 2, wherein the organopolysiloxane-based antifouling coating film A2 is a coating film formed from composition A2 containing a curable polyorganosiloxane and a lubricant.

9. The substrate with a laminated coating according to claim 8, wherein the lubricant is one or more selected from the group consisting of silicone oil, paraffin oil, oils and fats, (meth)acrylic polymers having hydrophilic groups, polyglycerin esters and polyalkylene glycols.

10. A method for manufacturing a substrate with a laminated coating, comprising the steps of (i) cleaning the antifouling coating R1 of a substrate with an antifouling coating R1 that is to be repaired or repainted, and (ii) forming an epoxy resin coating S1 on the antifouling coating R1 after step (i), wherein the antifouling coating R1 is an antifouling coating formed from a composition containing a silyl ester polymer having constituent units derived from triisopropylsilyl methacrylate.

11. A method for manufacturing a substrate with a laminated coating according to claim 10, comprising the step (iii) of forming an organopolysiloxane-based antifouling coating A2 on the side of the epoxy resin-based coating S1 formed in step (ii) that is opposite to the substrate.

12. A method for manufacturing a substrate with a laminated coating according to claim 10, comprising the steps of: (iv) forming a silicone tie coat T1 on the side of the epoxy resin coating film S1 formed in step (ii) opposite to the substrate; and (v) forming an organopolysiloxane antifouling coating film A2 on the side of the silicone tie coat T1 formed in step (iv) opposite to the epoxy resin coating film S1.

13. A method for manufacturing a substrate with a laminated coating according to any one of claims 10 to 12, wherein the step between step (i) and step (ii) is not a step of roughening the surface of the antifouling coating R1 after step (i).

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