Coating composition and coated film

Abstract

Provided is a coating composition comprising a silicon atom-containing resin, the silicon atom-containing resin comprising: structural units (A) derived from a monomer (a) having at least one silicon atom-containing group selected from the group consisting of the groups represented by formula (I), formula (II), formula (III), and formula (IV); structural units (B) derived from a monomer (b) having a triorganosiloxy carbonyl group; structural units (C) derived from a monomer (c) other than the monomers (a) and (b); the molecular weight of the monomer (a) is greater than 2500; the monomer (c) is a monomer whose solubility parameter SP of a homopolymer thereof is 9.5 or less and does not have a cyclic structure; the content of the structural units (A) is 11% by mass or more in all the structural units; and the content of the structural units (C) is 1% by mass or more and 60% by mass or less in all the structural units.

Description

Technical Field

[0001] This invention relates to coating compositions comprising silicon-containing resins. Furthermore, the invention also relates to coating films formed from the coating compositions and composite coating films having the coating films, as well as ships and underwater structures having the coating films or composite coating films. Background Technology

[0002] On ships, the attachment of organisms such as barnacles, mussels, and algae can hinder efficient operation and lead to problems such as fuel waste. Previously, antifouling coating compositions were applied to the surface of ships to prevent this attachment. For example, International Patent Publication No. 2011 / 046086 (Patent Document 1) discloses an antifouling coating composition comprising a silicone-containing resin as a carrier, and a thermoplastic resin and / or a plasticizer.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2011 / 046086 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] When the object to which the antifouling coating composition is applied is an object that moves in water (e.g., seawater), such as a ship, it is required that the coating film formed by the antifouling coating composition provides good antifouling performance during the movement of the object.

[0008] The object of this invention is to provide a coating composition that provides good antifouling properties during the movement of the coated object. Other objects of this invention are to provide a coating film formed from the coating composition and a composite coating film having the coating film, as well as ships and underwater structures having the coating film or the composite coating film.

[0009] Methods for solving problems

[0010] The present invention provides the following coating compositions, coating films, composite coating films, ships and underwater structures.

[0011] [1] A coating composition comprising a silicone-containing resin, said silicone-containing resin comprising:

[0012] Structural unit (A), which is a structural unit derived from monomer (a), which has at least one silicon-containing group selected from the group represented by formula (I), the group represented by formula (II), the group represented by formula (III) and the group represented by formula (IV).

[0013] Structural unit (B) is derived from monomer (b) having three organosilasiloxycarbonyl groups.

[0014] Structural unit (C), which is derived from the monomer (a) and monomer (c) other than the monomer (b);

[0015] The molecular weight of the monomer (a) is greater than 2500;

[0016] The monomer (c) is a monomer whose homopolymer solubility parameter SP is below 9.5 and which does not have a cyclic structure;

[0017] Of all the structural units contained in the silicon-containing resin, the content of structural unit (A) is 11% by mass or more;

[0018] In the silicon-containing atom resin, the content of the structural unit (C) is more than 1% by mass and less than 60% by mass.

[0019] [Chemical Formula 1]

[0020]

[0021] In equation (Ⅰ), a and b each independently represent any integer from 2 to 5, m represents any integer from 0 to 50, and n represents any integer from 3 to 270; R 1 ~R 5 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy;

[0022] [Chemical Formula 2]

[0023]

[0024] In equation (II), c and d each independently represent any integer from 2 to 5, and p represents any integer from 0 to 50; R 6 R 7 and R 8 Each independently represents an alkyl group, R a Or R b ;

[0025] R a yes

[0026] [Chemical Formula 3]

[0027]

[0028] In the formula, x represents any integer from 0 to 200, and R 23 ~R 27 The same or different indicates an alkyl group;

[0029] R b yes

[0030] [Chemical Formula 4]

[0031]

[0032] In the formula, y represents any integer from 1 to 200; R 28 and R 29 The same or different indicates an alkyl group;

[0033] [Chemical Formula 5]

[0034]

[0035] In equation (Ⅲ), e, f, g, and h each independently represent any integer from 2 to 5, q and s each independently represent any integer from 0 to 50, and r represents any integer from 3 to 270; R 9 ~R 12 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy;

[0036] [Chemical Formula 6]

[0037]

[0038] In equation (Ⅳ), i, j, k, and l each independently represent any integer from 2 to 5; t and u each independently represent any integer from 0 to 50; and v and w each independently represent any integer from 0 to 70. 13 ~R 22 Same or different indicates alkyl group.

[0039] [2] According to the coating composition of [1], the monomer (c) is of the following formula:

[0040] CH2=C(R A (COOR) B )

[0041] The alkyl methacrylate is indicated.

[0042] Among them, R A R is a hydrogen atom or a methyl group. B It is a chain alkyl group with 3 or more carbon atoms.

[0043] [3] According to the coating composition of [1] or [2], the monomer (a) is at least one selected from the monomer (a1) represented by formula (Ⅰ'), the monomer (a2) represented by formula (Ⅱ'), the monomer (a3) ​​represented by formula (Ⅲ'), and the monomer (a4) represented by formula (Ⅳ').

[0044] [Chemical Formula 7]

[0045]

[0046] In equation (Ⅰ'), R 31 Represents hydrogen atoms or methyl groups, a, b, m, n, and R. 1 ~R 5 It means the same as above;

[0047] [Chemical Formula 8]

[0048]

[0049] In formula (Ⅱ'), R 32 Represents hydrogen atoms or methyl groups, c, d, p, and R. 6 ~R 8 It means the same as above;

[0050] [Chemical Formula 9]

[0051]

[0052] In formula (Ⅲ'), R 33 and R 34 Each of these independently represents a hydrogen atom or a methyl group, e, f, g, h, q, r, s, and R. 9 ~R 12 It means the same as above;

[0053] [Chemical Formula 10]

[0054]

[0055] In equation (Ⅳ'), R 35 and R 36 Each of these independently represents a hydrogen atom or a methyl group, i, j, k, l, t, u, v, w, and R. 13 ~R 22 It means the same as above.

[0056] [4] In any one of [1] to [3], the monomer (b) is a monomer (b1) represented by the following formula (VⅡ');

[0057] [Chemical Formula 11]

[0058]

[0059] In formula (VⅡ'), R 43 R represents a hydrogen atom or a methyl group. 40 R 41 and R42 Same or different, indicating hydrocarbon groups with 1 to 20 carbon atoms.

[0060] [5] In any one of the coating compositions according to [1] to [4], the content of the structural unit (B) in all the structural units contained in the silicon-containing resin is 5% by mass or more and 40% by mass or less.

[0061] [6] The coating composition according to any one of [1] to [5] further comprises at least one selected from defoamers and anti-sagging agents.

[0062] [7] The coating composition according to any one of [1] to [6] further comprises a structural unit (D) derived from a monomer (d), the monomer (d) having at least one metal-containing group selected from groups represented by formula (V) and groups represented by formula (VI).

[0063] [Chemical Formula 12]

[0064]

[0065] In formula (V), M represents a divalent metal atom, and R 30 Indicates an organic acid residue or an alcohol residue;

[0066] [Chemical Formula 13]

[0067]

[0068] In formula (VI), M represents a divalent metal atom.

[0069] [8] According to the coating composition of [7], the monomer (d) is selected from at least one of the monomer (d1) represented by the following formula (V') and the monomer (d2) represented by the following formula (VI');

[0070] [Chemical Formula 14]

[0071]

[0072] In equation (V'), R 37 Represents a hydrogen atom or a methyl group, M and R 30 It means the same as above;

[0073] [Chemical Formula 15]

[0074]

[0075] In equation (VI'), R 38 and R 39Each can independently represent a hydrogen atom or a methyl group, with M representing the same meaning as above.

[0076] [9] A coating film formed from any one of the coating compositions described in [1] to [8].

[0077]

[10] A composite coating film having: a primer film formed by an anti-rust coating; and a coating film formed by any one of the coating compositions described in [1] to [8] stacked on the primer film.

[0078]

[11] A ship having the coating described in [9] or the composite coating described in

[10] .

[0079]

[12] An underwater structure having the coating described in [9] or the composite coating described in

[10] .

[0080] Invention Effects

[0081] A coating composition can be provided that exhibits good antifouling properties during the movement of the coated object. Furthermore, a coating film formed from the coating composition and a composite coating film having the coating film can be provided, as well as ships and underwater structures having the coating film or the composite coating film. Detailed Implementation

[0082] <Coating Composition>

[0083] The coating composition of the present invention (hereinafter also simply referred to as the "coating composition") comprises a specific silicone-containing resin described later. According to the coating composition of the present invention, a coating film exhibiting good antifouling properties during the movement of the coated object can be formed. Furthermore, according to the coating composition of the present invention, a coating film exhibiting good antifouling properties over a long period of time during the movement of the coated object can be formed. Hereinafter, the antifouling performance during movement will also be referred to as "dynamic antifouling property". The coating composition of the present invention is preferably used as an antifouling coating composition suitable for underwater moving bodies such as ships.

[0084] The following provides a detailed description of the components contained in or that may be contained in the coating composition.

[0085] (1) Silicon-containing resin

[0086] The silicone-containing resin contained in the coating composition comprises structural unit (A), structural unit (B), and structural unit (C). Structural unit (A) is a structural unit derived from monomer (a), which has at least one silicone-containing group selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV) above. Structural unit (B) is a structural unit derived from monomer (b) having a triorganosilyloxycarbonyl group. Structural unit (C) is a structural unit derived from monomer (c), which is a monomer other than monomer (a) and monomer (b), whose homopolymer solubility parameter SP is 9.5 or less, and which does not have a cyclic structure. The silicone-containing resin may contain structural units derived from monomers other than monomer (a), monomer (b), and monomer (c).

[0087] (1-1) Silicon-containing groups

[0088] The silicon-containing groups in monomer (a) are selected from at least one of the groups represented by formula (I), formula (II), formula (III), and formula (IV) above.

[0089] In equation (Ⅰ), a and b each independently represent any integer from 2 to 5, m represents any integer from 0 to 50, and n represents any integer from 3 to 270. 1 ~R 5 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy.

[0090] In equation (II), c and d each independently represent any integer from 2 to 5, and p represents any integer from 0 to 50. 6 R 7 and R 8 Each independently represents an alkyl group, R a Or R b .

[0091] In R a In R, x represents any integer from 0 to 200. 23 ~R 27 Same or different indicates alkyl group.

[0092] In R b In R, y represents any integer from 1 to 200. 28 and R 29 Same or different indicates alkyl group.

[0093] In equation (Ⅲ), e, f, g, and h each independently represent any integer from 2 to 5, q and s each independently represent any integer from 0 to 50, and r represents any integer from 3 to 270. 9 ~R 12 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy.

[0094] In equation (Ⅳ), i, j, k, and l each independently represent any integer from 2 to 5, t and u each independently represent any integer from 0 to 50, and v and w each independently represent any integer from 0 to 70. R 13 ~R 22 Same or different indicates alkyl group.

[0095] Silicon-containing resins may have two or more silicon-containing groups selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV) above. Alternatively, they may have two or more groups represented by formula (I), two or more groups represented by formula (II), two or more groups represented by formula (III), and / or two or more groups represented by formula (IV).

[0096] A preferred example of a silicone-containing resin is a (meth)acrylic resin having silicone-containing groups. In this specification, "(meth)acrylic acid" means at least one of methacrylic acid and acrylic acid.

[0097] (1-2) Monomer (a)

[0098] The monomer (a) is preferably selected from at least one of the monomers (a1) represented by formula (I'), (a2) represented by formula (II'), (a3) ​​represented by formula (III'), and (a4) represented by formula (IV'). By polymerizing the monomer composition containing such monomer (a), a silicon-containing resin comprising a structural unit (A) derived from monomer (a) can be obtained, wherein the monomer (a) is selected from monomer (a1), monomer (a2), monomer (a3), and monomer (a4). The silicon-containing resin has at least one silicon-containing group selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV).

[0099] Silicon-containing resins may contain two or more structural units (A) derived from monomer (a).

[0100] In equation (Ⅰ'), R 31 Represents hydrogen atoms or methyl groups, a, b, m, n, and R.1 ~R 5 It means the same as above.

[0101] In formula (Ⅱ'), R 32 Represents hydrogen atoms or methyl groups, c, d, p, and R. 6 ~R 8 It means the same as above.

[0102] In formula (Ⅲ'), R 33 and R 34 Each of these independently represents a hydrogen atom or a methyl group, e, f, g, h, q, r, s, and R. 9 ~R 12 It means the same as above.

[0103] In equation (Ⅳ'), R 35 and R 36 Each of these independently represents a hydrogen atom or a methyl group, i, j, k, l, t, u, v, w, and R. 13 ~R 22 It means the same as above.

[0104] The monomer (a1) represented by formula (Ⅰ'), the monomer (a2) represented by formula (Ⅱ'), the monomer (a3) ​​represented by formula (Ⅲ'), and the monomer (a4) represented by formula (Ⅳ') are each silicon-containing polymerizable monomers having the group represented by formula (Ⅰ), the group represented by formula (Ⅱ), the group represented by formula (Ⅲ), and the group represented by formula (Ⅳ).

[0105] The molecular weight of monomer (a) is greater than 2500. According to a coating composition comprising a silicone-containing resin, wherein the silicone-containing resin contains structural units (A) derived from this high molecular weight monomer (a), provided that the content of structural unit (A) in the silicone-containing resin is within the range specified later, and the silicone-containing resin also contains specified structural units (B) and (C), and the content of structural unit (C) in the silicone-containing resin is within the range specified later, the coating film formed by the coating composition can achieve excellent dynamic antifouling properties. The molecular weight of monomer (a) can be a number-average molecular weight. The number-average molecular weight of monomer (a) is the number-average molecular weight converted from polystyrene determined by gel permeation chromatography (GPC).

[0106] As at least one of the main factors contributing to the excellent dynamic antifouling properties, it is speculated that the silicon-containing resin has large molecular weight silicon-containing side chains, which generate an oily film on the coating surface moving in water, thereby increasing the high smoothness of the coating surface, the high elasticity of the coating, and the low interfacial free energy between the coating and water.

[0107] From the viewpoint of further improving dynamic antifouling properties, the molecular weight of monomer (a) is preferably 3000 or more, more preferably 4000 or more or 5000 or more, and may also be 10000 or more. The molecular weight of monomer (a) is generally 20000 or less, preferably 18000 or less, more preferably 15000 or less, and even more preferably 12000 or less. When the molecular weight of monomer (a) is too large, due to the immiscibility of the monomers in the monomer composition, which is a mixture of monomers used in the preparation of silicone atom-containing resin, or the immiscibility of the polymers generated by the polymerization of the monomer composition, the coating film formed by the coating composition is prone to become uneven in its composition, and the physical properties of the coating film may be reduced. One way to confirm whether the coating film is uneven in its composition is to prepare a coating film formed only from silicone atom-containing resin and check whether the coating film is transparent. If the coating film is transparent, it can be said that its composition is uniform; if it is cloudy, it can be said that it is uneven.

[0108] However, by including a specified amount of structural unit (C) derived from the monomer (c) described later in the silicon-containing atom resin, a coating film with uniform composition can be easily obtained even when using a monomer (a) with a large molecular weight.

[0109] Monomer (a) can be a combination of two or more monomers belonging to monomer (a). These two or more monomers can have different molecular weights, as long as they are greater than 2500.

[0110] The monomer (a1) is represented by the above formula (Ⅰ'). By using monomer (a1) as monomer (a), a silicon-containing resin that has silicon-containing groups represented by the above formula (Ⅰ) in the side chain can be obtained.

[0111] Silicon-containing resins can contain structural units derived from two or more monomers (a1).

[0112] In formula (Ⅰ') [and formula (Ⅰ) are the same.], 'a' is preferably 2 or 3.

[0113] b is preferably 2 or 3.

[0114] From the viewpoint of the coating's water resistance and adhesion to the substrate, m is preferably 0 or more and 25 or less, more preferably 0 or more and 20 or less. m can be 3 or more or 5 or more, or 10 or less or 8 or less.

[0115] From the viewpoint of the antifouling properties of the coating and its solubility in common organic solvents, n is generally 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, and even more preferably 45 or more and 160 or less.

[0116] R 1 ~R 5 The substituted phenyl groups and substituted phenoxy groups in the text are, for example, alkyl or halogen atoms.

[0117] R 1 ~R 5 Preferably, it is an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, and particularly preferably methyl or ethyl.

[0118] Commercially available products can also be used as monomers (a1). Examples of commercially available products with a molecular weight greater than 2500, all indicated by trade names, include: JNC Corporation's "FM-0721" (monoterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 5000), "FM-0725" (monoterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 10000), Shin-Etsu Chemical Industry Co., Ltd.'s "KF-2012" (monoterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4600), and "X-22-2426" (monoterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 12000), etc.

[0119] Monomer (a2) is represented by the above formula (Ⅱ'). By using monomer (a2) as monomer (a), a silicone-containing resin that has a silicon-containing group represented by the above formula (Ⅱ) in its side chain can be obtained. Commercially available products can also be used as monomer (a2).

[0120] Silicon-containing resins can contain structural units derived from two or more monomers (a2).

[0121] In formula (Ⅱ') [and formula (Ⅱ) are the same.], c is preferably 2 or 3.

[0122] d is preferably 2 or 3.

[0123] From the viewpoint of the coating's water resistance and adhesion to the substrate, p is preferably 0 or higher and 25 or lower, more preferably 0 or higher and 20 or lower. p can be 3 or higher or 5 or higher, or 10 or lower or 8 or lower.

[0124] From the viewpoint of solubility in common organic solvents, x is generally 0 or more and 200 or less, preferably 10 or more and 150 or less, and more preferably 20 or more and 125 or less.

[0125] From the viewpoint of solubility in common organic solvents, y is generally 1 or more and 200 or less, preferably 10 or more and 150 or less, and more preferably 20 or more and 125 or less.

[0126] R 6 ~R 8 and R 23 ~R 29 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, and even more preferably methyl or ethyl.

[0127] R 6 ~R 8 All are preferably alkyl groups.

[0128] Monomer (a3) ​​is represented by the above formula (Ⅲ'). By using monomer (a3) ​​as monomer (a), a silicon-containing resin of (meth)acrylic acid resin having silicon-containing atomic groups (which are crosslinking groups that crosslink the polymer backbone) represented by the above formula (Ⅲ) can be obtained.

[0129] Silicon-containing resins can contain structural units derived from two or more monomers (a3).

[0130] In equation (Ⅲ') [and equation (Ⅲ) are the same.], e and h are preferably 2 or 3 respectively.

[0131] f and g are preferably 2 or 3 respectively.

[0132] From the viewpoint of the coating's water resistance and adhesion to the substrate, q and s are preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, and even more preferably 0 or more and 20 or less. q and s can each be 3 or more or 5 or more, or 10 or less or 8 or less.

[0133] From the viewpoints of the coating's antifouling properties and solubility in common organic solvents, r is generally 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, and even more preferably 45 or more and 160 or less.

[0134] R 9 ~R 12 The substituted phenyl groups and substituted phenoxy groups in the text are, for example, alkyl or halogen atoms.

[0135] R 9 ~R 12Preferably, it is an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tert-butyl, and particularly preferably methyl or ethyl.

[0136] Commercially available products can also be used as a monomer (a3). Commercially available products with a molecular weight greater than 2500, for example, are all indicated by trade names. Examples include: "FM-7721" (diterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 5000) and "FM-7725" (diterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 10000) manufactured by JNC Corporation; "X-22-164B" (diterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 3200) and "X-22-164C" (diterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4800) and "X-22-164E" (diterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 7800) and "X-22-2445" (diterminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 3200) manufactured by Shin-Etsu Chemical Industry Co., Ltd.

[0137] Monomer (a4) is represented by the above formula (Ⅳ'). By using monomer (a4) as monomer (a), a silicone-containing resin of (meth)acrylic acid resin having a silicon-containing group (which is a crosslinking group that crosslinks the polymer backbone) represented by the above formula (Ⅳ) can be obtained. Commercially available products can also be used as monomer (a4).

[0138] Silicon-containing resins can contain structural units derived from two or more monomers (a4).

[0139] In Equation (Ⅳ') [Equation (Ⅳ) is the same.], i and l are preferably 2 or 3 respectively.

[0140] j and k are preferably 2 or 3.

[0141] From the viewpoint of the coating's water resistance and adhesion to the substrate, t and u are each preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, and even more preferably 0 or more and 20 or less. q and s can each be 3 or more or 5 or more, or 10 or less or 8 or less.

[0142] From the viewpoints of the coating's antifouling properties and solubility in common organic solvents, v and w are generally 0 or more and 70 or less, preferably 5 or more and 60 or less, and more preferably 10 or more and 50 or less.

[0143] R 13 ~R22 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, and even more preferably methyl or ethyl.

[0144] Referring to the above description, to ensure that the molecular weight of monomer (a) is greater than 2500, a~n, p~y, and R are appropriately selected. 1 ~R 29 .

[0145] From the viewpoint of improving dynamic antifouling properties and the availability of commercially available products, monomer (a) is preferably selected from at least one of monomers (a1) and (a3). As monomer (a), a combination of monomer (a1) and monomer (a3) ​​is also preferred.

[0146] From the viewpoints of dynamic antifouling and static antifouling (antifouling performance when the antifouling coating is placed in water (seawater)), the content of structural unit (A) derived from monomer (a) among all structural units contained in the silicone atomized resin is 11% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and may also be 35% by mass or more, 40% by mass or more, or 50% by mass or more. By making the content of structural unit (A) 11% by mass or more, a coating composition exhibiting sufficient dynamic antifouling performance can be obtained even without additional antifouling agent. Furthermore, from the viewpoints of coating film properties and the uniformity of the aforementioned coating film, the content of structural unit (A) among all structural units contained in the silicone atomized resin is preferably 90% by mass or less, more preferably 70% by mass or less, even more preferably 60% by mass or less, even more preferably 55% by mass or less, and may also be 50% by mass or less.

[0147] The silicon-containing resin may contain a structural unit (A') derived from a monomer (a'), which has at least one silicon-containing group selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV), and has a molecular weight of 2500 or less. However, from the viewpoint of dynamic antifouling properties, the content of structural unit (A') in all structural units contained in the silicon-containing resin is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 0% by mass.

[0148] From the viewpoint of dynamic antifouling, the ratio of the content of structural unit (A') to the total content of structural unit (A) and structural unit (A') is preferably 0.7 or less, more preferably 0.5 or less, even more preferably 0.4 or less, even more preferably 0.2 or less, and particularly preferably 0.

[0149] (1-3) Monomer (b)

[0150] Monomer (b) is a monomer having three organosilasiloxycarbonyl groups. By further containing structural units (B) derived from monomer (b) in the silicon-containing resin, dynamic antifouling properties can be improved. In addition, further containing structural units (B) can also help improve static antifouling properties.

[0151] Monomer (b) is preferably monomer (b1) represented by the above formula (VⅡ'). By polymerizing the monomer composition containing monomer (b1), a silicon-containing resin comprising a (meth)acrylic acid resin containing a structural unit (B) derived from monomer (b1) can be obtained. This silicon-containing resin has a -C(=O)-O-SiR structure. 40 R 41 R 42 It is a triorganosylsilyloxycarbonyl group.

[0152] Silicon-containing resins may contain two or more structural units (B) derived from monomers (b). For example, silicon-containing resins may contain two or more structural units (B) with different triorganosilyloxycarbonyl groups.

[0153] R in equation (VⅡ') 40 R 41 and R 42 "Same" or "different" refers to hydrocarbon residues with 1 to 20 carbon atoms (monovalent hydrocarbon groups). Examples of hydrocarbon residues with 1 to 20 carbon atoms include: straight-chain or branched alkyl groups with 20 or fewer carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl; cyclic alkyl groups that may have substituents, such as cyclohexyl and substituted cyclohexyl; and aryl groups that may have substituents, such as aryl and substituted aryl.

[0154] Examples of cyclic alkyl groups with substituents include cyclic alkyl groups substituted with halogens, alkyl groups with a maximum of about 18 carbon atoms, acyl groups, nitro groups, or amino groups. Examples of aryl groups with substituents include aryl groups substituted with halogens, alkyl groups with a maximum of about 18 carbon atoms, acyl groups, nitro groups, or amino groups.

[0155] Among them, R is preferred in terms of its tendency to maintain dynamic antifouling properties and static antifouling properties stably over a long period of time.40 R 41 and R 42 One or more of them are isopropyl, preferably R. 40 R 41 and R 42 All are isopropyl.

[0156] From the viewpoints of dynamic and static antifouling properties, among all the structural units contained in the silicon-containing atom resin, the content of structural units (B) derived from monomer (b) is preferably 2% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 10% by mass or more and 35% by mass or less.

[0157] From the perspective of dynamic antifouling and static antifouling, the content ratio ((B) / (A)) of structural unit (B) in the silicon-containing atom resin is preferably 1.5 or less by mass.

[0158] (1-4) Monomer (c)

[0159] Monomer (c) is a monomer other than monomers (a) and (b) mentioned above, whose homopolymer solubility parameter SP (hereinafter referred to as "SP") is 9.5 or less, and which does not have a cyclic structure. By further containing structural units (C) derived from monomer (c) in the silicon-containing atomized resin, dynamic antifouling properties can be improved. Furthermore, further containing structural units (C) can also improve static antifouling properties. Silicon-containing atomized resins may contain two or more structural units (C) derived from monomer (c).

[0160] As at least one major factor that can improve dynamic antifouling properties by further incorporating structural units (C), it is speculated that by using monomers (c) with small SP values ​​in homopolymers, the compatibility between monomers in the monomer composition used to prepare silicone-containing resins is improved, thereby increasing the random copolymerization with monomers (a) that contribute to dynamic antifouling properties during the polymerization of the monomer composition. The SP value of the homopolymer of monomer (c) is typically 7.0 or higher, preferably 8.0 or higher, and more preferably 9.0 or higher.

[0161] From the perspective of improving dynamic antifouling properties, monomer (c) is a monomer without a cyclic structure. Since monomer (c) without a cyclic structure is less hydrophobic than monomer with a cyclic structure, structural units (C) derived from this monomer are less likely to be locally present on the coating surface in a coating composition formed from a monomer composition containing this monomer. Therefore, compared to using monomers with cyclic structures, using monomers (c) without a cyclic structure can be considered as making it easier for structural units (A) derived from the hydrophobic monomer (a) to be locally present on the coating surface, resulting in improved dynamic antifouling properties.

[0162] In this specification, the solubility parameter SP of the homopolymer can be determined by the following method (reference: SUH, CLARKE, JPSA-1, 5, 1671-1681 (1967)).

[0163] At a test temperature of 20°C, 0.5 g of the homopolymer was weighed into a 100 mL beaker. 10 mL of a good solvent (acetone) was added using a pipette, and the solution was dissolved using a magnetic stirrer to prepare a diluted solution. Next, a low-SP poor solvent (n-hexane) was slowly added dropwise to this diluted solution using a 50 mL burette. The point at which the diluted solution became turbid was taken as the amount of low-SP poor solvent added. Separately, a high-SP poor solvent (ion-exchanged water) was slowly added dropwise to the same diluted solution, and the point at which the diluted solution became turbid was taken as the amount of high-SP poor solvent added. The SP value can be calculated from the amount of each poor solvent added until the turbidity point is reached using a known calculation method described in the aforementioned references, etc.

[0164] The monomer (c) is preferably a (meth)acrylic acid monomer, more preferably a (meth)acrylate, and even more preferably an alkyl (meth)acrylate. The alkyl (meth)acrylate as monomer (c) is preferably represented by the following formula.

[0165] CH2=C(R A (COOR) B )

[0166] In the above formula, R A R is a hydrogen atom or a methyl group. B It is a chain alkyl group having 3 or more carbon atoms. The chain alkyl group can be straight-chain or branched. R B The number of carbon atoms is usually less than 20, and preferably less than 12.

[0167] Specifically, monomers (c) can include: n-butyl acrylate (SP: 9.5), n-butyl methacrylate (SP: 9.3), isobutyl acrylate (SP: 9.5), isobutyl methacrylate (SP: 9.3), tert-butyl methacrylate (SP: 9.4), 2-ethylhexyl acrylate (SP: 8.4), 2-ethylhexyl methacrylate (SP: 8.3), lauryl methacrylate (SP: 7.8), stearyl methacrylate, isostearyl methacrylate, etc. Among these, monomers with an SP of 9.0 or higher are preferred for homopolymers, and n-butyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, etc. are more preferred.

[0168] From the viewpoints of dynamic and static antifouling properties, the content of structural units (C) derived from monomer (C) in all structural units contained in the silicon-containing atom resin is 1% by mass or more and 70% by mass or less, preferably 5% by mass or more and 50% by mass or less, more preferably 8% by mass or more and 45% by mass or less, and even more preferably 10% by mass or more and 40% by mass or less.

[0169] From the perspective of dynamic and static antifouling properties, the content ratio ((C) / (A)) of structural unit (C) in the silicon-containing atom resin is preferably 1.5 or less by mass.

[0170] (1-5) Monomer (d)

[0171] The silicon-containing resin may also have a structural unit (D) derived from the monomer (d), which has at least one metal-containing group selected from the groups represented by formula (V) and the groups represented by formula (VI) above. By having the structural unit (D) in addition to the silicon-containing resin, dynamic antifouling and static antifouling properties can be further improved.

[0172] Silicon-containing resins may also have both the groups represented by formula (V) and the groups represented by formula (VI) above.

[0173] The monomer (d) is preferably selected from at least one of the monomers (d1) represented by formula (V') and (d2) represented by formula (VI'). By polymerizing the monomer composition containing such monomer (d), a silicone-containing resin comprising a structural unit (D) derived from monomer (d) can be obtained, wherein the monomer (d) is selected from monomer (d1) and monomer (d2). The silicone-containing resin has at least one metal-containing group selected from the groups represented by formula (V) and (VI).

[0174] Silicon-containing resins can contain two or more structural units (D) derived from monomers (d).

[0175] The divalent metal atom M in formula (V') [and formula (V) are the same.] and formula (VI') [and formula (VI) are the same.] can be Mg, Zn, Cu, etc., with Zn or Cu being preferred.

[0176] In equation (V') [and equation (V) as well, R...] 30 Organic acid residues are preferred.

[0177] The monomer (d1) is represented by the above formula (V'). By using monomer (d1) as monomer (d), a silicone-containing resin that further has a metal atom group represented by the above formula (V) can be obtained.

[0178] As R 30 Organic acids that form organic acid residues include, for example: acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, tert-carbonic acid, isostearic acid, palmitic acid, cresolic acid, oleic acid, transoleic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, transricinoleic acid, brassinolic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitronaphthoic acid, pyruvic acid, and other monoprotic organic acids.

[0179] If the organic acid residue is a fatty acid residue, it tends to maintain a coating film without cracks or peeling for a long time, and is therefore preferred. In particular, zinc oleate (meth)acrylate or zinc tert-carbonate (meth)acrylate, which have high plasticizing properties, are preferred as monomers (d1).

[0180] In addition, other preferred organic acids include monocyclic organic acids other than aromatic organic acids. Examples of monocyclic organic acids include, for example, cycloalkyl organic acids such as cycloalkane acids, resin acids such as tricyclic resin acids, and their salts.

[0181] Examples of tricyclic resin acids include monocarboxylic acids having a diterpenoid hydrocarbon skeleton. Examples of monocarboxylic acids having a diterpenoid hydrocarbon skeleton include compounds having a rosinane, pirarin, isopirarin, or semacarne skeleton. More specifically, examples include abietic acid, neorosinic acid, dehydrorosinic acid, hydrogenated abietic acid, longleaf abietic acid, pirarinic acid, isopirarinic acid, levorotatory abietic acid, dextrorotatory abietic acid, sedar abietic acid, and their salts. From the viewpoint of dynamic antifouling properties of the coating, rosinic acid, hydrogenated abietic acid, and their salts are preferred.

[0182] As monocyclic organic acids, rosin and resin acids from pine trees can also be used. Examples of such organic acids include rosin derivatives, hydrogenated rosin derivatives, disproportionated rosin derivatives, and naphthenic acids. Rosin derivatives refer to resin rosin, wood rosin, and top-oil rosin. Considering their low cost and easy availability, excellent operability, and ease of improving dynamic and static antifouling properties, rosin derivatives, hydrogenated rosin derivatives, and disproportionated rosin derivatives are preferred.

[0183] The acid value of the monocyclic organic acid is preferably 100 mg KOH / g or more and 220 mg KOH / g or less, more preferably 120 mg KOH / g or more and 190 mg KOH / g or less, and even more preferably 140 mg KOH / g or more and 185 mg KOH / g or less.

[0184] As a form of R 30 Monocyclic organic acids, when used, tend to maintain the good dynamic antifouling properties and static antifouling properties of the coating film for a longer period of time.

[0185] The organic acid residues in the monomer (d1) can be formed from one organic acid or from two or more organic acids.

[0186] As having organic acid residues as R 30 Methods for producing monomers (d1) include, for example, reacting an inorganic metal compound with a carboxyl-containing free radical polymerizable monomer such as (meth)acrylic acid and a nonpolymerizable organic acid (the organic acid constituting the organic acid residues mentioned above) in an organic solvent containing an alcohol compound.

[0187] The structural unit (D) derived from the monomer (d1) can also be formed by reacting a resin obtained by polymerizing a monomer composition containing a carboxyl-containing free radical polymerizable monomer such as (meth)acrylic acid, a metal compound, and a non-polymerizable organic acid (the organic acid constituting the organic acid residues mentioned above).

[0188] Monomer (d2) is represented by the above formula (VI'). By using monomer (d2) as monomer (d), a silicone-containing resin of (meth)acrylic acid resin further having the metal-containing group (which is a crosslinking group that crosslinks the polymer backbone) represented by the above formula (VI) can be obtained.

[0189] Examples of monomers (d2) include: magnesium acrylate [(CH2=CHCOO)2Mg], magnesium methacrylate [(CH2=C(CH3)COO)2Mg], zinc acrylate [(CH2=CHCOO)2Zn], zinc methacrylate [(CH2=C(CH3)COO)2Zn], copper acrylate [(CH2=CHCOO)2Cu], and copper methacrylate [(CH2=C(CH3)COO)2Cu], etc. One or more of these can be selected as needed.

[0190] Methods for producing monomer (d2) include, for example, reacting a polymerizable unsaturated organic acid, such as (meth)acrylic acid, and a metal compound with water in an organic solvent containing an alcohol compound. In this case, preferably, the water content in the reactants is adjusted to 0.01% by mass or more and 30% by mass or less.

[0191] Silicon-containing atomized resins can contain both structural units derived from monomers (d1) and structural units derived from monomers (d2).

[0192] From the viewpoints of dynamic antifouling and static antifouling, when the silicon-containing atom resin contains structural units (D), the content of structural units (D) in all structural units contained in the silicon-containing atom resin is preferably 2% by mass or more and 30% by mass or less, more preferably 4% by mass or more and 25% by mass or less, and even more preferably 6% by mass or more and 20% by mass or less.

[0193] (1-6) Other monomers

[0194] Silicon-containing resins may also contain structural units (E) derived from other monomers (e) besides those mentioned above. Silicon-containing resins may contain more than two types of structural units (E).

[0195] As monomer (e), there is no particular limitation as long as it is an unsaturated monomer capable of copolymerizing with monomers (a) to (d), and examples of (meth)acrylates not belonging to monomer (c) can be included. Specifically, monomer (e) can include: methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, isobornyl methacrylate, glycidyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. Among them, monomer (e) preferably contains at least methyl methacrylate.

[0196] When a silicone-containing resin contains structural units (E), the content of structural units (E) in all structural units contained in the silicone-containing resin is typically 0.1% by mass or more and 86% by mass or less, preferably 5% by mass or more and 80% by mass or less, more preferably 10% 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. By making the content of structural units (E) 0.1% by mass or more, the balance of various properties of the obtained coating composition and coating film can be adjusted. By making the content of structural units (E) 86% by mass or less, a coating composition exhibiting sufficient dynamic antifouling properties can be obtained even without additional antifouling agents.

[0197] (1-7) Manufacturing method of silicon-containing atom resin

[0198] There are no particular limitations on the manufacturing method of silicone-containing resins. For example, they can be manufactured by reacting a monomer composition containing the above-mentioned monomers at a reaction temperature of 60–180°C for 5–14 hours in the presence of a free radical initiator. The polymerization conditions can be adjusted appropriately.

[0199] Examples of free radical initiators include: 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylpentanonitrile), 2,2-azobis(2-methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxide-2-ethylhexanoate.

[0200] Examples of polymerization methods include solution polymerization, emulsion polymerization, and suspension polymerization carried out in organic solvents. From the viewpoint of manufacturing efficiency of silicone-containing resins, solution polymerization is preferred. Examples of common organic solvents include toluene, xylene, methyl isobutyl ketone, and n-butyl acetate.

[0201] The number-average molecular weight of the silicone-containing resin is typically 2600 or more and 100,000 or less, preferably 3000 or more and 50,000 or less, and more preferably 5000 or more and 30,000 or less. When the number-average molecular weight of the silicone-containing resin is 2600 or more, the coating film formed by the coating composition tends to exhibit dynamic antifouling properties. When the number-average molecular weight of the silicone-containing resin is 100,000 or less, the silicone-containing resin tends to be easily and uniformly dispersed in the coating composition. The number-average molecular weight of the silicone-containing resin is the number-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0202] (1-8) Content of silicon-containing resin

[0203] The content of silicone-containing resin in the coating composition is preferably 25% by mass or more and 99% by mass or less, more preferably 30% by mass or more and 90% by mass or less, and even more preferably 35% by mass or more and 85% by mass or less. It can also be 80% by mass or less, 70% by mass or less, or 60% by mass or less. When the content of silicone-containing resin is less than 25% by mass, there is a tendency for reduced dynamic antifouling properties, static antifouling properties, and adhesion of the coating film to the substrate. The solid content of the coating composition refers to the total amount of components other than solvents contained in the coating composition.

[0204] (2) Other ingredients that may be contained in the coating composition

[0205] The coating composition may contain one or more other components besides silicone-containing resins. Examples of such other components include: defoamers, anti-sagging agents, plasticizers, antifouling agents, water binders, anti-color separation agents, anti-settling agents, film consumption regulators, UV absorbers, surface conditioners, viscosity modifiers, leveling agents, pigment dispersants, etc., as well as pigments and solvents. These additives, pigments, and solvents may be used individually or in combination of two or more.

[0206] Defoamers are agents that cause uneven surface formation of bubbles and inhibit bubble formation, or agents that locally thin the surface of existing bubbles and destroy them. By including both a defoamer and a silicone-containing resin in the coating composition, dynamic antifouling properties can obviously be further improved. Therefore, coating compositions preferably contain a defoamer.

[0207] Defoamers can be categorized into two types: silicone-based defoamers and non-silicone-based defoamers. Silicone-based defoamers contain surface-active polysiloxanes or their modifiers, while non-silicone-based defoamers are defoamers other than silicone-based defoamers (defoamers that do not contain polysiloxanes or their modifiers). Silicone-based defoamers can be fluorinated silicone-based defoamers. Fluorinated silicone-based defoamers are defoamers containing fluorinated polysiloxanes.

[0208] Examples of non-silicone defoamers include: higher alcohols, higher alcohol derivatives, fatty acids, fatty acid derivatives, paraffin waxes, (meth)acrylic acid polymers, and mineral oils. Examples of silicone defoamers include: oil-based, compound-based, self-emulsifying, and emulsion-based types.

[0209] Commercially available products can be used as defoamers. Examples of commercially available non-silicone defoamers include: mineral oil defoamers such as "BYK-030" manufactured by BYK Corporation; polymer defoamers such as "DISPARON OX68" manufactured by Kusunoki Chemical Co., Ltd. and "BYK-1790" manufactured by BYK Corporation. Examples of commercially available silicone defoamers other than fluorinated silicone defoamers include: silicone oil defoamers such as "KF-96" manufactured by Shin-Etsu Chemical Co., Ltd. and "BYK-081" manufactured by BYK Corporation. Examples of commercially available fluorinated silicone defoamers include: fluorosilicone oil defoamers such as "BYK-063", "BYK-065", and "BYK-066N" manufactured by BYK Corporation, and "FA-630" manufactured by Shin-Etsu Chemical Co., Ltd.

[0210] From the viewpoint of improving dynamic antifouling and defoaming properties, the content of defoamer relative to 100 parts by weight of silicone-containing resin is 0.002 parts by weight or more and 0.60 parts by weight or less, more preferably 0.004 parts by weight or more and 0.55 parts by weight or less, even more preferably 0.01 parts by weight or more and 0.40 parts by weight or less, and even more preferably 0.01 parts by weight or more and 0.20 parts by weight or less.

[0211] Anti-sagging agents are agents that inhibit sagging of the coating composition that may occur between the application of the coating composition to the substrate and the completion of the drying process. By including both an anti-sagging agent and a silicone-containing resin in the coating composition, dynamic antifouling properties can obviously be further improved. Therefore, coating compositions preferably contain an anti-sagging agent.

[0212] From the viewpoint of further improving dynamic antifouling properties, the coating composition preferably includes at least one selected from defoamers and anti-sagging agents, and more preferably includes both defoamers and anti-sagging agents.

[0213] Examples of anti-sagging agents include: amide-based anti-sagging agents; bentonite-based anti-sagging agents; polyethylene waxes such as oxidized polyethylene wax; hydrogenated castor oil wax; long-chain fatty acid ester polymers; polycarboxylic acids; silica microparticle anti-sagging agents; and mixtures of two or more of them.

[0214] Examples of amide-based anti-sagging agents include fatty acid amide waxes and polyamide waxes. Examples of fatty acid amide waxes include stearamide wax and oleamide wax.

[0215] Commercially available products can be used as anti-sagging agents. Examples of commercially available anti-sagging agents based on amide waxes include: TALEN7200-20 manufactured by Kyoei Chemical Co., Ltd., DISPARON 6900-20X and DISPARON RE-8000 manufactured by Kusunoki Chemical Co., Ltd., and MONORAL3300 manufactured by HS CHEM Co., Ltd. Other commercially available anti-sagging agents include: BENTON38 manufactured by ELEMENTIS JAPAN Co., Ltd., and TIXOGEL manufactured by BYK Co., Ltd., which are organobentonite-based anti-sagging agents.

[0216] From the viewpoint of improving dynamic antifouling and anti-sagging properties, the content of anti-sagging agent is 0.1 parts by mass or more and 6.0 parts by mass or less, more preferably 0.2 parts by mass or more and 5.0 parts by mass or less, even more preferably 0.25 parts by mass or more and 4.0 parts by mass or less, and even more preferably 0.25 parts by mass or more and 3.0 parts by mass or less, relative to 100 parts by mass of silicone atom resin.

[0217] The coating composition may contain plasticizers. The presence of plasticizers improves the crack resistance of the coating film. Furthermore, since the polishing rate (grinding speed) of the coating film can be controlled at an appropriate speed, it is also advantageous in terms of dynamic and static antifouling properties.

[0218] Examples of plasticizers include: chlorinated paraffin; chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyethylene ether; polypropylene sebate; partially hydrogenated terphenyl; polyvinyl acetate; poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, poly(meth)acrylate copolymers, polyvinyl chloride resins, polyvinyl chloride-vinyl acetate copolymers, polyvinyl chloride-vinyl chloride-propionic acid copolymers, polyvinyl chloride-isobutyl vinyl ether copolymers, polyvinyl chloride-isopropyl vinyl ether copolymers, polyvinyl chloride-ethyl vinyl ether copolymers, etc.; silicone oil; oil Fats and their refined products (waxes, castor oil, etc.); petrolatum; liquid paraffin; rosin, hydrogenated rosin, naphthenic acids, fatty acids and their divalent metal salts; phthalate esters such as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate (DIDP); aliphatic diester esters such as isobutyl adipate and dibutyl sebacate; diol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl esters; phosphate esters such as tricresyl phosphate, triaryl phosphate, and trichloroethyl phosphate; epoxy compounds such as epoxidized soybean oil and epoxidized octyl stearate; organotin compounds such as dioctyltin laurate and dibutyltin laurate; trioctyl trimellitate and triacetylene, etc.

[0219] Among the above, from the viewpoints of compatibility with silicone-containing resins and crack resistance of the coating, chlorinated paraffin, polyethylene ether, polyether polyol, rosin, vinyl chloride-isobutyl vinyl ether copolymer, phthalate, and phosphate are preferred.

[0220] The content of plasticizer in the coating composition is preferably 3 parts by mass and 100 parts by mass or less, more preferably 5 parts by mass and 50 parts by mass or less, and even more preferably 5 parts by mass and 40 parts by mass or less, relative to 100 parts by mass of silicone-containing resin. When the content of plasticizer is less than 3 parts by mass relative to 100 parts by mass of silicone-containing resin, there is a tendency that the improvement effect on crack resistance brought about by the addition of plasticizer cannot be confirmed. In addition, there is a tendency that the improvement effect on dynamic antifouling and static antifouling properties brought about by the addition of plasticizer cannot be confirmed. When the content of plasticizer exceeds 100 parts by mass relative to 100 parts by mass of silicone-containing resin, there is a tendency that the adhesion of the coating film to the substrate decreases and the dynamic antifouling properties of the coating film decrease.

[0221] The coating film formed by the coating composition of the present invention exhibits good dynamic antifouling properties and, consequently, good static antifouling properties due to the antifouling effect of the silicone-containing resin. Therefore, it is not necessary to contain an antifouling agent in addition to the silicone-containing resin. However, to further improve antifouling properties or to further improve the long-term durability of antifouling properties, an antifouling agent may be included in the coating composition as needed. Known antifouling agents can be used, such as inorganic compounds, metal-containing organic compounds, and metal-free organic compounds.

[0222] Examples of antifouling agents include: zinc oxide; cuprous oxide; manganese ethylene didithiocarbamate; zinc dimethyl dithiocarbamate; 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine; 2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyldiphenylurea; zinc ethylene didithiocarbamate; copper rhodane (cuprous thiocyanate); 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-di... Chloro-2-n-octyl-3(2H)isothiazolinone); N-(fluorodichloromethylthio)phthalimide; N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfonamide; metal salts of zinc (zinc pyridinethione) or copper (copper pyridinethione) of 2-pyridinethiol-1-oxide, etc.; tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 3- Iodo-2-propylbutylcarbamate; diiodomethyl-p-trisulfone; phenyl(bispyridyl)bismuth dichloride; 2-(4-thiazolyl)-benzimidazole; triphenylborone pyridinium salt; stearylamine-triphenylborone; laurylamine-triphenylborone; dimethyldithiocarbamoyl zinc ethylene bis(dithiocarbamate); 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide; 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide [Acyl]-1-fluoro-N-(4-methylphenyl)methanesulfinamide; N'-(3,4-dichlorophenyl)-N,N'-dimethylurea; N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine; 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxylonitrile; 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: metomididine).

[0223] The content of antifouling agent in the coating composition is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, and particularly preferably 0 parts by weight, relative to 100 parts by weight of silicone-containing resin.

[0224] As pigments, examples include: extender pigments such as: precipitating barium, talc, clay, chalk, white silica, alumina white, bentonite, calcium carbonate, magnesium carbonate, silicic acid, silicates, alumina hydrate, calcium sulfate, etc.; coloring pigments such as: titanium oxide, zirconium oxide, alkaline lead sulfate, tin oxide, carbon black, white lead, graphite, zinc sulfide, zinc oxide, chromium oxide, nickel titanium yellow, chromium titanium yellow, iron oxide yellow, iron oxide red (red lead), iron oxide black, azo red / yellow pigments, chrome yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, quinacridone, etc.

[0225] Examples of solvents include: hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, and petroleum solvents; ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and butyl cellosolve; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate; ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; and alcohols such as n-butanol and propanol.

[0226] (3) Preparation of coating composition

[0227] The coating composition can be prepared, for example, by adding other components as needed to a silicone-containing resin or a resin composition containing it (e.g., a solution or dispersion containing a silicone-containing resin), and mixing it using a mixer such as a ball mill, pebble ball mill, roller mill, sand mill, or high-speed disperser.

[0228] <Coatings and Composite Coatings>

[0229] The coating film of the present invention (hereinafter also simply referred to as "coating film") is a coating film formed from the above-described coating composition of the present invention. The coating film is a non-fouling coating film with anti-fouling properties. Because this non-fouling coating film is formed from the above-described coating composition of the present invention, it can exhibit good dynamic anti-fouling properties. Furthermore, this non-fouling coating film can be a coating film with uniform composition.

[0230] The coating film can be formed by applying the above-mentioned coating composition to the surface of the object using conventional methods, and then evaporating and removing the solvent at room temperature or under heating as needed. Examples of coating methods for the coating composition include, for instance, dip coating, spray coating, brush coating, roller coating, electrostatic coating, electrodeposition coating, and other conventionally known methods. The thickness of the coating film is, for example, 50 μm or more and 500 μm or less, preferably 100 μm or more and 400 μm or less.

[0231] Examples of objects to be coated include: ships and underwater structures. Examples of underwater structures include: various fishing nets such as aquaculture nets and other fishing gear; port facilities; oil booms; water intake equipment for power plants; piping for cooling; bridges; buoys; industrial water facilities; and seabed bases. The preferred object to be coated is a moving body in the water, such as: ships, fishing nets, and fishing gear.

[0232] The coating surface of the object to be coated can be pretreated as needed. In addition, a composite coating film can be formed on a primer film formed by other coatings such as anti-rust coatings (anti-corrosion coatings) on the object to be coated, and a coating film formed by the coating composition of the present invention can be formed.

[0233] According to the coating composition of the present invention, since the silicon-containing resin serving as the carrier itself exhibits good antifouling properties, the additional proportion of antifouling agent can be omitted or its proportion reduced. The coating composition of the present invention can form a transparent (highly transparent) antifouling film. This transparency is due not only to the omission or reduction of the proportion of antifouling agent, but also to the uniformity of the resin components contained in the coating composition.

[0234] Antifouling coatings formed from conventional antifouling coating compositions that primarily contain a large amount of cuprous oxide as an antifouling agent typically have a reddish hue due to the cuprous oxide content, thus limiting the color range of the coating. However, according to the present invention, the transparency of the resulting coating allows for various applications. Furthermore, in the case of forming a transparent coating, the coating composition of the present invention preferably does not contain coloring pigments.

[0235] For example, in a composite coating having a primer film formed of an anti-rust coating or the like and a coating film of the present invention formed on the primer film, by using the coating film of the present invention as a transparent antifouling coating and using paints of various shades as anti-rust coatings, it is possible to provide a coated object such as a ship that has antifouling properties and a color tone on the surface of the composite coating that is not previously available. Furthermore, by forming an intermediate coating film formed of paints of various shades between the primer film formed of an anti-rust coating or the like and the transparent antifouling coating, it is also possible to provide a coated object with a color tone not previously available.

[0236] As the coating material forming the intermediate coating film, various coatings can be used, such as antifouling coatings, epoxy resin coatings, polyurethane resin coatings, (meth)acrylic resin coatings, chlorinated rubber coatings, alkyd resin coatings, silicone resin coatings, fluoropolymer coatings, etc. The antifouling coating material forming the intermediate coating film can be the coating composition of the present invention, or it can be other antifouling coating compositions, such as conventional antifouling coating compositions containing a relatively large amount of antifouling agent.

[0237] The intermediate coating film can be formed over the entire surface of the primer film or on a portion of the primer film. Both the intermediate coating film and the primer film can be existing coatings in use. In this case, the coating composition of the present invention, and the film formed therefrom, can be used to repair existing coatings.

[0238] If the intermediate layer coating, which is formed between a primer film (such as an anti-rust coating) and a transparent antifouling coating, is formed into various shades of text, patterns, designs, or designs, then the coated object can be given a variety of design options. Similarly, by placing a thin film or sealing component with various shades and shapes of text, patterns, designs, or designs between the primer film and the transparent antifouling coating, instead of the intermediate layer coating formed by the paint between the primer film and the transparent antifouling coating, various design options can also be given to the coated object.

[0239] Example

[0240] The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited thereto.

[0241] <Resin Manufacturing Examples S1-S15, T1-T7: Manufacturing of Resins S1-S15, T1-T7>

[0242] In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, xylene [A] parts by mass as solvent is added, and the temperature is maintained at [B] °C. Then, a mixture consisting of 100 parts by mass of the monomers shown in Table 3 or Table 4 (in parts by mass), xylene [C] parts by mass as solvent, and tert-butyl peroxide-2-ethylhexanoate [D] parts by mass as free radical polymerization initiator is added to the dropping funnel and added dropwise to the four-necked flask at a constant rate for 3 hours. After the addition is completed, the mixture is kept at the temperature for [E] minutes. Then, a mixture consisting of xylene [F] parts by mass and 0.3 parts by mass of tert-butyl peroxide-2-ethylhexanoate is added dropwise to the four-necked flask at a constant rate for 30 minutes. After the addition is completed, the mixture is kept at the temperature for [G] hours, thereby obtaining a resin composition (solution) containing resin.

[0243] The values ​​of [A] to [G] in each of the resin manufacturing examples S1 to S15 and T1 to T7 are summarized in Table 1 and Table 2.

[0244] [Table 1]

[0245]

[0246] [Table 2]

[0247]

[0248] Hereinafter, the resins obtained in resin manufacturing examples S1 to S15 will be referred to as "resins S1 to S15", and the resin compositions (solutions) obtained in resin manufacturing examples S1 to S15 will be referred to as "resin compositions S1 to S15". The resins obtained in resin manufacturing examples T1 to T7 will be referred to as "resins T1 to T7", and the resin compositions (solutions) obtained in resin manufacturing examples T1 to T7 will be referred to as "resin compositions T1 to T7".

[0249] The monomers used in resin manufacturing examples S1-S15 and T1-T7, and their amounts (parts by mass), are shown in Tables 3 and 4. In Tables 3 and 4, monomer (a') refers to a monomer having a silicon-containing group selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV), but with a molecular weight (number average molecular weight) of 2500 or less. Furthermore, the values ​​in parentheses for each monomer belonging to monomer (a) and monomer (a') are the number average molecular weight of that monomer. The same applies to Table 7.

[0250] In Tables 3 and 4, "other monomers" refers to monomers that do not belong to any of the categories (a), (a'), (b), and (c). Furthermore, the values ​​in parentheses for each monomer belonging to (c) and "other monomers" represent the solubility parameter (SP) of that monomer's homopolymer. The same applies to Table 7.

[0251] The number-average molecular weight (Mn) of the obtained resins S1-S15 and T1-T7, as well as the solid content of the resin compositions S1-S15 and T1-T7, were determined. The results are presented in Tables 3 and 4. The determination methods are described below.

[0252] [i] Number-average molecular weight Mn

[0253] The number-average molecular weights (Mn) of monomer (a), monomer (a'), and resin are converted from the number-average molecular weights of polystyrene determined by GPC. The determination conditions are as follows.

[0254] Device: Tosoh Corporation "HLC-8220GPC"

[0255] Chromatographic column: TSKgel SuperHZM-M ×2

[0256] Eluent: Tetrahydrofuran

[0257] Measurement temperature: 35℃

[0258] Detector: RI

[0259] [ii] Solid content

[0260] The solid content of the resin composition is calculated using the following formula.

[0261] Solid content (mass%) = 100 × (total mass of raw materials used in the preparation of the solvent-removed resin composition) / (mass of the obtained resin composition)

[0262] [Table 3]

[0263]

[0264] [Table 4]

[0265]

[0266] <Resin Manufacturing Examples S16 and T8: Manufacturing of Resins S16 and T8>

[0267] In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, xylene [A] parts by mass as solvent was added, and the temperature was maintained at 95°C. Then, a mixture consisting of 100 parts by mass of the monomers shown in Table 7 (in parts by mass), xylene [B] parts by mass as solvent, and tert-butyl peroxide-2-ethylhexanoate [C] parts by mass as free radical polymerization initiator was added to the dropping funnel and added dropwise to the four-necked flask at a constant rate for 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 40 parts by mass of xylene and 0.3 parts by mass of tert-butyl peroxide-2-ethylhexanoate was added dropwise to the four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for [D] hours, thereby obtaining a resin composition (solution) containing a resin having a carboxyl group. The solid content of this resin composition was [E] by mass.

[0268] Next, in the same reaction vessel, 100 parts by mass of the above resin composition, parts by mass of copper acetate (II) [F], parts by mass of compound [G][H], and 60 parts by mass of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, n-butanol and xylene were added to obtain a resin composition (solution) containing the resin. The resin contained in this resin composition is a resin with carboxyl groups whose carboxyl groups have been converted to -COO. - Cu 2+ ( - The resin obtained by OOC-Y. Y is the structural part of compound [G] other than the carboxyl group.

[0269] The values ​​of [A] to [H] in resin manufacturing examples S16 and T8 are summarized in Table 5.

[0270] [Table 5]

[0271]

[0272] In Table 5, G1 and G2 represent the following.

[0273] G1: Hydrogenated rosin (HYPALE CH, acid value 160 mg KOH / g, manufactured by Arakawa Chemical Industry Co., Ltd.)

[0274] G2: WW Rosin (WW Rosin, acid value 160mgKOH / g, manufactured by Arakawa Chemical Industry Co., Ltd.)

[0275] Hereinafter, the resins obtained in resin manufacturing examples S16 and T8 will be referred to as "resin S16" and "T8", respectively, and the resin compositions (solutions) obtained in resin manufacturing examples S16 and T8 will be referred to as "resin compositions S16" and "T8", respectively.

[0276] <Resin Manufacturing Examples S17 and T9: Manufacturing of Resins S17 and T9>

[0277] In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, xylene [A] parts by mass as solvent was added, and the temperature was maintained at 100°C. Then, a mixture consisting of 100 parts by mass of the monomers shown in Table 7 (in parts by mass), xylene [B] parts by mass as solvent, and tert-butyl peroxide-2-ethylhexanoate [C] parts by mass as free radical polymerization initiator was added to the dropping funnel and added dropwise to the four-necked flask at a constant rate for 3 hours. After the addition was completed, the mixture was kept at the temperature for [D] minutes. Then, a mixture consisting of xylene [E] parts by mass and 0.3 parts by mass of tert-butyl peroxide-2-ethylhexanoate was added dropwise to the four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for [F] hours, thereby obtaining a resin composition (solution) containing a resin having a carboxyl group. The solid content of this resin composition is [G] by mass.

[0278] Next, in the same reaction vessel, 100 parts by mass of the above resin composition, parts by mass of zinc acetate (II) [H], parts by mass of compound [I][J], and 60 parts by mass of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, n-butanol and xylene were added to obtain a resin composition (solution) containing the resin. The resin composition contains a resin in which the carboxyl groups of the above-mentioned carboxyl-containing resin are converted to -COO. - Zn 2+ ( -The resin obtained by OOC-Y. Y is the structural part of compound [I] other than the carboxyl group.

[0279] The values ​​of [A] to [J] in resin manufacturing examples S17 and T9 are summarized in Table 6.

[0280] [Table 6]

[0281]

[0282] In Table 6, I1 and I2 represent the following.

[0283] I1: Naphthenic acid (NA-200, acid value 200mgKOH / g, manufactured by Daiwa Oil & Fat Co., Ltd.)

[0284] I2: Naphthenic acid (NA-165, acid value 165 mg KOH / g, manufactured by Daiwa Oil & Fat Co., Ltd.)

[0285] Hereinafter, the resins obtained in resin manufacturing examples S17 and T9 will be referred to as "resin S17" and "T9", respectively, and the resin compositions (solutions) obtained in resin manufacturing examples S17 and T9 will be referred to as "resin compositions S17" and "T9", respectively.

[0286] The monomers used in resin manufacturing examples S16-S17 and T8-T9, and their amounts (parts by mass), are shown in Table 7. Table 7 shows the monomers used in the manufacture of resins containing carboxyl groups.

[0287] According to the above determination method, the number-average molecular weight Mn of the obtained resins S16-S17 and T8-T9, and the solid content of the resin compositions S16-S17 and T8-T9 were determined. The results are shown in Table 7. The number-average molecular weight Mn refers to the molecular weight of the resin containing carboxyl groups (the carboxyl groups were converted to -COO). - Me 2+ ( - The determination was performed on the resin before the reaction of OOC-Y. Me is either Cu or Zn.

[0288] [Table 7]

[0289]

[0290] The detailed information on the abbreviations of the monomers shown in Tables 3, 4 and 7 is as follows.

[0291] (1) FM-0721: "FM-0721" manufactured by JNC Corporation, a single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 5000, in formula (Ⅰ'), m=0, b=3, n=65, R 1 ~R4 and R 31 It is methyl, R 5 Monomer of n-butyl

[0292] (2) FM-0725: "FM-0725" manufactured by JNC Corporation, a single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 10000, in formula (Ⅰ'), m=0, b=3, n=132, R 1 ~R 4 and R 31 It is methyl, R 5 Monomer of n-butyl

[0293] (3) KF-2012: “KF-2012” manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4600, in formula (Ⅰ'), m=0, R 1 ~R 5 and R 31 Monomer of methyl

[0294] (4) X-22-2426: X-22-2426 manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl modified organopolysiloxane, with a molecular weight of 12000. In formula (Ⅰ'), m=0, R 1 ~R 5 and R 31 Monomer of methyl

[0295] (5) FM-7721: "FM-7721" manufactured by JNC Corporation, a two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 5000, in formula (Ⅲ'), q and s=0, f and g=3, r=64, R 9 ~R 12 R 33 and R 34 Monomer of methyl

[0296] (6) FM-7725: "FM-7725" manufactured by JNC Corporation, a two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 10000, in formula (Ⅲ'), q and s=0, f and g=3, r=131, R 9 ~R 12 R 33 and R 34 Monomer of methyl

[0297] (7) X-22-164B: X-22-164B manufactured by Shin-Etsu Chemical Co., Ltd., a two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 3200, in formula (Ⅲ'), q and s=0, R 9 ~R 12 R 33 and R 34 Monomer of methyl

[0298] (8) X-22-164E: X-22-164E manufactured by Shin-Etsu Chemical Co., Ltd., a two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 7800, in formula (Ⅲ'), q and s=0, R 9 ~R 12 R 33 and R 34 Monomer of methyl

[0299] (9) FM-0711: "FM-0711" manufactured by JNC Corporation, a single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 1000, in formula (Ⅰ'), m=0, b=3, n=10, R 1 ~R 4 and R 31 It is methyl, R 5 Monomer of n-butyl

[0300] (10) X-22-174ASX: X-22-174ASX manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 900, in formula (Ⅰ'), m=0, R 1 ~R 5 and R 31 Monomer of methyl

[0301] (11) X-22-174BX: X-22-174BX manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 2300, in formula (Ⅰ'), m=0, R 1 ~R 5 and R 31 Monomer of methyl

[0302] (12) FM-7711: "FM-7711" manufactured by JNC Corporation, a two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 1000, in formula (Ⅲ'), q and s=0, f and g=3, r=10, R 9 ~R 12 R 33 and R 34 Monomer of methyl

[0303] (13) TIPSA: Triisopropylsilyl acrylate

[0304] (14) TIPSMA: Triisopropylsilyl methacrylate

[0305] (15) t-BMA: tert-butyl methacrylate (SP: 9.4)

[0306] (16) n-BMA: n-butyl methacrylate (SP: 9.3)

[0307] (17) EHMA: 2-Ethylhexyl methacrylate (SP: 8.3)

[0308] (18) n-BA: n-butyl acrylate (SP: 9.5)

[0309] (19) MMA: Methyl methacrylate (SP: 10.7)

[0310] (20) EA: Ethyl acrylate (SP: 10.5)

[0311] (21) CHMA: Cyclohexyl methacrylate (SP: 9.1)

[0312] (22) AA: Acrylic acid (SP: 23.8)

[0313] In the above, SP is the solubility parameter of the homopolymer of the monomer, which is determined according to the method described above.

[0314] <Examples 1-24, Comparative Examples 1-11>

[0315] According to the proportions (parts by mass) in Tables 8 to 11, an antifouling coating composition is prepared by mixing any of the resin compositions obtained in the manufacturing examples and other components shown in Tables 8 to 11 using a high-speed disperser. The proportions (parts by mass) shown in Tables 8 to 11 are tangible proportions, and in the case of solvents, they are proportions containing solvents, etc.

[0316] (Evaluation of resin compositions and antifouling coating compositions)

[0317] [a] Evaluation of the transparency of coatings formed from resin compositions

[0318] The resin compositions obtained in each manufacturing example were coated onto a glass plate, and the dried film thickness was 100 μm. The plates were then dried indoors for two days and nights to obtain test plates with a coating formed solely of resin. The transparency of the coating was evaluated visually according to the following criteria. The evaluation results are shown in Tables 8 to 11. A result of 5 is preferred.

[0319] 5: Transparent coating

[0320] 3: The coating is semi-transparent.

[0321] 1: Whitening of the coating

[0322] [b] Evaluation of the dynamic antifouling properties of coatings formed from antifouling paint compositions (open drum test)

[0323] The antifouling coating compositions obtained in the examples and comparative examples were applied to sandblasted plates pre-coated with anti-rust coatings, and the dried film thickness was 300 μm. The plates were then dried indoors for 2 days and nights to obtain test plates with antifouling coatings.

[0324] The obtained test plate was mounted on the side of a rotating cylinder and rotated approximately 10 nautical miles per hour in natural seawater for 24 months. The attachment area of ​​marine organisms was determined, and the results were evaluated according to the following criteria. The evaluation results at 6, 12, 18, and 24 months are shown in Tables 8 to 11. An evaluation result of 3 or higher is preferred.

[0325] 5: The surface area covered by marine organisms is between 0% and 5%.

[0326] 4: The surface area covered by marine organisms is more than 5% but less than 10%.

[0327] 3: The surface area covered by marine organisms is more than 10% but less than 15%.

[0328] 2: The surface area covered by marine organisms is more than 15% but less than 30%.

[0329] 1: The attachment area of ​​marine organisms is over 30%.

[0330] [c] Evaluation of the static antifouling properties of coatings formed from antifouling paint compositions (raft static antifouling test)

[0331] The antifouling coating compositions obtained in the examples and comparative examples were applied to sandblasted plates pre-coated with anti-rust coatings, and the dried film thickness was 300 μm. The plates were then dried indoors for 2 days and nights to obtain test plates with antifouling coatings.

[0332] The obtained test plates were immersed in a raft in Aioi Bay, Ako City, Hyogo Prefecture, for a 24-month bioattachment experiment. The attachment area of ​​marine organisms was determined, and the results were evaluated according to the following criteria. The evaluation results at 6, 12, 18, and 24 months are shown in Tables 8 to 11. An evaluation result of 3 or higher is preferred.

[0333] 5: The surface area covered by marine organisms is between 0% and 5%.

[0334] 4: The surface area covered by marine organisms is more than 5% but less than 10%.

[0335] 3: The surface area covered by marine organisms is more than 10% but less than 15%.

[0336] 2: The surface area covered by marine organisms is more than 15% but less than 30%.

[0337] 1: The attachment area of ​​marine organisms is over 30%.

[0338] [Table 8]

[0339]

[0340] [Table 9]

[0341]

[0342] [Table 10]

[0343]

[0344] [Table 11]

[0345]

[0346] The details of each component recorded in Tables 8 to 11 are as follows.

[0347] (1) Defoamer: BYK-066N manufactured by BYK Corporation, non-volatile component: 0.7% by mass

[0348] (2) Plasticizer: BASF's "LUTONAL A25", polyvinyl ether, non-volatile component: 95% by mass

[0349] (3) Pigment 1: DuPont's "TI-PURE R-900", titanium dioxide pigment

[0350] (4) Pigment 2: Bayferox 130, iron oxide red pigment manufactured by Lanxess.

[0351] (5) Anti-sagging agent: HS CHEM "MONORAL3300", non-volatile component: 20% by mass.

Claims

1. A coating composition comprising a silicon atom-containing resin, wherein the silicon atom-containing resin comprises: a structural unit (A) derived from a monomer (a) having at least one silicon atom-containing group selected from the group consisting of a group represented by the following formula (I), a group represented by the following formula (II), a group represented by the following formula (III), and a group represented by the following formula (IV); a structural unit (B) derived from a monomer (b) having a triorganosiloxy carbonyl group; a structural unit (C) derived from a monomer (c) other than the monomer (a) and the monomer (b); the molecular weight of the monomer (a) is greater than 2500; the monomer (b) is a monomer (bl) represented by the following formula (VII); the monomer (c) is a monomer having a solubility parameter SP of 9.0 or greater and 9.5 or less of a homopolymer thereof and does not have a cyclic structure; the monomer (c) is an alkyl (meth)acrylate represented by the following formula: the content of the structural unit (A) is 11% by mass or greater in all the structural units contained in the silicon atom-containing resin; the content of the structural unit (C) is 1% by mass or greater and 60% by mass or less in all the structural units contained in the silicon atom-containing resin; [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] the monomer (a) is at least one selected from the group consisting of a monomer (al) represented by the following formula (I'), a monomer (a2) represented by the following formula (II'), a monomer (a3) represented by the following formula (III'), and a monomer (a4) represented by the following formula (IV'); [Chemical Formula 8] [Chemical Formula 9] [Chemical Formula 10] [Chemical Formula 11] the content of the structural unit (B) is 5% by mass or greater and 40% by mass or less in all the structural units contained in the silicon atom-containing resin. The coating composition further comprises at least one selected from the group consisting of an antifoaming agent and an anti-sagging agent. The silicon atom-containing resin further has a structural unit (D) derived from a monomer (d) having at least one metal atom-containing group selected from the group consisting of a group represented by the following formula (V) and a group represented by the following formula (VI); [Chemical Formula 12] [Chemical Formula 13] In formula (VI), M represents a divalent metal atom. The monomer (d) is at least one selected from the group consisting of a monomer (dl) represented by the following formula (V') and a monomer (d2) represented by the following formula (VI'); [Chemical Formula 14] [Chemical Formula 15] 7. A coating film formed from the coating composition of claim 1. A primer coating film formed from an antirust coating material; CH2=C(R A )(COOR B ) and a coating film formed from the coating composition of claim 1 layered on the primer coating film. wherein, R A is a hydrogen atom or a methyl group, R B is a chain alkyl group having 3 or more carbon atoms; 9. A ship comprising the coating film of claim 7 or the composite coating film of claim 8.

10. An underwater structure comprising the coating film of claim 7 or the composite coating film of claim 8. ​ In formula (I), a and b each independently represent any one of an integer from 2 to 5, m represents any one of an integer from 0 to 50, n represents any one of an integer from 3 to 270; R 1 to R 5 each independently represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group; ​ In formula (II), c and d each independently represent any one of integers from 2 to 5, p represents any one of integers from 0 to 50; R 6 , R 7 , and R 8 each independently represent an alkyl group, R a , or R b ; R a is ​ wherein x represents any integer from 0 to 200, R 23 to R 27 are the same or different, each representing an alkyl group; R b is ​ wherein y represents any integer from 1 to 200; R 28 and R 29 are the same or different, each representing an alkyl group; ​ In formula (III), e, f, g, and h each independently represent any one of integers from 2 to 5, q and s each independently represent any one of integers from 0 to 50, r represents any one of integers from 3 to 270; R 9 to R 12 each independently represent an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group; ​ In formula (IV), i, j, k, and l each independently represent any one of integers from 2 to 5, t and u each independently represent any one of integers from 0 to 50, v and w each independently represent any one of integers from 0 to 70; R 13 to R 22 are the same or different, each represent an alkyl group; ​ In formula (VII), R 43 represents a hydrogen atom or a methyl group, R 40 , R 41 , and R 42 are the same or different, and each represents a hydrocarbon group having 1 to 20 carbon atoms.

2. The coating composition according to claim 1, wherein, ​ ​ In the formula (I'), R 31 represents a hydrogen atom or a methyl group, a, b, m, n and R 1 to R 5 represent the same meanings as described above; ​ In the formula (II'), R 32 represents a hydrogen atom or a methyl group, c, d, p and R 6 to R 8 represent the same meanings as described above; ​ In the formula (III), R 33 and R 34 each independently represents a hydrogen atom or a methyl group, e, f, g, h, q, r, s and R 9 to R 12 represent the same meanings as described above; ​ In the formula (IV), R 35 and R 36 each independently represents a hydrogen atom or a methyl group, i, j, k, 1, t, u, v, w and R 13 to R 22 represent the same meanings as described above.

3. The coating composition according to claim 1 or 2, wherein, ​ 4. The coating composition according to claim 1 or 2, wherein, ​ 5. The coating composition according to claim 1 or 2, wherein, ​ ​ In formula (V), M represents a divalent metal atom, R 30 represents an organic acid residue or an alcohol residue; ​ ​ 6. The coating composition according to claim 5, wherein, ​ ​ In the formula (V), R 37 represents a hydrogen atom or a methyl group, M and R 30 represent the same meanings as described above; ​ In the formula (VI), R 38 and R 39 each independently represents a hydrogen atom or a methyl group, and M represents the same meaning as described above. ​ 8. A composite coating film comprising: ​ ​ ​ ​

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