Tycoat Composition

Abstract

To provide a tie-coat composition having good adhesion to a silicone-based antifouling coating film formed from a silicone-based antifouling coating composition containing curable silicone. Furthermore, to provide a laminated antifouling coating film with good adhesion between the tie-coat layer and the antifouling coating film and excellent antifouling properties, and a method for manufacturing the same, in which a tie-coat layer formed from the tie-coat composition and an antifouling coating film formed from a silicone-based antifouling coating composition are laminated in this order. [Solution] A tiecoat composition containing epoxy resin (A), amine curing agent (B), and oxime group-containing organosilane (C).

Description

[Technical Field]

[0001] The present invention relates to a tiecoat composition, a laminated antifouling coating film, and a method for producing the same. [Background technology]

[0002] Self-polishing antifouling paint compositions, applied to ships, underwater structures, fishing materials, etc., to prevent fouling caused by the attachment of aquatic organisms, prevent the attachment of organisms by gradually releasing the antifouling agent contained in the paint. On the other hand, silicone-based antifouling paints, which do not require antifouling agents to exhibit antifouling properties, are attracting attention as environmentally friendly antifouling paints. For example, Patent Document 1 discloses an antifouling coating composition which is a curable organopolysiloxane composition. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2017-88653 [Overview of the project] [Problems that the invention aims to solve]

[0004] Conventionally, when forming an antifouling coating film on a substrate using a silicone-based antifouling coating composition such as the antifouling coating described in Patent Document 1, a primer coating film formed using a two-component curing epoxy coating was required. However, it has been found that when a two-component curing epoxy coating is used as the primer layer, the adhesion between the primer layer and the antifouling coating film formed from the silicone-based antifouling coating composition may be poor. The present invention aims to provide a tie-coat composition having good adhesion to a silicone-based antifouling coating film formed from a silicone-based antifouling coating composition containing curable silicone. Furthermore, the present invention aims to provide a laminated antifouling coating film having good adhesion between the tie-coat layer and the antifouling coating film and excellent antifouling properties, and a method for manufacturing the same, in which a tie-coat layer formed from the tie-coat composition and an antifouling coating film formed from a silicone-based antifouling coating composition are laminated in this order. [Means for solving the problem]

[0005] In view of the above problems, the inventors conducted diligent research and found that the above problems can be solved by a tiecoat composition containing an epoxy resin (A), an amine curing agent (B), and an oxime group-containing organosilane (C) on a substrate. The present invention relates to the following [1] to [9]. [1] A tiecoat composition comprising an epoxy resin (A), an amine curing agent (B), and an oxime group-containing organosilane (C). [2] The tiecoat composition according to [1], wherein the oxime group-containing organosilane (C) is a compound represented by the following formula (1).

[0006] [ka] (In formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a methyl group, a vinyl group, or a phenyl group.

[0007] [3] The Tycoat composition according to [1] or [2], wherein the content of the oxime group-containing organosilane (C) in the nonvolatile components of the Tycoat composition is 3% by mass or more and 20% by mass or less. [4] The tie coat composition according to any one of [1] to [3], wherein the oxime group-containing organosilane (C) is at least one selected from the group consisting of methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, and vinyltris(methylisobutylketoxime)silane. [5] The tie coat composition according to any one of [1] to [4], wherein the tie coat composition is for the tie coat layer of an antifouling paint composition containing a curable silicone (a). [6] A laminated antifouling coating is formed by laminating a tie coat layer and an antifouling coating in this order. The tie coat layer is formed from a tie coat composition containing an epoxy resin (A), an amine curing agent (B), and an oxime group-containing organosilane (C) represented by the following formula (1).

[0008] [ka] (In formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a methyl group, a vinyl group, or a phenyl group. The antifouling coating film is formed by an antifouling paint composition selected from the group consisting of (i) to (iii) below, which contains a curable silicone (a). (i) An antifouling coating composition containing a polyorganosiloxane (a1) having ketoxime groups at both ends, wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is 1.5% by mass or less. (ii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends and an organosilane (a3) ​​represented by the following formula (I), wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 1.0% by mass.

[0009] [ka] (In formula (I), R 3 Each of the following independently represents a substituted or unsubstituted hydrocarbon group with 1 to 10 carbon atoms, Y is a ketoxime group with a total of 3 to 6 carbon atoms, and a is 0 or 1. (iii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends, at least one organosilicon crosslinking agent selected from the group consisting of organosilanes having at least two hydrolyzable groups in one molecule and their partially hydrolyzed condensates, and a curing catalyst, wherein the content of hydrophilic lubricants in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 0.1% by mass. A laminated antifouling coating that satisfies either condition A or condition B below. Condition A: X is a phenyl group, and the antifouling paint composition is (i) above. Condition B: X is a methyl group or a vinyl group, and the antifouling coating composition is selected from the group consisting of (i) to (iii) above.

[0010] [7] The laminated antifouling coating according to [6], wherein the lubricant having hydrophilic groups is at least one selected from the group consisting of polyether-modified silicone oil, acrylic polymer having hydrophilic groups, and glycerin condensate ester. [8] A step of applying a tie coat composition to form a tie coat layer, and A method for producing a laminated antifouling coating film according to [6] or [7], comprising the step of applying the Tie Coat composition and then applying the antifouling coating composition onto the Tie Coat layer within 5 hours. [9] A method for manufacturing a laminated antifouling coating film according to [6] or [7], comprising the steps of applying a tiecoat composition to form a tiecoat layer, and applying an antifouling coating composition onto the tiecoat layer within 36 hours after applying the tiecoat composition. [Effects of the Invention]

[0011] According to the present invention, a tie coat composition having good adhesion to a silicone-based antifouling coating film formed from a silicone-based antifouling coating composition containing a curable silicone is provided. Further, the present invention provides a laminated antifouling coating film in which a tie coat layer formed from the tie coat composition and an antifouling coating film formed from the silicone-based antifouling coating composition are laminated in this order, which has good adhesion between the tie coat layer and the antifouling coating film and is excellent in antifouling property, and a method for producing the same. [Modes for Carrying Out the Invention]

[0012] Hereinafter, the laminated antifouling coating film of the present invention and the coating material for forming the same will be described in detail. Each component in the present specification may be used alone, or two or more thereof may be used in combination. In the present specification, a homopolymer and a copolymer may be collectively referred to as "polymer" without particular distinction. That is, the term "polymer" may be a homopolymer or a copolymer. "(Meth)acrylate" is a general term for acrylate and methacrylate, and may be acrylate or methacrylate. "(Meth)acrylic" is a general term for acrylic and methacrylic, and may be acrylic or methacrylic. "(Meth)acrylic acid" is a general term for acrylic acid and methacrylic acid, and may be acrylic acid or methacrylic acid. The same applies to other examples. In the present specification, the description of "A to B" indicating a numerical range means a numerical range including the endpoints A and B, and when A < B, it means A or more and B or less, and when A > B, it means A or less and B or more. In addition, when a plurality of preferred lower limit values and upper limit values are described, a numerical range obtained by appropriately combining the described lower limit values and upper limit values is also considered to be described.

[0013] [Tie Coat Composition] The tiecoat composition of this embodiment contains an epoxy resin (A), an amine curing agent (B), and an oxime group-containing organosilane (C). By using the tiecoat composition of this embodiment as a tiecoat layer, which is an undercoat layer of an antifouling paint composition containing curable silicone (a), a laminated antifouling coating film with excellent adhesion to the antifouling coating film formed from the antifouling paint composition can be obtained. The detailed reasons why the above effects are achieved are unknown, but some explanations are as follows. The Tycoat composition containing epoxy resin (A) and amine-based curing agent (B) exhibits excellent adhesion to the substrate, and further, by containing oxime group-containing organosilane (C), it is believed that its adhesion to antifouling coatings formed from antifouling coating compositions containing curable silicone (a) is also improved. The mechanism by which the effects of the present invention are obtained is not limited to the above. The following describes in detail the tie-coat composition and the antifouling paint composition used in the laminated antifouling coating film of this embodiment.

[0014] <Epoxy resin (A)> The tiecoat composition of this embodiment contains epoxy resin (A). Examples of epoxy resin (A) include compounds containing two or more epoxy groups in one molecule. One type of epoxy resin (A) may be used, or two or more types may be used.

[0015] The epoxy equivalent of epoxy resin (A) is preferably 800 g / eq or less, more preferably 100 g / eq to 600 g / eq, even more preferably 200 g / eq to 400 g / eq, and even more preferably 250 g / eq to 350 g / eq, from the standpoint of lowering the viscosity and VOC (volatile organic compound) content of the tie coat composition, as well as forming an undercoat layer with excellent oil resistance, solvent resistance, chemical resistance, and corrosion resistance. The epoxy equivalent is calculated based on JIS K 7236:2001.

[0016] Examples of epoxy resins (A) include bisphenol-type epoxy resins, phenol novolac-type epoxy resins, cresol-type epoxy resins, glycidyl ether-type epoxy resins, glycidyl ester-type epoxy resins, glycidylamine-type epoxy resins, dicyclopentadiene-type epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and fatty acid-modified epoxy resins.

[0017] Examples of bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol AD ​​type epoxy resin. Examples of bisphenol A type epoxy resins include bisphenol A diglycidyl ether, bisphenol A polypropylene oxide diglycidyl ether, and bisphenol A ethylene oxide diglycidyl ether. In addition to the above, other examples of bisphenol A type epoxy resins include hydrogenated bisphenol A diglycidyl ether and hydrogenated bisphenol A propylene oxide diglycidyl ether.

[0018] As the epoxy resin (A), bisphenol-type epoxy resin and phenol novolac-type epoxy resin are more preferred, bisphenol A-type epoxy resin and phenol novolac-type epoxy resin are even more preferred, and using bisphenol A-type epoxy resin and phenol novolac-type epoxy resin in combination is even more preferred. From the viewpoint of easily obtaining a Tiecoat composition that has excellent curability, low viscosity, and can form a coating film with good coating film properties, it is preferable that the Tiecoat composition contains a bisphenol A type epoxy resin, and from the viewpoint of improving solvent resistance when the antifouling coating composition is applied, it is even more preferable to use a phenol novolac type epoxy resin in combination.

[0019] The viscosity of epoxy resin (A) at 25°C, as measured with an E-type viscometer (TOKIMEC, FMD type, rotation speed: 60 rpm), is preferably 800 mPa·s or more, more preferably 1,500 mPa·s or more, preferably 30,000 mPa·s or less, more preferably 20,000 mPa·s or less, for example, 800 to 30,000 mPa·s.

[0020] Examples of epoxy resins include "Epicote 828 (product name), general name: bisphenol A diglycidyl ether" (manufactured by Shell Corporation, weight-average molecular weight approximately 360, epoxy equivalent 180-190 g / eq, viscosity 12,000-15,000 mPa·s / 25℃), "Epotote YDF-170 (product name), general name: bisphenol F diglycidyl ether" (manufactured by Toto Chemical Co., Ltd., epoxy equivalent 160-180 g / eq, viscosity 2,000-5,000 mPa·s), and "Frep 50 (product name)" (manufactured by Toray Thiocol Co., Ltd., epoxy equivalent approximately 330 g / eq, viscosity approximately 2 7,000 mPa·s / 25℃), "Frep 60 (product name)" (manufactured by Toray Thiocol Co., Ltd., epoxy equivalent approx. 280 g / eq, viscosity approx. 17,000 mPa·s / 25℃), "Epicote 828X-90 (product name), general name: bisphenol A diglycidyl ether xylene solution" (828 type epoxy resin, manufactured by Shell Co., Ltd., weight-average molecular weight approx. 360, epoxy equivalent approx. 210 g / eq, viscosity approx. 800 mPa·s / 25℃), "Epicote 834X-85 (product name), general name: bisphenol A type epoxy xylene solution" (834 type epoxy resin, Shell Corporation, weight-average molecular weight approximately 470, epoxy equivalent approximately 282 g / eq, viscosity approximately 3000 mPa·s / 25℃), "Epicote 1001X-75 (product name), general name: bisphenol A type epoxy xylene solution" (1001 type epoxy resin, Shell Corporation, weight-average molecular weight approximately 900, epoxy equivalent approximately 633 g / eq, viscosity approximately 10000 mPa·s / 25℃), "jER828" (Mitsubishi Chemical Corporation, epoxy equivalent: 180~200 g / eq, solids content: 100% by mass), "E-028-90X" (Otake Akishin Chemical Co., Ltd., 828 type epoxy Xylene resin, solid content epoxy equivalent: 180-200 g / eq, xylene-free product, solid content: 90% by mass), "AER260" (Bisphenol A type epoxy resin, manufactured by Asahi Kasei Epoxy Co., Ltd., epoxy equivalent: 190 g / eq, solid content: 100% by mass), "jER834-X90" (manufactured by Mitsubishi Chemical Corporation, solid content epoxy equivalent: 230-270 g / eq, xylene-free product, solid content: 90% by mass), "E-834-85X(T)" (manufactured by Otake Akishin Chemical Co., Ltd., solid content epoxy equivalent: approximately 230-270 g / eq, xylene-free product, solid content: 85% by mass), "jER1001-X75 (manufactured by Mitsubishi Chemical Corporation, solid content epoxy equivalent: 450-500 g / eq, xylene-free product, solid content: 75% by mass), E-001-75X (manufactured by Ohtake Akishin Chemical Co., Ltd., solid content epoxy equivalent: approximately 450-500 g / eq, xylene-free product, solid content: 75% by mass), jER807 (manufactured by Mitsubishi Chemical Corporation, bisphenol F type diglycidyl ether resin, epoxy equivalent: 1 Examples include 60-175 g / eq, solids content: 100% by mass, "Frep 60" (polysulfide-modified epoxy resin, manufactured by Toray Fine Chemicals Co., Ltd., epoxy equivalent: approximately 280 g / eq, solids content: 100% by mass), "YD-172-X75" (dimer acid-modified epoxy resin, manufactured by Kokuto Chemical Co., Ltd., solids content epoxy equivalent: 600-700 g / eq, xylene-free version, solids content: 75% by mass), and "EPICLON 5300-70" (novolac-type epoxy resin, manufactured by DIC Corporation, epoxy equivalent: 300-340 g / eq, xylene / isobutyl alcohol-free version, solids content: 70% by mass). In the present invention, one or more of these epoxy resins may be included.

[0021] The content of epoxy resin (A) in the Tycoat composition is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less, based on the total content of epoxy resin (A), amine curing agent (B), and oxime group-containing organosilane (C), from the viewpoint of easily forming an undercoat layer that is excellent in adhesion to the substrate and antifouling coating film, oil resistance, solvent resistance, chemical resistance, and corrosion resistance. The content of epoxy resin (A) in the non-volatile components of the Tycoat composition is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of being able to easily form an undercoat layer that is excellent in adhesion to the substrate and antifouling coating film, oil resistance, solvent resistance, chemical resistance and corrosion resistance, etc.

[0022] <Amine curing agent (B)> The amine curing agent (B) is preferably a polyamine having two or more primary or secondary amino groups in one molecule. Specifically, as the amine curing agent (B), amine compounds of aliphatic, alicyclic, aromatic, heterocyclic and the like are preferable, and an aliphatic amine curing agent is more preferable from the viewpoints that a tie-coat composition having excellent curability and a long pot life can be easily obtained. These amine compounds are distinguished by the type of carbon to which the amino group is bonded. For example, the aliphatic amine curing agent refers to a compound having at least one amino group bonded to an aliphatic carbon. As the amine curing agent (B), one type may be used, or two or more types may be used.

[0023] The amine curing agent (B) is considered to be not only a curing agent for the epoxy resin (A) in the present composition, but also to act as a curing catalyst that catalyzes the reaction with the oxime group-containing organosilane (C).

[0024] Examples of the aliphatic amine curing agent include alkylene polyamines, polyalkylene polyamines, alkylaminoalkylamines, and polyoxyalkylene polyamines, and among these, polyoxyalkylene polyamines are preferable from the viewpoint that a tie-coat composition having a long pot life can be easily obtained.

[0025] Examples of the alkylene polyamine include compounds represented by the formula: "H2N-R 1 -NH2" (R 1 is a divalent hydrocarbon group having 1 to 12 carbon atoms.), and specific examples thereof include methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,5-diaminopentane, 1,6-diaminohexane, and trimethylhexamethylenediamine.

[0026] Examples of the polyalkylene polyamine include compounds represented by the formula: "H2N-(C m H 2m NH) nExamples of compounds represented by H (where m is an integer from 1 to 10, and n is an integer from 2 to 10, preferably an integer from 2 to 6) include, specifically, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine, and triethylene-bis(trimethylene)hexamine.

[0027] Examples of alkylaminoalkylamines include those with the formula: "R 2 2N-(CH2) p -NH2" (R 2 These are independently hydrogen atoms or C1-C8 alkyl groups (where at least one R) 2 A is an alkyl group having 1 to 8 carbon atoms, and p is an integer from 1 to 6. Examples of compounds represented by ) include dimethylaminoethylamine, diethylaminoethylamine, dibutylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dipropylaminopropylamine, dibutylaminopropylamine, and dimethylaminobutylamine.

[0028] Examples of polyoxyalkylene polyamines include polyoxyethylenediamine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxypropylene-polyoxyethylenediamine, trimethylolpropanepoly(oxypropylene)triamine, and glycerylpoly(oxypropylene)triamine.

[0029] Examples of alicyclic amine compounds include cyclohexanediamine, diaminodicyclohexylmethane (especially 4,4'-methylenebis(cyclohexylamine) [PACM]), 4,4'-isopropylidenebiscyclohexylamine, norbornanediamine (NBDA), and 2,4-di(4-aminocyclohexylmethyl)aniline.

[0030] Examples of amine curing agents (B) include polyamides of the amine compounds mentioned above, and their modified products. These include fatty acid modified products such as polyamidoamines, amine adducts with epoxy compounds, Mannich modified products (e.g., phenalkamine, phenalkamide), Michael adducts, ketimines, and aldimines.

[0031] Among these, as the amine curing agent (B), Mannich-modified amine is preferred, and MXDA Mannich-modified amine is more preferred, because it allows for easy acquisition of a Tiecoat composition with excellent curing speed, especially at low temperatures (5°C or below), and allows for easy formation of an undercoat coating with a good balance of adhesion to the antifouling coating and strength.

[0032] 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.

[0033] 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. 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 unsaturated hydrocarbon groups. Examples of the unsaturated hydrocarbon group include an alkylene group having approximately 1 to 10 carbon atoms, and a phenyl group containing an alkylene group having approximately 1 to 10 carbon atoms.

[0034] 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).

[0035] 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.

[0036] Examples of the aforementioned aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, etc., and one or more of these may be used.

[0037] In the Mannich condensation described above, theoretically equimolar amounts of phenols, aldehydes, and MXDA should be used. However, 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 approximately 50 to 180°C for approximately 3 to 12 hours. After the reaction is complete, the reaction product may be heated under reduced pressure to remove water and unreacted substances.

[0038] 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.

[0039] The amine curing agent (B) may be obtained by conventionally known methods, or a commercially available product may be used. Commercially available products include, for example, the polyamide "PA-66S (product name)" (manufactured by Otake Akishin Chemical Co., Ltd., active hydrogen equivalent 377 g / eq), and specific modified polyamides include, for example, the epoxy adduct polyamide with an epoxy compound added, "PA-23 (product name)" (manufactured by Otake Akishin Chemical Co., Ltd., active hydrogen equivalent 80-150 g / eq), and the Mannich modified polyamines "Ankamin 2724 (product name)" (manufactured by Evonik Japan Co., Ltd., active hydrogen equivalent 255 g / eq), "Cardolite CM-5055 (product name)" (manufactured by Cardolite Corp., active hydrogen equivalent 150-250 g / eq), "MAD-204(A) (product name)" (manufactured by Otake Akishin Chemical Co., Ltd., active hydrogen equivalent 202 g / eq), and "Cardolite Lite 2001 LV" (Cardolite Examples include products manufactured by Corp. (active hydrogen equivalent 125 g / eq), etc.

[0040] The number of functional groups in the amine curing agent (B) is preferably 2 to 6, and more preferably 2 to 3, from the viewpoint of easily forming a coating film with excellent topcoat compatibility (e.g., adhesion to a topcoat film (preferably an antifouling coating film) that can be formed on a coating film formed from the tiecoat composition).

[0041] The active hydrogen equivalent of the amine curing agent (B) is preferably 20 g / eq or more, more preferably 40 g / eq or more, preferably 1,000 g / eq or less, and more preferably 500 g / eq or less, from the viewpoint of easily obtaining a tiecoat composition that is superior in terms of topcoat suitability, curability, coating hardness, and corrosion resistance of the coating film.

[0042] The number-average molecular weight (Mn) of the amine curing agent (B) is preferably 100 to 5,000, more preferably 200 to 3,000, and even more preferably 350 to 2,000, from the viewpoint of easily obtaining a tiecoat composition that is excellent in terms of topcoat compatibility, curability, storage stability, coating hardness, and corrosion resistance.

[0043] When the Tiecoat composition is a two-component composition having a first component (main component) and a second component (curing agent), or a three-component composition having a first component (main component), a second component (curing agent), and a third component (additive), the amine curing agent (B) is included in the second component. The viscosity of this second component at 25°C, as measured with an E-type viscometer, is preferably 100,000 mPa·s or less, more preferably 10,000 mPa·s or less, even more preferably 3,000 mPa·s or less, and even more preferably 1,000 mPa·s or less, and preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 200 mPa·s or more, from the viewpoint of obtaining a paint composition with superior handling and painting workability.

[0044] The content of the amine curing agent (B) in the Tycoat composition is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, based on the total content of the epoxy resin (A), amine curing agent (B), and oxime group-containing organosilane (C), from the viewpoint of easily forming a coating film with excellent topcoat compatibility, oil resistance, solvent resistance, chemical resistance, and corrosion resistance. The content of the non-volatile amine curing agent (B) in the Tycoat composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 16% by mass or less, and even more preferably 12% by mass or less, from the viewpoint of being able to easily form a coating film that is excellent in terms of topcoat compatibility, oil resistance, solvent resistance, chemical resistance and corrosion resistance.

[0045] From the viewpoint of easily forming a coating film with excellent corrosion resistance, coating hardness, drying properties, and suitability for topcoat application, it is desirable to use the amine curing agent (B) in an amount such that the reaction ratio calculated by the following formula (1) is preferably 0.3 or more, more preferably 0.4 or more, preferably 1.0 or less, more preferably 0.8 or less, and even more preferably 0.7 or less, for example, an amount between 0.3 and 1.0. Reaction ratio = {(Amount of amine curing agent (B) / Active hydrogen equivalent of amine curing agent (B)) + (Amount of component reactive with epoxy resin (A) / Functional group equivalent of component reactive with epoxy resin (A))} / {(Amount of epoxy resin (A) / Epoxy equivalent of epoxy resin (A)) + (Amount of component reactive with amine curing agent (B) / Functional group equivalent of component reactive with amine curing agent (B))} ... (1) Here, the "component reactive with amine curing agent (B)" in formula (1) above refers, for example, to the component reactive with amine curing agent (B) in the other components listed below, and the "component reactive with epoxy resin (A)" refers, for example, to the component reactive with epoxy resin (A) in the other components listed below. The "functional group equivalent" of each of the above components means the mass (g) per 1 mole of functional group obtained by dividing the mass of 1 mole of these components by the number of moles of functional groups contained therein.

[0046] <Oxime group-containing organosilane (C)> In this embodiment, the Tycoat composition contains an oxime group-containing organosilane (C). The oxime group-containing organosilane (C) is not particularly limited as long as it is an organosilicon compound having an oxime group, but from the viewpoint of reactivity, it is preferable that it is a compound having at least two oxime groups. The oxime group-containing organosilane (C) is preferably a compound represented by the following formula (1).

[0047] [ka] (In formula (1), R 1 and R 2 Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a methyl group, a vinyl group, or a phenyl group.

[0048] In formula (1), R 1 and R 2Examples of alkyl groups with 1 to 4 carbon atoms represented by R include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl groups. Among these, R 1 and R 2 Both are methyl groups, R 1 and R 2 One is a methyl group, the other is an ethyl group, R 1 and R 2 Preferably, one of them is a methyl group and the other is an isobutyl group, R 1 and R 2 One is a methyl group, the other is an ethyl group, R 1 and R 2 It is more preferable that one of the groups is a methyl group and the other is an isobutyl group.

[0049] In formula (1), X represents a methyl group, a vinyl group, or a phenyl group, and from the viewpoint of reactivity, a methyl group or a vinyl group is preferred, and a methyl group is more preferred.

[0050] The oxime group-containing organosilane (C) is preferably at least one selected from the group consisting of methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, and vinyltris(methylisobutylketoxime)silane.

[0051] The content of oxime group-containing organosilane (C) in the Tycoat composition is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and even more preferably 8% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total of epoxy resin (A), amine curing agent (B), and oxime group-containing organosilane (C), from the viewpoint of substrate adhesion and topcoat coating suitability. Furthermore, the content of oxime group-containing organosilane (C) in the nonvolatile components of the Tycoat composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and even more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 12% by mass or less, from the viewpoint of substrate adhesion and topcoat coating suitability.

[0052] <Other ingredients> The Tycoat composition may further contain other components. Examples of other components include silane coupling agents, gypsum, pigments, anti-sagging agents, anti-settlement agents, hardening accelerators, solvents, (pigment) dispersants, and defoaming agents. These other components may be used individually or in combination of two or more types. Other components can be conventionally known components, and commercially available products may also be used.

[0053] (Silane coupling agent) The Tiecoat composition may contain a silane coupling agent, and it is preferable to include a silane coupling agent for the purpose of improving the suitability of the topcoat coating, curability, and adhesion to the substrate, as well as reducing the viscosity of the Tiecoat composition. Furthermore, it is also possible to improve the corrosion resistance of the coating film formed from the Tiecoat composition. One type of silane coupling agent may be used, or two or more types may be used.

[0054] 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 the suitability of the topcoat coating, curability, and adhesion to the substrate, as well as reducing the viscosity of the tie-coat composition.

[0055] 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 represents a functional group that can react with organic matter (e.g., amino group, vinyl group, epoxy group, mercapto group, halogeno group, a group in which part of a hydrocarbon group is substituted with 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 represents a hydrolyzable group (e.g., an alkoxy group such as a methoxy group or ethoxy group)].

[0056] 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.

[0057] 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).

[0058] When the Tiecoat composition contains a silane coupling agent, the content of the silane coupling agent in the nonvolatile components of the Tiecoat composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of being able to lower the viscosity of the Tiecoat composition and improve paintability, as well as improving topcoat suitability, curability, and adhesion to the substrate.

[0059] (plaster) The Tycoat composition may contain gypsum. By including gypsum in the Tycoat composition, a coating film with excellent water resistance, saltwater resistance, and corrosion resistance can be easily formed. You may use one type of gypsum, or you may use two or more types.

[0060] Examples of the gypsum include crystalline gypsum (CaSO4·2H2O), hemihydrate gypsum (CaSO4·0.5H2O), and anhydrous gypsum (CaSO4), with hemihydrate gypsum and / or anhydrous gypsum being preferred. These may be natural or artificial products. There are no particular restrictions on the shape, but it is preferable that it be in powder form.

[0061] Anhydrous gypsum and hemihydrate gypsum have the property of hardening when they absorb moisture and also retain moisture. Therefore, it is thought that coating films containing anhydrous gypsum and / or hemihydrate gypsum have the effect of retaining moisture and relieving internal stress in the coating film through a plasticizing effect, thus improving the suitability for topcoat application.

[0062] Hemihydrate gypsum comes in α-type and β-type, but the β-type is preferred in terms of the strength of the resulting coating film. An example of hemihydrate gypsum is "FT-2" (average particle size 15 μm) manufactured by Noritake Co., Ltd. Furthermore, anhydrous gypsum comes in three types: Type I, Type II, and Type III, but is not particularly limited to any one type. An example of anhydrous gypsum is "AS Gypsum" manufactured by San-Es Gypsum Co., Ltd.

[0063] When the Tiecoat composition contains gypsum, the amount is not particularly limited, but from the viewpoint of excellent suitability for topcoat application and the ability to easily form a coating film with suppressed cracking, it is preferably 5 to 100 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of epoxy resin (A). When the Tiecoat composition contains gypsum, the amount is not particularly limited, but from the viewpoint of excellent suitability for topcoat coating and the ability to easily form a coating film with suppressed cracking, specifically, the amount of gypsum in the nonvolatile components of the Tiecoat composition is preferably 1% by mass or more and 40% by mass or less, more preferably 3% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and even more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0064] (Pigment) The Tiecoat composition may contain a pigment, and it is preferable that it contains a pigment. Examples of such pigments include extender pigments, coloring pigments, and rust-preventive pigments, and they may be organic or inorganic.

[0065] Examples of extender pigments include zinc oxide, talc, mica, (precipitating) barium sulfate, (potassium) feldspar, kaolin, alumina white, wollastonite, clay, glass flakes, aluminum flakes, flaky iron oxide, magnesium carbonate, barium carbonate, calcium carbonate, dolomite, and silica. Talc, mica, silica, (precipitating) barium sulfate, and (potassium) feldspar are particularly preferred.

[0066] If the Thai Coat composition contains an extender pigment, the content of the extender pigment is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, and preferably 85% by mass or less, more preferably 75% by mass or less, even more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less.

[0067] Examples of coloring pigments include inorganic pigments such as carbon black, titanium dioxide (also called titanium white), iron oxide (red iron oxide), yellow iron oxide, and ultramarine; and organic pigments such as cyanine blue and cyanine green. Carbon black, titanium dioxide, and red iron oxide are particularly preferred.

[0068] If the tiecoat composition contains a coloring pigment, the content of the coloring pigment is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, in the nonvolatile components of the tiecoat composition.

[0069] Examples of rust-preventive pigments include zinc powder, zinc alloy powder, zinc phosphate compounds, calcium phosphate compounds, aluminum phosphate compounds, magnesium phosphate compounds, zinc phosphite compounds, calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdate compounds, zinc cyanamide compounds, borate compounds, nitro compounds, and complex oxides.

[0070] If the tiecoat composition contains a pigment, the total pigment content in the nonvolatile components of the tiecoat composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less.

[0071] (Drip stopper) It is preferable for the tie-coat composition to contain an anti-sagging agent, as this allows for adjustment of properties such as anti-sagging during painting. One type of anti-slip agent may be used, or two or more types may be used.

[0072] 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.

[0073] If the tie coat composition contains an anti-sagging agent, the content of the anti-sagging agent in the non-volatile components of the tie coat composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0074] (Anti-settling agent) It is preferable for the Thai Coat composition to contain a settling inhibitor, as this can reduce the precipitation that may occur during storage of the Thai Coat composition and improve the agitability of the Thai Coat composition. The settling inhibitor may be of one type or two or more types.

[0075] 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.

[0076] If the Tycoat composition contains a settling inhibitor, its content is preferably 0.03% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.3% by mass or more, and preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, of the nonvolatile components of the Tycoat composition.

[0077] (Curing accelerator) The Tiecoat composition preferably contains a curing accelerator to further improve the curing speed and low-temperature curing properties. The hardening accelerator may be one type or two or more types.

[0078] 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 a tiecoat composition with excellent curing speed and low temperature (below 5°C) curing properties.

[0079] 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.

[0080] 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-Cure400", manufactured by Sartomer).

[0081] When the Tycoat composition contains a curing accelerator, the amount of the accelerator is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, even more preferably 0.1% by mass or more, and preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.3% by mass or less, in the nonvolatile components of the Tycoat composition, in order to easily obtain a Tycoat composition with excellent curing speed and low-temperature curing properties.

[0082] (solvent) From the viewpoint of maintaining the paint viscosity within an appropriate range, the tie-coat composition preferably contains a 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.

[0083] If the Tiecoat composition contains a solvent, the amount is not particularly limited, but considering the coating properties, it is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, and preferably 60% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less.

[0084] ((Pigment) Dispersant) The tiecoat composition may contain a (pigment) dispersant for the purpose of improving the dispersibility of pigments, etc. Various conventionally known organic and inorganic dispersants can be used as the (pigment) dispersant. 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.

[0085] If the Tycoat composition contains a (pigment) dispersant, its content is preferably 0.01% by mass or more, preferably 10% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less, of the nonvolatile components of the Tycoat composition.

[0086] (Antifoaming agent) It is preferable for the Tiecoat composition to contain an antifoaming agent, as this can suppress the generation of bubbles during manufacturing or painting, or break bubbles that have formed in the Tiecoat composition, and easily form a coating film with desired physical properties. When the Tiecoat composition contains an antifoaming agent, the amount of the antifoaming agent in the nonvolatile components of the Tiecoat composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. When the amount of the antifoaming agent is within the above range, the generation of foam can be sufficiently suppressed, and a coating film with the desired physical properties can be easily formed.

[0087] Tycoat composition is suitable as a primer for various types of paints, and in particular, Tycoat composition is suitable as a primer layer for antifouling paint compositions containing curable silicone (a).

[0088] <Method for producing Thai Coat composition> The Tycoat composition can be manufactured using known methods as appropriate. For example, each of the above-mentioned components can be placed in a stirring vessel all at once or in any order, and then mixed, dispersed, or dissolved using known stirring and mixing means. Means of stirring and mixing include, for example, using a paint shaker, high-speed disperser, sand grind mill, basket mill, ball mill, three-roll mill, loss mixer, or planetary mixer. Mixing (kneading) may be carried out while heating or cooling depending on the season and environment.

[0089] The Tycoat composition may be a one-component paint containing the above components, or a multi-component paint such as a two-component paint consisting of a main component and a curing agent, or a three-component paint consisting of a main component, a curing agent, and an additive. From the viewpoint of storage stability, the Tycoat composition is preferably a multi-component paint, and is more preferably a two-component paint having a main component (first component) containing at least epoxy resin (A) and a curing agent (second component) containing at least amine curing agent (B), or a three-component paint having a main component (first component) containing at least epoxy resin (A), a curing agent (second component) containing at least amine curing agent (B), and an additive (third component) containing at least oxime group-containing organosilane (C). In the case of a two-component paint, it is preferable that, for example, the first component contains an epoxy resin (A), a pigment, an anti-sagging agent, and an anti-settling agent, and the second component contains an amine curing agent (B) and a curing accelerator. In the case of a three-component paint, it is preferable that, for example, the first component contains an epoxy resin (A), a pigment, an anti-sagging agent, and an anti-settling agent, the second component contains an amine curing agent (B) and a curing accelerator, and the third component contains an oxime group-containing organosilane (C). The components constituting the tiecoat composition (the first and second components, or the first to third components) are usually stored, kept, or transported in separate containers and mixed together immediately before use.

[0090] [Laminated antifouling coating] The laminated antifouling coating of the present invention is a laminated antifouling coating in which a substrate, an undercoat layer, and an antifouling coating are laminated in this order, and is used as a substrate with a laminated antifouling coating, in which an undercoat layer and an antifouling coating are laminated on the substrate in this order. The above-mentioned laminated antifouling coating film is formed in which the undercoat layer is made of a tiecoat composition containing epoxy resin (A), amine curing agent (B), and oxime group-containing organosilane (C) represented by the following formula (1).

[0091] [ka] (In formula (1), R 1 and R 2Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a methyl group, a vinyl group, or a phenyl group.

[0092] The antifouling coating film is formed by an antifouling paint composition selected from the group consisting of (i) to (iii) below, which contains a curable silicone (a). (i) An antifouling coating composition containing a polyorganosiloxane (a1) having ketoxime groups at both ends, wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is 1.5% by mass or less. (ii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends and an organosilane (a3) ​​represented by the following formula (I), wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 1.0% by mass.

[0093] [ka] (In formula (I), R 3 Each of the following independently represents a substituted or unsubstituted hydrocarbon group with 1 to 10 carbon atoms, Y is a ketoxime group with a total of 3 to 6 carbon atoms, and a is 0 or 1. (iii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends, at least one organosilicon crosslinking agent selected from the group consisting of organosilanes having at least two hydrolyzable groups in one molecule and their partially hydrolyzed condensates, and a curing catalyst, wherein the content of hydrophilic lubricants in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 0.1% by mass. It is preferable that either condition A or condition B below is met. Condition A: X is a phenyl group, and the antifouling paint composition is (i) above. Condition B: X is a methyl group or a vinyl group, and the antifouling coating composition is selected from the group consisting of (i) to (iii) above. In the following description, the antifouling paint composition described in (i) above will also be referred to as antifouling paint composition (i), the antifouling paint composition described in (ii) above will also be referred to as antifouling paint composition (ii), and the antifouling paint composition described in (iii) above will also be referred to as antifouling paint composition (iii).

[0094] According to the present invention, a laminated coating film is provided in which a primer layer formed by a tiecoat composition and an antifouling coating film formed by an antifouling coating composition have good adhesion. The detailed reasons why the above effects are achieved are unknown, but some explanations are as follows. When an antifouling paint composition contains an organopolysiloxane (a1) having ketoxime groups at both ends as a curable silicone (a), the antifouling paint composition containing the curable silicone (a) exhibits excellent adhesion to the undercoat layer. Therefore, in antifouling paint composition (i), if the polyether-modified silicone oil content is 1.5% by mass or less, it exhibits good adhesion to the undercoat layer, and also exhibits good adhesion even when X in formula (1) of the oxime group-containing organosilane (C) contained in the undercoat layer is a bulky, sterically hindered phenyl group. On the other hand, in antifouling coating compositions (ii) and (iii), which contain a polyorganosiloxane (a2) having a hydroxyl group, excellent adhesion to the undercoat can be obtained by setting the content of the hydrophilic lubricant and polyether-modified silicone oil within a specific range, from the viewpoint of adhesion to the undercoat. In this case, the oxime group-containing organosilane (C) contained in the Tycoat composition has X as either a methyl group or a vinyl group.

[0095] <Tycoat composition> In the laminated antifouling coating film, the components of the Tiecoat composition and their content are the same as those exemplified in the Tiecoat composition of this embodiment described above, and the preferred embodiment is also the same.

[0096] <Antifouling paint composition> The antifouling paint composition used to form the antifouling coating of the laminated antifouling coating of this embodiment is an antifouling paint composition containing curable silicone (a) and selected from the group consisting of (i) to (iii) below. (i) An antifouling coating composition containing a polyorganosiloxane (a1) having ketoxime groups at both ends, wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is 1.5% by mass or less. (ii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends and an organosilane (a3) ​​represented by the following formula (I), wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 1.0% by mass.

[0097] [ka] (In formula (I), R 3 Each of the following independently represents a substituted or unsubstituted hydrocarbon group with 1 to 10 carbon atoms, Y is a ketoxime group with a total of 3 to 6 carbon atoms, and a is 0 or 1. (iii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends, at least one organosilicon crosslinking agent selected from the group consisting of organosilanes having at least two hydrolyzable groups in one molecule and their partially hydrolyzed condensates, and a curing catalyst, wherein the content of hydrophilic lubricants in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 0.1% by mass. The individual components contained in the antifouling paint composition will be described in detail.

[0098] (Curing silicone (a)) The curable silicone (a) contains an organopolysiloxane (a1) having ketoxime groups at both ends, or a polyorganosiloxane (a2) having hydroxyl groups at both ends and an organosilane (a3) ​​represented by the following formula (I), or a polyorganosiloxane (a2) having hydroxyl groups at both ends and containing at least one organosilicon crosslinking agent selected from the group consisting of organosilanes having at least two hydrolyzable groups in one molecule and their partially hydrolyzed condensates. Each of these will be described below.

[0099] (Organopolysiloxane (a1) having ketoxime groups at both ends) A polyorganosiloxane having ketoxime groups at both ends (hereinafter also referred to as "polyorganosiloxane (a1)") has at least a polyorganosiloxane structure as the main chain and a reactive site having ketoxime groups, with the reactive site located at both ends. The main chain has a polyorganosiloxane structure, and examples of polyorganosiloxane structures include polydimethylsiloxane structures and polymethylphenylsiloxane structures, with polydimethylsiloxane structures being preferred. Alkylene groups and polyoxyalkylene groups may be present in block form within the main chain. Furthermore, an alkylene group or a polyoxyalkylene group may be present as a linking site between the main chain and the reactive site. The reactive sites react with each other on the polyorganosiloxane (a1) or with the organosilicon crosslinking agent (b) contained in the antifouling coating composition (described later) to form a crosslinked structure, which then becomes a silicone cured body and forms an antifouling coating film. They may also react with the silane coupling agent (described later) to form part of the silicone cured body.

[0100] The reactive site preferably has a ketoximusilyl group, and its position is preferably at both ends of the main chain. As a polyorganosiloxane having ketoxime groups at both ends, compounds represented by the following formula (II) are preferred.

[0101] [ka] (In formula (II), R 11 , R 12 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, or a halogenated alkyl group, R 21 ~R 24 Each of the following independently represents an alkyl group with 1 to 4 carbon atoms, n represents an integer between 10 and 10,000, and a represents an integer between 1 and 3.

[0102] In formula (II), n represents an integer between 10 and 10,000, preferably between 100 and 1,000, and can be appropriately selected so that the kinematic viscosity and weight-average molecular weight, as described later, fall within a suitable range. 'a' represents an integer between 1 and 3, preferably 1 or 2, and more preferably 2. R 11 and R 12 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. Note that there are multiple R's. 11 These may be the same or different, and also R 12 When there are multiple instances, R 12 These can be the same or different. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 or 2, and even more preferably 1. The number of carbon atoms in the alkenyl group is preferably 2 to 6, more preferably 2 to 3, and a vinyl group (-CH=CH2) is particularly preferred. The aryl group preferably has 6 to 8 carbon atoms and may have substituents such as alkyl groups on the aromatic ring, such as phenyl groups, tolyl groups (methylphenyl groups), xylyl groups (dimethylphenyl groups), and naphthyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 9, and examples include the benzyl group, 2-phenylethyl group, 2-naphthylethyl group, and diphenylmethyl group. The number of carbon atoms in the halogenated alkyl group is preferably 1 to 6. Examples include groups in which some or all of the hydrogen atoms contained in the alkyl group are replaced with halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Among these, R 11 It is preferably a methyl group, R 12 It is preferable that it be a vinyl group.

[0103] In formula (II), R 21 ~R 24 Each of these independently represents an alkyl group having 1 to 4 carbon atoms, with examples including the methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, and isobutyl group. Among these, -ON=C(R 21 R 22 ) or -ON=C(R 23 R 24 The ketoxime group represented by ) is preferably a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, or a methyl isobutyl ketoxime group.

[0104] (Organopolysiloxane (a2) having hydroxyl groups at both ends, and organosilane (a3) ​​represented by formula (I)) The antifouling coating composition may contain a polyorganosiloxane having hydroxyl groups at both ends (hereinafter also referred to as "polyorganosiloxane (a2)") and an organosilane (a3) ​​represented by the following formula (I).

[0105] [ka] (In formula (I), R 3 Each of the following independently represents a substituted or unsubstituted hydrocarbon group with 1 to 10 carbon atoms, Y is a ketoxime group with a total of 3 to 6 carbon atoms, and a is 0 or 1.

[0106] A polyorganosiloxane having hydroxyl groups at both ends (hereinafter also referred to as "polyorganosiloxane (a2)") has at least a polyorganosiloxane structure as the main chain and a reactive site having hydroxyl groups, with the reactive site located at both ends. The main chain has a polyorganosiloxane structure, and examples of polyorganosiloxane structures include polydimethylsiloxane structures and polymethylphenylsiloxane structures, with polydimethylsiloxane structures being preferred. Alkylene groups and polyoxyalkylene groups may be present in block form within the main chain. Furthermore, an alkylene group or a polyoxyalkylene group may be present as a linking site between the main chain and the reactive site. The silanol group reacts with an organosilane represented by formula (I), described later (hereinafter also referred to as "organosilane (a3)") to obtain a polyorganosiloxane having ketoxime groups at both ends (polyorganosiloxane (a1)). Polyorganosiloxane (a2) reacts with the reactive sites of polyorganosiloxane (a1) obtained by the above reaction to form a cross-linked structure, becoming a silicone cured body and forming an antifouling coating. It may also react with the silane coupling agents (f and j) described later to form part of the silicone cured body.

[0107] As the polyorganosiloxane (a2), a compound represented by the following formula (III) is preferred.

[0108] [ka] (In equation (III), p represents an integer between 10 and 10,000, b represents an integer between 1 and 3, R 13 and R 14 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an alkoxy group, an aryl group, an aralkyl group, or an alkyl halogenated group.

[0109] In formula (III), p represents an integer between 10 and 10,000, preferably between 100 and 1,000, and can be appropriately selected so that the viscosity and weight-average molecular weight described later are within a suitable range. b represents an integer between 1 and 3, preferably 1 or 2, and more preferably 1. R 13 and R 14 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. Note that there are multiple R's. 13 These may be the same or different, and also R 14 When there are multiple instances, R 14 These can be the same or different. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, even more preferably 1 or 2, and even more preferably 1. The number of carbon atoms in the alkenyl group is preferably 2 to 6, more preferably 2 to 3, and a vinyl group (-CH=CH2) is even more preferred. The number of carbon atoms in the alkoxy group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. The aryl group preferably has 6 to 8 carbon atoms and may have substituents such as alkyl groups on the aromatic ring, such as phenyl groups, tolyl groups (methylphenyl groups), xylyl groups (dimethylphenyl groups), and naphthyl groups. The number of carbon atoms in the aralkyl group is preferably 7 to 9, and examples include the benzyl group, 2-phenylethyl group, 2-naphthylethyl group, and diphenylmethyl group. The number of carbon atoms in the halogenated alkyl group is preferably 1 to 6. Examples include groups in which some or all of the hydrogen atoms contained in the alkyl group are replaced with halogen atoms such as fluorine, chlorine, bromine, and iodine atoms. Among these, R 13 and R 14 It is preferable that it be a methyl group.

[0110] Organosilane (a3) ​​is represented by the following formula (I).

[0111] [ka] (In formula (I), R 3 Each of the following independently represents a substituted or unsubstituted hydrocarbon group with 1 to 10 carbon atoms, Y is a ketoxime group with a total of 3 to 6 carbon atoms, and a is 0 or 1.

[0112] In formula (I), a is either 0 or 1, and is preferably 1 from the viewpoint of the reactivity of the resulting polyorganosiloxane. R 3 Each of these independently represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. The number of carbon atoms in the alkyl group is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. The number of carbon atoms in the alkenyl group is preferably 2 to 6, more preferably 2 to 3, and a vinyl group (-CH=CH2) is preferred. Among these, R 3 It is preferable that it be a vinyl group. Y is a ketoxime group or an alkoxy group having 1 to 4 carbon atoms, and is preferably a ketoxime group. The ketoxime group is a ketoxime group with a total of 3 to 6 carbon atoms, preferably a dimethyl ketoxime group, a methyl ethyl ketoxime group, a diethyl ketoxime group, a methyl isopropyl ketoxime group, or a methyl isobutyl ketoxime group, and more preferably a methyl ethyl ketoxime group or a methyl isobutyl ketoxime group.

[0113] Polyorganosiloxane (a2) and organosilane (a3) ​​should be mixed according to the stoichiometric ratio, and it is preferable to add an excess amount of organosilane (a3) ​​relative to the stoichiometric ratio. Specifically, the amount of organosilane (a3) ​​blended with 100 parts by mass of polyorganosiloxane (a2) is preferably 1 part by mass or more, more preferably 3 parts by mass or more, even more preferably 5 parts by mass or more, and preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 15 parts by mass or less.

[0114] (Organopolysiloxane (a2) and organosilicon crosslinking agent having hydroxyl groups at both ends) The curable silicone (a) is an organopolysiloxane (a2) having hydroxyl groups at both ends as described above, and may be cured by reaction with at least one organosilicon crosslinking agent selected from the group consisting of organosilanes having at least two hydrolyzable groups in one molecule and their hydrolysis condensates. That is, the polyorganosiloxane (a2) may react with the organosilicon crosslinking agent (b) described later, contained in the antifouling paint composition, to form a crosslinked structure, becoming a cured silicone body and forming an antifouling coating film. It may also react with the silane coupling agent (f or j) described later to form part of the cured silicone body.

[0115] The weight-average molecular weight (Mw) of the curable silicone (a) and polyorganosiloxane (a1) 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, and even more preferably 20,000 or more, and preferably 1,000,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and even more preferably 40,000 or less, from the viewpoint of improving coating workability, curability of the antifouling coating composition, and strength of the formed coating film.

[0116] The viscosity of the curable silicone (a) and polyorganosiloxane (a1) 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, and even more preferably 1,000 mPa·s or more, from the viewpoint of improving the workability of the antifouling coating composition, the workability of the coating composition, the curability, and the strength and flexibility of the formed coating film. Furthermore, it is preferably 100,000 mPa·s or less, more preferably 10,000 mPa·s or less, and even more preferably 7,000 mPa·s or less. The viscosity of the curable silicone (a) and polyorganosiloxane (a1) at 25°C was measured using a Type B rotational viscometer (e.g., Model: BM, manufactured by Tokyo Keiki Co., Ltd.). Furthermore, as described later, when polyorganosiloxane (a1) or polyorganosiloxane (a2) and silica particles (d) are kneaded together and then added to the antifouling coating composition, the viscosity of the kneaded mixture is preferably 20 mPa·s or more, more preferably 100 mPa·s or more, even more preferably 500 mPa·s or more, and even more preferably 800 mPa·s or more. And preferably 3,000,000 mPa·s or less, more preferably 1,500,000 mPa·s or less, and even more preferably 1,000,000 mPa·s or less.

[0117] The content of curable silicone (a) in the nonvolatile components of the antifouling coating composition is preferably 40% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, and preferably 90% by mass or less, more preferably 88% by mass or less, from the viewpoint of improving the strength of the antifouling coating film formed. Here, "non-volatile components of the antifouling coating composition" refers to the components excluding the organic solvent (k) described later and the volatile components contained as solvents in each component, and can be considered as the antifouling coating film. Furthermore, the "non-volatile components of the antifouling coating composition" are measured by the method described in the examples. The "content of each component in the antifouling coating" can be calculated from the content of each component after subtracting the organic solvent (k), the volatile components contained in each component as a solvent, and the components that detach and volatilize after the curing reaction, as described later. The components of antifouling coating compositions other than curable silicone (a) will be described below.

[0118] <Organosilicon crosslinking agent (b)> If the antifouling coating composition is antifouling coating composition (iii), the antifouling coating composition contains organosilicon crosslinking agent (b). Furthermore, antifouling coating compositions (i) and (ii) may also contain organosilicon crosslinking agent (b) to improve curing speed, the strength of the antifouling coating film, and adhesion to the substrate. Moreover, the organosilicon crosslinking agent is not limited to those intended for these functions; for example, it may be formulated to function as a wetting agent for pigments.

[0119] The organosilicon crosslinking agent (b) is an organosilane having three or four hydrolyzable groups on a silicon atom, and if it has three hydrolyzable groups, it also has one additional hydrocarbon group, and includes its partial condensates. However, compounds corresponding to the above organosilane (a3) ​​are excluded. The hydrolyzable groups are present in groups of three or four per silicon atom. An alkoxy group is preferred as the hydrolyzable group. The alkoxy group is 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.

[0120] Examples of organosilicon crosslinking agents (b) include tetraethyl orthosilicate, a partially hydrolyzed condensate of tetraethyl orthosilicate, and alkyltrialkoxysilane, with tetraethyl orthosilicate and a partially hydrolyzed condensate of tetraethyl orthosilicate being preferred. Examples of commercially available tetraethyl orthosilicate include "Ethyl Silicate 28" manufactured by Colcoat and "Orthosilicate Ethyl" manufactured by Tama Chemical Industry Co., Ltd. Commercially available partially hydrolyzed condensates of tetraethyl orthosilicate include "Silicate 40" manufactured by Tama Chemical Industry Co., Ltd., and "WACKER SILICATE TES 40 WN" manufactured by Asahi Kasei Wacker Silicone Co., Ltd. Examples of commercially available alkyltrialkoxysilanes include "KBM-13" manufactured by Shin-Etsu Chemical Co., Ltd.

[0121] The organosilicon crosslinking agent (b) may be used alone or in combination of two or more types. The content of the organosilicon crosslinking agent in the antifouling coating composition (iii) is preferably 0.3% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 12% by mass or less, and even more preferably 8% by mass or less, of the nonvolatile components of the antifouling coating composition. Furthermore, the content of the organosilicon crosslinking agent (b) in the antifouling coating composition (iii) is preferably 0.4 parts by mass or more, more preferably 1 part by mass or more, even more preferably 4 parts by mass or more, and even more preferably 5 parts by mass or more, and preferably 25 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 15 parts by mass or less, and even more preferably 12 parts by mass or less, with respect to 100 parts by mass of curable silicone (a). If the antifouling coating composition (i) or (ii) contains an organosilicon crosslinking agent (b), the content of the organosilicon crosslinking agent (b) in the nonvolatile components of the antifouling coating composition is preferably 0.1% by mass or more and 5% by mass or less, and more preferably 0.5% by mass or more and 3% by mass or less. If the antifouling paint composition (i) or (ii) contains an organosilicon crosslinking agent (b), the content of the organosilicon crosslinking agent (b) in the antifouling paint composition relative to 100 parts by mass of curable silicone (a) is preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 3 parts by mass or less.

[0122] <Hydrophilic lubricant (c)> In this embodiment, the antifouling coating composition may contain a hydrophilic lubricant (c). The hydrophilic lubricant (c) may be used alone or in combination of two or more types.

[0123] The hydrophilic lubricant (c) is preferably at least one selected from the group consisting of polyether-modified silicone oil (c1), hydrophilic acrylic polymer (c2), and glycerin condensate ester (c3). Each of these will be described below.

[0124] (Polyether-modified silicone oil (c1)) Polyether-modified silicone oil has low interfacial tension and its properties do not change easily even in low-temperature environments. Therefore, it easily moves to the surface of antifouling coatings, and can efficiently improve the adhesion prevention (antifouling) and damage resistance of aquatic organisms.

[0125] The viscosity of the polyether-modified silicone oil (c1) 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, even more preferably 80 mPa·s or more, and 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 of imparting slipperiness to aquatic organisms, improving antifouling properties, and improving the applicability of the antifouling paint composition. In this specification, the viscosity of polyether-modified silicone oil (c1) at 25°C refers to the viscosity measured using a B-type rotational viscometer.

[0126] The kinematic viscosity of the polyether-modified silicone oil (c1) at 25°C is preferably 10 mm, from the viewpoint of providing slipperiness to aquatic organisms, improving antifouling properties, and improving the applicability of antifouling paint compositions. 2 / s or more, more preferably 30 mm 2 / s or more, more preferably 50mm 2 / s or more, more preferably 100mm 2 It is 1 / s or more, and preferably 5,000 mm 2 / s or less, more preferably 3,000 mm 2 / s or less, more preferably 1,000 mm 2 / s or less, more preferably 500mm 2 It is less than or equal to / s.

[0127] Examples of polyether-modified silicone oil 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, with the side-chain modified type and both-end modified type being preferred. The polyether (polyalkylene glycol) constituting the polyether group (polyalkylene glycol group) of the polyether-modified silicone oil can be polyethylene glycol, polypropylene glycol, or a copolymer of ethylene glycol and propylene glycol, with the copolymer of polyethylene glycol and polypropylene glycol being preferred. From the viewpoint of improving the antifouling properties of the antifouling coating film formed and facilitating the formation of the coating film, the proportion of the polyether substructure in the structure of the polyether-modified silicone oil is preferably 10% to 60% by mass, and more preferably 15% to 50% by mass.

[0128] When an antifouling coating composition contains a polyether-modified silicone oil containing ethyleneoxy(-OC2H4-) structural units, from the viewpoint of imparting good antifouling properties to the formed antifouling coating film, the total mass of the ethyleneoxy(-OC2H4-) substructure is preferably 0.1 parts by mass or more and 20 parts by mass or less, and more preferably 0.3 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the silicone's dimethylsiloxane substructure (-(CH3)2Si-O-).

[0129] A commercially available example of the aforementioned polyether-modified silicone oil is "X-22-4272" (manufactured by Shin-Etsu Chemical Co., Ltd., double-ended type, kinematic viscosity (25℃): 270 mm²). 2 / s), "KF-6020" (manufactured by Shin-Etsu Chemical Co., Ltd., side chain type, kinematic viscosity (25℃): 180 mm) 2 / s), "FZ-2203" (manufactured by Toray Dow Corning Co., Ltd., block type), "FZ-2160" (manufactured by Toray Dow Corning Co., Ltd., double-ended type), "Polyflow KL-402" (manufactured by Kyoeisha Chemical Co., Ltd., kinematic viscosity (25℃): 350mm 2 Examples include / s).

[0130] (Hydrophilic acrylic polymer (c2)) In this embodiment, the hydrophilic acrylic polymer (c2) used in the antifouling coating composition preferably contains structural units derived from a monomer having a hydrophilic group, more preferably contains structural units derived from a monomer having a hydrophilic group and structural units derived from a hydrophobic monomer, and even more preferably consists of structural units derived from a monomer having a hydrophilic group and structural units derived from a hydrophobic monomer. The content of constituent units derived from monomers having hydrophilic groups in the hydrophilic acrylic polymer (c2) is preferably 1% by mass or more and 100% by mass or less, more preferably 3% by mass or more and 80% by mass or less, even more preferably 5% by mass or more and 70% by mass or less, and even more preferably 10% by mass or more and 60% by mass or less. Because acrylic polymers possess hydrophilic groups, the hydrophilic portions of the acrylic polymers in the antifouling coating dissolve or swell and gradually migrate to the surface of the antifouling coating, thereby effectively preventing the adhesion of aquatic organisms. Furthermore, because they have an acrylic structure, they undergo gradual hydrolysis, which changes their affinity for water, allowing them to maintain their antifouling properties over a long period of time. From the viewpoint of antifouling properties, polyether groups and hydroxyl groups are preferred as the hydrophilic group of the monomer having the hydrophilic group, and polyether groups are more preferred.

[0131] Furthermore, the content of constituent units derived from hydrophobic monomers in the hydrophilic acrylic polymer (c2) is preferably 99% by mass or less, more preferably 97% by mass or less, even more preferably 95% by mass or less, and even more preferably 90% by mass or less, and preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. By possessing hydrophobic monomers, it is believed that the material has a high affinity for other components of the antifouling coating, such as curable silicone (a) and its cured products, and can uniformly exhibit a sliding effect on the surface of the antifouling coating.

[0132] From the viewpoint of antifouling properties, monomers having polyalkylene glycol groups, monomers having hydroxyl groups, and monomers having alkoxyalkyl groups are preferred as the monomers having hydrophilic groups, and monomers having polyalkylene glycol groups are more preferred. Specifically, from the viewpoint of improving antifouling properties, one or more selected from polyalkylene glycol (meth)acrylate, hydroxyalkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 4-(meth)acryloylmorpholin, and vinylpyrrolidone are preferred, 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.

[0133] Examples of polyalkylene glycol (meth)acrylate include those 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 the alkoxy group being preferred. In particular, polyalkylene glycols in which one end is directly esterified with (meth)acrylic acid are preferred, and those in which the other end is an alkoxy group are more preferred. The terminal (meth)acrylic acid is preferably acrylic acid or 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.

[0134] 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. 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.

[0135] 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, aryloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol methacrylate, 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.

[0136] Commercially available polyalkylene glycol (meth)acrylates include NK Ester AM-90G (methoxy polyethylene glycol #400 acrylate), NK Ester AM-130G (methoxy polyethylene glycol #550 acrylate), NK Ester M-90G (methoxy polyethylene 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.

[0137] Examples of the hydroxyalkyl (meth)acrylate include hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate. Examples of commercially available hydroxyalkyl (meth)acrylates include Light Ester HOA(N) (2-hydroxyethyl acrylate), Light Ester HO-250(N) (2-hydroxyethyl methacrylate), and Light Ester HOP(N) (2-hydroxypropyl methacrylate), all manufactured by Kyoeisha Chemical Co., Ltd.

[0138] Examples of the alkoxyalkyl (meth)acrylate include methoxyethyl (meth)acrylate. The tetrahydrofurfuryl (meth)acrylate is preferably tetrahydrofurfuryl acrylate or tetrahydrofurfuryl methacrylate, with tetrahydrofurfuryl acrylate being more preferred. The 4-(meth)acryloylmorpholin is preferably 4-acryloylmorpholin or 4-methacryloylmorpholin, and more preferably 4-acryloylmorpholin. 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.

[0139] 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. The number of carbon atoms in the alkyl group of the alkyl(meth)acrylate is preferably 1 to 30, more preferably 4 to 18, even more preferably 4 to 8, and still more preferably 4 to 6. Furthermore, the alkyl group is branched, linear, or cyclic, with branched or linear being preferred, and branched being more preferred. 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, and isooctyl (meth)acrylate. Examples include methacrylate, 2-ethylhexyl(meth)acrylate, 3,5,5-trimethylhexyl(meth)acrylate, lauryl(meth)acrylate, cetyl(meth)acrylate, stearyl(meth)acrylate, isostearyl(meth)acrylate, phenyl(meth)acrylate, and benzyl(meth)acrylate, among which n-butyl(meth)acrylate, isobutyl(meth)acrylate, and 2-ethylhexyl(meth)acrylate are preferred.

[0140] The number of carbon atoms in the aromatic group of the aryl (meth)acrylate is preferably 6 to 10, and more preferably 6 to 7. Specific examples of the aryl (meth)acrylate include phenyl (meth)acrylate and benzyl (meth)acrylate.

[0141] Examples of (meth)acrylic group-containing silicones include methacrylic group-containing silicones and acrylic group-containing silicones, with methacrylic group-containing silicones being preferred. The (meth)acrylic group-containing silicone is preferably such that the (meth)acrylic group is bonded to one end of the silicone main chain via a linking group, or that the (meth)acrylic group is directly bonded to one end of the silicone main chain, and is preferably such that the (meth)acrylic group is bonded to one end of the silicone main chain via a linking group. The linking group is preferably a trimethylene group. The silicone main chain is preferably composed of a linear or branched dimethylsilicone (polydimethylsiloxane), and more preferably a linear dimethylsilicone. Furthermore, it is more preferable that an alkyl group having 1 to 6 carbon atoms is present at the end opposite to the (meth)acrylic group, and it is preferable that a butyl group is present. Examples of commercially available (meth)acrylic group-containing silicones 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. By including the (meth)acrylic group-containing silicone, the antifouling properties of the formed antifouling coating can be improved.

[0142] When an antifouling coating composition contains an acrylic polymer (c2) having a hydrophilic group having an ethyleneoxy(-C2H4O-) substructure, from the viewpoint of imparting good antifouling properties to the formed antifouling coating film, the total mass of the ethyleneoxy(-C2H4O-) substructure is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the silicone dimethylsiloxane substructure (-(CH3)2Si-O-).

[0143] The weight-average molecular weight (Mw) of the hydrophilic acrylic polymer (c2) is preferably 1,000 or more, more preferably 3,000 or more, even more preferably 5,000 or more, and even more preferably 7,000 or more, and preferably 150,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and even more preferably 30,000 or less, from the viewpoint of antifouling properties and viscosity of the antifouling paint composition. It is preferable that the weight-average molecular weight (Mw) of the acrylic polymer (c2) having hydrophilic groups is within the above range, as this can impart good antifouling properties to the antifouling coating.

[0144] (Glycerol condensate ester (c3)) As the glycerin condensate ester (c3) used in the antifouling paint composition, the glycerin condensate ester represented by the following formula (1) is preferred. By including the glycerin condensate ester represented by the following formula (1), good slipperiness can be imparted to the antifouling coating film formed from the antifouling paint composition, and the ability to inhibit the adhesion of aquatic organisms (antifouling properties) can be improved.

[0145] [ka] (In formula (1) above, n is an integer between 2 and 20, and R is independently a hydrogen atom or R 1 It shows C(=O)- and at least one R is R 1 C(=O)- and R 1 (This represents a monovalent hydrocarbon group with 7 to 23 carbon atoms.)

[0146] In formula (1), n ​​is an integer between 2 and 20, preferably 3 or more, preferably 16 or less, more preferably 12 or less, and even more preferably 10 or less, from the viewpoint of stain resistance and availability. Each R is independently a hydrogen atom or R 1 It shows C(=O)- and at least one R is R 1 C(=O)- and R 1 R represents a monovalent hydrocarbon group with 7 to 23 carbon atoms. At least one R is R 1 Being C(=O)- is preferable because it provides excellent paintability, leveling properties, appearance, smoothness, and adhesion of the antifouling coating composition. R 1 The number of carbon atoms is preferably 9 or more, more preferably 11 or more, even more preferably 15 or more, and preferably 21 or less, more preferably 19 or less, from the viewpoint of antifouling properties. The monovalent hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. It may also be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, it may be linear, branched, or cyclic. Examples of monovalent hydrocarbon groups include alkyl groups, alkenyl groups, aryl groups, and aralkyl groups. Among these, R 1 It is preferable that it contains a branched hydrocarbon group, more preferably a branched hydrocarbon group, even more preferably a branched aliphatic hydrocarbon group, and even more preferably a branched alkyl group. R is preferably an isostearoyl group, a 2-ethylhexanoyl group, a ricinoleinoyl group, and more preferably an isostearoyl group.

[0147] Glycerol condensate esters (C3) are condensation ester compounds of a fatty acid with 8 to 24 carbon atoms and polyglycerol. Polyglycerin is a compound obtained by condensing glycerin, and glycerin condensate ester (b3) is a compound obtained by mixing and heating a fatty acid with 8 to 24 carbon atoms with polyglycerin. Examples of fatty acids with 8 to 24 carbon atoms include octanoic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid, lauric acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, erucic acid, hydroxystearic acid, ricinoleic acid, and coconut oil fatty acids. Among these, isostearic acid, 2-ethylhexanoic acid, and ricinoleic acid are preferred, with isostearic acid being more preferred. Furthermore, in terms of the workability of the antifouling coating composition, the antifouling properties of the formed antifouling coating film, and the adhesion to the binder layer, it is preferable that at least one R is a hydrogen atom in the compound represented by formula (1). In other words, it is preferable that at least some of the hydroxyl groups remain intact rather than being a complete esterified product.

[0148] The compound represented by formula (1) has n+2 Rs. Of the n+2 Rs, R is R 1The proportion of C(=O)- is preferably 10% or more, more preferably 20% or more, even more preferably 35% or more, and even more preferably 40% or more, and preferably 95% or less, more preferably 90% or less, and even more preferably 85% or less.

[0149] The glycerin condensate ester (C3) is preferably fluid at 25°C, and more preferably liquid. The fluidity of the glycerin condensate ester (C3) is thought to enhance its mobility within the antifouling coating, thereby improving its surface lubrication effect. Furthermore, it is preferable because it reduces the viscosity of the antifouling coating composition, resulting in better application.

[0150] The glycerin condensate ester (c3) may be a commercially available product, such as the EMALEX series (manufactured by Nippon Emulsion Co., Ltd.), the NIKKOL series (manufactured by Nikko Chemicals Co., Ltd.), the Sunsoft series, the Sunoil series (manufactured by Taiyo Kagaku Co., Ltd.), and the SY Glister / S Face series (manufactured by Sakamoto Pharmaceutical Co., Ltd.). Among these, EMALEX DISG-2, DISG-3, DISG-6, DISG-10, TISG-2, and TISG-10 are preferred in the EMALEX series, NIKKOL Decaglyn 5-ISV and 10-ISV are preferred in the NIKKOL series, and S Face IS-1005P and IS-1009P are preferred in the SY Glister / S Face series.

[0151] The content of the hydrophilic lubricant (c) in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less. The content of the hydrophilic lubricant (b) in the nonvolatile components of the antifouling coating composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of suppressing the adhesion of aquatic organisms and improving antifouling properties, and preferably 15% by mass or less, more preferably 12% by mass or less, and even more preferably 9% by mass or less, from the viewpoint of improving adhesion with the undercoat layer formed from the tiecoat composition. When the lubricant contains two or more hydrophilic groups, it is preferable that the total content is as described above.

[0152] In the antifouling coating composition (i), the content of polyether-modified silicone oil in the nonvolatile components of the antifouling coating composition is 1.5% by mass or less, from the viewpoint of adhesion to the underlying undercoat layer. If the content exceeds 1.5% by mass, the adhesion to the undercoat layer will be poor. Furthermore, in the antifouling coating composition (ii), the content of polyether-modified silicone oil in the nonvolatile components of the antifouling coating composition is less than 1.0% by mass from the viewpoint of adhesion to the underlying undercoat layer. If the content is 1.0% by mass or more, the adhesion to the undercoat layer is poor. Furthermore, in the antifouling coating composition (iii), the content of polyether-modified silicone oil in the nonvolatile components of the antifouling coating composition is less than 0.1% by mass, preferably 0.01% by mass or less, and more preferably not contained at all, from the viewpoint of adhesion to the underlying undercoat layer. If the content is 0.1% by mass or more, the adhesion to the undercoat layer is poor.

[0153] <Silica particles (d)> The antifouling coating composition preferably contains silica particles (d) from the viewpoint of hardness, flexibility, and strength of the antifouling coating film formed, and examples of silica particles (d) include hydrophobic silica particles (d1) and hydrophilic silica particles (d2). The silica particles (d) not only improve the physical properties of the antifouling coating film that is formed, but also enhance the fluidity and thixotropy of the antifouling coating composition. The antifouling paint composition preferably contains at least one selected from the group consisting of hydrophobic silica particles (d1) and hydrophilic silica particles (d2), preferably containing at least hydrophobic silica particles (d1), and more preferably containing both hydrophobic silica particles (d1) and hydrophilic silica particles (d2). Hydrophobic silica particles (d1) are preferable to add from the viewpoint of hardness, flexibility, and strength of the formed antifouling coating film, and from the viewpoint of improving the fluidity and thixotropy of the antifouling coating composition. Hydrophilic silica particles (d2) tend to decrease viscosity when added, but they have the function of improving the antifouling properties of the formed antifouling coating film.

[0154] Dry-processed silica and wet-processed silica are preferred as silica particles (d), with dry-processed silica being more preferred. Hydrophobic silica particles (d1) are hydrophobic treated silica (silica whose surface has been hydrophobicized), obtained by treating the hydroxyl groups (silanol groups) bonded to the silicon atoms on the silica surface with a hydrophobic treatment agent, and examples include aqueous wet silica and hydrophobic fumed silica. Examples of hydrophobic treatment agents include organodisilazane, organoalkoxysilane, organochlorosilane, cyclic organopolysilazane, and linear organopolysiloxane, but among these, organodisilazane, organoalkoxysilane, and organochlorosilane are preferred. More specifically, hexamethyldisilazane, hexaethyldisilazane, hexapropyldisilazane, 1,3-diethyl-1,1,3,3-tetramethyldisilazane, 1,3-dimethyl-1,1,3,3-tetraethyldisilazane, 1,3-divinyltetramethyldisilazane, 1,3-diallyltetramethyldisilazane, 1,3-dibutenyltetramethyldisilazane, 1,3-dipentenyltetramethyldisilazane, 1,3-dihexenyltetramethyldisilazane, 1,3-diheptenyltetramethyldisilazane, 1,3-dioctenyltetramethyldisilazane, 1,3-dinonenyltetramethyldisilazane, 1,3-di Examples include silazane compounds such as dekenyltetramethyldisilazane, 1,3-divinyltetraethyldisilazane, and 1,3-dimethyltetravinyldisilazane; alkoxysilane compounds such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, and butenyltrimethoxysilane; and chlorosilane compounds such as trimethylchlorosilane, triethylchlorosilane, tripropylchlorosilane, dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dimethylvinylchlorosilane, and allyldimethylchlorosilane. Due to factors such as workability and reactivity with silanol groups on the silica surface, it is preferable to use silazane compounds or chlorosilane compounds, and it is more preferable to use methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and 1,3-divinyltetramethyldisilazane, and it is even more preferable to use hexamethyldisilazane, 1,3-divinyltetramethyldisilazane, and dimethyldichlorosilane. Examples of commercially available hydrophobic silica include "AEROSIL R974" and "AEROSIL RX200" manufactured by Nippon Aerosil Co., Ltd.

[0155] The hydrophilic silica particles (d2) are untreated silica (surface-untreated silica), and include dry-process silica (fumed silica, anhydrous silica), wet-process silica (hydrated silica), etc. Dry-process silica is preferred, and fumed silica is more preferred. Examples of commercially available hydrophilic silica include "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd.

[0156] When the antifouling coating composition (i) contains silica particles (d), the amount of silica particles (d) in the nonvolatile components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, from the viewpoint of improving the strength and hardness of the antifouling coating film formed. Furthermore, if the antifouling coating composition (i) contains silica particles (d), the amount of silica particles (d) per 100 parts by mass of curable silicone (a) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and 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, from the viewpoint of improving the strength and hardness of the antifouling coating film formed.

[0157] When the antifouling coating composition (ii) contains silica particles (d), the content of silica particles (d) in the nonvolatile components of the antifouling coating composition is preferably 0.03% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, and preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of improving the strength and hardness of the antifouling coating film formed. Furthermore, if the antifouling coating composition (ii) contains silica particles (d), the amount of silica particles (d) per 100 parts by mass of curable silicone (a) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less, from the viewpoint of improving the strength and hardness of the antifouling coating film formed.

[0158] When the antifouling coating composition (iii) contains silica particles (d), the amount of silica particles (d) in the nonvolatile components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, even more preferably 1% by mass or more, even more preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of improving the strength and hardness of the antifouling coating film formed. Furthermore, if the antifouling coating composition (iii) contains silica particles (d), the amount of silica particles (d) per 100 parts by mass of curable silicone (a) 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, and preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less, from the viewpoint of improving the strength and hardness of the antifouling coating film formed.

[0159] When using both hydrophobic silica particles (d1) and hydrophilic silica particles (d2) as silica particles (d), the ratio of the content of hydrophobic silica particles (d1) to hydrophilic silica (d2) in the antifouling coating composition (d1 / d2) is preferably 5 / 95 or more and 90 / 10 or less, more preferably 10 / 80 or more and 80 / 20 or less, even more preferably 15 / 85 or more and 70 / 30 or less, and even more preferably 20 / 80 or more and 60 / 40 or less.

[0160] <Curing catalyst (e)> Antifouling coating composition (iii) contains a curing catalyst (e) to improve the curing speed and the film strength of the antifouling coating. Similarly, antifouling coating compositions (i) and (ii) may also contain a curing catalyst (e). Examples of curing catalysts (e) include tin compounds, metal salts of carboxylic acid compounds other than tin compounds (hereinafter also referred to as "carboxylic acid metal salts"), tertiary amine compounds, and titanium compounds. The antifouling paint composition (iii) preferably contains at least one selected from the group consisting of tin compounds and alkali metal salts of carboxylic acid compounds as a curing catalyst.

[0161] The aforementioned tin compounds include dibutyltin diacetate, dibutyltin diacetoacetonate, dioctyltin diacetoacetonate, dibutyltin dilaurate, dibutyltin diolate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, bis(dibutyltin laurate) oxide, dibutylbis(triethoxysiloxy)tin, bis(dibutyltin acetate) oxide, and dibutyltin Examples include tin bis(ethyl maleate), dioctyl tin bis(ethyl maleate), tin naphthenate, tin oleate, etc. Dibutyltin diacetate, dibutyltin diacetoacetonate, dioctyl tin diacetoacetonate, dibutyltin dilaurate, dibutyltin diolate, dibutyltin oxide, dibutyltin dimethoxide, dibutyltin dipentanoate, dibutyltin dioctoate, dibutyltin dineodecanoate, and dioctyl tin diacetoacetonate are preferred, with dibutyltin dilaurate being more preferred. Examples of commercially available tin compounds include "NEOSTANN U-100" manufactured by Nitto Chemical Co., Ltd. and "Gleck TL" manufactured by DIC Corporation.

[0162] Examples of the carboxylic acid metal salts include alkali metal salts such as potassium acetate, potassium 2-ethylhexanoate, potassium octanoate, potassium decanoate, potassium versatate, sodium acetate, sodium 2-ethylhexanoate, sodium octanoate, sodium decanoate, sodium versatate, lithium oxalate, lithium 2-ethylhexanoate, lithium octanoate, lithium decanoate, and lithium versatate; bismuth 2-ethylhexanoate, bismuth neodecanoate, bismuth acetate, bismuth octanoate, zinc acetate, zinc benzoate, and 2-ethylhexanoate. Examples include transition metal salts such as zinc acetate, zinc n-octoate, zinc stearate, zinc naphthenate, zinc oxalate, zinc neodecanoate, zinc 3-oxopentanoate, zinc 3-oxobutanoate, zirconium acetate, zirconium 2-ethylhexanoate, zirconium n-butoxide, zirconium tert-butoxide, zirconium isopropoxide, zirconium n-propoxide, iron 2-ethylhexanoate, and cobalt naphthenate; and rare earth metal salts such as cerium acetate, cerium 2-ethylhexanoate, cerium octanoate, cerium decanoate, and cerium versatate.

[0163] The tertiary amine compound is a compound having a tertiary amino group, and examples include 1,6-hexanediamine-N,N,N,N-tetramethyl, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,2-dimethylimidazole.

[0164] Examples of the aforementioned titanium compounds include tetraisopropoxytitanium, tetra-N-butoxytitanium, tetrakis(2-ethylhexoxy)titanium, dipropoxybis(acetylacetonato)titanium, and titanium isopropoxyoctyl glycol. Other curing catalysts include alkoxyaluminum compounds. The curing catalyst (e) may be used alone or in combination of two or more types.

[0165] When the antifouling paint composition (i) contains a curing catalyst (e), the content of the curing catalyst (e) in the nonvolatile components of the antifouling paint composition is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, from the viewpoint of improving the curing speed. When the antifouling paint composition (i) contains a curing catalyst (e), the content of the curing catalyst (e) in the antifouling paint composition relative to 100 parts by mass of curable silicone (a) is preferably 0.003 parts by mass or more and 30 parts by mass or less, more preferably 0.03 parts by mass or more and 5 parts by mass or less, and even more preferably 0.3 parts by mass or more and 3 parts by mass or less.

[0166] When the antifouling coating composition (ii) contains a curing catalyst (e), the content of the curing catalyst (e) in the nonvolatile components of the antifouling coating composition is preferably 0.001% by mass or more and 10% by mass or less, more preferably 0.01% by mass or more and 3% by mass or less, and even more preferably 0.1% by mass or more and 1% by mass or less, from the viewpoint of improving the curing speed. When the antifouling paint composition (ii) contains a curing catalyst (e), the content of the curing catalyst (e) in the antifouling paint composition relative to 100 parts by mass of curable silicone (a) is preferably 0.003 parts by mass or more and 30 parts by mass or less, more preferably 0.03 parts by mass or more and 5 parts by mass or less, and even more preferably 0.3 parts by mass or more and 3 parts by mass or less.

[0167] From the viewpoint of improving the curing speed, the content of the curing catalyst (e) in the nonvolatile components of the antifouling coating composition (iii) is preferably 0.03% by mass or more and 15% by mass or less, more preferably 0.1% by mass or more and 10% by mass or less, even more preferably 0.3% by mass or more and 5% by mass or less, and even more preferably 0.3% by mass or more and 3% by mass or less. The content of the curing catalyst (e) in the antifouling paint composition (iii) relative to 100 parts by mass of curable silicone (a) is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.3 parts by mass or more and 10 parts by mass or less, and even more preferably 0.5 parts by mass or more and 5 parts by mass or less.

[0168] Further, the total content of the tin compound and the metal carboxylate in the non-volatile components of the antifouling coating composition (iii) is preferably 0.03 mass% or more and 15 mass% or less, more preferably 0.1 mass% or more and 5 mass% or less, and still more preferably 0.3 mass% or more and 3 mass% or less, from the viewpoint of improving the curing rate. The total content of the tin compound and the metal carboxylate in the antifouling coating composition (iii) relative to 100 parts by mass of the curable silicone (a) is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.3 parts by mass or more and 10 parts by mass or less, and still more preferably 0.5 parts by mass or more and 8 parts by mass or less.

[0169] <Silane Coupling Agent (f) Having Amino Group> In the present embodiment, the antifouling coating composition may contain a silane coupling agent (f) having an amino group (hereinafter also referred to as "amino group-containing silane coupling agent (f)") from the viewpoints of improving adhesion to the undercoat layer and curability, and the antifouling coating composition (i) preferably contains the amino group-containing silane coupling agent (f) from the viewpoint of adhesion to the undercoat layer. The amino group-containing silane coupling agent (f) is an organoalkoxysilane that has at least one alkoxy group and at least one amino group on a silicon atom. As the alkoxy group, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred. 1 to 3 alkoxy groups are bonded to the silicon atom, preferably 2 to 3 alkoxy groups are bonded, and more preferably 3 alkoxy groups are bonded. In the present embodiment, when the antifouling coating contains the amino group-containing silane coupling agent (f), it reacts particularly with the epoxy group of the tie-coat composition, and the adhesion between the antifouling coating film formed from the antifouling coating composition and the undercoat layer formed from the tie-coat composition becomes favorable.

[0170] Examples of amino group-containing silane coupling agents (f) include N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (also known as 3-(2-aminoethylamino)propyltrimethoxysilane), N-(2-aminoethyl)-3-aminopropyltriethoxysilane (also known as 3-(2-aminoethylamino)propyltriethoxysilane), 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane. A condensate of the above compound may be used as the amino group-containing silane coupling agent (f). The amino group-containing silane coupling agent (f) may be used alone or in combination of two or more types.

[0171] When the antifouling coating composition contains an amino group-containing silane coupling agent (f), the content of the amino group-containing silane coupling agent (f) in the nonvolatile components of the antifouling coating composition is preferably 0.03% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.2% by mass or more, and preferably 1.5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less, from the viewpoint of improving the adhesion of the formed antifouling coating film to the undercoat layer.

[0172] <Coloring pigment (g)> It is also preferable that the antifouling paint composition contains a coloring pigment (g). The inclusion of a colored pigment (g) in the antifouling paint composition can enhance the strength of the coating film. The coloring pigment (g) is 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 and phthalocyanine blue. From the viewpoint of the workability of manufacturing and coating the antifouling paint composition, storage stability, and the antifouling properties of the formed antifouling coating film, it is preferable that the pigment be an inorganic pigment, and among these, it is preferable that it be one or more selected from iron oxide, titanium dioxide, carbon black, zinc oxide, aluminum silicate, alumina white, and barium sulfate, and more preferably one or more selected from iron oxide, titanium dioxide, and carbon black.

[0173] 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 from the viewpoint of stability and availability of the antifouling coating and antifouling paint composition, the rutile type is preferred.

[0174] When the antifouling coating composition contains a colored pigment (g), the amount of colored pigment (g) in the nonvolatile components of the antifouling coating composition is preferably 0.3% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 15% by mass or less, and even more preferably 3% by mass or more and 10% by mass or less, from the standpoint of excellent antifouling properties of the formed antifouling coating film, as well as the manufacturing workability, coating workability, and storage stability of the antifouling coating composition.

[0175] <Other pigments (h)> Other pigments besides the silica particles (d) and coloring pigments (g) include mica, calcium carbonate, barium carbonate, potassium feldspar, kaolin, and glass short fibers. These inorganic fillers may be used individually or in combination of two or more types. Furthermore, the inorganic fillers mentioned above may be surface-treated; for example, calcium carbonate may be colloidal calcium carbonate.

[0176] When the antifouling coating composition contains other pigments (h), the content of other pigments (h) in the nonvolatile components of the antifouling coating composition is preferably 0.3% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 18% by mass or less, and even more preferably 3% by mass or more and 16% by mass or less, from the standpoint of excellent antifouling properties of the formed antifouling coating film, as well as the manufacturing workability, coating workability, and storage stability of the antifouling coating composition.

[0177] <Biological repellent (i)> The antifouling paint composition preferably contains a biological repellent (i) for the purpose of enhancing the antifouling properties of the antifouling coating film formed. The biological repellent (i) is released from the antifouling coating in water and has the effect of suppressing the adhesion of aquatic organisms to the surface of the antifouling coating, thereby improving its antifouling properties. The biological repellent (i) is preferably one that has a repellent effect on aquatic organisms and a certain elution rate into water, and is preferably one or more selected from copper pyrithione, zinc pyrithione, 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). From the viewpoint of elution from the antifouling coating and repellent effect on a wide range of biological species, one or more selected from copper pyrithione and zinc pyrithione are more preferable, and from the viewpoint of elution, copper pyrithione is even more preferable. The biological repellent (i) may be used alone or in combination of two or more.

[0178] When the antifouling coating composition contains a biological repellent (i), the amount of the biological repellent (i) in the nonvolatile components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of the strength and antifouling properties of the antifouling coating film and the coatability of the antifouling coating composition.

[0179] <Silane coupling agents other than amino group-containing silane coupling agents (j)> The antifouling paint composition may contain a silane coupling agent (j) other than an amino group-containing silane coupling agent (hereinafter also referred to as "other silane coupling agents (j)"). Other silane coupling agents (j) are organic alkoxysilanes having at least one alkoxy group and at least one organic reactive group on a silicon atom. 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. Examples of the aforementioned organic reactive groups include mercapto groups, epoxy groups, isocyanate groups, ureido groups, vinyl groups, acrylic groups, methacrylic groups, and styryl groups, with mercapto groups, epoxy groups, isocyanate groups, and ureido groups being preferred.

[0180] Other examples of silane coupling agents (j) include 3-glycidoxypropyltrimethoxysilane, 3-isocyanatetopropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane. As the other silane coupling agent (j), a condensate of the above compound may be used. The other silane coupling agent (j) may be used alone or in combination of two or more types.

[0181] <Lubricants other than (c) hydrophilic lubricants (k)> The antifouling paint composition may contain a lubricant (k) other than the lubricant (c) having a hydrophilic group (hereinafter also referred to as "other lubricants (k)"). The other lubricant (k) is preferably fluid at 25°C, and more preferably liquid. The fluidity of the other lubricant (k) enhances its mobility within the antifouling coating, thereby improving its surface lubrication effect. Furthermore, it can reduce the viscosity of the antifouling coating composition, resulting in improved applicability. Other lubricants (k) preferably include oils. Examples of other slipping agents (k) include silicone oil (hereinafter also referred to as silicone oil (k1)), paraffin oil (hereinafter also referred to as paraffin oil (k2)), and fats and oils, among which silicone oil (k1) is preferred. Examples of the paraffin oil include liquid paraffin and the like. The fats and oils are esters of fatty acids and glycerin, and examples thereof include animal fats and oils, vegetable fats and oils, and the like.

[0182] ≪Silicone oil (k1)≫ Examples of the silicone oil as the other slipping agent (k) (hereinafter referred to as silicone oil (k1)) include dimethyl silicone (polydimethylsiloxane, unmodified silicone) (hereinafter also referred to as unmodified silicone (k1-1)), and modified silicones other than polyether-modified silicone oil (hereinafter also referred to as modified silicone (k1-2)). The modified silicone (k1-2) is obtained by substituting a part of the methyl groups of dimethyl silicone with an organic group other than a methyl group, and may have a reactive group at one terminal. Silicone oil has low interfacial tension and its properties are less likely to change even in environments such as low temperatures, so it easily migrates to the surface of the antifouling coating film, and can efficiently improve the anti-adhesion property against aquatic organisms (antifouling property) and damage resistance.

[0183] When the silicone oil (k1) has a reactive group at one terminal, examples of the reactive group include a silanol group, an oxime silyl group, an acyloxysilyl group, an alkoxysilyl group, an alkenyloxysilyl group, an aminosilyl group, an amidosilyl group, and the like. A silanol group, an oxime silyl group, an acyloxysilyl group, an alkoxysilyl group, and an alkenyloxysilyl group are preferred; a silanol group, an oxime silyl group, an alkoxysilyl group, and an alkenyloxysilyl group are more preferred; a silanol group, an oxime silyl group, and an alkenyloxysilyl group are still more preferred; a silanol group and an oxime silyl group are even more preferred; and an oxime silyl group is particularly preferred. As the oxime group, an oxime group having 1 to 10 carbon atoms is preferred, a dimethyl ketoxime group, methyl ethyl ketoxime group, diethyl ketoxime group, methyl isopropyl ketoxime group, and methyl isobutyl ketoxime group are more preferred, and a methyl isobutyl ketoxime group is even more preferred. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferred, a methoxy group, ethoxy group, propoxy group, and butoxy group are preferred, a methoxy group and ethoxy group are more preferred, and a methoxy group is even more preferred. Two or more of these groups, namely oxime groups or alkoxy groups, may be bonded to one silicon atom; it is preferred that two or more oxime groups or alkoxy groups are bonded to one silicon atom, and it is more preferred that two oxime groups are bonded to one silicon atom.

[0184] The viscosity of the silicone oil (k1) 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, still more preferably 60 mPa·s or more, and still even more preferably 80 mPa·s or more, and is preferably 10,000 mPa·s or less, more preferably 5,000 mPa·s or less, even more preferably 4,000 mPa·s or less, from the viewpoints of imparting slipperiness against aquatic organisms, improving antifouling properties, and improving the applicability of the antifouling coating composition. In this specification, the viscosity of the silicone oil (k1) at 25°C refers to the viscosity measured with a B-type rotational viscometer.

[0185] Further, the kinematic viscosity of the silicone oil (k1) at 25°C is preferably 10 mm 2 / s or more, more preferably 30 mm 2 / s or more, even more preferably 50 mm 2 / s or more, and is preferably 5,000 mm 2 / s or less, more preferably 4,000 mm 2 / s or less, even more preferably 3,500 mm 2 / s or less.

[0186] Examples of the modified silicone (k1-2) include phenyl-modified silicones, long-chain alkyl-modified silicones, higher fatty acid ester-modified silicones, fluorinated alkyl-modified silicones, carbinol-modified silicones, carboxy-modified silicones, amino-modified silicones, epoxy-modified silicones, methacryl-modified silicones, mercapto-modified silicones, and phenol-modified silicones. Among such modified silicones, phenyl-modified silicones are preferred as the modified silicone (k1-2) from the viewpoints of achieving good antifouling properties, imparting appropriate thixotropy to the antifouling coating composition, and improving its coatability. Phenyl-modified silicones are also preferred from the viewpoint of obtaining an antifouling coating film with excellent transparency. Examples of the structure of the modified silicone (k1-2) include side chain modified type, both-terminal modified type, one-terminal modified type, block type, side chain and one-terminal modified type, and side chain and both-terminal modified type.

[0187] Commercially available products of the unmodified silicone (k1-1) include "KF-96-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 100 mm 2 / s), "KF-96-1,000cs" (manufactured by Shin-Etsu Chemical Co., Ltd., kinematic viscosity (25°C): 1,000 mm 2 / s), and the like.

[0188] The phenyl modification rate of the phenyl-modified silicone is preferably 3% to 50%, more preferably 3% to 20%, and still more preferably 4% to 10%, from the viewpoints of antifouling properties and facilitating the formation of the antifouling coating film. The phenyl modification rate is the percentage of the number of phenyl groups relative to the total number of phenyl groups and methyl groups bonded to silicon atoms. The kinematic viscosity of the phenyl-modified silicone at 25°C is preferably 10 mm, from the viewpoints of the antifouling properties of the formed antifouling coating film and the coating workability of the antifouling coating composition 2 / s to 5,000 mm 2 / s or less, more preferably 50 mm 2 / s to 4,000 mm 2 / s or less, more preferably 80 mm 2 / s or more 3,500mm 2 It is less than or equal to / s. A commercially available phenyl-modified silicone is "KF-50-100cs" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25℃): 100 mm²). 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). Furthermore, a commercially available product of one-terminated methyl ethyl ketoxime-side-chain phenyl-modified silicone is "BCA-011" (manufactured by Shin-Etsu Chemical Co., Ltd., phenyl modification rate = 5%, kinematic viscosity (25℃): 100 mm²). 2 ( / s) is one example.

[0189] Paraffin oil (k2) The paraffin oil (k2) is not particularly limited; any paraffin oil with a suitable kinematic viscosity, as described later, may be appropriately selected and used from among known paraffin oils. Liquid paraffin is preferred as the paraffin oil (k2). The kinematic viscosity of paraffin oil (k2) at 25°C is preferably 10 mm, from the viewpoint of antifouling properties and the workability of the antifouling coating composition. 2 / s or more, more preferably 50mm 2 / s or more, more preferably 100mm 2 It is 1 / s or more, and 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.

[0190] If the antifouling coating composition contains other lubricants (k), the content of other lubricants (k) in the nonvolatile components of the antifouling coating composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 3% by mass or more, even more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, and even more preferably 10% by mass or less.

[0191] <Slip-preventing agent / settling prevention agent (l)> Examples of the aforementioned anti-sagging and anti-settling agent (l) include organic clay waxes (stearate salts, lecithin salts, alkyl sulfonates, etc. of Al, Ca, and Zn), organic waxes (polyethylene wax, oxidized polyethylene wax, amide wax, polyamide wax, hydrogenated castor oil wax, etc.), and mixtures of organic clay waxes and organic waxes.

[0192] When the antifouling paint composition contains a sagging agent / settling inhibitor (l), the content of the sagging agent / settling inhibitor (l) in the nonvolatile components of the antifouling paint composition is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, even more preferably 0.05% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, and even more preferably 1% by mass or less.

[0193] <Dehydrating agent (m)> Examples of dehydrating agents other than the organosilicon crosslinking agent (b) include zeolites, porous alumina, and orthoesters such as alkyl orthoformate, orthoboric acid, and isocyanate compounds.

[0194] <Organic solvent (n)> The antifouling paint composition may contain an organic solvent (n) to maintain a low viscosity and improve the workability of the paint. Examples of organic solvents (n) include aromatic hydrocarbon organic solvents, aliphatic hydrocarbon organic solvents, alicyclic hydrocarbon organic solvents, ketone organic solvents, alcohol organic solvents, and ester organic solvents, with aromatic hydrocarbon organic solvents and ketone organic solvents being preferred, and aromatic hydrocarbon organic solvents being more preferred. 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 aforementioned ketone-based organic solvents include acetylacetone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethyl carbonate. Examples of the aforementioned alcohol-based organic solvents include n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol. Examples of the ester-based organic solvents include ethyl acetate, propyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate. The organic solvent (n) may be used alone or in combination of two or more types.

[0195] When the antifouling coating composition contains an organic solvent (n), the content of the organic solvent (n) in the antifouling coating composition is preferably 3% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more, from the viewpoint of improving coating workability, and preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less, from the viewpoint of suppressing sagging during coating and reducing environmental impact.

[0196] <Other optional components> Other optional components include enzymes, flame retardants, and thermal conductivity modifiers. Examples of enzymes include serine proteases, cysteine ​​proteases, metalloproteinases, cellulases, hemicellulases, pectinases, and glycosidases. Examples of the aforementioned flame retardants include antimony oxide and paraffin oxide. Examples of the aforementioned thermal conductivity improvers include boron nitride and aluminum oxide.

[0197] <Aspects of antifouling paint compositions> The antifouling coating composition may be a one-component antifouling coating composition in which the above components are made up of one composition, or a multi-component antifouling coating composition in which the above components are made up of two or more compositions and mixed before application. However, a multi-component antifouling coating composition is preferred from the viewpoint of preventing deterioration during storage, while a one-component antifouling coating composition is preferred from the viewpoint of ease of application. Examples of the multi-component antifouling coating composition include a two-component antifouling coating composition and a multi-component antifouling coating composition with three or more components. From the viewpoint of ease of application, a two-component antifouling coating composition is preferred, while from the viewpoint of preventing deterioration during storage, a multi-component antifouling coating composition with three or more components is preferred.

[0198] Among these, the antifouling coating composition (i) may be a one-component antifouling coating composition, while the antifouling coating composition (ii) and the antifouling coating composition (iii) are preferably multi-component antifouling coating compositions.

[0199] (Method for manufacturing antifouling paint composition) The aforementioned antifouling paint composition is preferably manufactured as follows. First, it is preferable to have a step of kneading polyorganosiloxane (a1) and silica particles (d). Heating may also be performed during or after kneading. By kneading these in advance, the affinity between the two components is improved, and the aggregation of silica and the increase in viscosity of the antifouling coating composition can be suppressed. The heating conditions are preferably 100°C or higher, more preferably 100°C to 300°C, and even more preferably 140°C to 200°C. The pressure is preferably normal pressure or reduced pressure, and the processing time is preferably 3 hours to 30 hours.

[0200] The antifouling paint composition is obtained by mixing and stirring the aforementioned components. If the antifouling coating composition is a one-component antifouling coating composition, it is obtained by appropriately adding polyorganosiloxane (a) and optional components such as an organosilicon crosslinking agent (b), a hydrophilic lubricant (c), silica particles (d), a curing catalyst (e), a silane coupling agent having an amino group (f), a coloring pigment (g), other pigments (h), a biological repellent (i), another silane coupling agent (j), another lubricant (k), an anti-sagging agent (l), a dehydrating agent (m), and an organic solvent (n), and mixing and stirring.

[0201] When the antifouling coating composition is antifouling coating composition (ii), it is preferably a multi-component antifouling coating composition, more preferably a two-component antifouling coating composition, and it is preferable that the main component contains polyorganosiloxane (a2) and the curing agent contains organosilane (a3). Furthermore, when the antifouling coating composition (ii) contains a curing catalyst (e), it is preferable that the curing agent contains the curing catalyst (e). When the antifouling coating composition is antifouling coating composition (iii), it is preferably a multi-component antifouling coating composition, more preferably a two-component or three-component antifouling coating composition, and it is preferable that the main component contains polyorganosiloxane (a2), and the curing agent contains an organosilicon compound (b) and a curing catalyst (e). When it is a three-component antifouling coating composition, it is preferable that the additive contains a lubricant (c) having a hydrophilic group. Furthermore, in antifouling coating compositions (ii) and (iii), it is preferable that the silica particles (d), coloring pigment (g), and biological repellent (i) are contained in the same liquid (main component) as the polyorganosiloxane (a1) and / or polyorganosiloxane (a2). The hydrophilic lubricant (c) and other lubricants (i) may be included in any of the liquids, but are preferably included in the curing agent or additive. Mixing and stirring should preferably be carried out at a temperature between 0°C and 50°C.

[0202] <Anti-fouling coating> The antifouling coating is an antifouling coating formed from the antifouling paint composition described above. The antifouling coating can be formed by applying or impregnating a substrate with at least the Tiecoat composition, drying it to form a primer layer, applying or impregnating the antifouling paint composition described above onto the primer layer, and then drying and curing it. Furthermore, it is preferable that the antifouling coating is an antifouling coating used for the purpose of preventing contamination of the substrate by aquatic organisms in water.

[0203] [Laminated antifouling coating, substrate with laminated antifouling coating, and method for manufacturing the same] The laminated antifouling coating of this embodiment comprises, in this order, a tie-coat layer formed from a tie-coat composition and an antifouling coating film formed from an antifouling paint composition. It may also optionally comprise, in this order, a one-component or two-component epoxy resin-based primer coating film, an optional old antifouling coating film, a tie-coat layer formed from a tie-coat composition, and an antifouling coating film formed from an antifouling paint composition. Furthermore, the substrate with the antifouling coating of this embodiment preferably comprises, in this order: a substrate, optionally a one-component or two-component epoxy resin-based primer coating, optionally an existing antifouling coating, a tie-coat layer formed from the tie-coat composition, and an antifouling coating formed from the antifouling paint composition. In other words, the laminated antifouling coating of this embodiment preferably comprises, in this order, a one-component or two-component epoxy resin-based primer coating, a tie-coat layer formed from the tie-coat composition of this embodiment, and an antifouling coating formed from an antifouling paint composition, or, more preferably, a one-component or two-component epoxy resin-based primer coating, an old antifouling coating, a tie-coat layer formed from the tie-coat composition, and an antifouling coating formed from an antifouling paint composition. In the former case, the one-component or two-component epoxy resin-based primer coating is provided as a lower layer to the tie-coat layer formed from the tie-coat composition, and the antifouling coating formed from the antifouling paint composition is provided as an upper layer. In the latter case, the old antifouling coating is provided as a lower layer to the tie-coat layer formed from the tie-coat composition, and the antifouling coating formed from the antifouling paint composition is provided as an upper layer. Here, "old antifouling coating" refers to an antifouling coating that has been used, and which necessitates the application of a different antifouling coating. In other words, the old antifouling coating is the underlying antifouling coating when a new antifouling coating is formed on top of the old antifouling coating.

[0204] In the oxime group-containing organosilane (C) represented by formula (1) contained in the Tycoat composition, if X in formula (1) is a phenyl group, the antifouling coating composition is antifouling coating composition (i). Furthermore, in the oxime group-containing organosilane (C) represented by formula (1) contained in the Tycoat composition, if X in formula (1) is a methyl group or a vinyl group, the antifouling coating composition is one of the antifouling coating compositions selected from the group consisting of antifouling coating compositions (i) to antifouling coating compositions (iii).

[0205] The method for manufacturing the substrate with the laminated antifouling coating preferably includes the following steps (1) to (4). Step (1): A process of applying or impregnating a substrate, which has a one-component or two-component epoxy primer coating and optionally an existing antifouling coating, with a Tiecoat composition to obtain a coated or impregnated body. Step (2): A step of drying the coated or impregnated material obtained in step (1) to form a primer layer. Step (3): A step of applying or impregnating the undercoat layer with an antifouling paint composition to obtain a coated body or an impregnated body. Step (4): A step of drying and curing the coating or impregnated material obtained in step (3) to form an antifouling coating film.

[0206] <Process (1) and Process (3)> Step (1) is a step of applying or impregnating a substrate having a one-component or two-component epoxy-based primer coating and optionally an existing antifouling coating with the Tiecoat composition of this embodiment to obtain a coated body or an impregnated body. Step (3) is a step of applying or impregnating an antifouling coating composition onto the primer layer formed by the Tiecoat composition to obtain a coated body or an impregnated body. Steps (1) and (3) are preferably steps in which a coated body is obtained by coating. Known methods for applying the tiecoat composition or antifouling coating composition include brush painting, roller painting, spray painting, roll coater painting, flow coater painting, slit coater painting, gravure coater painting, spin coater painting, curtain roll coater painting, electrostatic painting, dipping painting, silk screen printing, and spin painting, with brush painting, roller painting, and spray painting being preferred. The thickness of the coating film formed in steps (1) and (3) is set so that the final coating film has the thickness described later. The coating film may be formed in one coat or in two or more coats. The thickness of the undercoat layer formed from the Tiecoat composition is not particularly limited, but is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 50 μm or more, and preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 150 μm or less. The undercoat layer being in this configuration is preferable because it has excellent adhesion to the upper antifouling coating and the lower layer. The thickness of the antifouling coating is not particularly limited, but is preferably 50 μm or more, more preferably 75 μm or more, even more preferably 100 μm or more, and preferably 500 μm or less, more preferably 400 μm or less, and even more preferably 300 μm or less. When the antifouling coating is in this configuration, it becomes an antifouling coating with excellent long-term antifouling properties.

[0207] <Process (2) and Process (4)> Step (2) is a step of drying the coated or impregnated body obtained in step (1) to form a coating film, and step (4) is a step of drying and curing the coated or impregnated body obtained in step (3) to form a coating film. The coated or impregnated material obtained by the method described above is preferably left to stand under conditions of, for example, 0°C to 23°C. In step (4), the drying and curing step is preferably carried out by leaving the material for 0.5 days to 14 days, more preferably 1 day to 10 days, to dry or dry and cure, thereby obtaining a coating film. The drying and curing described above may be carried out under heating and / or while blowing air.

[0208] Antifouling coatings formed from an antifouling paint composition containing curable silicone (a) have the problem of poor adhesion to the undercoat layer. When the time in step (2), i.e., the time (interval) between the formation of the undercoat layer and the formation of the antifouling coating by the antifouling paint composition, is long, the adhesion between the undercoat layer and the antifouling coating tends to decrease further. Therefore, it is necessary to shorten the interval between the formation of the undercoat layer and the formation of the antifouling coating, which imposes significant constraints on the process. The manufacturing method for the laminated antifouling coating film of this embodiment preferably includes the steps of applying the Tiecoat composition to form a base coat layer, and applying the antifouling coating composition on top of the base coat layer after applying the Tiecoat composition. Preferably, after applying the tiecoat composition of this embodiment to form a base coat layer, an antifouling coating composition is applied to the base coat layer within 5 hours. When applied within 5 hours, good adhesion can be obtained by satisfying either of the above-described conditions A or B. Furthermore, by using the tie-coat composition of this embodiment, good adhesion can be obtained even when the interval described above is extended for a long period, for example, more than 5 hours and 36 hours or less, preferably more than 5 hours and 30 hours or less.

[0209] [Laminated antifouling coating and substrate with laminated antifouling coating] The laminated antifouling coating of this embodiment comprises, in this order, a primer layer formed from the above-described tiecoat composition and an antifouling coating film formed from the above-described antifouling paint composition. Furthermore, the substrate with a laminated antifouling coating comprises, in this order, the substrate, a primer layer formed from the Tiecoat composition, and an antifouling coating formed from the antifouling paint composition described above. In a substrate with a laminated antifouling coating, the undercoat layer may be formed directly on the substrate, but it is preferable that the undercoat layer be formed on a coating selected from the group consisting of a one-component or two-component epoxy coating and an existing antifouling coating, and it is preferable to provide an antifouling layer formed on the undercoat layer using the antifouling paint composition containing the above-mentioned curable silicone.

[0210] <Epoxy-based primer coating> An example of an epoxy coating is the two-component epoxy resin-based primer coating described in Japanese Patent No. 4271280. The laminated coating substrate of this embodiment exhibits excellent adhesion even when coating and drying are performed at low temperatures. Therefore, the coating and drying temperatures may be, for example, 15°C or lower, 10°C or lower, or 5°C or lower.

[0211] Here, the above-mentioned substrate is not particularly limited, but is preferably a substrate that comes into contact with seawater or freshwater, more preferably at least one selected from ships, underwater structures, fishing materials, water supply and drainage pipes and equipment used on or underwater, more preferably ships and underwater structures, and particularly preferably ships. Specifically, examples include ships (e.g., 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, including both shipbuilding and repair of these vessels), underwater structures (e.g., oil pipelines, water intake pipes, circulating water pipes, water inlets and outlets for factories and thermal / nuclear power plants, submarine cables, seawater utilization equipment (seawater pumps, etc.), mega-floats, coastal roads, underwater tunnels, port facilities, various underwater civil engineering structures in canals and waterways, etc.), fishing materials (e.g., ropes, fishing nets, fishing gear, floats or buoys, etc.), water inlets and outlets for seawater in factories and thermal / nuclear power plants, etc., and equipment used underwater and on the water (solar panels, observation windows for instruments and equipment, camera lenses, underwater lights, underwater sensors, etc.).

[0212] The material of the above-mentioned base material is not particularly limited, but examples include steel, aluminum, wood, FRP, glass, and plastic, especially in ships, and glass and plastic, etc., in equipment used on or underwater. Furthermore, the above-mentioned substrate may be treated with other treatment agents such as rust inhibitors. [Examples]

[0213] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0214] [Non-volatile content concentration] The non-volatile components of the paint and each component refer to the heat residue after drying the paint and each component in a constant temperature oven at 108°C for 3 hours. Specifically, the heat residue is the residue obtained by weighing 1.0 g of the sample onto a flat-bottomed dish, spreading it uniformly using a wire of known mass, and drying it in a constant temperature oven at 1 atmosphere and 108°C for 3 hours. The content ratio (non-volatile content concentration) (mass%) of the non-volatile components of the paint and each component was calculated from the amount of heat residue.

[0215] [Preparation of Thai Coat Composition] <Preparation of Tycoat Composition B-1> Each component was added to a container according to the proportions (parts by mass) listed for the main components in Table 2. The mixture was stirred using a high-speed disperser at room temperature (23°C) until homogeneous, and then dispersed at 56-60°C for 30 minutes. The main components were then prepared by cooling to below 30°C. In addition, the curing agent components were prepared by mixing and stirring each component in a separate container according to the proportions (parts by mass) listed in Table 2. In addition, the additive components were prepared by mixing and stirring each component in a separate container according to the proportions (parts by mass) listed in Table 2. Tiecoat composition B-1 was prepared by mixing these main components, hardener components, and additive components before painting.

[0216] <Preparation of Tycoat Compositions B-2 to B-12> Thai Coat compositions B-2 to B-12 were prepared in the same manner as Thai Coat composition B-1, except that each component listed in Table 2 was used in the amounts listed in Table 2. Thai Coat composition B-12 is a comparative example of Thai Coat composition. The components used in Thai Coat compositions B-1 to B-12 are shown in Table 1 below.

[0217] [Table 1]

[0218] [Table 2]

[0219] [Preparation of antifouling paint composition] <Preparation of antifouling paint composition A-1> Each component was added to a container according to the proportions (parts by mass) listed in Table 5, and the mixture was stirred using a high-speed disperser for 30 minutes until homogeneous to prepare a one-component antifouling paint A-1. More specifically, each component except the polyorganosiloxane paste, hydrophilic lubricant, lubricant, and silane coupling agent was mixed and stirred with 15 parts by mass of xylene, and then the polyorganosiloxane paste, hydrophilic lubricant, lubricant, silane coupling agent, and the remaining xylene were stirred and mixed to prepare the antifouling paint composition.

[0220] <Preparation of antifouling paint compositions A-2 to A-6> Similar to A-1, each component was mixed and stirred in a container according to the proportions (parts by mass) listed in Table 5 to prepare one-component antifouling paint compositions A-2 to A-6. The components used in the antifouling paint compositions A-1 to A-6 and A-7 to A-21 described later are shown in Tables 3 and 4 below.

[0221] [Table 3]

[0222]

Table 4

[0223] The (meth)acrylic polymer having a hydrophilic group used as "Lubricant-2 having a hydrophilic group" in Table 4 above was produced as follows. The reaction was carried out under normal pressure and a nitrogen atmosphere. A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel was charged with 42.86 parts by mass of methyl amyl ketone, and heated with stirring until the methyl amyl ketone reached 100°C. While maintaining the temperature of the reaction mixture at 100±5°C, a mixture consisting of 40.0 parts by mass of NK Ester AM-90G (methoxypolyethylene glycol acrylate, average number of polyethylene glycol units: 9, manufactured by Shin-Nakamura Chemical Co., Ltd.), 60.0 parts by mass of isobutyl acrylate, and 4.0 parts by mass of 2,2'-azobis(2-methylbutyronitrile) was added dropwise into the reaction vessel over 4 hours. Thereafter, the mixture was stirred for 2 hours while maintaining the temperature at 100±5°C to obtain a polymer solution. The resulting solution had a solid content of 70.3 mass% and a viscosity of 109 mPa·s, and the weight average molecular weight (Mw) of the polymer was 9,100.

[0224] The physical properties of the obtained polymer were measured as follows. 〔Solid content of polymer solution〕 The solid content (mass%) was determined by dividing the mass of the solid content obtained by drying the polymer solution at 108°C and 1 atmosphere for 3 hours by the mass of the polymer solution before drying.

[0225] 〔Viscosity of polymer solution〕 Using an E-type viscometer (TV-25, manufactured by Toki Sangyo Co., Ltd.), the viscosity (mPa·s) of the polymer solution at a liquid temperature of 25°C was measured.

[0226] 〔Average molecular weight of polymer〕 The weight average molecular weight (Mw) of the polymer was measured using gel permeation chromatography (GPC) under the following conditions. <GPC Conditions> Apparatus: "HLC-8420GPC" (manufactured by Tosoh Corporation) Columns: "TSKgel SuperH2000" and "TSKgel SuperH4000" (both manufactured by Tosoh Corporation, 6mm inner diameter, 15cm length) were connected 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 polymer solution and filtered through a membrane filter to obtain a sample for GPC measurement.

[0227] [Table 5]

[0228] <Preparation of antifouling paint composition A-7> A two-component antifouling coating consisting of a main component and a hardener component was prepared by mixing and stirring each component in a container according to the proportions (parts by mass) listed in Table 6. More specifically, for the main component of the two-component antifouling coating, the components other than the curable polyorganosiloxane and polyorganosiloxane paste were mixed and stirred with 10 parts by mass of xylene, and then the curable polyorganosiloxane, polyorganosiloxane paste, and the remaining xylene were stirred and mixed to prepare the antifouling coating composition.

[0229] <Preparation of antifouling paint compositions A-8 to A-13> Similar to A-7, each component was mixed and stirred in a container according to the proportions (parts by mass) listed in Table 6 to prepare two-component antifouling paint compositions A-8 to A-13.

[0230] [Table 6]

[0231] <Preparation of antifouling paint composition A-14> A three-component antifouling coating consisting of a main component, a hardener component, and an additive component was prepared by mixing and stirring each component in a container according to the proportions (parts by mass) listed in Table 7. More specifically, for the main component of the three-component paint composition, the components other than the curable polyorganosiloxane and polyorganosiloxane paste were mixed and stirred with 10 parts by mass of xylene, and then the curable polyorganosiloxane, polyorganosiloxane paste, and the remaining xylene were stirred and mixed to prepare the main component of the antifouling paint.

[0232] <Preparation of antifouling paint compositions A-15 to A-21> Similar to A-14, each component was mixed and stirred in a container according to the proportions (parts by mass) listed in Table 7 to prepare three-component antifouling paint compositions A-15 to A-21.

[0233] [Table 7]

[0234] [Adhesion evaluation test] <Method for preparing laminated coatings for adhesion evaluation> "Banno 500" (epoxy resin-based anticorrosive paint, manufactured by Chugoku Marine Paints Co., Ltd.) was applied to a sandblasted steel plate so that the dry film thickness was 150 μm, and then dried at room temperature (23°C, 50% RH) for one day to form an anticorrosive coating. Various tie-coat compositions were applied to the formed anticorrosive coating film to a dry film thickness of 100 μm, and dried at room temperature for 2, 6, and 24 hours to form tie-coat layers and create a laminated undercoat film. Test plates with antifouling coatings were prepared by applying various antifouling coating compositions to the formed laminated undercoat film to a dry film thickness of 200 μm and drying them at room temperature for one day.

[0235] <Conditions for evaluating adhesion> (Initial evaluation) Laminated test panels coated with antifouling paint in the order described above were dried at room temperature for one day after application of the antifouling paint composition, and then their adhesion was evaluated using the following evaluation method. (Evaluation after immersion) After evaluating the initial adhesion, the samples were immersed in fresh water at room temperature, and after 3 days, the adhesion was evaluated again using the same method as for the initial adhesion.

[0236] <Method for evaluating adhesion> A single cut was made in the silicone-based antifouling coating on the surface of the coating on the above test plate using a single blade specified in JIS K5600-5-6:1999. When the surface was rubbed perpendicular to the cut with a paper cloth, the degree of delamination between the coating and the coating formed from the paint compositions of the example and comparative example was evaluated according to the following criteria. (Evaluation Criteria) 0: No paint damage other than cuts is observed. 1: There is slight paint damage around the cut, but no other damage. 2: Delamination of the paint film is observed around the cut, but the delamination does not spread further. 3. Delamination occurs within a range of less than 10 mm from the cut. 4. Delamination occurs in an area of ​​10 mm or more from the cut. 5: The paint film no longer exists.

[0237] [Dynamic antifouling evaluation test] "Banno 500" (epoxy resin-based anticorrosive paint, manufactured by Chugoku Marine Paints Co., Ltd.) was applied to a sandblasted steel plate so that the dry film thickness was 150 μm, and then dried at room temperature (23°C, 50% RH) for one day to form an anticorrosive coating. Various tie-coat compositions were applied to the formed anticorrosive coating film to a dry film thickness of 100 μm, and dried at room temperature for 24 hours to form a tie-coat layer, thereby forming a laminated undercoat film. Test plates with antifouling coatings were prepared by applying various antifouling coating compositions to the formed laminated undercoat film to a dry film thickness of 200 μm and drying them at room temperature for one day. 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 where slime was attached to the total surface of the antifouling film on the test plate was calculated by visual observation and evaluated according to the following evaluation criteria. (Evaluation Criteria) 5: The area on which marine organisms attach is less than 10% of the entire test board. 4: The area on which marine organisms attach is between 10% and 30% of the entire test board. 3: The area on which marine organisms attach is between 30% and 50% of the entire test board. 2: The area on which marine organisms attach is between 50% and 80% of the entire test board. 1: The area on which marine organisms attach covers 80% or more of the entire test board.

[0238] The evaluation results are shown in Tables 8 to 10 below. Examples 1 to 40 are for antifouling coating composition (i), Examples 41 to 85 are for antifouling coating composition (ii), and Examples 86 to 127 are for antifouling coating composition (iii).

[0239] [Table 8-1]

[0240] [Table 8-2]

[0241] [Table 8-3]

[0242] [Table 8-4]

[0243] [Table 8-5]

[0244] Table 8-6

[0245] Table 9-1

[0246] Table 9-2

[0247] Table 9-3

[0248] Table 9-4

[0249] Table 9-5

[0250] Table 9-6

[0251] Table 9-7

[0252] Table 10-1

[0253] Table 10-2

[0254] [Table 10-3]

[0255] [Table 10-4]

[0256] [Table 10-5]

[0257] [Table 10-6]

[0258] [Table 10-7]

[0259] [Table 10-8]

[0260] The examples and comparative examples show that the laminated antifouling coating of the present invention provides a laminated antifouling coating with excellent antifouling properties and adhesion.

Claims

1. It contains epoxy resin (A), amine curing agent (B), and oxime group-containing organosilane (C), A tycoat composition in which the oxime group-containing organosilane (C) is a compound represented by the following formula (1). 【Chemistry 1】 (In formula (1), R1 and R2 each independently represent an alkyl group having 1 to 4 carbon atoms, and X represents a methyl group, a vinyl group, or a phenyl group.)

2. The Thai Coat composition according to claim 1, wherein the content of the oxime group-containing organosilane (C) in the nonvolatile components of the Thai Coat composition is 3% by mass or more and 20% by mass or less.

3. The tiecoat composition according to claim 1 or 2, wherein the oxime group-containing organosilane (C) is at least one selected from the group consisting of methyltris(methylethylketoxime)silane, vinyltris(methylethylketoxime)silane, methyltris(methylisobutylketoxime)silane, and vinyltris(methylisobutylketoxime)silane.

4. The tie-coat composition according to claim 1 or 2, wherein the tie-coat composition is for use as a tie-coat layer of an antifouling paint composition containing a curable silicone (a).

5. This is a laminated antifouling coating in which a tie coat layer and an antifouling coating film are laminated in this order. The tie coat layer is formed from a tie coat composition containing an epoxy resin (A), an amine curing agent (B), and an oxime group-containing organosilane (C) represented by the following formula (1). 【Chemistry 2】 (In formula (1), R １ and R ２ Each of these independently represents an alkyl group having 1 to 4 carbon atoms, and X represents a methyl group, a vinyl group, or a phenyl group. The antifouling coating film is formed from an antifouling paint composition selected from the group consisting of (i) to (iii) below, which contains a curable silicone (a). (i) An antifouling coating composition containing a polyorganosiloxane (a1) having ketoxime groups at both ends, wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is 1.5% by mass or less. (ii) An antifouling coating composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends and an organosilane (a3) ​​represented by the following formula (I), wherein the content of a hydrophilic lubricant in the nonvolatile components of the antifouling coating composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 1.0% by mass. 【Transformation 3】 (In formula (I), R ３ Each of the following independently represents a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms, Y is a ketoxime group with a total of 3 to 6 carbon atoms, and a is 0 or 1. (iii) An antifouling paint composition comprising a polyorganosiloxane (a2) having hydroxyl groups at both ends, at least one organosilicon crosslinking agent selected from the group consisting of organosilanes having at least two hydrolyzable groups in one molecule and their partially hydrolyzed condensates, and a curing catalyst, wherein the content of a lubricant having hydrophilic groups in the nonvolatile components of the antifouling paint composition is 0% by mass or more and 16% by mass or less, and the content of polyether-modified silicone oil is less than 0.1% by mass. A laminated antifouling coating that satisfies either condition A or condition B below. Condition A: X is a phenyl group, and the antifouling paint composition is (i) above. Condition B: X is a methyl group or a vinyl group, and the antifouling coating composition is selected from the group consisting of (i) to (iii) above.

6. The laminated antifouling coating film according to claim 5, wherein the lubricant having hydrophilic groups is at least one selected from the group consisting of polyether-modified silicone oil, hydrophilic acrylic polymer, and glycerin condensate ester.

7. The process involves applying a tie coat composition to form a base coat layer, and The process includes applying a Tiecoat composition, followed by applying an antifouling paint composition onto the Tiecoat layer within 5 hours. A method for manufacturing a laminated antifouling coating film according to claim 5 or 6.

8. The process involves applying a tie coat composition to form a base coat layer, and The process includes applying a Tiecoat composition, followed by applying an antifouling paint composition onto the Tiecoat layer within 36 hours. A method for manufacturing a laminated antifouling coating film according to claim 5 or 6.

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