Substrate with laminated coating

Abstract

To provide 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. [Solution] A substrate with a laminated coating comprising, in this order, a substrate, an antifouling coating A1 containing a silyl ester polymer (a1) having structural units derived from trialkylsilyl methacrylate (a11), and an epoxy resin coating S1.

Description

[Technical Field]

[0001] The present invention relates to a substrate with a laminated coating and a method for producing the same. [Background technology]

[0002] Surfaces of substrates exposed to water (oceans, rivers, lakes, etc.) for extended periods, such as ships, underwater structures, and fishing nets, are prone to the attachment and proliferation of various aquatic organisms, including animals like oysters, mussels, and barnacles, plants like seaweed, and bacteria. When these aquatic organisms attach to and proliferate on the substrate surface, various problems can arise. For example, if the substrate is a ship, the surface roughness increases from the waterline to the bottom of the hull, which can result in a decrease in the ship's speed and an increase in fuel consumption. If the substrate is an underwater structure, the anti-corrosion coating applied to the substrate surface may be damaged, potentially leading to a decrease in the strength and function of the coating, and a significant shortening of its lifespan. Furthermore, if the substrate is a fishing net such as an aquaculture net or a fixed net, the mesh can become clogged with aquatic organisms, causing serious problems such as oxygen deprivation and death of farmed or fished organisms. Furthermore, if the substrate is a seawater supply and drainage pipe for thermal power plants or nuclear power plants, the seawater (cooling water) supply and drainage pipes may become blocked or the flow velocity may decrease, causing problems in the circulation system.

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

[0004] By the way, when antifouling coatings are used for a long period of time, they will wear out, deteriorate, be damaged, or peel off. Therefore, in order to maintain their antifouling performance, it is necessary to periodically repair or repaint the antifouling coating. Prior to such repair painting or repainting, if the work of removing the antifouling coating film (hereinafter also referred to as "old antifouling coating film") that has been consumed or deteriorated on the substrate surface in advance is carried out, it will take extra labor and cost. Therefore, from the viewpoints of economy, work efficiency, etc., it is desirable to directly apply a new antifouling paint for repair painting on the old antifouling coating film. On the other hand, when a new antifouling paint is overcoated on the surface of such an old antifouling coating film, the antifouling coating film (new antifouling coating film) formed from the newly applied antifouling paint often has a problem with adhesion to the old antifouling coating film. Therefore, before applying a new antifouling paint on the old antifouling coating film, an epoxy resin-based coating film may be formed on the old antifouling coating film (for example: Patent Document 1).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] In recent years, when applying an organopolysiloxane-based antifouling paint to a newly built ship, after roughening the coating film surface of the old antifouling coating film applied before flooding in the final dock with a power tool equipped with a non-woven abrasive or the like, an epoxy resin-based coating film or the like is formed (hereinafter this method is also referred to as "epoxy coating system"). However, conventionally, this epoxy coating system has generally been applicable to the case where the old antifouling coating film is an antifouling coating film formed from a crosslinked metal salt copolymer-based antifouling paint.

[0007] On the other hand, in recent years, due to the increasing demand for silicone-based antifouling paints, the antifouling performance when the period from flooding to the final dock becomes long due to changes in the marine environment, and the increasing demand in rivers (freshwater environment) where crosslinked metal salt copolymer-based antifouling paints cannot be applied, etc., it has been found that it is necessary to improve the epoxy coating system. Furthermore, since the aforementioned surface roughening process is time-consuming and costly, it is desirable, from the standpoint of economic efficiency and work efficiency, to be able to form a laminated coating film with excellent adhesion between the old antifouling coating film and the epoxy resin coating film without surface roughening.

[0008] This invention was made in view of the above, and aims 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. [Means for solving the problem]

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

[0010] In this specification, "A~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" refers to 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 or the like. Furthermore, in the following explanation, "(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] Base material, Antifouling coating A1 containing a silyl ester polymer (a1) having a structural unit derived from trialkylsilyl methacrylate (a11), and Epoxy resin coating S1 A substrate with a laminated coating containing the following in this order.

[0012] [2] Base material, Antifouling coating A1 containing a silyl ester polymer (a1) having a structural unit derived from trialkylsilyl methacrylate (a11), Epoxy resin coating film S1, and Organopolysiloxane-based antifouling coating A2 A laminated coated substrate as described in [1], comprising the elements in this order.

[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 substrate with a laminated coating according to any one of [1] to [3], wherein the antifouling coating A1 further comprises copper or a copper compound (a2). [5] A substrate with a laminated coating 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 substrate with a laminated coating according to any one of [1] to [5], wherein the content of 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 substrate with a laminated coating film 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 step (i) of cleaning the antifouling coating R1 of a substrate with an antifouling coating R1 that is to be repaired or repainted, Step (i) above: (ii) Forming an epoxy resin coating film S1 on the antifouling coating film R1 after step (i) above. Includes, The antifouling coating R1 is an antifouling coating formed from a composition containing a silyl ester polymer having structural units derived from triisopropylsilyl methacrylate. A method for manufacturing a substrate with a laminated coating.

[0018]

[11] A method for manufacturing a laminated coated substrate 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] Step (iv) of 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, A method for manufacturing a laminated coated substrate according to

[10] or

[11] , comprising step (v) forming an organopolysiloxane-based antifouling coating A2 on the side of the silicone-based tie coat T1 formed in step (iv) that is opposite to the epoxy resin-based coating 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). [Effects of the Invention]

[0021] According to 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-based coating formed thereon, even without roughening the surface of the antifouling coating. In particular, according to 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 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 an antifouling coating that can be formed on the epoxy resin coating. Thus, according to the present invention, it is possible to provide a substrate with a laminated coating that has excellent adhesion between each layer without roughening the surface of the antifouling coating, and therefore, a desired substrate with a laminated coating can be obtained in a way that is superior in terms of economy and work efficiency. [Modes for carrying out the invention]

[0022] <Laminated coating substrate> The laminated coated substrate according to the present invention (hereinafter also referred to as "this laminated coated 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 unclear, it has been found that, only 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), can a laminated coating substrate with excellent adhesion between the antifouling coating A1 and the epoxy resin coating S1 formed thereon can be obtained 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, and even further, 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 substrate with the laminated coating is not particularly limited as long as it includes the substrate, the antifouling coating A1, and the coating S1 in this order. However, from the viewpoint of better exhibiting the effects of the present invention, it is preferable that the antifouling coating A1 and the coating S1 are in contact with each other. The substrate with the laminated coating preferably comprises the substrate, antifouling coating A1, coating S1, and organopolysiloxane-based antifouling coating A2 in this order. It is preferable to include a silicone-based tie coat T1 between the coating film S1 and the antifouling coating film A2, in order to easily obtain a laminated coating substrate with superior adhesion between the coating film S1 and the antifouling coating film A2. In this case, it is preferable that the coating film S1 and the tie coat T1 are in contact, and that the tie coat T1 and the antifouling coating film 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 contain films (layers) other than the antifouling coating A1, coating S1, tie coat T1, and antifouling coating A2.

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

[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 old antifouling coating is used, as this allows the effects of the present invention to be better demonstrated. These old antifouling coatings may be referred to as "old antifouling coating A1" and / or "antifouling coating R1" below. Furthermore, the descriptions of "antifouling coating A1" in this specification also apply to "old antifouling coating A1" and "antifouling coating R1".

[0026] Examples of the aforementioned old antifouling coating include an antifouling coating that has been used for a predetermined period of time. The antifouling coating applied to the bottom of a ship, etc., generally has a defined service life appropriate to its operating conditions, and is usually repainted after its service life has expired. In terms of specific service life, small vessels such as fishing boats and pleasure boats have a service life of 3 to 6 months. Large vessels such as crude oil tankers and container ships have a service life of 12 to 90 months. Thus, the service life varies widely depending on the type of operation, such as the route the vessel travels, and is not particularly limited.

[0027] The film 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] [Antifouling paint composition A1] The antifouling coating composition A1 contains a silyl ester polymer (a1) having a structural unit derived from trialkylsilyl methacrylate (a11).

[0029] [Siyl ester polymer (a1)] The silyl ester polymer (a1) is not particularly limited as long as it has a constituent unit 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 a constituent unit derived from trialkylsilyl methacrylate (a11) and a constituent unit 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, because it can easily form an antifouling coating A1 that has a good balance of long-term antifouling properties and crack resistance. For the synthesis of the copolymer (a11-12), one type of (a11) may be used, or two or more types may be used.

[0031] The content of constituent units derived from (a11) relative to 100% by mass of all constituent units of 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 with 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, from the viewpoint that it is possible to easily obtain a laminated coating substrate with superior adhesion between the antifouling coating A1 and the coating film S1 formed thereon. If the content of constituent units derived from (a11) in the antifouling coating A1 is less than the lower limit, the adhesion of the antifouling coating A1 to the coating S1 may decrease. Therefore, it is preferable that the content of constituent units derived from (a11) in the antifouling coating A1 be greater than or equal to the lower limit, as it is possible to easily obtain a laminated coating substrate with superior adhesion between the antifouling coating A1 and the coating 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 it is possible to easily form an antifouling coating A1 with superior antifouling properties. The content can be calculated by multiplying the content of polymer (a1) in the antifouling coating film A1 by the content of constituent units derived from (a11) in the polymer (a1).

[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 (a12-2).

[0035] • 2-Methoxyethyl (meth)acrylate (a12-1) The copolymer (a11-12) is preferably composed of constituent units derived from (a12-1) because it can easily form an antifouling coating A1 with superior antifouling properties. When (a12-1) is used in the synthesis of 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, wearable, 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 it is possible to easily form an antifouling coating film A1 which has excellent antifouling properties and physical properties.

[0038] • Other ethylenically unsaturated monomers (a12-2) (a12-2) is not particularly limited as long as it is an ethylenically unsaturated monomer other than those specified in (a11) and (a12-1), 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] (a12-2) For example, 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; Alkyl(meth)acrylates 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, etc., 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, etc. (meth)acrylic acid esters; 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; Styrene compounds such as styrene and ammonium styrenesulfonate; These are some examples.

[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 adjusted.

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

[0043] Examples of the other components mentioned above include 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 the oligomer or polymer is typically 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 (product name, manufactured by JNC Corporation, polydimethyl silicone with one end methacryloxy group), KF-2012 (product name, manufactured by Shin-Etsu Chemical Co., Ltd., polydimethyl silicone with one end methacryloxy group); Polymers such as alkyd resins containing unsaturated groups; These are some examples.

[0045] <Solid content acid value of polymer (a1)> The solid content 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 paint 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" refers to the number of milligrams of potassium hydroxide required to neutralize the free acid present in 1 gram of a sample, and is expressed in units of "mgKOH / g". The aforementioned solid content acid value can be measured specifically 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 polymer (a1) include, for example, copolymerizing monomers having an acid group, or using a polymerization initiator having an acid group. Examples of monomers having the acid group include unsaturated carboxylic acids, vinyl sulfonic acid, and vinylphosphonic 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. The monomer having an acidic group may be one type or two or more types.

[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 a polymer (a1) in which Mw is within the aforementioned range exhibits good hydrolysis resistance, good abrasion resistance (coating film wear resistance), further improved antifouling properties, and a tendency 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 that is excellent in 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 the value (polystyrene equivalent) 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 water resistance and various physical properties (crack resistance and antifouling properties of the coating film) over a long period of time, the solid content of the 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 the polymer (a1) can also be said to be the content of the polymer (a1) in the antifouling coating film 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 ingredients] The 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-settling agents, dehydrating agents, and solvents.

[0053] <Copper or copper compounds (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. The copper or copper compound (a2) may be used individually or in combination of two or more types.

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

[0056] As for the aforementioned cuprous oxide, those that have been surface-treated with glycerin, stearic acid, lauric acid, sucrose, lecithin, mineral oil, etc., are preferred in terms of stain resistance 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 Industrier AS, "Red Copp97N Premium" manufactured by AMERICAN CHEMET Co., "Purple Copp" manufactured by AMERICAN CHEMET Co., and "LoLoTint97" manufactured by AMERICAN CHEMET Co.

[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 70% by mass, and even more preferably 40 to 65% 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 is preferably composed of rosins and / or monocarboxylic acid compounds, as this can further improve the antifouling properties of the antifouling coating film A1 that is formed, and in particular improve its static antifouling properties. Furthermore, by using rosins and / or monocarboxylic acid compounds, the renewal of the resulting antifouling coating A1 from the surface in water can be promoted, and if the antifouling coating A1 contains an antifouling agent, the release of the antifouling agent into water can be promoted, thereby enhancing the antifouling properties of the antifouling coating A1, and it is also possible to impart a moderate water resistance to the antifouling coating A1. Rosins and / or monocarboxylic acid compounds may be used individually or in combination of two or more.

[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 hydrocarbon or alicyclic hydrocarbon. Among these, abietic acid, neoabietic acid, dehydroabietic acid, parastolic acid, isopimaric acid, pimaric acid, trimethylisobutenylcyclohexenecarboxylic acid, versatic acid, stearic acid, naphthenic acid, etc. are preferred. Rosins containing abietic acid, palastic acid, isopimaric acid, etc. as main components are also preferred. Examples of rosins include gum rosin, wood rosin, tall oil rosin, hydrogenated rosin, disproportionated rosin, rosin metal salts and other rosin derivatives, 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 150 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> The antifouling coating composition A1 may contain an organic antifouling agent (excluding copper or a copper compound (a2)). Organic antifouling agents may be used individually or in combination of two or more types.

[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 ingredients> The antifouling coating composition A1 may contain other binder components besides the polymer (a1) in order to impart properties such as static antifouling, water resistance, crack resistance, and strength to the antifouling coating film A1 that is formed. Examples of other binder components include acrylic (co)polymers (acrylic resins), vinyl polymers, n-paraffins, and terpene phenols. Other binder components may be used individually or in combination of two or more types.

[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 esters may be used individually or in combination of 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. The aforementioned metal ester group is preferably a polyvalent metal ester group, and more preferably a divalent metal ester group. 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 with a carboxylic acid.

[0069] Examples of metals that constitute the aforementioned 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, a metal selected from the group consisting of copper and zinc is 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-acryloyloxypropionic acid), copper di(3-acryloyloxypropionic acid), zinc (meth)acrylate (naphthenate), and copper (meth)acrylate (naphthenate). The metal ester group-containing unsaturated monomer may be used as a single material or as a combination of two or more materials.

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

[0072] Other binder components may be commercially available products, such as "Dianal BR-106" (acrylic polymer) manufactured by Mitsubishi Chemical Corporation, or 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 or inorganic coloring pigments. Examples of organic coloring pigments include Pigment Black 7 (carbon black), Pigment Red 170 (naphthol red), and Pigment Blue 15 (phthalocyanine blue). Examples of inorganic coloring pigments include red iron oxide (Fe2O3), black iron oxide (Fe3O4), titanium dioxide (titanium white / TiO2), and yellow iron oxide. Furthermore, the antifouling paint composition A1 may contain coloring agents other than coloring pigments, such as dyes, along with or instead of coloring pigments.

[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] <Body pigments> The antifouling coating composition A1 may contain extender pigments, as it allows for the easy formation of 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 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 also contain a (pigment) dispersant to improve the dispersibility of the coloring pigments, extender pigments, etc. The pigment dispersant may be one type or two or more types.

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

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

[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, C9, styrene, dichloropentadiene, and their hydrogenated versions. A specific example is "Quinton 1500 / 1700" manufactured by Nippon Zeon Co., Ltd.

[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, relative to 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] <Drip stopper> The antifouling coating composition A1 may contain a drip-preventing agent (a run-preventing agent) in order to reduce dripping when the composition A1 is applied to a substrate. One type of anti-dripping 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 an anti-sagging agent makes it easy to obtain an antifouling coating composition A1 with excellent storage stability. Furthermore, when a coating film (topcoat) made of the same or a different antifouling coating composition is formed on the antifouling coating film A1 after it has been formed, it is preferable because it is easy to suppress a decrease in adhesion (interlayer adhesion, recoating ability) between the antifouling coating film A1 and the topcoat.

[0089] Commercially available anti-dripping agents include "Disparon A630-20X" and "Disparon 4200-20" manufactured by Kusumoto Kasei Co., Ltd., and "ASA 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 prevention agent> The antifouling coating composition A1 may contain a settling inhibitor, which can suppress the formation of precipitates and improve agitability during storage. The settling inhibitor may be of one type or two or more types.

[0092] Examples of anti-settlement agents include Al, Ca, or Zn stearate, polyethylene wax, and oxidized polyethylene wax, among which oxidized polyethylene wax is preferred. A commercially available example of polyethylene oxide 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 dehydrating agents and organic dehydrating agents. As inorganic dehydrating agents, synthetic zeolite, anhydrous gypsum, and hemihydrate gypsum are preferred. 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), keep the viscosity of composition A1 low, and improve spray atomization. The solvent may be the solvent used in synthesizing polymer (a1), or it may be a solvent added separately when mixing 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, organic solvents such as aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ketones, esters, and alcohols can be used, with aromatic hydrocarbon organic solvents being preferred. Examples of aromatic hydrocarbon organic solvents include toluene, xylene, and mesitylene. 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-based organic solvents include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate. Examples of ester-based organic solvents include propylene glycol monomethyl ether acetate. Examples of alcohol-based organic solvents include isopropanol, n-butanol, and propylene glycol monomethyl ether.

[0099] If the antifouling coating composition A1 contains a solvent, its content 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 S1> The coating film S1 is not particularly limited as long as it is an epoxy resin-based 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. This laminated coating substrate has a specific antifouling coating A1, and a coating S1 is formed on top of it. Therefore, the adhesion between the antifouling coating A1 and the coating S1 is excellent, and the type of coating S1 is not particularly limited as long as it is epoxy resin based, and it has excellent adhesion to the antifouling coating 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. Furthermore, if necessary, composition S1 may be a three-component or more composition containing other components besides the main component and curing agent component. These main components, curing agents, 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 preferable because it exhibits adhesive strength to the coating film it comes into contact with, has excellent mechanical properties, and can be easily cured using the amine-based curing agent described later. 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. Also, 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 a 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 cP or more, more preferably 10,000 cP 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 Akishin 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 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 aforementioned range, it is preferable because 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.

[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. When two or more epoxy resins are blended into composition S1, the epoxy equivalent of the epoxy resins is the total epoxy equivalent of the two or more epoxy resins. Specifically, when y parts by mass (solids) of epoxy resin e1 with a solid epoxy equivalent of a and z parts by mass (solids) of epoxy resin e2 with a solid epoxy equivalent of b are blended, the epoxy equivalent of the epoxy resins 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 aforementioned 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] In addition, the "solid content" in composition S1 and each of the raw materials used in composition S1 refers to the mass excluding volatile components. The solid content of each raw material containing volatile components such as solvents refers to the residue remaining after drying in a hot air dryer at 105°C for 3 hours to allow the volatile components to evaporate. Furthermore, 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] Furthermore, 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, the coating strength (hardness) is not too high, and a coating film S1 with sufficient strength can be easily formed. Therefore, the ratio of their use ((i):(ii)) by mass is preferably 300:100 to 100:300, more preferably 200:100 to 100:200, and even more preferably 150:100 to 100:150.

[0115] [Amine-based curing agent] The amine-based 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). For example, amine compounds containing two or more amino groups in one molecule are included. Specifically, examples include aliphatic amine curing agents, alicyclic amine curing agents, aromatic amine curing agents, aromatic aliphatic amine curing agents, heterocyclic amine curing agents, and the like. One type of amine-based curing agent may be used, or two or more types may be used.

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

[0117] The alkylene polyamine is, for example, of the formula: "H2N-R 1 -NH2" (R 1 A is a divalent hydrocarbon group having 1 to 12 carbon atoms. Examples of compounds represented by ( ) 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, trimethylhexamethylenediamine, etc.

[0118] Examples of the aforementioned polyalkylene polyamine include those with the formula: "H2N-(C m H 2m NH)n Compounds represented by "H" (where m is an integer from 1 to 10, n is from 2 to 10, preferably an integer from 2 to 6) include, specifically, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, bis(hexamethylene)triamine, triethylene-bis(trimethylene)hexamine, etc.

[0119] Examples of the alkylaminoalkylamine include compounds represented by the formula: "R 2 2N-(CH2) p -NH2" (R 2 is independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms (however, at least one R 2 is an alkyl group having 1 to 8 carbon atoms), and p is an integer from 1 to 6). Compounds include, specifically, dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, dimethylaminobutylamine, etc.

[0120] Examples of aliphatic amine curing agents other than these include tetra(aminomethyl)methane, tetrakis(2-aminoethylaminomethyl)methane, 1,3-bis(2'-aminoethylamino)propane, 2,2'-[ethylenebis(iminotrimethyleneimino)]bis(ethanamine), tris(2-aminoethyl)amine, bis(cyanoethyl)diethylenetriamine, polyoxyalkylene polyamine (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, mensendiamine (MDA), and the like.

[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. More specifically, 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. More specifically, 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, Mannich-modified amines are preferred as amine-based curing agents because they allow for easy acquisition of a composition S1 with excellent curing speed, particularly at low temperatures (5°C or below), and enable the easy formation of a coating film S1 with a good balance of adhesion and strength to the antifouling coating film A1. MXDA Mannich-modified amines are more preferred.

[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 approximately 1 to 10 carbon atoms, and phenyl groups containing alkylene groups having approximately 1 to 10 carbon atoms. 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); 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-Mannich-modified amines obtained by reacting the aforementioned phenols, aldehydes, and MXDA in a Mannich condensation reaction, the Mannich-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 enables the easy 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 when the solid content is normally adjusted to 50-100% by mass is preferably 100-100,000 cPs / 25°C, and more preferably 500-10,000 cPs / 25°C, in order to easily obtain a composition S1 with excellent handling and coating properties.

[0137] As for amine-based curing agents, it is preferable to use both in combination, as using a solid curing agent (I) at 25°C improves the initial curability of the resulting composition S1, and using a liquid curing agent (II) at 25°C allows for the easy formation of a coating film S1 with high initial strength. The ratio of the amounts of hardening agent (I) to (II) used ((I):(II), solid content mass ratio) is preferably 100:0.1 to 0.1:100, and more preferably 100:10 to 10:100. When the ratio of the amounts of curing agents (I) and (II) used is within the above range, a composition S1 having the desired curability can be easily obtained, and a coating film S1 having the desired strength and durability can be easily formed.

[0138] 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 solids of amine curing agent (B) / Active hydrogen equivalent of solids of amine curing agent (B)) + (Amount of solids of component reactive with epoxy resin (A) / Functional group equivalent of solids of component reactive with epoxy resin (A))} / {(Amount of solids of epoxy resin (A) / Epoxy equivalent of solids of epoxy resin (A)) + (Amount of solids of component reactive with amine curing agent (B) / Functional group equivalent of solids of component reactive with amine curing agent (B))}

[0139] Here, the "component that reacts with epoxy resin (A)" in the above formula is, for example, the silane coupling agent listed below, and the "component that reacts with amine curing agent (B)" is, for example, the silane coupling agent listed below. As the silane coupling agent, a silane coupling agent having an amino group or an epoxy group as a reactive group can be used. Therefore, depending on the type of reactive group, it is necessary to determine whether the silane coupling agent is reactive with the epoxy resin (A) or with the amine curing agent (B), and to 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 solids of a and z parts by mass (solids) of epoxy resin e2 having an epoxy equivalent of solids of b, the above "(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.

[0140] The "functional group equivalent" of each component refers to the mass (g) per mole of functional group obtained by dividing the mass of 1 mole of these components by the number of moles of functional groups contained within it.

[0141] [Pigments] The aforementioned pigments are not particularly limited as long as they are pigments other than gypsum listed below, and examples include extender pigments, coloring pigments, and rust-preventive pigments, and may be either organic or inorganic. One type of pigment may be used, or two or more types may be used.

[0142] 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. The presence of the extender pigment in composition S1 is preferable because it allows for the easy formation of a coating film S1 with excellent properties such as crack resistance. One type of extender pigment may be used, or two or more types may be used.

[0143] 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.

[0144] 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 pigment, talc and mica are preferred because they are inexpensive, readily available, and can easily form a coating film S1 that exhibits superior effects.

[0145] If composition S1 contains an extender pigment, the amount is preferably such that the PVC is within the following range, 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, in order to easily form a coating film S1 that has excellent adhesion to the antifouling coating film A1.

[0146] 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 type of coloring pigment may be used, or two or more types may be used.

[0147] If composition S1 contains a coloring pigment, the amount is preferably such that the PVC is within the following range, 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.

[0148] 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.

[0149] The pigment volume concentration (PVC) in composition S1 is preferably 25-50%, more preferably 30-48%. When the PVC is within the aforementioned range, a 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 and suppression of blistering and cracking can be easily formed.

[0150] The PVC in composition S1 refers to the total volume concentration of pigment 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

[0151] 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 volumes 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, they 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.

[0152] [Optional ingredients] 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; hardening 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 (co)polymers [including polyvinyl 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.

[0153] <plaster> The inclusion of gypsum in composition S1 allows for the easy formation of a coating film S1 with excellent water resistance, saltwater resistance, and corrosion resistance. You may use one type of gypsum, or you may use two or more types.

[0154] 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. The shape is not particularly limited, but it is preferably in powder form.

[0155] 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.

[0156] Hemihydrate gypsum comes in α-type and β-type, but β-type is preferred in terms of the strength of the resulting coating film S1. An example of hemihydrate gypsum is "FT-2" (average particle size 15 μm) manufactured by Noritake Co., Ltd.

[0157] Furthermore, anhydrous gypsum comes in three types: Type I, Type II, and Type III, but there are no particular restrictions. An example of anhydrous gypsum is "AS Gypsum" manufactured by San-Es Gypsum Co., Ltd.

[0158] 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 50 parts by mass, per 100 parts by mass of epoxy resin.

[0159] <Curing accelerator> Composition S1 preferably contains a curing accelerator in order to further improve the curing speed and low-temperature curing properties. The hardening accelerator may be one type or two or more types.

[0160] As the curing accelerator, any conventionally known curing accelerator used in paints may be used, but tertiary amines and 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.

[0161] The tertiary amine is not particularly limited, but for example, triethanolamine, dialkylaminoethanol {[CH3(CH2) n Examples include 2NCH2CH2OH, 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 Ltd., trade name "Ankamin K-54" (manufactured by Air Products Japan Co., Ltd.)). Among these, 2,4,6-tri(dimethylaminomethyl)phenol is preferred.

[0162] The acrylic acid ester is not particularly limited, but polyfunctional acrylic acid esters are preferred. Examples of commercially available polyfunctional acrylic esters include polyfunctional acrylic esters (product name "M-Cure 400", manufactured by Sartomer).

[0163] 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.

[0164] <Plasticizer> It is preferable that composition S1 contains a plasticizer, as this 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. The plasticizer may be one type or two or more types.

[0165] 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.

[0166] 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.

[0167] <(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 Corporation, "DisperBYK101" manufactured by BYK CHEMIE). The pigment dispersant may be one type or two or more types.

[0168] 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.

[0169] <Drip stopper> It is preferable if composition S1 contains an anti-sagging agent, as this allows for adjustment of properties such as anti-sagging during painting. One type of anti-dripping agent may be used, or two or more types may be used.

[0170] 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 be used, including "Disparon 6650" and "Disparon A630-20XC" from Kusumoto Kasei Co., Ltd., "ASAT-250F" from Ito Seiyu Co., Ltd., and "Benton 27" from Elementis Specialties, Inc.

[0171] 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.

[0172] <Settling prevention agent> 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. The settling inhibitor may be of one type or two or more types.

[0173] Examples of the aforementioned settling inhibitors include organic clay-based Al, Ca, or Zn amine salts, polyethylene wax, and polyethylene oxide wax, among which polyethylene oxide wax is preferred. Commercially available products may be used as the settling inhibitor, such as "Disparon 4200-20X" manufactured by Kusumoto Kasei Co., Ltd.

[0174] 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.

[0175] <solvent> The solvent can be a conventionally known solvent with a wide range of boiling points, and specifically includes 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; ketoneic solvents such as methyl ethyl ketone, methyl isobutyl ketone, and methyl amyl ketone; and 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; among these, xylene, n-butyl alcohol, methyl isobutyl ketone, and propylene glycol monomethyl ether are preferred. One type of solvent may be used, or two or more types may be used.

[0176] 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.

[0177] <Silane coupling agent> It is preferable that composition S1 contains a silane coupling agent, as this not only further improves the adhesion of the formed coating film S1 to the antifouling coating film A1, but also improves the corrosion resistance of the formed coating film S1. The silane coupling agent may be used as a single agent or as a set of two or more agents.

[0178] 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 substrate and reducing the viscosity of composition S1.

[0179] Silane coupling agents include, for example, those with the formula: "X-SiMe n Y 3-nIt is preferable that the compound is represented by "[n is 0 or 1, X is 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 one of 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 one of these groups), Me is a methyl group, and Y is a hydrolyzable group (e.g., alkoxy groups such as methoxy and ethoxy groups)].

[0180] 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.

[0181] 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).

[0182] When composition S1 contains a silane coupling agent, its content 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 lower the viscosity of composition S1, improve paintability, and easily form a coating S1 with excellent adhesion to the antifouling coating A1.

[0183] <Base material> This laminated coating-coated substrate can maintain its antifouling properties for extended periods in a wide range of industrial fields, including ships, fisheries, and underwater structures, even when exposed to water (oceans, rivers, lakes, etc.) for long periods. Examples of such substrates include ships (large steel vessels such as container ships and tankers, fishing boats, FRP boats, wooden boats, 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 tanks, 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.

[0184] There are no particular restrictions on the material of the base material. 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.

[0185] 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.

[0186] Examples of compositions for forming the aforementioned undercoat include zinc-based 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 coating typically contains an epoxy resin and an amine-based curing agent for epoxy resins. In addition, it may optionally contain thermoplastic resins (e.g., vinyl copolymers), rosins, plasticizers, extender pigments, coloring pigments, rust-preventive pigments, solvents, curing accelerators, coupling agents, anti-sagging agents, anti-settlement agents, and the like. Furthermore, composition S1 may be used as the composition for forming the undercoat film.

[0187] 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.

[0188] <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).

[0189] The antifouling coating A2 is preferably a coating formed from a composition containing a curable polyorganosiloxane and a lubricant.

[0190] 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.

[0191] [Composition A2] Composition A2 preferably contains a curable polyorganosiloxane and a lubricant. Furthermore, the antifouling paint composition A1 may be used as composition A2.

[0192] [Curing polyorganosiloxane] When composition A2 contains a curable polyorganosiloxane, an antifouling coating A2 with excellent antifouling properties can be easily formed. The curable polyorganosiloxane may be used as a single type or as a combination of two or more types.

[0193] 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.

[0194] Examples of polyorganosiloxane structures include polydimethylsiloxane structures and polymethylphenylsiloxane structures, with polydimethylsiloxane structures being preferred, and alkylene groups and polyoxyalkylene groups may be present in block-like structures. Furthermore, for example, alkylene groups or polyoxyalkylene groups may be present as linkage sites between the main chain and the reactive groups.

[0195] 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, alkoxysilyl groups, and alkenyloxysilyl groups are preferred, silanol groups, oximesilyl groups, alkoxysilyl groups, and alkenyloxysilyl groups are more preferred, and silanol groups and oximesilyl groups are even more preferred.

[0196] As the oxime group, an oxime group having 1 to 10 carbon atoms is preferred, a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, and a methyl isobutyl ketoxime group are more preferred, and a methyl ethyl ketoxime group and a methyl isobutyl ketoxime group are even more preferred.

[0197] As for the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are more preferred, a methoxy group and an ethoxy group are even more preferred, and a methoxy group is particularly preferred.

[0198] 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.

[0199] 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.

[0200] 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.

[0201] 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.

[0202] [ka] [In formula (A1), R 11 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, an aralkyl group having 7 to 16 carbon atoms, or a halogenated alkyl group having 1 to 16 carbon atoms, and R 12 each independently represent a hydroxy group or a hydrolyzable group. When there are a plurality of R 11 to R 13 , they may be the same or different from each other. Also, r represents an integer of 1 to 3, and p represents 10 to 10,000.]

[0203] The alkyl group in R 11 and R 13 is a group having 1 to 16 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.

[0204] The alkenyl group in R 11 and R 13 is a group having 2 to 16 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a heptenyl group, a hexenyl group, and a cyclohexenyl group.

[0205] The aryl group in R 11 and R 13 is a group having 6 to 16 carbon atoms, and may have a substituent such as an alkyl group on the aromatic ring. Examples thereof include a phenyl group, a tolyl group (methylphenyl group), a xylyl group (dimethylphenyl group), and a naphthyl group.

[0206] The aralkyl group in R 11 and R 13 is a group having 7 to 16 carbon atoms, and examples thereof include a benzyl group, a 2-phenylethyl group, a 2-naphthylethyl group, and a diphenylmethyl group.

[0207] The halogenated alkyl group in R 11 and R 13The halogenated alkyl group in this context is a group having 1 to 16 carbon atoms, and examples include groups 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.

[0208] 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.

[0209] 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.

[0210] 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.

[0211] R 12 The oxime group in this 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.

[0212] R 12 The acyloxy group (RC(=O)O-) in this compound 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. Examples include the acetoxy group, propionyloxy group, butyryloxy group, and benzoyloxy group.

[0213] R 12 In R, the preferred alkoxy group is one with a total of 1 to 10 carbon atoms. 12In the alkoxy group, one or more oxygen atoms may be present between one or more carbon atoms. R 12 Specific examples of alkoxy groups in this context include methoxy, ethoxy, propoxy, butoxy, methoxyethoxy, and ethoxyethoxy groups.

[0214] R 12 The alkenyloxy group in is preferably an alkenyloxy group having 3 to 10 carbon atoms, such as isopropenyloxy, isobutenyloxy, and 1-ethyl-2-methylvinyloxy.

[0215] 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.

[0216] R 12 The amide group in this is preferably an amide group having a total of 2 to 10 carbon atoms, such as N-methylacetamide, N-ethylacetamide, and N-methylbenzamide.

[0217] R 12 The aminooxy group in is preferably an aminooxy group having a total of 2 to 10 carbon atoms, such as the N,N-dimethylaminooxy group and the N,N-diethylaminooxy group.

[0218] 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.

[0219] R 12 When is a hydroxyl group, r is preferably 1, R12 If the substituent is not a hydroxyl group, r is preferably 2.

[0220] p is preferably 100 to 1,000, and it is preferable to adjust it as appropriate to satisfy the following weight-average molecular weight. Note that p is -(SiR 13 This refers to the average number of repetitions of (2-O).

[0221] 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 standpoint of improving workability during the manufacture of composition A2, and improving the coating workability, 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.

[0222] 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, and particularly preferably 3,000 mPa·s or less, from the standpoint of improving workability during the manufacture of composition A2, and improving the coating workability, curability, and strength of the antifouling coating film A2 formed by composition A2. In this specification, the viscosity of curable polyorganosiloxanes at 25°C is the viscosity measured using a Type B rotational viscometer (e.g., Model BM, manufactured by Tokyo Keiki Co., Ltd.).

[0223] As the curable polyorganosiloxane, commercially available products may be used. Examples of such commercially available products include "DMS-S35" manufactured by GELEST and "KE-445" manufactured by Shin-Etsu Chemical Co., Ltd. Further, as the curable polyorganosiloxane, the compounds described in JP-A-2001-139816 can also be used.

[0224] From the viewpoint of easily forming an antifouling coating film A2 excellent in antifouling property and strength, the content of the curable polyorganosiloxane in Composition A2 is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less. For the same reason, the content of the curable polyorganosiloxane in 100% by mass of the solid content of Composition A2 is preferably 45% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and preferably 85% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.

[0225] The "solid content" in each raw material used in Composition A2 refers to the components excluding the organic solvents and volatile components contained in each raw material 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.

[0226] 〈Sliding agent〉 Composition A2 may contain a sliding agent from the viewpoint of easily obtaining Composition A2 excellent in coating workability and antifouling property. Further, Composition A2 containing a sliding agent can impart slipperiness to the formed antifouling coating film A2 and improve the adhesion inhibitory property (antifouling property) of aquatic organisms. One type of sliding agent may be used, or two or more types may be used.

[0227] 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.

[0228] 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.

[0229] The lubricant is preferably one or more selected from oils and polymers having hydrophilic groups. Examples of the aforementioned oils include silicone oil, paraffin oil, and fats and oils, with silicone oil being preferred among these. Examples of the hydrophilic polymer include hydrophilic (meth)acrylic polymers, polyglycerin esters, and polyalkylene glycols, with hydrophilic (meth)acrylic polymers being preferred.

[0230] The lubricant is preferably 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, more preferably one or more selected from silicone oil and (meth)acrylic polymers having hydrophilic groups, 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 (meth)acrylic polymer having hydrophilic groups, and it is more preferable to include both silicone oil and a (meth)acrylic polymer having hydrophilic groups.

[0231] • Silicone oil The aforementioned 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 improve the adhesion prevention (antifouling) and damage resistance of aquatic organisms. One type of silicone oil may be used, or two or more types may be used.

[0232] 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 A2 for aquatic organisms, and improve antifouling properties. Note that the viscosity of silicone oil at 25°C refers to the viscosity measured using a Type B rotational viscometer.

[0233] 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 50mm 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 It is less than or equal to / s. The kinematic viscosity of the silicone oil at 25°C was measured in accordance with JIS Z 8803:2011.

[0234] 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.

[0235] Examples of silicone oils include dimethyl silicone (polydimethylsiloxane, unmodified silicone) and modified silicone. The silicone oil is preferably a silicone oil that does not have reactive groups. Examples of such reactive groups include the reactive groups described in the section on curable polyorganosiloxanes.

[0236] A commercially available product may be used as the dimethyl silicone, such as "KF-96-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25℃): 100 mm²). 2 / s), "KF-96-1,000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25℃): 1,000 mm) 2 Examples include / s).

[0237] 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 silicone, polyether-modified silicone, long-chain alkyl-modified silicone, higher fatty acid ester-modified silicone, alkyl fluoride-modified silicone, carbinol-modified silicone, carboxy-modified silicone, amino-modified silicone, epoxy-modified silicone, (meth)acrylic-modified silicone, mercapto-modified silicone, and phenol-modified silicone.

[0238] 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.

[0239] 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.

[0240] 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 that it is possible to easily form an antifouling coating A2 which has 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.

[0241] The kinematic viscosity of the phenyl-modified silicone at 25°C is preferably 10 to 5,000 mm², considering the workability of the resulting composition A2 and the antifouling properties of the formed antifouling coating film A2. 2 / s, more preferably 50-4,000mm 2 / s, more preferably 80-3,500 mm 2 It is less than or equal to / s.

[0242] 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℃): 100 mm) is a suitable 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).

[0243] 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.

[0244] 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.

[0245] The polyether (polyalkylene glycol) constituting the polyether group (polyalkylene glycol group) of polyether-modified silicone can be polyethylene glycol, polypropylene glycol, or a copolymer of ethylene glycol and propylene glycol, with a copolymer of polyethylene glycol and polypropylene glycol being preferred.

[0246] 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.

[0247] In polyether-modified silicones, when the polyether group has both an ethylene oxy (EO) group and a propylene oxy (PO) group, the molar ratio [EO / PO] of the ethylene oxy (EO) group to the propylene oxy (PO) group in the polyether group is preferably 0.5 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.

[0248] The molar ratio of EO groups to PO groups in the polyether-modified silicone is, for example, 1 It can be measured by 1H-NMR. in particular, 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 non-methyl group portion of the PO group (approximately 3-4 ppm) obtained by 1H-NMR, it can be calculated using the following formula. EO / PO = {([integral value at approximately 3-4 ppm] - [integral value at approximately 0.8-1.2 ppm]) / 4} / {[integral value at approximately 0.8-1.2 ppm] / 3}

[0249] When composition A2 contains a polyether-modified silicone containing an ethylene oxy substructure (-OC2H4-), the formed antifouling coating film A2 can be given good antifouling properties. Therefore, the total content of the ethylene oxy substructure is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, per 100 parts by mass of the dimethylsiloxane substructure (-Si(CH3)2-O-) of the silicone.

[0250] The kinematic viscosity of the polyether-modified silicone at 25°C is preferably 10 to 5,000 mm², considering the workability of the resulting composition A2 and the antifouling properties of the formed antifouling coating film A2. 2 / s, more preferably 50~2,000mm 2 / s, more preferably 100-500mm 2 It is / s.

[0251] 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 a suitable commercially available product. 2 / s), "KF-6020" (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type, kinematic viscosity (25℃): 180 mm) 2 Examples include the "FZ-2203" (manufactured by Toray Dow Corning Co., Ltd., block type).

[0252] 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.

[0253] • Paraffin oil The paraffin oil is not particularly limited, but liquid paraffin is preferred. You may use one type of paraffin oil, or two or more types.

[0254] The kinematic viscosity of the paraffin oil at 25°C is preferably 10 mm, considering the coating workability of the resulting composition A2 and the antifouling properties of the formed antifouling coating film A2. 2 / s or more, more preferably 50mm 2 / s or more, more preferably 100 mm 2 The value is 1 / s or more, preferably 5,000 mm 2 / s or less, more preferably 2,000 mm 2 / s or less, more preferably 500mm 2 It is less than or equal to / s.

[0255] When composition A2 contains paraffin oil, the solid content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, preferably 20% by mass or less, and 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.

[0256] ·Oils and fats Examples of the aforementioned oils and fats include esters obtained using fatty acids and glycerol, and include animal fats and fats, vegetable fats and fats, etc. You may use one type of oil or two or more types.

[0257] • (meth)acrylic polymer having hydrophilic groups The (meth)acrylic polymer having hydrophilic groups preferably contains structural units derived from a monomer having hydrophilic groups, more preferably contains structural units derived from a monomer having hydrophilic groups and structural units derived from a hydrophobic monomer, and even more preferably consists of structural units derived from a monomer having hydrophilic groups and structural units derived from a hydrophobic monomer. However, it contains constituent units derived from (meth)acrylic monomers. The (meth)acrylic polymer having hydrophilic groups may be used individually or in combination of two or more types.

[0258] 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.

[0259] 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.

[0260] As the hydrophilic group, ether groups and hydroxyl groups are preferred from the viewpoint of antifouling properties, and ether groups are more preferred.

[0261] 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.

[0262] 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.

[0263] Examples of polyalkylene glycol (meth)acrylates include compounds in which one end of the polyalkylene glycol is directly esterified to (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.

[0264] The terminal (meth)acrylic acid is preferably acrylic acid and methacrylic acid, with acrylic acid being more preferred. The terminal alkoxy group can be a methoxy group, a phenoxy group, an octoxy group, etc., with methoxy and phenoxy groups being preferred, and methoxy groups being more preferred.

[0265] 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.

[0266] 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.

[0267] 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, allyloxypoly(ethylene glycol-propylene 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, nonylphenoxypolypropylene glycol acrylate, etc., with methoxypolyethylene glycol mono(meth)acrylate being preferred.

[0268] As the polyalkylene glycol (meth)acrylate, commercially available products may be used, 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-ethylhexyl-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.

[0269] Examples of the hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Commercially available hydroxyalkyl (meth)acrylates may be used, and examples of such commercial products include 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.

[0270] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate.

[0271] Examples of the tetrahydrofurfuryl (meth)acrylate include tetrahydrofurfuryl acrylate and tetrahydrofurfuryl methacrylate, with tetrahydrofurfuryl acrylate being more preferred.

[0272] The 4-(meth)acryloylmorpholine is preferably 4-acryloylmorpholine or 4-methacryloylmorpholine, and more preferably 4-acryloylmorpholine.

[0273] Examples of 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.

[0274] 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.

[0275] Because it has constituent units derived from hydrophobic monomers, it is thought to have high affinity with other components of the formed antifouling coating A2, such as silicone crosslinked bodies, and to be able to uniformly exhibit a sliding effect on the surface of the antifouling coating A2.

[0276] Examples of the hydrophobic monomer include alkyl (meth)acrylates having branched, linear, or cyclic alkyl groups with 1 to 30 carbon atoms, aryl (meth)acrylates having aromatic groups with 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.

[0277] 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.

[0278] 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, isostearyl(meth)acrylate, etc. Among these, n-butyl(meth)acrylate, isobutyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate are preferred.

[0279] The aromatic group of the aryl (meth)acrylate preferably has 6 to 7 carbon atoms. Specific examples of aryl (meth)acrylates include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0280] As the (meth)acrylic group-containing silicone, a methacrylic group-containing silicone is preferred. (Meth)acrylic group-containing silicones are preferably compounds in which the (meth)acrylic group is bonded to one end of the silicone main chain via a linking group, or compounds in which the (meth)acrylic group is directly bonded to one end of the silicone main chain, and compounds in which the (meth)acrylic group is bonded to one end of the silicone main chain via a linking group are 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 the (meth)acrylic group, and it is preferable that a butyl group is present.

[0281] The silicone main chain is preferably composed of a linear or branched dimethylsilicone (polydimethylsiloxane), and more preferably of a linear dimethylsilicone.

[0282] Commercially available silicones containing (meth)acrylic groups may be used, and examples of such commercially available products include Cylaprene TM-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.

[0283] 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, considering the viscosity of the resulting composition A2 and the antifouling properties of the formed antifouling coating A2.

[0284] 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.

[0285] • Polyglycerin ester Polyglycerol fatty acid esters are preferred as the polyglycerol esters. Polyglycerol esters may be used individually or in combination of two or more types.

[0286] Polyglycerol fatty acid esters are, for example, esters obtained using polyglycerol and fatty acids, and 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. Examples of polyglycerol fatty acid esters include the S-Face series manufactured by Sakamoto Pharmaceutical Co., Ltd.

[0287] • Polyalkylene glycol Examples of the polyalkylene glycol include polyethylene glycol, polypropylene glycol, copolymers of ethylene glycol and propylene glycol, and alkyl ethers thereof. Polyalkylene glycol may be used individually or in combination of two or more types.

[0288] [Optional ingredients] Composition A2 may contain optional components other than the curable polyorganosiloxane and lubricant. Examples of such optional components include at least one 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-settlement agents other than polyethylene oxide wax, wetting and dispersing agents other than polyethylene oxide wax, enzymes, flame retardants, and heat conduction improvers.

[0289] [Silica particles] Composition A2 preferably contains silica particles because it can also have good fluidity and thixotropy, and can easily form an antifouling coating A2 with excellent hardness, flexibility, and strength. Silica particles may be used individually or in combination of two or more types.

[0290] Dry-processed silica and wet-processed silica are preferred as silica particles, with dry-processed silica being more preferred.

[0291] 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 they contain at least hydrophobic silica particles. Furthermore, hydrophobic silica particles are preferably added in order to improve the fluidity and thixotropy of composition A2, and in terms of the hardness, flexibility, and strength of the antifouling coating film A2 that is formed. Furthermore, hydrophilic silica particles are preferable to add because they tend to reduce the viscosity of composition A2 and improve the antifouling properties of the antifouling coating film A2 that is formed.

[0292] 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.

[0293] 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.

[0294] 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.

[0295] Examples of hydrophilic silica particles include untreated silica (surface-untreated silica), and more specifically, dry-process silica (fumed silica, anhydrous silica), wet-process silica (hydrated silica), etc. Dry-process silica is preferred, and fumed silica is more preferred. Commercially available hydrophilic silica particles may be used, such as "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd.

[0296] 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.

[0297] 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 film A2 with excellent strength and hardness.

[0298] <Pyrithione metal salts> 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. Among these, copper pyrithione is preferred because it can easily form an antifouling coating A2 with excellent antifouling properties. One type of pyrithione metal salt may be used, or two or more types may be used.

[0299] 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.

[0300] <Oxide Polyethylene Wax> Composition A2 may contain polyethylene oxide wax because it is easy to prepare, has excellent dispersibility, and allows for easy acquisition of a composition A2 with excellent storage stability. Polyethylene oxide wax may be used in the form of one type or two or more types.

[0301] Examples of oxidized polyethylene waxes include resins obtained by oxidizing polyethylene and introducing polar groups. Such polyethylene oxide waxes may be synthesized by conventionally known methods or may be commercially available. Examples of commercially available products include "Disparon 4200-20" manufactured by Kusumoto Chemical Co., Ltd. and "ASA-D-120" manufactured by Ito Seiyu Co., Ltd.

[0302] The acid value of the polyethylene oxide wax is preferably 10 mg KOH / g or more, more preferably 15 mg KOH / g or 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.

[0303] 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.

[0304] Furthermore, when composition A2 contains a pyrithione metal salt and polyethylene oxide wax, the solid content of polyethylene oxide wax per 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.

[0305] <Coloring pigments> Composition A2 preferably contains a coloring pigment. The inclusion of a coloring pigment in composition A2 can increase the film strength of the antifouling coating A2 that is formed. One type of coloring pigment may be used, or two or more types may be used.

[0306] 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 composition A2 contains at least an inorganic pigment, in terms of ease of preparation, coating workability, storage stability, and the antifouling properties of the formed antifouling coating film A2. It is more preferable that it contains one or more selected from iron oxide, titanium oxide, 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 oxide, and carbon black, and particularly preferable that it contains one or more selected from iron oxide and titanium oxide.

[0307] Examples of the aforementioned iron oxides include red iron oxide, yellow iron oxide, and black iron oxide. As the titanium dioxide, 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.

[0308] 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 workability, and storage stability, and to easily form an antifouling coating film A2 which is excellent in antifouling properties.

[0309] 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 that is easy to prepare, easy to coat, and has excellent storage stability.

[0310] <Organic solvents> Composition A2 may contain an organic solvent, as this can help maintain a low viscosity and improve coating workability. One type of organic solvent may be used, or two or more types may be used.

[0311] 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.

[0312] Examples of the aforementioned aromatic hydrocarbon organic solvents include toluene, xylene, and mesitylene, with xylene being preferred. Examples of the aliphatic hydrocarbon organic solvents include pentane, hexane, heptane, and octane. Examples of the aforementioned alicyclic hydrocarbon organic solvents include cyclohexane, methylcyclohexane, and ethylcyclohexane. Examples of the ketone-based organic solvent include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate, with acetylacetone being preferred. Examples of the aforementioned alcohol-based organic solvents include ethanol, n-propanol, isopropyl alcohol, n-butanol, and isobutanol. Examples of the ester-based organic solvents include ethyl acetate, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate.

[0313] If composition A2 contains an organic solvent, the content 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 workability, 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.

[0314] <Curing catalyst> Composition A2 preferably contains a curing catalyst, as this can improve the curing speed and the film strength of the antifouling coating. The curing catalyst may be of one type or of two or more types.

[0315] 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.

[0316] Examples of the tin compounds include dibutyltin diacetate, dibutyltin acetacetonate, dibutyltin dilaurate, dibutyltin dilate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, bis(dibutyltin laurate) oxide, dibutylbis(triethoxysiloxy)tin, bis(dibutyltin acetate) oxide, dibutyltin bis(ethyl maleate), dioctyltin bis(ethyl maleate), tin naphthenate, tin oleate, etc. Dibutyltin diacetate, dibutyltin acetacetonate, dibutyltin dilaurate, dibutyltin dilate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, and dibutyltin dineodecanoate are preferred, with dibutyltin dilaurate being more preferred.

[0317] Commercially available tin compounds may be used, such as "NEOSTANN U-100" manufactured by Nitto Chemical Co., Ltd. and "Gleck TL" manufactured by DIC Corporation.

[0318] Examples of the aforementioned titanium compounds include tetraisopropoxytitanium, tetra-N-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctyl glycol.

[0319] 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.

[0320] 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.

[0321] Examples of metals that form metal salts include alkali metals such as lithium, sodium, and potassium, as well as 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, with alkali metals and zinc being more preferred.

[0322] 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.

[0323] If 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.

[0324] 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 the solid content of the curable polyorganosiloxane.

[0325] <Organosilicon crosslinking agent> Composition A2 preferably contains an organosilicon crosslinking agent, as this can improve the curing speed, the strength of the formed antifouling coating A2, and the adhesion to the coating S1 and tie coat T1. Furthermore, organosilicon crosslinking agents are not limited to those intended for these functions; for example, they may also be incorporated for the purpose of functioning as a wetting agent for colored pigments, etc. One organosilicon crosslinking agent may be used, or two or more may be used.

[0326] Examples of organosilicon crosslinking agents include organosilanes in which three or four hydrolyzable groups are bonded to a silicon atom, and also include their partial condensates. In addition, an example of an organic silane in which three hydrolyzable groups are bonded to a silicon atom is an organic silane in which one more hydrocarbon group is bonded to a silicon atom. The hydrolyzable group is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. The hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a methyl group, an ethyl group, or a propyl group, and even more preferably a methyl group or an ethyl group.

[0327] 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.

[0328] Commercially available tetraethyl orthosilicate may be used, and examples of such commercial products include "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 partially hydrolyzed condensate of tetraethyl orthosilicate. Examples of such commercial products include "Silicate 40" manufactured by Tama Chemical Industry Co., Ltd. and "WACKER SILICATE TES 40 WN" manufactured by Asahi Kasei Wacker Silicone Co., Ltd. A commercially available alkyltrialkoxysilane may be used as the alkyltrialkoxysilane, and examples of such commercially available products include "KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd. Commercially available oximesilanes may be used, including "X-93-4096" (vinylmethyltris(methylisobutylketoxime)silane) manufactured by Shin-Etsu Chemical Co., Ltd., and "MTO(MOS)" (methyltris(methylethylketoxime)silane) and "VTO(VOS)" (vinyltris(methylethylketoxime)silane) manufactured by Toray Industries, Inc.

[0329] 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.

[0330] <Silane coupling agent> Composition A2 may contain a silane coupling agent, as this can improve the curing speed, the curability of the formed antifouling coating A2, and the adhesion to the coating S1 and tie coat T1. Composition A2 preferably 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. The silane coupling agent may be used as a single agent or as a set of two or more agents.

[0331] Examples of silane coupling agents include organic alkoxysilanes having at least one alkoxy group and at least one organic reactive group.

[0332] 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.

[0333] 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. Amino groups, mercapto groups, epoxy groups, isocyanate groups, and ureido groups are preferred, amino groups, mercapto groups, and epoxy groups are more preferred, and amino groups are even more preferred.

[0334] Preferred organic reactive groups containing an amino group include the 2-(aminoethyl)-3-aminopropyl group and the 3-aminopropyl group.

[0335] 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. 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane are preferred, with 3-(2-aminoethylamino)propyltrimethoxysilane being more preferred. As the silane coupling agent, a condensate of the above-mentioned compound may be used.

[0336] 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.

[0337] 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.

[0338] <Biological repellents other than pyrithione metal salts> It is preferable that composition A2 contains a biological repellent other than a pyrithione metal salt (hereinafter also simply referred to as "biological repellent") for the purpose of enhancing the antifouling properties of the antifouling coating film A2 that is formed. The biological repellent can suppress the adhesion of aquatic organisms to the surface of the antifouling coating A2, thereby improving its antifouling properties. A single biological repellent may be used, or two or more types may be used.

[0339] As a biological repellent, it is preferable to have a repellent effect on aquatic organisms and a certain 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.

[0340] 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, relative to 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.

[0341] <Pigments other than silica particles and colored pigments> Examples of pigments other than the silica particles and coloring pigments mentioned above include talc, mica, calcium carbonate, barium carbonate, potassium feldspar, kaolin, and glass short fibers. Silica particles and pigments other than coloring pigments may be used individually or in combination of two or more types.

[0342] <Dehydrating agents other than organosilicon crosslinking agents> Examples of dehydrating agents other than the organosilicon crosslinking agent include zeolites, porous alumina, orthoesters such as alkyl orthoformates, orthoboric acid, and isocyanate compounds. In addition to organosilicon crosslinking agents, one type of dehydrating agent may be used, or two or more types may be used.

[0343] <Anti-sagging and anti-settlement agents other than polyethylene oxide wax> Other anti-sagging and anti-settling agents besides the aforementioned oxidized polyethylene wax include organic clay waxes (such as stearate salts, lecithin salts, and alkyl sulfonates of Al, Ca, and Zn), organic waxes (such as polyethylene wax, amide wax, polyamide wax, and hydrogenated castor oil wax), and mixtures of organic clay wax and organic wax. Other than polyethylene oxide wax, one type of anti-sagging agent or anti-settling agent may be used, or two or more types may be used.

[0344] <Wetting and dispersing agents other than polyethylene oxide wax> Other wetting and dispersing agents besides the aforementioned oxidized polyethylene wax include known organic or inorganic wetting and dispersing agents, such as wetting and dispersing agents having a silicone main chain. As a wetting and dispersing agent other than polyethylene oxide wax, commercially available products may be used, such as "KP-578" and "KF-6106" manufactured by Shin-Etsu Chemical Co., Ltd. In addition to polyethylene oxide wax, one type of wetting and dispersing agent may be used, or two or more types may be used.

[0345] <enzyme> Examples of the aforementioned 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.

[0346] <Flame retardant> Examples of the aforementioned flame retardants include antimony oxide and paraffin oxide. Flame retardants may be used in the form of one type or two or more types.

[0347] <Thermal conductivity improver> Examples of the aforementioned thermal conductivity improvers include boron nitride and aluminum oxide. The thermal conductivity modifier may be of one type or of two or more types.

[0348] [Aspects of composition A2] Composition A2 may be a one-component antifouling paint composition in which each of the above raw materials is used as one composition, or it may be a two-component or more type antifouling paint composition in which each of the above raw materials is used as two or more agents and mixed before application. 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 type antifouling paint composition is preferred in terms of application workability. Examples of the two-component antifouling coating composition include two-component antifouling coating compositions and antifouling coating compositions with three or more components. In terms of ease of application, two-component antifouling coating compositions are preferred, while in terms of suppressing deterioration during storage, antifouling coating compositions with three or more components are preferred.

[0349] 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. If composition A2 contains at least one selected from silica particles, pyrithione metal salt, polyethylene oxide wax, coloring pigment, and biological repellent, it is preferable that the silica particles, pyrithione metal salt, polyethylene oxide wax, coloring pigment, and biological repellent are included in the same agent as the curable polyorganosiloxane.

[0350] [Method for manufacturing composition A2] The aforementioned composition A2 is preferably manufactured as follows. First, it is preferable to have a step of kneading the curable polyorganosiloxane and silica particles. Heating may also be performed 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 normal pressure or reduced pressure, and the processing time is preferably 3 to 30 hours. Furthermore, when the optional component is incorporated into composition A2, composition A2 can be produced by mixing the resulting kneaded product with the optional component.

[0351] <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. Tycoat T1 is preferably a coating film formed from a composition containing a curable polyorganosiloxane and a lubricant.

[0352] 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.

[0353] [Composition T1] Composition T1 preferably contains a curable polyorganosiloxane and a lubricant. For example, composition T1 can be the same as composition A2. That is, composition A2 can be used to form both the tie coat T1 and the antifouling coating A2. In some cases, there may be little difference in composition between tie coat T1 and the antifouling coating A2. 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 a tie coat T1 and an antifouling coating A2 on a coating film S1, the composition T1 for forming the tie coat T1 and the composition A2 for forming the 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.

[0354] ≪Method for manufacturing substrates with laminated coatings≫ This laminated coated 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. The 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.

[0355] 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.

[0356] Examples of the application methods include using painting means such as air sprayers, airless sprayers, brushes, and rollers. The drying (curing) method can be appropriately selected depending on the composition used, but for example, it may be air-dried (at room temperature) or dried using a drying method such as a heater.

[0357] The aforementioned 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 should be repaired or repainted. However, from the viewpoint of better demonstrating the effects of the present invention, it is preferable that the antifouling coating A1 be R1 (old antifouling coating). Such a laminated coated substrate containing an antifouling coating R1 can be manufactured, for example, by a method including the steps of (i) cleaning the antifouling coating R1 of the substrate and (ii) 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 is preferably an antifouling coating formed from the antifouling paint composition A1. The laminated coated substrate including the antifouling coating R1 may include a step (iii) 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), and may also include 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 side of the tie coat T1 formed in step (iv) opposite to the coating S1. These steps (ii) to (v) correspond to steps (III) to (VI), respectively.

[0358] 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 limitations 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 can be done with water at a pressure of about 5 to 10 MPa, and the washing time is not particularly limited as long as it can remove foreign matter adhering to the antifouling coating R1, but for example it is 1 to 10 seconds.

[0359] Conventionally, when forming an epoxy resin coating on an existing antifouling coating, a step was performed between step (i) and step (ii) to roughen the surface of the existing antifouling coating using a power tool equipped with a nonwoven abrasive material, in order to improve adhesion between these 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 with a power tool. For this reason, the effects of the present invention are more fully realized, and from the viewpoint of economy and work efficiency, it is preferable that 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) with a power tool, is not included between step (i) and step (ii). [Examples]

[0360] 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.

[0361] <Manufacturing Example a1-1> Manufacturing of copolymer solution (a1-1) The following reactions were 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), 500 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 addition was complete, the reaction mixture was stirred at 80°C for 1 hour and 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 solution 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).

[0362] <Production Examples a1-2 and ca1-1~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. Note that "MAAc" in Table 1 is an abbreviation for methacrylic acid.

[0363] 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.

[0364] <Method for measuring the solid content (heat 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, 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 cooled to room temperature, and then weighed again to measure the mass of the residual material in the metal test dishes. The solid content (mass %) in the copolymer solutions was calculated using the following formula. Solid content (mass%) in copolymer solution = Mass of residual material after heating (g) × 100 / Mass of copolymer solution weighed out (g)

[0365] <Method for measuring the viscosity of copolymer solutions> The viscosity (in 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 Viscometer TV-25" (manufactured by Toki Sangyo Co., Ltd.) Rotor used: Standard rotor (1°34' × R24) Measurement temperature: 25℃

[0366] <Method for measuring the weight-average molecular weight (Mw) of copolymers> The weight-average molecular weight (Mw) of the 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: 0.35mL / min Detector: RI Column constant temperature bath temperature: 40℃ Calibration curve: Standard polystyrene and styrene monomers Sample preparation method: Each copolymer solution was diluted with THF, and the filtrate obtained by filtering through a membrane filter was used as the GPC measurement sample.

[0367] <Method for measuring the solid content 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 each 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. Blank measurements were performed using the same procedure as above, except that the copolymer solution was not used, and the solid content acid value of the copolymer solution was calculated according to the following formula.

[0368] Diluent: Toluene: Ethanol: Ultrapure water = 100:95:5 (volume ratio) Equipment: "Automatic titrator CPM-1750" (manufactured by Hiranuma Sangyo Co., Ltd.) Titration solution: Ethanol potassium hydroxide solution (manufactured by Junsei Chemical Co., Ltd.) (s=0.1 mol / L, f=1.001, or s=0.01 mol / L, f=1.005)

[0369] Solid content acid value (mgKOH / g) = {(qr) × s × 56.11 × f} / (p × solid content in copolymer solution / 100) f: Factor of potassium hydroxide solution p: Weight of the copolymer solution weighed into the beaker (unit: g) q: The titration volume (in mL) to the point of maximum slope of the titration curve when using a copolymer solution. r: Titration volume (in mL) to the point of maximum slope of the titration curve in the blank measurement. s: Molar concentration of the titration solution (unit: mol / L)

[0370] <Manufacturing 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 mixture was heated to 75°C while stirring. Next, 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 a 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 a metal ester group monomer.

[0371] <Production Example Ca1-3> Production 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).

[0372] <Production Example Ca1-4> Production 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 over 6 hours using the dropping device. 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).

[0373] 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.

[0374] <Method for measuring the solid content (heat residue) in copolymer solutions> The copolymer solutions (Ca1-3) and (Ca1-4) were dried in a hot air dryer at 105°C for 3 hours to volatilize the solvents, and the residual heat was measured. The solid content (mass%) in the copolymer solution was calculated using the following formula. Solid content (mass%) in copolymer solution = Residue after heating (g) × 100 / Mass of copolymer solution placed in hot air dryer (g)

[0375] <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.).

[0376] <Method for measuring the weight-average molecular weight (Mw) of copolymers> The Mw of the copolymers in copolymer solutions (ca1-3) and (ca1-4) was measured using GPC under the following conditions. GPC measurement conditions Equipment: "HLC-8320GPC" (manufactured by Tosoh Corporation) Column: Two "TSKgel SuperAWM-H" columns and one "TSKgel SuperAW2500" column connected together (both manufactured by Tosoh Corporation, inner diameter 6mm / length 15cm) Eluent: N,N-dimethylformamide (DMF) (with 20 mM lithium bromide added) Flow rate: 0.600ml / min Detector: RI Column constant temperature bath temperature: 40℃ Standard material: Polystyrene Sample preparation method: A small amount of calcium chloride was added to each copolymer solution to dehydrate it, and the resulting filtrate was filtered through a membrane filter and used as the GPC measurement sample.

[0377] [Table 1]

[0378] <Manufacturing Example A1-1> Manufacturing of Antifouling Coating Composition A1-1 In a poly container, 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 28, 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. Subsequently, 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 poly container, and the mixture was stirred for 1 hour using a paint shaker to disperse these components. After dispersion, 1.5 parts by mass of 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).

[0379] <Manufacturing Examples A1-2 to A1-6 and Manufacturing Examples cA1-1 to cA1-5> Manufacturing of antifouling paint compositions A1-2 to A1-6 and antifouling paint compositions cA1-1 to cA1-5 An antifouling coating composition was obtained in the same manner as in Production 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. Table 3 shows the details of each ingredient listed in Table 2.

[0380] [Table 2]

[0381] [Table 3]

[0382] <Manufacturing Example S1-1> Manufacturing of epoxy resin-based paint composition S1-1 In a 1000 mL poly container, 20.0 parts by mass of epoxy resin 1, 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, 1.0 part by mass of anti-slip agent 1, 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. 200 parts by mass of glass beads were added, 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 1, 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 2 were mixed in a 250 mL poly container and dispersed in a paint shaker for 10 minutes until homogeneous. 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-based coating composition S1-1 was obtained.

[0383] <Manufacturing Examples S1-2 to S1-9> Manufacturing of epoxy resin-based paint compositions S1-2 to S1-9 Except for changing the types and amounts (numerical values, parts by mass) of raw materials used as shown in Table 4, the main component and curing agent component were prepared in the same manner as in Production Example S1-1 to obtain an epoxy resin-based coating composition. Table 5 shows the details of each ingredient listed in Table 4.

[0384] [Table 4]

[0385] [Table 5]

[0386] <Preparation of compound products (compounds 1-5) of curable silicone and silica particles> The curable silicone and silica particles shown in Table 6 were kneaded in the amounts indicated in Table 6 to obtain a mixture. Note that the viscosity values ​​in Table 6 are all values ​​at 25°C and were measured using a Type B rotational viscometer 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.

[0387] [Table 6]

[0388] <Synthesis of (meth)acrylic polymers having hydrophilic groups> The 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, 42.86 parts by mass of methyl amyl ketone were charged, and the mixture was 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. Subsequently, the mixture was stirred for 2 hours while maintaining the temperature at 100±5°C to obtain a solution of a hydrophilic (meth)acrylic polymer.

[0389] [Solid content] The obtained solution of the hydrophilic (meth)acrylic polymer was dried at 105°C and 1 atm for 3 hours. The mass of the solids obtained was divided by the mass of the solution before drying to determine the solid content (mass%). The solid content was 70.3% by mass.

[0390] 〔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.). The viscosity was 109 mPa·s.

[0391] [Weight average molecular weight (Mw)] The hydrophilic (meth)acrylic polymer Mw was measured using gel permeation chromatography (GPC) under the following conditions. The value of Mw was 9,100. ·GPC conditions Equipment: "HLC-8420GPC" (manufactured by Tosoh Corporation) Column: A combination of "TSKgel SuperH2000" and "TSKgel SuperH4000" (both manufactured by Tosoh Corporation, 6mm inner diameter, 15cm length) linked together. Eluent: Tetrahydrofuran (THF) Flow rate: 0.600mL / min Detector: RI Column constant temperature bath temperature: 40℃ Standard material: 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.

[0392] <Manufacturing Examples A2-1 to A2-3> Manufacturing of organopolysiloxane-based antifouling coating compositions A2-1 to A2-3 According to the mixing amounts (numerical values, parts by mass) listed in Table 7, each of the raw materials listed in Table 7 was 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. The main component was prepared by mixing and stirring the components other than curable polyorganosiloxane 1 and kneaded product-1 listed in Table 7 with 10 parts by mass of xylene to prepare a mixture, and then stirring and mixing curable polyorganosiloxane 1, kneaded product-1 and the remaining xylene into the mixture to prepare the main component. Furthermore, when applying each of compositions 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. Table 9 shows the details of each ingredient listed in Table 7.

[0393] <Manufacturing Examples A2-4~A2-7 and T1-1~T1-3> Manufacturing of organopolysiloxane-based antifouling coating compositions A2-4~A2-7 and silicone-based tie-coat compositions T1-1~T1-3 According to the mixing amounts (numerical values, parts by mass) listed in Table 8, each raw material listed in Table 8 was mixed and stirred to prepare 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). The compositions listed in Table 8 were prepared by mixing and stirring each component except the kneaded material and lubricant with 10 parts by mass of xylene to prepare the mixture, and then stirring and mixing in the kneaded material, lubricant, and remaining xylene. Table 9 shows the details of each ingredient listed in Table 8.

[0394] <Drip-proof properties> Using a box-type sag tester as 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 anti-sagging properties of the applied composition were measured. A sample was deemed acceptable if the amount of composition that flowed into the space between the coated compositions was less than half the volume of the space. The coating thickness (wet film thickness) was gradually increased, and the limit of the wet film thickness (μm) at which this acceptable level could be maintained was measured. Furthermore, the anti-slip properties were tested using the compositions obtained in Production Examples A2-1 to A2-7 and T1-1 to T1-3 immediately after preparation, and also using the compositions after being stored for 30 days under a temperature of 50°C. The results are shown in Tables 7 and 8.

[0395] <Appearance of the coating film> The appearance of the coating on each tin plate, for which the anti-sagging properties were measured, was visually evaluated according to the following criteria. The results are shown in Tables 7 and 8.

[0396] • Evaluation criteria 3: No aggregates were observed, and the coating surface was in good condition. 2: Aggregates are observed, but no abnormalities (such as unevenness or wrinkles in the coating) are found on the surface of the coating. 1: Aggregates are observed, and abnormalities are also found in the surface condition of the coating (unevenness and wrinkles in the coating, etc.).

[0397] <Dynamic stain resistance> A sandblasting plate coated with epoxy-based anticorrosive paint ("Banno 500" manufactured by Chugoku Marine Paints Ltd.) was then coated with an intermediate coating paint ("CMP Bioclentai Coat" manufactured by Chugoku Marine Paints Ltd.) to a thickness of 100 μm after drying (curing). After drying at room temperature for 24 hours, each composition obtained in Production Examples A2-1 to A2-7 and T1-1 to T1-3 was applied at room temperature to a thickness of 200 μm after drying (curing), and the plate was left at room temperature for one week to produce a test plate with an antifouling coating.

[0398] A test plate coated with an antifouling film, mounted on the side of a rotating rotor, was immersed in the sea off the coast of Kure, Hiroshima Prefecture, and rotated at a speed of approximately 15 knots. The test plate was positioned so that the antifouling film surface was sufficiently exposed to sunlight, creating conditions conducive to slime formation. Six months and twelve months after immersion in the sea, the ratio of the area of ​​slime-covered region to the total surface area of ​​the antifouling film on the test plate was calculated by visual observation and evaluated according to the following evaluation criteria. The results are shown in Tables 7 and 8.

[0399] • Evaluation criteria 5: No slime attached 4: The area where slime adheres is between 20% and 40% of the entire surface of the antifouling coating. 3: The area where slime adheres is between 40% and 60% of the entire surface of the antifouling coating. 2: The area where slime adheres covers 60% to less than 80% of the entire surface of the antifouling coating. 1: Slime adheres to more than 80% of the entire surface of the antifouling coating.

[0400] [Table 7]

[0401] [Table 8]

[0402] [Table 9]

[0403] Note that the kinematic viscosity values ​​in Table 9 are all values ​​at 25°C and were measured in accordance with JIS Z 8803:2011.

[0404] [Examples 1-54 and Comparative Examples 1-45] A sandblasted steel plate (300mm long x 100mm wide x 2.3mm thick) was coated with epoxy-based anticorrosive paint ("Banno 500" manufactured by Chugoku Marine Paints Ltd.) to a dry film thickness of 150 μm, and then dried at room temperature for one day to form an anticorrosive coating. An epoxy-based binder paint ("Banno 500N" manufactured by Chugoku Marine Paints Ltd.) was applied to the formed anticorrosive coating film to a dry thickness of 100 μm, and dried at room temperature for one day to form a laminated primer coating film. Each of the antifouling coating compositions listed in Table 2 was applied to the formed laminated undercoat film to a dry film thickness of 100 μm, and dried at room temperature for 7 days to form antifouling coating film A1, thereby preparing test plates with antifouling coating film A1. The prepared test plates were immersed in the Seto Inland Sea for three months to create test plates with the old antifouling coating A1.

[0405] The surface of the prepared test panel 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. Subsequently, 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 week to form the epoxy resin coating S1, thereby preparing test panel 1 with epoxy resin coating S1. Tables 10 and 11 show the reference numerals of the manufacturing examples (compositions) used to form the antifouling coating A1 and epoxy resin coating S1 in each example and comparative example.

[0406] <Adhesion> The surface of the epoxy resin coating S1 on test plate 1 was washed with water at a water pressure of 10 MPa for 3 to 5 seconds from a distance of 10 cm from the coating surface. The degree of peeling (adhesion) of the epoxy resin coating S1 from the old antifouling coating A1 was then visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 10 and 11.

[0407] • Evaluation criteria 5: No peeling is observed at all. 4: Peeling with a peeling length of 1 mm or less is observed. 3: Peeling is observed with a peeling length exceeding 1 mm and not exceeding 5 mm. 2: Peeling is observed with a length exceeding 5 mm but less than or equal to 1 cm. 1: Peeling exceeding 1 cm in length is observed.

[0408] [Table 10]

[0409] [Table 11]

[0410] [Examples 55-198] A test plate with the old antifouling coating A1 was prepared in the same manner as in Example 1. The surface of the prepared test panel 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. Subsequently, 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 the epoxy resin coating S1, thereby preparing a test panel with the epoxy resin coating S1. On the epoxy resin coating S1 of the prepared epoxy resin coating test plate, each composition listed in Table 8 was applied to the epoxy resin coating S1 to a dry film thickness of 200 μm, and dried at room temperature for one day to form an antifouling coating A2, thereby preparing 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.

[0411] <Delamination> On the surface of the antifouling coating A2 of test plate 2, which was prepared with antifouling coating A2, a single cut was made using a single blade specified in JIS J5600-5-6, reaching the epoxy resin coating S1. The surface was then rubbed 20 times perpendicular to the cut using a paper cloth. During this process, the degree of delamination between the antifouling coating A2 and the epoxy resin coating S1 was visually observed and evaluated according to the following evaluation criteria. The results are shown in Tables 12 and 13. The delamination was observed using two methods: one using test plate 2 with the antifouling coating A2 applied the day after it was prepared (hereinafter referred to as "initial delamination"), and another using test plate 2 with the prepared antifouling coating A2 applied after being immersed in fresh water at 23°C for three months (hereinafter referred to as "accelerated delamination").

[0412] • Evaluation criteria 5: No damage is observed to the anti-fouling coating A2 except for the cuts. 4: Delamination occurred within a range of less than 1 mm from the cut. 3: Delamination occurred in a range of 1 mm to less than 3 mm from the cut. 2: Delamination occurred in a range of 3 mm to less than 10 mm from the cut. 1: Delamination occurred in an area of ​​10 mm or more from the cut.

[0413] [Table 12]

[0414] [Table 13]

[0415] [Examples 199-702] Test plates with epoxy resin coating S1 were prepared in the same manner as in Example 55, etc. A test plate with an epoxy resin coating S1 was prepared, and a silicone tie-coat composition T1-2 or T1-3, as described in Table 8, was applied to the epoxy resin coating S1 to a dry film thickness of 100 μm. The plate was then dried at room temperature for one day to form a tie-coat T1, and a test plate with tie-coat T1 was prepared. On the Tie Coat T1 of the prepared Tie Coat T1 test panel, each of the stain coating 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 an antifouling coating A2, thereby preparing a test panel 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.

[0416] <Delamination> On the surface of the antifouling coating A2 of the prepared test plate 3, a single cut reaching the epoxy resin coating S1 was made using a single blade specified in JIS J5600-5-6, and the surface was rubbed 20 times perpendicular to the cut with a paper cloth. At this time, the degree of delamination between the epoxy resin coating S1 and the test plate was visually observed and evaluated using the same evaluation criteria as in Example 55, etc. The results are shown in Tables 14 to 17. The delamination was observed using two methods: one using test plate 3 with the antifouling coating A2 applied the day after it was prepared (hereinafter referred to as "initial delamination"), and another using test plate 3 with the prepared antifouling coating A2 applied after being immersed in fresh water at 23°C for three months (hereinafter referred to as "accelerated delamination").

[0417] [Table 14]

[0418] [Table 15]

[0419] [Table 16]

[0420] Table 17

Claims

1. base material, Antifouling coating A1 containing a silyl ester polymer (a1) having a structural unit derived from trialkylsilyl methacrylate (a11), and Epoxy resin coating S1 A substrate with a laminated coating containing the following in this order.

2. base material, Antifouling coating film A1 containing a silyl ester polymer (a1) having a structural unit derived from trialkylsilyl methacrylate (a11), Epoxy resin coating film S1, and Organopolysiloxane-based antifouling coating A2 A substrate with a laminated coating according to claim 1, comprising the above in this order.

3. The laminated coated substrate according to claim 2, wherein a silicone tie coat T1 is included 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. (i) A step of cleaning the antifouling coating R1 of a substrate with an antifouling coating R1 that is to be repaired or repainted, Step (ii) is to form an epoxy resin-based coating film S1 on the antifouling coating film R1 after step (i). Includes, The antifouling coating R1 is an antifouling coating formed from a composition containing a silyl ester polymer having structural units derived from triisopropylsilyl methacrylate. A method for manufacturing a substrate with a laminated coating.

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. Step (iv) is to form 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 A method for manufacturing a substrate with a laminated coating according to claim 10, comprising step (v) of forming an organopolysiloxane-based antifouling coating A2 on the side of the silicone-based tie coat T1 formed in step (iv) that is opposite to the epoxy resin-based coating 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 to include a step of roughening the surface of the antifouling coating R1 after step (i).

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