Coating composition and coating film

Abstract

Provided is a coating composition comprising a silicon atom-containing resin, the silicon atom-containing resin comprising: a structural unit (A) which is a structural unit derived from a monomer (a) having at least one silicon atom-containing group selected from the group consisting of groups represented by formula (I), formula (II), formula (III), and formula (IV); a structural unit (B) that is a structural unit derived from a monomer (b) that is a (meth) acrylic acid ester represented by formula (b); 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 content of the structural unit (A) in all the structural units is greater than 20% by mass; the monomer (c) is a monomer which has a homopolymer solubility parameter SP of 9.5 or less and does not have a cyclic structure; the content of the constituent unit (C) in all the constituent units is greater than 2 mass%.

Description

Technical Field

[0001] The present invention relates to a coating composition containing a silicon atom-containing resin, a coating film formed from the coating composition, a composite coating film having the coating film, and a ship and an underwater structure having the coating film or the composite coating film. Background Art

[0002] In ships, the attachment of organisms such as barnacles, mussels, and algae can hinder efficient operation and lead to problems such as fuel waste. In the past, in order to prevent the attachment of organisms, an antifouling coating composition was applied to the surface of the ship. For example, in International Publication No. 2011 / 046086 (Patent Document 1), an antifouling coating composition is disclosed, which includes a silicon atom-containing resin as a carrier, and a thermoplastic resin and / or a plasticizer.

[0003] Prior art literature

[0004] Patent Literature

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

[0006] Problems to be solved by the invention

[0007] When the object to be coated with the antifouling coating composition is an object moving in water (eg, seawater) such as a ship, the coating film formed by the antifouling coating composition is required to exhibit good antifouling performance while the object is moving.

[0008] The object of the present invention is to provide a coating composition which can exert good antifouling performance during the movement of the coated object. Another object of the present invention is to provide a coating film formed by the coating composition and a composite coating film having the coating film, as well as a ship and an underwater structure having the coating film or the composite coating film.

[0009] Means of solving problems

[0010] The present invention provides the following coating composition, coating film, composite coating film, ship and underwater structure.

[0011] [1] A coating composition comprising a silicon atom-containing resin, wherein the silicon atom-containing resin comprises:

[0012] Structural unit (A), wherein the structural unit (A) is a structural unit derived from a monomer (a), wherein the monomer (a) has at least one silicon-atom-containing group selected from 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);

[0013] A structural unit (B), the structural unit (B) being a structural unit derived from a monomer (b) which is a (meth)acrylate represented by the following formula (b);

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

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

[0016] The content of the structural unit (A) is greater than 20% by mass among all the structural units contained in the silicon atom-containing resin;

[0017] The monomer (c) is a monomer having a solubility parameter SP of a homopolymer of 9.5 or less and having no cyclic structure;

[0018] The content of the structural unit (C) is greater than 2% by mass among all the structural units contained in the silicon atom-containing resin;

[0019] [Chemical formula 1]

[0020]

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

[0022] [Chemical formula 2]

[0023]

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

[0025] Ra is

[0026] [Chemical formula 3]

[0027]

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

[0033] [Chemical formula 5]

[0034]

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

[0036] [Chemical formula 6]

[0037]

[0038] In formula (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, v and w each independently represent any integer from 0 to 70; R 13 ~R 22 The same or different, represents an alkyl group;

[0039] CH 2 =C(R A )(COOR B ) (b)

[0040] In formula (b), R A represents a hydrogen atom or a methyl group; R B It represents a monovalent group including one or more selected from the group consisting of a hydroxyl group, a carboxyl group, and an oxyalkylene chain.

[0041] [2] The coating composition according to [1], wherein R in the formula (b) B It represents a monovalent group containing an oxyalkylene chain.

[0042] [3] The coating composition according to [1] or [2], wherein the monomer (a) is at least one selected from the group consisting of a monomer (a1) 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');

[0043] [Chemical formula 7]

[0044]

[0045] In formula (I'), R 31 represents a hydrogen atom or a methyl group, a, b, m, n and R 1 ~R 5 Means the same as above;

[0046] [Chemical formula 8]

[0047]

[0048] In formula (II'), R 32 represents a hydrogen atom or a methyl group, c, d, p and R 6 ~R 8 Means the same as above;

[0049] [Chemical formula 9]

[0050]

[0051] In formula (III'), R 33 and R 34 Each independently represents a hydrogen atom or a methyl group, and e, f, g, h, q, r, s and R 9 ~R 12 Means the same as above;

[0052] [Chemical formula 10]

[0053]

[0054] In formula (IV'), R 35 and R 36 Each independently represents a hydrogen atom or a methyl group, and i, j, k, l, t, u, v, w and R 13 ~R 22 Means the same as above.

[0055] [4] The coating composition according to any one of [1] to [3], further comprising a structural unit (D) derived from a monomer (d) having a triorganosiloxycarbonyl group.

[0056] [5] The coating composition according to [4], wherein the monomer (d) is a monomer (d1) represented by the following formula (VII');

[0057] [Chemical formula 11]

[0058]

[0059] In formula (VⅡ'), R 43 represents a hydrogen atom or a methyl group, R 40 , R 41 and R 42 The same or different groups represent a hydrocarbon group having 1 to 20 carbon atoms.

[0060] [6] The coating composition according to any one of [1] to [5], wherein the content of the structural unit (B) is 1% by mass or more and 30% by mass or less of all the structural units contained in the silicon atom-containing resin.

[0061] [7] The coating composition according to any one of [1] to [6], wherein the solubility parameter SP of the homopolymer of the monomer (b) is 10.0 or more.

[0062] [8] The coating composition according to any one of [1] to [7], further comprising at least one selected from a defoaming agent and an anti-sagging agent.

[0063] [9] The coating composition according to any one of [1] to [8], wherein the silicon atom-containing resin further comprises a structural unit (E) derived from a monomer (e), wherein the monomer (e) comprises at least one metal atom-containing group selected from a group represented by the following formula (V) and a group represented by the following formula (VI);

[0064] [Chemical formula 12]

[0065]

[0066] In formula (V), M represents a divalent metal atom, R 30 represents an organic acid residue or an alcohol residue;

[0067] [Chemical formula 13]

[0068]

[0069] In formula (VI), M represents a divalent metal atom.

[0070]

[10] The coating composition according to [9], wherein the monomer (e) is at least one selected from a monomer (e1) represented by the following formula (V') and a monomer (e2) represented by the following formula (VI');

[0071] [Chemical formula 14]

[0072]

[0073] In formula (V'), R 37 Represents a hydrogen atom or a methyl group, M and R 30 Means the same as above;

[0074] [Chemical formula 15]

[0075]

[0076] In formula (VI'), R 38 and R 39 Each independently represents a hydrogen atom or a methyl group, and M has the same meaning as above.

[0077]

[11] A coating film formed from the coating composition according to any one of [1] to

[10] .

[0078]

[12] A composite coating film comprising: a primer coating film formed of an anti-rust paint; and a coating film formed of the coating composition described in any one of [1] to

[10] laminated on the primer coating film.

[0079]

[13] A ship having the coating described in

[11] or the composite coating described in

[12] .

[0080]

[14] An underwater structure having the coating described in

[11] or the composite coating described in

[12] .

[0081] Effects of the Invention

[0082] A coating composition can be provided, which can exert good antifouling performance during the movement of the coated object. In addition, a coating film formed by the coating composition and a composite coating film having the coating film, as well as a ship and an underwater structure having the coating film or the composite coating film can be provided. DETAILED DESCRIPTION

[0083] <Coating composition>

[0084] The coating composition of the present invention (hereinafter, also referred to as "coating composition") contains a specific silicon atom-containing resin described later. According to the coating composition of the present invention, a coating film that exerts good antifouling performance during the movement of the coated object can be formed. In addition, according to the coating composition of the present invention, a coating film that exerts good antifouling performance for a long time during the movement of the coated object can be formed. Hereinafter, the antifouling performance during the movement is also referred to as "dynamic antifouling property". The coating composition of the present invention can be preferably used as an antifouling coating composition suitable for underwater mobile bodies such as ships.

[0085] Hereinafter, the components contained or which may be contained in the coating composition will be described in detail.

[0086] (1) Silicon-containing resin

[0087] The silicon-containing resin contained in the coating composition includes structural units (A), structural units (B) and structural units (C). Structural unit (A) is a structural unit derived from monomer (a), and monomer (a) has at least one silicon-containing group selected from the group represented by the above formula (I), the group represented by the above formula (II), the group represented by the above formula (III) and the group represented by the above formula (IV). Structural unit (B) is a structural unit derived from monomer (b), and monomer (b) is a (meth)acrylate represented by the above formula (b). Structural unit (C) is a structural unit derived from monomer (c), and monomer (c) is a (meth)acrylate represented by the above formula (b).

[0088] (c) is a monomer other than monomer (a) and monomer (b), and its homopolymer has a solubility parameter SP of 9.5 or less and does not have a cyclic structure. The silicon-atom-containing resin may contain a structural unit derived from other monomers other than monomer (a), monomer (b) and monomer (c). An example of the structural unit is structural unit (D), which is derived from a monomer (d) having a triorganosiloxycarbonyl group.

[0089] (1-1) Silicon-containing groups

[0090] The silicon atom-containing group contained in the monomer (a) is at least one selected from the group represented by the above formula (I), the group represented by the above formula (II), the group represented by the above formula (III) and the group represented by the above formula (IV).

[0091] In formula (I), a and b each independently represent an integer of 2 to 5, m represents an integer of 0 to 50, and n represents an integer of 3 to 270. 1 ~R 5 Each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

[0092] In formula (II), c and d each independently represent an integer of 2 to 5, and p represents an integer of 0 to 50. 6 , R 7 and R 8 Each independently represents an alkyl group, R a or R b .

[0093] In R a In the formula, x represents any integer from 0 to 200. 23 ~R 27 The same or different groups represent an alkyl group.

[0094] In R b In the formula (a), y represents any integer from 1 to 200. 28 and R 29 The same or different groups represent an alkyl group.

[0095] In formula (III), e, f, g and h each independently represent an integer of 2 to 5, q and s each independently represent an integer of 0 to 50, and r represents an integer of 3 to 270. 9 ~R 12 Each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

[0096] In formula (IV), i, j, k and l each independently represent an integer of 2 to 5, t and u each independently represent an integer of 0 to 50, and v and w each independently represent an integer of 0 to 70. 13 ~R 22 The same or different groups represent an alkyl group.

[0097] The silicon-atom-containing resin may have two or more silicon-atom-containing groups selected from the group represented by the above formula (I), the group represented by the above formula (II), the group represented by the above formula (III), and the group represented by the above formula (IV). In this case, it may also have two or more groups represented by the above formula (I), two or more groups represented by the above formula (II), two or more groups represented by the above formula (III), and / or two or more groups represented by the above formula (IV).

[0098] A preferred example of the silicon atom-containing resin is a (meth)acrylic resin having a silicon atom-containing group. In the present specification, "(meth)acrylic acid" means at least one of methacrylic acid and acrylic acid.

[0099] (1-2) Monomer (a)

[0100] Monomer (a) is preferably at least one selected from the group consisting of monomer (a1) represented by the above formula (I'), monomer (a2) represented by the above formula (II'), monomer (a3) ​​represented by the above formula (III'), and monomer (a4) represented by the above formula (IV'). By polymerizing a monomer composition containing such a monomer (a), a silicon-containing resin as a (meth)acrylic resin containing 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 group represented by the above formula (I), the group represented by the above formula (II), the group represented by the above formula (III), and the group represented by the above formula (IV).

[0101] The silicon atom-containing resin may contain two or more structural units (A) derived from the monomer (a).

[0102] In formula (I'), R 31 represents a hydrogen atom or a methyl group, a, b, m, n and R 1 ~R 5 Means the same as above.

[0103] In formula (II'), R 32 represents a hydrogen atom or a methyl group, c, d, p and R 6 ~R 8 Means the same as above.

[0104] In formula (III'), R 33 and R 34 Each independently represents a hydrogen atom or a methyl group, and e, f, g, h, q, r, s and R 9 ~R 12 Means the same as above.

[0105] In formula (IV'), R 35 and R 36 Each independently represents a hydrogen atom or a methyl group, and i, j, k, l, t, u, v, w and R 13 ~R 22 Means the same as above.

[0106] The monomer (a1) represented by the above formula (I'), the monomer (a2) represented by the above formula (II'), the monomer (a3) ​​represented by the above formula (III') and the monomer (a4) represented by the above formula (IV') are each a silicon atom-containing polymerizable monomer having a group represented by the above formula (I), a group represented by the above formula (II), a group represented by the above formula (III) and a group represented by the above formula (IV).

[0107] The molecular weight of monomer (a) is greater than 2500. According to the coating composition containing a silicon-containing resin, and the silicon-containing resin contains a structural unit (A) derived from such a monomer (a) with a large molecular weight, under the premise that the content of the structural unit (A) in the silicon-containing resin is within the specified range described below, the silicon-containing resin also contains a specified structural unit (B) and a structural unit (C), and the content of the structural unit (C) in the silicon-containing resin is within the specified range described below, the coating film formed by the coating composition can obtain 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 a polystyrene-converted number average molecular weight measured by gel permeation chromatography (GPC).

[0108] As at least one major factor for obtaining excellent dynamic antifouling properties, it is speculated that the silicon-containing resin has a silicon-containing side chain with a large molecular weight, thereby generating an oil-like film on the surface of the coating film moving in water, thereby increasing the high smoothness of the coating film surface, the high elasticity of the coating film, and the low interfacial free energy between the coating film and water. In addition, it is also speculated that the silicon-containing resin further contains a hydrophilic structural unit (B) derived from the monomer (b), thereby forming a hydrophobic-hydrophilic region-like structure in which micro-scale hydrophilic regions are randomly distributed on the surface of the coating film, thereby easily inhibiting the attachment of organisms.

[0109] From the viewpoint of being able to further improve the dynamic antifouling property, 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 usually 20000 or less, preferably 18000 or less, more preferably 15000 or less, and further preferably 12000 or less. When the molecular weight of monomer (a) is too large, due to the incompatibility of monomers in the monomer composition of the mixture of monomers used in the preparation of the silicon-containing resin, or the incompatibility of polymers generated by the polymerization of the monomer composition, the coating formed by the coating composition is prone to become uneven in its composition, and then the coating property may be reduced. One method for confirming whether the coating is uneven in its composition is to make a coating formed only by the silicon-containing resin, and confirm whether the coating is transparent. If the coating is transparent, it can be said that its composition is uniform, and if it is turbid, it can be said to be uneven.

[0110] However, by containing a predetermined amount of a structural unit (C) derived from a monomer (c) described below in the silicon atom-containing resin, a coating film having a uniform composition can be easily obtained even when a monomer (a) having a large molecular weight is used.

[0111] The monomer (a) may be a combination of two or more monomers belonging to the monomer (a). The two or more monomers may have different molecular weights as long as they are greater than 2,500.

[0112] The monomer (a1) is represented by the above formula (I'). By using the monomer (a1) as the monomer (a), a silicon-containing resin can be obtained which is a (meth)acrylic resin having a silicon-containing group represented by the above formula (I) in a side chain.

[0113] The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a1).

[0114] The same also applies to formula (I). In formula (I'), a is preferably 2 or 3.

[0115] b is preferably 2 or 3.

[0116] From the viewpoint of water resistance of the coating film, adhesion to the substrate, etc., m is preferably 0 to 25, more preferably 0 to 20. m may be 3 or more or 5 or more, or 10 or less or 8 or less.

[0117] From the viewpoint of antifouling properties of the coating film and solubility in common organic solvents, n is usually 3 to 270, preferably 35 to 245, more preferably 45 to 205, further preferably 45 to 160.

[0118] R 1 ~R 5 The substituents of the substituted phenyl group and the substituted phenoxy group are, for example, an alkyl group and a halogen atom.

[0119] R 1 ~R 5 It is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, further 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 a methyl or ethyl group.

[0120] As the monomer (a1), commercially available products may also be used. Commercially available products having a molecular weight greater than 2500, for example, are all represented by trade names, such as "FM-0721" (single-end methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5000), "FM-0725" (single-end methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 10000) manufactured by JNC Corporation, "KF-2012" (single-end methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 4600), "X-22-2426" (single-end methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 12000) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0121] Monomer (a2) is represented by the above formula (II'). By using monomer (a2) as monomer (a), a silicon-containing resin as a (meth) acrylic resin having a silicon-containing group represented by the above formula (II) in the side chain can be obtained. Commercially available products can also be used as monomer (a2).

[0122] The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a2).

[0123] The same also applies to formula (II). In formula (II'), c is preferably 2 or 3.

[0124] d is preferably 2 or 3.

[0125] From the viewpoint of water resistance of the coating film, adhesion to the substrate, etc., p is preferably 0 to 25, more preferably 0 to 20. p may be 3 or more or 5 or more, or 10 or less or 8 or less.

[0126] From the viewpoint of solubility in common organic solvents, x is usually 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.

[0127] From the viewpoint of solubility in common organic solvents, y is usually 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.

[0128] R 6 ~R 8 and R 23 ~R 29 The alkyl group in 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, further preferably methyl or ethyl.

[0129] R 6 ~R 8 All are preferably alkyl groups.

[0130] Monomer (a3) ​​is represented by the above formula (III'). By using monomer (a3) ​​as monomer (a), a silicon-containing resin as a (meth)acrylic resin having a silicon-containing group represented by the above formula (III) (the silicon-containing group is a crosslinking group that crosslinks the main chains of the polymer) can be obtained.

[0131] The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a3).

[0132] The same also applies to formula (III). In formula (III), e and h are preferably 2 or 3 each.

[0133] f and g are preferably 2 or 3, respectively.

[0134] From the viewpoints of water resistance of the coating film, adhesion to the substrate, etc., q and s are each preferably 0 to 30, more preferably 0 to 25, and even more preferably 0 to 20. q and s may each be 3 to 5, or 10 to 8.

[0135] From the viewpoint of antifouling properties of the coating film, solubility in common organic solvents, etc., r is usually 3 to 270, preferably 35 to 245, more preferably 45 to 205, and further preferably 45 to 160.

[0136] R 9 ~R 12 The substituents of the substituted phenyl group and the substituted phenoxy group are, for example, an alkyl group and a halogen atom.

[0137] R 9 ~R 12 It is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, further 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 a methyl or ethyl group.

[0138] As the monomer (a3), a commercially available product may be used. Examples of commercially available products having a molecular weight greater than 2500 are denoted by trade names, such as “FM-7721” (organopolysiloxane modified with methacryloxyalkyl at both ends, molecular weight: 5000) and “FM-7725” (organopolysiloxane modified with methacryloxyalkyl at both ends, molecular weight: 10000) manufactured by JNC Corporation, “X-22-164B” (organopolysiloxane modified with methacryloxyalkyl at both ends, molecular weight: 3200) and “X-22-164C” (organopolysiloxane modified with methacryloxyalkyl at both ends, molecular weight: 4800) manufactured by Shin-Etsu Chemical Co., Ltd., “X-22-164E” (organopolysiloxane modified with methacryloxyalkyl at both ends, molecular weight: 7800) and “X-22-2445” (organopolysiloxane modified with acryloxyalkyl at both ends, molecular weight: 3200) and the like.

[0139] Monomer (a4) is represented by the above formula (IV'). By using monomer (a4) as monomer (a), a silicon-containing resin as a (meth) acrylic resin having a silicon-containing group represented by the above formula (IV) (the silicon-containing group is a cross-linking group that cross-links the main chains of the polymer) can be obtained. Commercially available products can also be used as monomer (a4).

[0140] The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a4).

[0141] The same also applies to formula (IV). ] i and l in formula (IV') are preferably 2 or 3 each.

[0142] j and k are preferably 2 or 3, respectively.

[0143] From the viewpoint of water resistance of the coating film, adhesion to the substrate, etc., t and u are each preferably 0 to 30, more preferably 0 to 25, and even more preferably 0 to 20. q and s may each be 3 to 5, or 10 to 8.

[0144] From the viewpoint of antifouling properties of the coating film, solubility in ordinary organic solvents, and the like, v and w are usually 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.

[0145] R 13 ~R 22 The alkyl group in 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, further preferably methyl or ethyl.

[0146] Referring to the above description, the molecular weight of monomer (a) is greater than 2500 and a to n, p to y and R are appropriately selected. 1 ~R 29 .

[0147] From the viewpoint of improving dynamic antifouling properties and facilitating the acquisition of commercial products, the monomer (a) is preferably at least one selected from the group consisting of the monomer (a1) and the monomer (a3). As the monomer (a), a combination of the monomer (a1) and the monomer (a3) ​​is also preferably used.

[0148] From the viewpoint of dynamic antifouling property and static antifouling property (antifouling property when the antifouling coating film is statically placed in water (seawater)), the content of the structural unit (A) derived from the monomer (a) in all the structural units contained in the silicon atom-containing resin is greater than 20% by mass, preferably 21% by mass or more, more preferably 25% by mass or more, and may also be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 50% by mass or more. By making the content of the structural unit (A) greater than 20% by mass, a coating composition showing sufficient dynamic antifouling property can be obtained even without additionally containing an antifouling agent. In addition, from the viewpoint of the physical properties of the coating film and the uniformity of the above-mentioned coating film, the content of the structural unit (A) in all the structural units contained in the silicon atom-containing resin is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less.

[0149] The silicon-containing resin may contain a structural unit (A') derived from a monomer (a'), wherein the monomer (a') 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), and has a molecular weight of 2500 or less. However, from the viewpoint of dynamic antifouling properties, the content of the structural unit (A') in all the 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, further preferably 5% by mass or less, and particularly preferably 0% by mass.

[0150] From the viewpoint of dynamic antifouling properties, the ratio of the content of the structural unit (A') to the total content of the structural unit (A) and the structural unit (A') is preferably 0.7 or less, more preferably 0.5 or less, further preferably 0.4 or less, further preferably 0.2 or less, and particularly preferably 0.

[0151] (1-3) Monomer (b)

[0152] Monomer (b) is a monomer of (meth)acrylate represented by the above formula (b). By making the silicon-atom-containing resin further contain a structural unit (B) derived from monomer (b), dynamic antifouling properties can be improved. In addition, by further containing a structural unit (B), static antifouling properties can also be improved. Furthermore, by further containing a structural unit (B), the softening resistance of the coating film formed by the coating composition can be excellent. Furthermore, by containing a structural unit (B) derived from monomer (b) and a structural unit (E) derived from a monomer (e) described later, the coating film consumption rate can be appropriately increased.

[0153] In the above formula (b), R A represents a hydrogen atom or a methyl group. B The silicon-containing resin may contain structural units derived from two or more monomers (b). In addition, the monomer (b) may be a monomer having two or more groups selected from a hydroxyl group, a carboxyl group, and an oxyalkylene chain.

[0154] From the viewpoint of improving dynamic antifouling properties, static antifouling properties, and softening resistance, the R B It preferably contains at least an oxyalkylene chain. The alkylene group contained in the oxyalkylene chain may be a straight chain or a branched chain, and the number of carbon atoms of the alkylene group is, for example, 1 to 24, preferably 1 to 13, more preferably 1 to 6, and further preferably 2 or 3. Examples of the alkylene group include -CH 2 -、-(CH 2 ) 2 -、-(CH 2 ) 3 -、-CH(CH 3 )CH 2 -、-CH 2 CH(CH 3 )-wait.

[0155] From the viewpoint of improving dynamic antifouling properties and static antifouling properties, the solubility parameter SP (hereinafter also referred to as "SP") of the homopolymer of monomer (b) is preferably 10.0 or more, more preferably 10.5 or more, and further preferably 11.0 or more. The SP of the homopolymer of monomer (b) is usually 25 or less, preferably 15 or less. The details of SP are described later.

[0156] Examples of the monomer (b) include: hydroxyl group-containing alkyl (meth)acrylates having 1 to 20 carbon atoms in the ester portion, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; carboxyl group-containing alkyl (meth)acrylates having 1 to 20 carbon atoms in the ester portion; alkoxyalkyl (meth)acrylates having 1 to 20 carbon atoms in the ester portion, such as methoxyethyl (meth)acrylate; and methoxypolyethylene glycol (meth)acrylate [-OC 2 H 4 - is repeated for example 1 to 50, preferably 1 to 24, more preferably 2 to 14, and still more preferably 2 to 9], (meth)acrylate methoxypolypropylene glycol〔-OC 3 H 6 -The number of repetitions is, for example, 1 to 50, preferably 1 to 24, more preferably 2 to 14, and still more preferably 2 to 9〕, such as (meth)acrylates whose ester portion contains a polyalkylene glycol chain; (meth)acryloyloxyethylsuccinic acid, (meth)acryloyloxyethylphthalic acid, (meth)acryloyloxyethylhexahydrophthalic acid, (meth)acryloyloxypropylphthalic acid, (meth)acryloyloxypropylhexahydrophthalic acid, etc. (meth)acrylates whose ester portion contains a polyalkylene glycol chain and a carboxyl group, etc.

[0157] Among the above, monomer (b) is preferably an alkoxyalkyl (meth)acrylate having 1 to 20 carbon atoms in the ester portion, a (meth)acrylate having a polyalkylene glycol chain in the ester portion, and / or a (meth)acrylate having a polyalkylene glycol chain and a carboxyl group in the ester portion.

[0158] From the viewpoint of dynamic antifouling property and static antifouling property, the content of the structural unit (B) derived from the monomer (b) in all the structural units contained in the silicon atom-containing resin is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 30% by mass or less, further preferably 5% by mass or more and 30% by mass or less, and may also be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less. In addition, from the viewpoint of improving softening resistance, the content of the structural unit (B) derived from the monomer (b) in all the structural units contained in the silicon atom-containing resin is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.

[0159] (1-4) Monomer (c)

[0160] Monomer (c) is a monomer other than the above-mentioned monomer (a) and monomer (b), and is a monomer whose homopolymer has an SP of 9.5 or less and does not have a cyclic structure. By making the silicon-containing resin further contain a structural unit (C) derived from the monomer (c), the dynamic antifouling property can be improved. In addition, by further containing a structural unit (C), it can also be beneficial to improve the static antifouling property. The silicon-containing resin may contain two or more structural units (C) derived from the monomer (c).

[0161] As at least one major factor that enables the dynamic antifouling property to be improved by further containing the structural unit (C), it is presumed that the compatibility of the monomers in the monomer composition for preparing the silicon atom-containing resin is improved by using a monomer (c) having a small homopolymer SP, thereby improving the random copolymerizability with the monomer (a) contributing to the dynamic antifouling property during the polymerization of the monomer composition. The homopolymer SP of the monomer (c) is usually 7.0 or more, preferably 8.0 or more, and more preferably 9.0 or more.

[0162] From the viewpoint of improving dynamic antifouling properties, monomer (c) is a monomer without a cyclic structure. Since the hydrophobicity of the monomer (c) without a cyclic structure is lower than that of the monomer with a cyclic structure, the coating composition is formed by a monomer composition containing the monomer, and in the coating film formed by the coating composition, the structural unit (C) derived from the monomer is more difficult to be locally present on the coating film surface. Therefore, compared with the use of a monomer with a cyclic structure, when a monomer (c) without a cyclic structure is used, it can be considered that the structural unit (A) derived from the hydrophobic monomer (a) can be easily locally present on the coating film surface, as a result, it is easy to improve dynamic antifouling properties.

[0163] In the present specification, the solubility parameter SP of a homopolymer can be measured by the following method (reference: SUH, CLARKE, JPSA-1, 5, 1671-1681 (1967)).

[0164] At a measurement temperature of 20°C, weigh 0.5 g of the homopolymer into a 100 mL beaker, add 10 mL of a good solvent (acetone) using a hole pipette, and dissolve it using a magnetic stirrer to prepare a dilute solution. Next, use a 50 mL burette to slowly drop a low SP poor solvent (n-hexane) into the dilute solution, and take the point at which the dilute solution becomes turbid as the amount of the low SP poor solvent added. In addition, slowly drop a high SP poor solvent (ion exchange water) into the above-mentioned dilute solution, and take the point at which the dilute solution becomes turbid as the amount of the high SP poor solvent added. The SP value can be calculated by the known calculation method described in the above-mentioned references, etc., from the amount of each of the above-mentioned poor solvents added until the turbidity point is reached.

[0165] The monomer (c) is preferably a (meth)acrylic monomer, more preferably a (meth)acrylic acid ester, and still more preferably an alkyl (meth)acrylate. The alkyl (meth)acrylate as the monomer (c) is preferably represented by the following formula.

[0166] CH 2 =C(R C )(COOR D )

[0167] In the above formula, R C is a hydrogen atom or a methyl group, R D is a chain alkyl group having 3 or more carbon atoms. The chain alkyl group may be linear or branched. D The number of carbon atoms in is usually 20 or less, preferably 12 or less.

[0168] Specific examples of the monomer (c) 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 them, monomers having a homopolymer SP of 9.0 or more are preferred, and n-butyl acrylate, n-butyl methacrylate, tert-butyl methacrylate, etc. are more preferred.

[0169] From the viewpoint of dynamic antifouling property and static antifouling property, the content of the structural unit (C) derived from the monomer (c) in all the structural units contained in the silicon atom-containing resin is greater than 2 mass %. From the viewpoint of dynamic antifouling property and static antifouling property, the content of the structural unit (C) in all the structural units contained in the silicon atom-containing resin is preferably 3 mass % or more and 60 mass % or less, more preferably 5 mass % or more and 50 mass % or less, further preferably 8 mass % or more and 45 mass % or less, and further preferably 10 mass % or more and 40 mass % or less.

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

[0171] The silicon-containing resin may further contain a structural unit (D) derived from a monomer (d). Monomer (d) is a monomer having a triorganosiloxycarbonyl group. By making the silicon-containing resin further contain a structural unit (D) derived from a monomer (d), dynamic antifouling properties can be improved. In addition, by further containing a structural unit (D), static antifouling properties can also be improved.

[0172] Monomer (d) is preferably a monomer (d1) represented by the above formula (VII'). By polymerizing a monomer composition containing monomer (d1), a silicon-containing resin as a (meth)acrylic resin containing a structural unit (D) derived from monomer (d1) can be obtained. The silicon-containing resin has -C(=O)-O-SiR 40 R 41 R 42 as a triorganosiloxycarbonyl group.

[0173] The silicon atom-containing resin may contain two or more structural units (D) derived from the monomer (d). For example, the silicon atom-containing resin may contain two or more structural units (D) having different triorganosiloxycarbonyl groups.

[0174] R in formula (VII') 40 , R 41 and R 42 The same or different hydrocarbon residues (monovalent hydrocarbon groups) having 1 to 20 carbon atoms are mentioned. Examples of the hydrocarbon residues having 1 to 20 carbon atoms include: a linear or branched alkyl group having 20 or less 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; a cyclic alkyl group which may have a substituent, such as cyclohexyl and substituted cyclohexyl; and an aryl group which may have a substituent, such as aryl and substituted aryl.

[0175] Examples of the cyclic alkyl group having a substituent include cyclic alkyl groups substituted with halogen, alkyl groups having a carbon number of up to about 18, acyl groups, nitro groups, or amino groups. Examples of the aryl group having a substituent include aryl groups substituted with halogen, alkyl groups having a carbon number of up to about 18, acyl groups, nitro groups, or amino groups.

[0176] Among them, R is preferred because it tends to be able to stably maintain dynamic antifouling properties and static antifouling properties for a long period of time. 40 , R 41 and R 42 At least one of them is isopropyl, and more preferably R 40 , R 41 and R 42 All are isopropyl.

[0177] From the viewpoint of dynamic antifouling properties and static antifouling properties, when the silicon atom-containing resin contains the structural unit (D), the content of the structural unit (D) derived from the monomer (d) in all the structural units contained in the silicon atom-containing resin is preferably 2 mass % or more and 50 mass % or less, more preferably 5 mass % or more and 40 mass % or less, and further preferably 10 mass % or more and 35 mass % or less.

[0178] (1-6) Monomer (e)

[0179] The silicon-containing resin may further include a structural unit (E) derived from a monomer (e) having at least one metal-containing group selected from the group represented by the above formula (V) and the group represented by the above formula (VI). By further including the structural unit (E) in the silicon-containing resin, dynamic antifouling properties can be improved. Furthermore, by further including the structural unit (E), static antifouling properties can also be improved.

[0180] The silicon atom-containing resin may have both the group represented by the above formula (V) and the group represented by the above formula (VI).

[0181] Monomer (e) is preferably at least one selected from the monomer (e1) represented by the above formula (V') and the monomer (e2) represented by the above formula (VI'). By polymerizing a monomer composition containing such a monomer (e), a silicon-atom-containing resin as a (meth)acrylic resin containing a structural unit (E) derived from the monomer (e) can be obtained, wherein the monomer (e) is selected from the monomer (e1) and the monomer (e2). The silicon-atom-containing resin has at least one metal-atom-containing group selected from the group represented by the above formula (V) and the group represented by the above formula (VI).

[0182] The silicon atom-containing resin may contain two or more structural units (E) derived from the monomer (e).

[0183] The divalent metal atom M in formula (V') [the same applies to formula (V).] and formula (VI') [the same applies to formula (VI).] may be Mg, Zn, Cu or the like, and preferably Zn or Cu.

[0184] R in formula (V') (the same applies to formula (V)) 30 An organic acid residue is preferred.

[0185] The monomer (e1) is represented by the above formula (V'). By using the monomer (e1) as the monomer (e), a silicon atom-containing resin which is a (meth)acrylic resin further having a metal atom-containing group represented by the above formula (V) can be obtained.

[0186] As R 30 Examples of organic acids that form organic acid residues in the ester include acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, versatile carbonic acid, isostearic acid, palmitic acid, cresol acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, ricinoleic acid, brassinoic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthoic acid, purvinic acid and other monobasic organic acids.

[0187] Among them, when the organic acid residue is a fatty acid residue, it is preferred because a coating film without cracks or peeling tends to be maintained for a long time. In particular, as the monomer (e1), zinc (meth)acrylate oleate or zinc (meth)acrylate versatate carbonate, which have high plasticity, is preferably used.

[0188] In addition, other preferred organic acids include monocyclic organic acids other than aromatic organic acids. Examples of the monocyclic organic acids include organic acids having a cycloalkyl group such as cycloalkane acid, resin acids such as tricyclic resin acids, and salts thereof.

[0189] Examples of tricyclic resin acids include monobasic acids having a diterpene hydrocarbon skeleton. Examples of monobasic acids having a diterpene hydrocarbon skeleton include compounds having abietane, pimarane, isopimarane, and abietic skeletons. More specifically, examples include abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, palustric acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandarac pimaric acid, and salts thereof. Among these, abietane, hydrogenated abietic acid, and salts thereof are preferred from the viewpoint of the dynamic antifouling properties of the coating film.

[0190] As the monocyclic organic acid, for example, rosin, pine resin acid, etc. can also be used. As such organic acids, for example, rosins, hydrogenated rosins, disproportionated rosins, naphthenic acid, etc. can be cited. Rosins refer to gum rosin, wood rosin, tall oil rosin, etc. In view of being cheap and easy to obtain, having excellent workability, and being easy to improve dynamic antifouling properties and static antifouling properties, rosins, hydrogenated rosins, and disproportionated rosins are preferred.

[0191] The acid value of the monovalent cyclic organic acid is preferably 100 mgKOH / g to 220 mgKOH / g, more preferably 120 mgKOH / g to 190 mgKOH / g, and further preferably 140 mgKOH / g to 185 mgKOH / g.

[0192] As the formation of R 30 When a monocyclic organic acid having an acid value within the above range is used, there is a tendency that the coating film can maintain good dynamic antifouling properties and static antifouling properties for a longer period of time.

[0193] The organic acid residue contained in the monomer (e1) may be composed of one organic acid or two or more organic acids.

[0194] As having an organic acid residue as R 30 The method for producing the monomer (e1) can be, for example, a method of reacting an inorganic metal compound, a carboxyl-containing free radical polymerizable monomer such as (meth)acrylic acid, and a non-polymerizable organic acid (an organic acid constituting the above-mentioned organic acid residue) in an organic solvent containing an alcohol compound.

[0195] The structural unit (E) derived from the monomer (e1) can also be formed by a method in which a resin obtained by polymerizing a monomer composition containing a carboxyl group-containing free radical polymerizable monomer such as (meth)acrylic acid is reacted with a metal compound and a non-polymerizable organic acid (the organic acid constituting the above-mentioned organic acid residue).

[0196] Monomer (e2) is represented by the above formula (VI'). By using monomer (e2) as monomer (e), a silicon-containing resin as a (meth)acrylic resin further having a metal atom-containing group represented by the above formula (VI) (the metal atom-containing group is a crosslinking group that crosslinks the main chains of the polymer) can be obtained.

[0197] Examples of the monomer (e2) include magnesium acrylate [(CH 2 =CHCOO) 2 Mg], magnesium methacrylate [(CH 2 =C(CH 3 )COO) 2Mg], zinc acrylate [(CH 2 =CHCOO) 2 Zn], zinc methacrylate [(CH 2 =C(CH 3 )COO) 2 Zn], copper acrylate [(CH 2 =CHCOO) 2 Cu], copper methacrylate [(CH 2 =C(CH 3 )COO) 2 Cu], etc. These can be appropriately selected and used alone or in combination of two or more as required.

[0198] As a method for producing the monomer (e2), for example, there can be mentioned a method of reacting a polymerizable unsaturated organic acid such as (meth)acrylic acid and a metal compound together with water in an organic solvent containing an alcohol compound. In this case, preferably, the water content in the reactant is adjusted to 0.01 mass % or more and 30 mass % or less.

[0199] The silicon atom-containing resin may contain both a structural unit derived from the monomer (e1) and a structural unit derived from the monomer (e2).

[0200] From the viewpoint of dynamic antifouling properties and further from the viewpoint of static antifouling properties, when the silicon atom-containing resin contains the structural unit (E), the content of the structural unit (E) in all the structural units contained in the silicon atom-containing resin is preferably from 2 mass % to 30 mass %, more preferably from 4 mass % to 25 mass %, and further preferably from 6 mass % to 20 mass %.

[0201] (1-7) Other monomers

[0202] The silicon atom-containing resin may contain a structural unit (F) derived from another monomer (f) other than the above. The silicon atom-containing resin may contain two or more types of structural units (F).

[0203] Monomer (f) is not particularly limited as long as it is an unsaturated monomer copolymerizable with monomers (a) to (e), and examples thereof include (meth)acrylates that do not belong to monomers (b) and (c). Monomer (e) specifically includes: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, and glycidyl (meth)acrylate. Among them, monomer (f) preferably contains at least methyl methacrylate.

[0204] In the case where the silicon-containing resin includes a structural unit (F), the content of the structural unit (F) is usually 0.1% by mass or more and less than 78% by mass, preferably 5% by mass or more and 75% by mass or less, more preferably 10% by mass or more and 70% by mass or less, and further preferably 10% by mass or more and 60% by mass or less. By making the content of the structural unit (F) more than 0.1% by mass, the balance of each characteristic of the obtained coating composition and the coating film can be adjusted. By making the content of the structural unit (F) less than 78% by mass, even if an antifouling agent is not contained separately, a coating composition showing sufficient dynamic antifouling properties can be obtained.

[0205] (1-8) Method for producing silicon atom-containing resin

[0206] The method for producing the silicon atom-containing resin is not particularly limited, and the resin can be produced by, for example, reacting a monomer composition mixed with the above monomers in the presence of a radical initiator at a reaction temperature of 60 to 180° C. for 5 to 14 hours. The polymerization reaction conditions can be adjusted appropriately.

[0207] Examples of the radical initiator include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxy-2-ethylhexanoate.

[0208] Examples of the polymerization method include solution polymerization, emulsion polymerization, and suspension polymerization in an organic solvent. From the viewpoint of the production efficiency of the silicon-containing resin, solution polymerization is preferred. Examples of the organic solvent include common organic solvents such as toluene, xylene, methyl isobutyl ketone, and n-butyl acetate.

[0209] The number average molecular weight of the silicon atom-containing resin is generally more than 2600 and less than 100000, preferably more than 3000 and less than 50000, more preferably more than 5000 and less than 30000. When the number average molecular weight of the silicon atom-containing resin is more than 2600, there is a tendency that the coating film formed by the coating composition can show dynamic antifouling properties. When the number average molecular weight of the silicon atom-containing resin is less than 100000, there is a tendency that the silicon atom-containing resin is easily evenly dispersed in the coating composition. The number average molecular weight of the silicon atom-containing resin is the number average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

[0210] (1-9) Silicon atom-containing resin content

[0211] The content of the silicon-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, more preferably 35% by mass or more and 85% by mass or less, and may be 80% by mass or less, 70% by mass or less, or 60% by mass or less. When the content of the silicon-containing resin is less than 25% by mass, there is a tendency that the dynamic antifouling property, the static antifouling property, and the adhesion of the coating film to the substrate are reduced. The solid content contained in the coating composition refers to the sum of the components other than the solvent contained in the coating composition.

[0212] (2) Other ingredients that may be contained in the coating composition

[0213] The coating composition may contain one or more other components other than the silicon-containing resin. Other components include, for example, defoamers, anti-sagging agents, plasticizers, antifouling agents, water-binding agents, anti-color separation agents, anti-settling agents, coating film consumption regulators, ultraviolet absorbers, surface regulators, viscosity regulators, leveling agents, pigment dispersants and other additives, pigments and solvents. These additives, pigments and solvents may be used alone or in combination of two or more.

[0214] The defoamer is an agent that has the effect of making the surface of the bubbles to be formed uneven and inhibiting the formation of bubbles, or an agent that has the effect of locally thinning the surface of the bubbles that have been formed and destroying the bubbles. It is obvious that the dynamic antifouling property can be further improved by making the coating composition contain the defoamer and the silicon atom-containing resin at the same time. Therefore, the coating composition preferably contains the defoamer.

[0215] Examples of defoamers include silicone defoamers and non-silicone defoamers. Silicone defoamers are defoamers containing surface-active polysiloxane or its modified product, and non-silicone defoamers are defoamers other than silicone defoamers (defoamers not containing polysiloxane or its modified product). Silicone defoamers may be fluorine-modified silicone defoamers. Fluorine-modified silicone defoamers are defoamers containing fluorine-modified polysiloxane.

[0216] Examples of non-silicone defoamers include higher alcohols, higher alcohol derivatives, fatty acids, fatty acid derivatives, paraffins, (meth)acrylic polymers, mineral oils, etc. Examples of silicone defoamers include oil-based, complex-based, self-emulsifying, and emulsion-based defoamers.

[0217] As the defoaming agent, a commercial product can be used. As commercial products of non-silicone defoaming agents, for example, mineral oil defoaming agents such as "BYK-030" manufactured by BYK; polymer defoaming agents such as "DISPARON OX68" manufactured by Kusumoto Chemicals Co., Ltd. and "BYK-1790" manufactured by BYK; etc. As commercial products of silicone defoaming agents other than fluorine-modified silicone defoaming agents, for example, silicone oil defoaming agents such as "KF-96" manufactured by Shin-Etsu Chemical Co., Ltd. and "BYK-081" manufactured by BYK; etc. As commercial products of fluorine-modified silicone defoaming agents, for example, fluorosilicone oil defoaming agents such as "BYK-063", "BYK-065", and "BYK-066N" manufactured by BYK and "FA-630" manufactured by Shin-Etsu Chemical Co., Ltd. can be listed.

[0218] From the viewpoint of improving dynamic antifouling properties and defoaming properties, the content of the defoaming agent is 0.002 parts by mass or more and 0.60 parts by mass or less, more preferably 0.004 parts by mass or more and 0.55 parts by mass or less, further preferably 0.01 parts by mass or more and 0.40 parts by mass or less, and still more preferably 0.01 parts by mass or more and 0.20 parts by mass or less, relative to 100 parts by mass of the silicon atom-containing resin.

[0219] The anti-sagging agent is an agent that has an inhibitory effect on the sagging of the coating composition that may occur between the coating composition being applied to the coated object and the completion of the drying of the coating film. By making the coating composition contain both the anti-sagging agent and the silicon-containing resin, it is obvious that the dynamic antifouling property can be further improved. Therefore, the coating composition preferably contains the anti-sagging agent.

[0220] Examples of the anti-sagging agent include amide anti-sagging agents, bentonite anti-sagging agents, polyethylene waxes such as oxidized polyethylene wax, hydrogenated castor oil wax, long-chain fatty acid ester polymers, polycarboxylic acids, silica fine particle anti-sagging agents, and mixtures of two or more thereof.

[0221] Examples of the amide anti-sagging agent include amide wax anti-sagging agents such as fatty acid amide wax and polyamide wax. Examples of the fatty acid amide wax include stearic acid amide wax and oleic acid amide wax.

[0222] As the anti-sagging agent, a commercial product can be used. Examples of commercial products of amide wax anti-sagging agents include "TALEN7200-20" manufactured by Kyoeisha Chemical Co., Ltd., "DISPARON 6900-20X" and "DISPARON RE-8000" manufactured by Kusumoto Chemical Co., Ltd., and "MONORAL3300" manufactured by HS CHEM. Examples of other commercial products of anti-sagging agents include "BENTON38" manufactured by ELEMENTIS JAPAN and "TIXOGEL" manufactured by BYK, etc., which are organic bentonite anti-sagging agents.

[0223] From the viewpoint of improving dynamic antifouling and anti-sagging properties, the content of the anti-sagging agent is from 0.1 parts by mass to 6.0 parts by mass, more preferably from 0.2 parts by mass to 5.0 parts by mass, further preferably from 0.25 parts by mass to 4.0 parts by mass, and even more preferably from 0.25 parts by mass to 3.0 parts by mass, relative to 100 parts by mass of the silicon atom-containing resin.

[0224] The coating composition may contain a plasticizer. By containing a plasticizer, the crack resistance of the coating film can be improved. In addition, 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 antifouling properties and static antifouling properties.

[0225] Examples of the plasticizer include chlorinated paraffins; chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyethylene ethers; polypropylene sebacate; partially hydrogenated terphenyls; polyvinyl acetate; poly(meth)acrylic acid alkyl esters such as methyl (meth)acrylate copolymers, ethyl (meth)acrylate copolymers, propyl (meth)acrylate copolymers, butyl (meth)acrylate copolymers, and cyclohexyl (meth)acrylate copolymers; polyether polyols; alkyd resins; polyester resins; vinyl chloride resins such as vinyl chloride-vinyl acetate copolymers, vinyl chloride-vinyl propionate copolymers, vinyl chloride-isobutyl vinyl ether copolymers, vinyl chloride-isopropyl vinyl ether copolymers, and vinyl chloride-ethyl vinyl ether copolymers; silicone oils; oils Grease and its refined products (wax, castor oil, etc.); vaseline; liquid paraffin; rosin, hydrogenated rosin, cyclohexyl phthalate, fatty acids and their divalent metal salts; phthalates such as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate, diisodecyl phthalate (DIDP), etc.; aliphatic dibasic acid esters such as isobutyl adipate and dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl esters; phosphate esters such as tricresyl phosphate (tricresyl phosphate), triaryl phosphoric acid (triaryl phosphate ester), trichloroethyl phosphate, etc.; epoxy compounds such as epoxidized soybean oil and octyl epoxystearate; organic tin compounds such as dioctyltin laurate and dibutyltin laurate; trioctyl trimellitate, triacetylene, etc.

[0226] Among the above, chlorinated paraffin, polyvinyl ether, polyether polyol, rosin, vinyl chloride-isobutyl vinyl ether copolymer, phthalic acid ester, and phosphoric acid ester are preferred from the viewpoint of compatibility with the silicon atom-containing resin and crack resistance of the coating film.

[0227] Relative to 100 parts by mass of silicon-containing resin, the content of the plasticizer in the coating composition is preferably 3 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, and further preferably 5 parts by mass or more and 40 parts by mass or less. When the content of the plasticizer is less than 3 parts by mass relative to 100 parts by mass of silicon-containing resin, there is a tendency that the improvement effect of crack resistance brought by the addition of the plasticizer cannot be confirmed, and in addition, there is a tendency that the improvement effect of dynamic antifouling and static antifouling brought by the addition of the plasticizer cannot be confirmed. When the content of the plasticizer exceeds 100 parts by mass relative to 100 parts by mass of silicon-containing resin, there is a tendency that the adhesion of the coating film to the substrate is reduced and the dynamic antifouling of the coating film is reduced.

[0228] The coating film formed by the coating composition of the present invention can exert good dynamic antifouling properties and further can exert good static antifouling properties due to the antifouling effect based on the silicon-atom-containing resin, so it is not necessary to contain an antifouling agent in addition to the silicon-atom-containing resin. However, in order to further improve the antifouling property, or in order to further improve the long-term persistence of the antifouling property, the coating composition may also contain an antifouling agent as required. As the antifouling agent, known antifouling agents can be used, for example, inorganic compounds, metal-containing organic compounds, and metal-free organic compounds, etc. can be listed.

[0229] Examples of the antifouling agent include zinc oxide; cuprous oxide; manganese ethylenebisdithiocarbamate; zinc dimethyldithiocarbamate; 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine; 2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyldiphenylurea; zinc ethylenebisdithiocarbamate; rhodamine copper (cuprous thiocyanate); 4,5-dichloro-2-octyl-4-isothiazoline-3-one (4,5-dichloro-2-octyl-4-isothiazoline-3-one); chloro-2-octyl-3(2H)isothiazolone); N-(fluorodichloromethylthio)phthalimide; N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfonamide; metal salts such as zinc salt (zinc pyrithione) or copper salt (copper pyrithione); tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 3- Iodo-2-propylbutylcarbamate; diiodomethyl trisulfone; phenyl(bipyridyl)bismuth dichloride; 2-(4-thiazolyl)-benzimidazole; triphenylboron pyridinium salt; stearylamine triphenylboron; laurylamine triphenylboron; zinc ethylene dimethyldithiocarbamoyl bis(dithiocarbamate); 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide; 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide [4-(2-(4-methylphenyl)ethyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide; 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-carbonitrile; 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (common name: medetomidine).

[0230] The content of the antifouling agent in the coating composition is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 0 parts by mass, based on 100 parts by mass of the silicon atom-containing resin.

[0231] Examples of the pigment include: extender pigments such as precipitated barium, talc, clay, chalk, white silica, alumina white, bentonite, calcium carbonate, magnesium carbonate, silicic acid, silicates, aluminum oxide hydrate, calcium sulfate, and the like; coloring pigments such as titanium oxide, zirconium oxide, basic lead sulfate, tin oxide, carbon black, white lead, graphite, zinc sulfide, zinc oxide, chromium oxide, nickel titanium yellow, chrome 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, and the like.

[0232] Examples of the solvent 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.

[0233] (3) Preparation of coating composition

[0234] The coating composition can be prepared, for example, as follows: other components are added as needed to a silicon atom-containing resin or a resin composition containing the same (for example, a solution or dispersion containing a silicon atom-containing resin), and the mixture is mixed using a mixer such as a ball mill, a pebble mill, a roller mill, a sand mill, or a high-speed disperser.

[0235] <Coatings and composite coatings>

[0236] The coating film of the present invention (hereinafter, also referred to as "coating film") is a coating film formed by the coating composition of the present invention. The coating film is an antifouling coating film having antifouling properties. The antifouling coating film is formed by the coating composition of the present invention, and thus can exhibit good dynamic antifouling properties.

[0237] The coating film can be formed by applying the coating composition to the surface of the object to be coated according to a conventional method, and then volatilizing and removing the solvent at room temperature or under heating as needed. As the coating method of the coating composition, for example, there can be cited the conventionally known methods such as dipping, spraying, brushing, roller coating, electrostatic coating, and electrodeposition coating. 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.

[0238] Examples of the coated object 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; pipes such as cooling water pipes; bridges; buoys; industrial water facilities; and seabed bases. The coated object is preferably an underwater mobile body, and examples of the underwater mobile body include ships, fishing nets, and fishing gear.

[0239] The coated surface of the above-mentioned coated object can be pre-treated as needed. In addition, a coating film formed by the coating composition of the present invention can be formed on a primer coating film formed by other coatings such as rust-proof coating (anti-corrosion coating) formed on the coated object to form a composite coating film.

[0240] According to the coating composition of the present invention, since the silicon-containing resin as a carrier itself can show good antifouling properties, the antifouling agent separately formulated can be omitted or its formulation amount can be reduced. Therefore, according to the coating composition of the present invention, a transparent (highly transparent) antifouling coating film can be formed.

[0241] The antifouling coating film formed by the conventional antifouling coating composition mainly containing a large amount of cuprous oxide as an antifouling agent usually has a reddish hue due to the cuprous oxide contained, and the hue of the coating film is limited. However, according to the present invention, various applications can be carried out by utilizing the transparency of the obtained coating film. In addition, when forming a transparent coating film, the coating composition of the present invention preferably does not contain a coloring pigment.

[0242] For example, in a composite coating film having a primer coating film formed of an antirust paint or the like and a coating film of the present invention formed on the primer coating film, by using the coating film of the present invention as a transparent antifouling coating film and using coatings of various tones as the antirust paint, it is possible to provide a coated object such as a ship having antifouling properties and having a tones that have not been previously available on the surface formed by the composite coating film. In addition, by forming a midcoat coating film formed of coatings having various tones between the primer coating film formed of an antirust paint or the like and the transparent antifouling coating film, it is also possible to provide a coated object having tones that have not been previously available.

[0243] As the coating material forming the mid-coat film, various coating materials such as antifouling coating materials, epoxy resin coating materials, polyurethane resin coating materials, (meth) acrylic resin coating materials, chlorinated rubber coating materials, alkyd resin coating materials, silicone resin coating materials, and fluororesin coating materials can be used. The antifouling coating material forming the mid-coat film can be the coating composition of the present invention, or can be other antifouling coating compositions such as conventional antifouling coating compositions containing a relatively large amount of antifouling agents.

[0244] The middle coating film can be formed on the entire surface of the primer film, or can be formed on a part of the surface of the primer film. The middle coating film and the primer film can be old films in use. In this case, the coating composition of the present invention and the film formed therefrom can be used to repair the old film.

[0245] If the intermediate coating film between the primer coating film formed of the antirust paint and the transparent antifouling coating film is formed into, for example, various tones of characters, patterns, designs, or patterns, various designs can be given to the coated object. By placing a film or a sealing member having various tones of characters, patterns, designs, or patterns between the primer coating film and the transparent antifouling coating film, instead of the intermediate coating film formed of the paint between the primer coating film and the transparent antifouling coating film, various designs can also be given to the coated object.

[0246] Example

[0247] Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0248] <Resin Production Examples S1 to S12, T1 to T10: Production of Resins S1 to S12, T1 to T10>

[0249] In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube and a temperature controller, xylene [A] parts by mass as a solvent was added, and the temperature was maintained at [B]°C. Then, a mixed solution consisting of the monomers shown in Table 3 or Table 4 in the amounts (unit: parts by mass) shown in the table (a total of 100 parts by mass), xylene [C] parts by mass as a solvent, and tert-butyl peroxy-2-ethylhexanoate [D] parts by mass as a radical polymerization initiator was added to the dropping funnel, and the mixture was dripped into the four-necked flask at a constant rate for [E] hours, and the temperature was kept for [F] minutes after the dripping was completed. Then, a mixed solution consisting of xylene [G] parts by mass and tert-butyl peroxy-2-ethylhexanoate [H] parts by mass was dripped into the four-necked flask at a constant rate for 30 minutes, and the temperature was kept for [I] hours after the dripping was completed, thereby obtaining a resin composition (solution) containing a resin.

[0250] Tables 1 and 2 summarize the numerical values ​​of [A] to [I] in each of Resin Production Examples S1 to S12 and T1 to T10.

[0251] [Table 1]

[0252]

[0253] [Table 2]

[0254]

[0255] Hereinafter, the resins obtained in Resin Manufacturing Examples S1 to S12 are referred to as "resins S1 to S12", respectively, and the resin compositions (solutions) obtained in Resin Manufacturing Examples S1 to S12 are referred to as "resin compositions S1 to S12", respectively. The resins obtained in Resin Manufacturing Examples T1 to T10 are referred to as "resins T1 to T10", respectively, and the resin composition "solutions" obtained in Resin Manufacturing Examples T1 to T10 are referred to as "resin compositions T1 to T10", respectively.

[0256] The monomers used in the resin manufacturing examples S1 to S12 and T1 to T10 and their usage 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 atom-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), but having a molecular weight (number average molecular weight) of 2500 or less. In addition, the values ​​in parentheses of each monomer belonging to monomer (a) and monomer (a') are the number average molecular weights of the monomers. The same is true for Table 6.

[0257] In Tables 3 and 4, other monomers refer to monomers that do not belong to any of monomers (a), monomers (a'), monomers (b), monomers (c) and monomers (d). In addition, the values ​​in parentheses of each monomer belonging to monomer (c) and other monomers are the solubility parameters SP of the homopolymers of the monomers. The same applies to Table 6.

[0258] The number average molecular weight Mn of the obtained resins S1 to S12 and T1 to T10 and the solid content of the resin compositions S1 to S12 and T1 to T10 were measured. The results are shown in Tables 3 and 4. The measurement method is as follows.

[0259] 〔i〕Number average molecular weight Mn

[0260] The number average molecular weight Mn of the monomer (a), the monomer (a') and the resin is a polystyrene-equivalent number average molecular weight measured by GPC. The measurement conditions are as follows.

[0261] Device: Tosoh Corporation "HLC-8220GPC"

[0262] Chromatographic column: TSKgel SuperHZM-M×2

[0263] Eluent: Tetrahydrofuran

[0264] Measurement temperature: 35℃

[0265] Detector: RI

[0266] 〔ii〕Solid content

[0267] The solid content of the resin composition was calculated according to the following formula.

[0268] Solid content (mass %) = 100 × (total mass of raw materials used in the preparation of the resin composition excluding the solvent) / (mass of the obtained resin composition)

[0269] [Table 3]

[0270]

[0271] [Table 4]

[0272]

[0273] <Resin Production Examples S13 and S14: Production of Resins S13 and S14>

[0274] In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube and a temperature controller, xylene [A] mass parts as a solvent was added, and the temperature was maintained at [B] °C. Then, a mixed solution consisting of the monomers shown in Table 6 (a total of 100 mass parts) in the amount (unit: mass parts) shown in the table, 10 mass parts of xylene as a solvent, and tert-butyl peroxy-2-ethylhexanoate [C] mass parts as a free radical polymerization initiator was added to the dropping funnel, and it was dripped into the four-necked flask at a constant rate for 3 hours, and the temperature was kept for 30 minutes after the dripping was completed. Then, a mixed solution consisting of xylene [D] mass parts and 0.3 mass parts of tert-butyl peroxy-2-ethylhexanoate was dripped into the four-necked flask at a constant rate for 30 minutes, and the temperature was kept for [E] hours after the dripping was completed, thereby obtaining a resin composition (solution) containing a resin having a carboxyl group. The solid content of the resin composition is [F] mass %.

[0275] Next, add 100 parts by mass of the above-mentioned resin composition, parts by mass of copper (II) acetate [G], parts by mass of compound [H] [I] and 60 parts by mass of xylene to the same reaction vessel, raise the temperature to reflux temperature, remove the distilled acetic acid, water and the mixed solution of the solvent, add an equal amount of xylene, and continue the reaction for 18 hours. The endpoint of the reaction is determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, add n-butanol and xylene to obtain a resin composition (solution) containing resin. The resin contained in the resin composition is the carboxyl group of the above-mentioned resin having a carboxyl group converted to -COO - Cu 2+ ( - Y is a structural part other than the carboxyl group of the compound [H].

[0276] Table 5 summarizes the numerical values ​​of [A] to [I] in each of Resin Production Examples S13 and S14.

[0277] [Table 5]

[0278]

[0279] H1 and H2 in Table 5 represent the following.

[0280] H1: Hydrogenated rosin (HYPALE CH, acid value 160 mgKOH / g, manufactured by Arakawa Chemical Industries, Ltd.)

[0281] H2: Naphthenic acid (NA-200, acid value 200 mgKOH / g, manufactured by Yamato Oil & Fats Industries)

[0282] Hereinafter, the resins obtained in Resin Production Examples S13 and S14 are respectively referred to as “resins S13, S14”, and the resin compositions (solutions) obtained in Resin Production Examples S13 and S14 are respectively referred to as “resin compositions S13, S14”.

[0283] <Resin Production Example S15: Production of Resin S15>

[0284] In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube and a temperature controller, 50 parts by mass of xylene as a solvent are added, and the temperature is maintained at 95°C. Then, a mixed solution consisting of the monomers (a total of 100 parts by mass) shown in the table of Table 6 (unit: parts by mass), 10 parts by mass of xylene as a solvent, and 1.2 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a free radical polymerization initiator is added to the dropping funnel, and it is dripped into the four-necked flask at a constant speed for 3 hours, and the temperature is kept for 30 minutes after the dripping is completed. Then, a mixed solution consisting of 40 parts by mass of xylene and 0.3 parts by mass of tert-butyl peroxy-2-ethylhexanoate is dripped into the four-necked flask at a constant speed for 30 minutes, and the temperature is kept for 1 hour after the dripping is completed, thereby obtaining a resin composition (solution) containing a resin having a carboxyl group. The solid content of the resin composition is 50.2% by mass.

[0285] Next, add 100 parts by mass of the above-mentioned resin composition, 18.6 parts by mass of zinc (II) acetate, 33.2 parts by mass of cyclohexane acid (NA-165, acid value 165 mgKOH / g, manufactured by Yamato Oil & Fats Industries) and 60 parts by mass of xylene to the same reaction vessel, raise the temperature to reflux temperature, remove the distilled acetic acid, water and the mixed solution of the solvent, add an equal amount of xylene, and continue the reaction for 18 hours. The endpoint of the reaction is determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, add n-butanol and xylene to obtain a resin composition (solution) containing resin. The resin contained in the resin composition is the carboxyl group of the above-mentioned resin having a carboxyl group converted to -COO- Zn 2+ ( - Y is a structural part other than the carboxyl group of cyclohexane acid.

[0286] Hereinafter, the resin obtained in Resin Production Example S15 is referred to as “resin S15”, and the resin composition (solution) obtained in Resin Production Example S15 is referred to as “resin composition S15”.

[0287] The monomers used in Resin Production Examples S13 to S15 and the amounts (parts by mass) thereof are shown in Table 6. Table 6 shows the monomers used in the production of the resin having a carboxyl group.

[0288] The number average molecular weight Mn of the obtained resins S13 to S15 and the solid content of the resin compositions S13 to S15 were measured according to the above-mentioned measurement method. The results are shown in Table 6. The number average molecular weight Mn is the number average molecular weight of the resin having a carboxyl group (carboxyl groups are converted to -COO - Me 2+ ( - OOC-Y) before the reaction of the resin) measured. Me is Cu or Zn.

[0289] [Table 6]

[0290]

[0291] The details of the abbreviations of the monomers shown in Tables 3, 4, and 6 are as follows.

[0292] (1) FM-0721: “FM-0721” manufactured by JNC Corporation, a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5000, wherein m=0, b=3, n=65, R 1 ~R 4 and R 31 is methyl, R 5 Monomers containing n-butyl

[0293] (2) FM-0725: "FM-0725" manufactured by JNC Corporation, a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 10,000, wherein m=0, b=3, n=132, R 1 ~R 4 and R 31 is methyl, R 5 Monomers containing n-butyl

[0294] (3) KF-2012: “KF-2012” manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 4600, wherein m=0, R 1 ~R 5 and R 31 Methyl monomer

[0295] (4) X-22-2426: "X-22-2426" manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 12,000, wherein m=0, R 1 ~R 5 and R 31 Methyl monomer

[0296] (5) FM-7725: "FM-7725" manufactured by JNC Corporation, an organopolysiloxane modified with methacryloyloxyalkyl groups at both ends, molecular weight: 10,000, wherein q and s = 0, f and g = 3, r = 131, R 9 ~R 12 , R 33 and R 34 Methyl monomer

[0297] (6) X-22-164B: "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd., organopolysiloxane modified with methacryloyloxyalkyl groups at both ends, molecular weight: 3200, wherein q and s = 0, R 9 ~R 12 , R 33 and R 34 Methyl monomer

[0298] (7) X-22-164E: "X-22-164E" manufactured by Shin-Etsu Chemical Co., Ltd., organopolysiloxane modified with methacryloyloxyalkyl groups at both ends, molecular weight: 7800, wherein q and s = 0, R 9 ~R 12 , R 33 and R 34 Methyl monomer

[0299] (8) FM-0711: “FM-0711” manufactured by JNC Corporation, a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1000, wherein m=0, b=3, n=10, R 1 ~R 4 and R 31 is methyl, R 5 Monomers containing n-butyl

[0300] (9) X-22-174ASX: "X-22-174ASX" manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 900, wherein m=0, R 1 ~R 5 and R 31 Methyl monomer

[0301] (10) X-22-174BX: "X-22-174BX" manufactured by Shin-Etsu Chemical Co., Ltd., a single-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 2300, wherein m=0, R 1 ~R 5 and R 31 Methyl monomer

[0302] (11) HEMA: 2-Hydroxyethyl methacrylate (SP: 13.5)

[0303] (12)MEMA: 2-methoxyethyl methacrylate (SP: 10.7)

[0304] (13) MEA: 2-methoxyethyl acrylate (SP: 10.7)

[0305] (14) M-40G: methoxy polyethylene glycol methacrylate (number of repetitions of oxyethylene chains = 4, SP: 13.7)

[0306] (15) M-90G: methoxy polyethylene glycol methacrylate (number of repetitions of oxyethylene chains = 9, SP: 13.9)

[0307] (16) M-230G: methoxy polyethylene glycol methacrylate (number of repetitions of oxyethylene chains = 23, SP: 21)

[0308] (17) SA: Methacryloyloxyethyl succinic acid (SP: 12.8)

[0309] (18) CB-1: Methacryloyloxyethyl phthalic acid (SP: 13.2)

[0310] (19) t-BMA: tert-butyl methacrylate (SP: 9.4)

[0311] (20) n-BMA: n-butyl methacrylate (SP: 9.3)

[0312] (21) EHMA: 2-ethylhexyl methacrylate (SP: 8.3)

[0313] (22) n-BA: n-butyl acrylate (SP: 9.5)

[0314] (23) TIPSA: Triisopropylsilyl acrylate

[0315] (24) TIPSMA: triisopropylsilyl methacrylate

[0316] (25) MMA: Methyl methacrylate (SP: 10.7)

[0317] (26) EA: Ethyl acrylate (SP: 10.5)

[0318] (27) AA: Acrylic acid (SP: 23.8)

[0319] In the above, SP is the solubility parameter of the homopolymer of the monomer, which is measured according to the above method.

[0320] <Examples 1 to 19, Comparative Examples 1 to 11>

[0321] According to the proportions (parts by mass) in Tables 7 to 9, any of the resin compositions obtained in the preparation examples and other components shown in Tables 7 to 9 were mixed using a high-speed disperser to prepare antifouling coating compositions. The proportions (parts by mass) shown in Tables 7 to 9 are tangible proportions, and when a solvent or the like is included, the proportions containing the solvent or the like are included.

[0322] (Evaluation of antifouling coating composition)

[0323] [a] Evaluation of dynamic antifouling properties of coating films formed from antifouling coating compositions (open drum test)

[0324] The antifouling coating compositions obtained in Examples and Comparative Examples were applied to a sandblasted plate previously coated with an antirust coating to a dry film thickness of 300 μm, and dried by leaving the plate indoors for 2 days and nights to obtain a test plate having an antifouling coating film.

[0325] The obtained test plate was mounted on the side of a rotating drum, and the test plate surface was rotated about 10 nautical miles per hour in natural seawater. The test was conducted for 24 months, and the attachment area of ​​marine organisms was obtained and evaluated according to the following criteria. The evaluation results at the time points of 6 months, 12 months, 18 months, and 24 months of the test are shown in Tables 7 to 9. The evaluation result is preferably 3 or more.

[0326] 5: The attachment area of ​​marine organisms is 0% or more and less than 5%

[0327] 4: The attachment area of ​​marine organisms is more than 5% and less than 10%

[0328] 3: The attachment area of ​​marine organisms is more than 10% and less than 15%

[0329] 2: The attachment area of ​​marine organisms is more than 15% and less than 30%

[0330] 1: The attachment area of ​​marine organisms is more than 30%

[0331] [b] Evaluation of static antifouling properties of coating films formed from antifouling coating compositions (raft static antifouling test)

[0332] The antifouling coating compositions obtained in Examples and Comparative Examples were applied to a sandblasted plate previously coated with an antirust coating to a dry film thickness of 300 μm, and dried by leaving the plate indoors for 2 days and nights to obtain a test plate having an antifouling coating film.

[0333] The obtained test plate was immersed in a raft in Aioi Bay, Ako City, Hyogo Prefecture, and a biological adhesion test was conducted for 24 months to determine the adhesion area of ​​marine organisms and evaluate according to the following criteria. The evaluation results at the time points of 6 months, 12 months, 18 months, and 24 months of the test are shown in Tables 7 to 9. The evaluation result is preferably 3 or more.

[0334] 5: The attachment area of ​​marine organisms is 0% or more and less than 5%

[0335] 4: The attachment area of ​​marine organisms is more than 5% and less than 10%

[0336] 3: The attachment area of ​​marine organisms is more than 10% and less than 15%

[0337] 2: The attachment area of ​​marine organisms is more than 15% and less than 30%

[0338] 1: The attachment area of ​​marine organisms is more than 30%

[0339] [c] Softening resistance of coating film

[0340] The antifouling coating composition obtained in the examples and comparative examples was applied to a sandblasted plate pre-coated with an antirust coating, and the dry film thickness was 300 μm, and the plate was dried by placing it indoors for 2 days and nights to obtain a test plate with an antifouling coating film. The obtained test plate was immersed in a raft in Aioi Bay, Ako City, Hyogo Prefecture for a total of 12 months, and the softening resistance of the coating film was evaluated according to the following criteria. The softening resistance was measured by touching the coating film of the test plate. The evaluation results are shown in Tables 7 to 9. The evaluation results are preferably 3 or more. It is believed that the softening of the coating film is caused by the swelling of the coating film due to water absorption.

[0341] 5: No softening of the membrane was observed even after immersion for 12 months

[0342] 4: Membrane softening was confirmed when the immersion time exceeded 7 months but was less than 12 months

[0343] 3: When the immersion time is more than 3 months but less than 7 months, the film softening is confirmed

[0344] 2: When the immersion time is more than 1 month but less than 3 months, the film softening is confirmed

[0345] 1: Softening of the membrane was observed when the immersion time was less than 1 month

[0346] [Table 7]

[0347]

[0348] [Table 8]

[0349]

[0350] [Table 9]

[0351]

[0352] The details of the components described in Tables 7 to 9 are as follows.

[0353] (1) Defoamer: BYK-066N, non-volatile content: 0.7% by mass

[0354] (2) Plasticizer: "LUTONAL A25" manufactured by BASF, polyvinyl ethyl ether, non-volatile content: 95% by mass

[0355] (3) Pigment 1: "TI-PURE R-900" manufactured by DuPont, titanium oxide pigment

[0356] (4) Pigment 2: "Bayferox 130" manufactured by LANXESS, red iron oxide pigment

[0357] (5) Anti-sagging agent: "MONORAL 3300" manufactured by HS CHEM, non-volatile content: 20% by mass.

Claims

1. A coating composition comprising a silicon-containing resin, wherein the silicon-containing resin comprises: Structural unit (A), wherein the structural unit (A) is a structural unit derived from a monomer (a), wherein the monomer (a) has at least one silicon-atom-containing group selected from 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), the structural unit (B) being a structural unit derived from a monomer (b) which is a (meth)acrylate represented by the following formula (b); A structural unit (C), wherein the structural unit (C) is derived from the monomer (a) and a monomer (c) other than the monomer (b); The molecular weight of the monomer (a) is greater than 2500; The content of the structural unit (A) is greater than 20% by mass among all the structural units contained in the silicon atom-containing resin; The monomer (c) is a monomer having a solubility parameter SP of a homopolymer of 9.5 or less and having no cyclic structure; The content of the structural unit (C) is greater than 2% by mass among all the structural units contained in the silicon atom-containing resin; [Chemical formula 1] In formula (I), a and b each independently represent an integer from 2 to 5, m represents an integer from 0 to 50, and n represents an integer from 3 to 270; R 1 ~R 5 Each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group; [Chemical formula 2] In formula (II), c and d each independently represent an integer from 2 to 5, p represents an integer from 0 to 50; R 6 , R 7 and R 8 Each independently represents an alkyl group, R a or R b ; R a yes [Chemical formula 3] In the formula, x represents any integer from 0 to 200, R 23 ~R 27 The same or different, represents an alkyl group; R b yes [Chemical formula 4] In the formula, y represents any integer from 1 to 200; R 28 and R 29 The same or different, represents an alkyl group; [Chemical formula 5] In formula (III), e, f, g and h each independently represent an integer from 2 to 5, q and s each independently represent an integer from 0 to 50, and r represents an integer from 3 to 270; R 9 ~R 12 Each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group; [Chemical formula 6] In formula (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, v and w each independently represent any integer from 0 to 70; R 13 ~R 22 The same or different, represents an alkyl group; CH2=C(R A )(COOR B ) (b) In formula (b), R A represents a hydrogen atom or a methyl group; R B It represents a monovalent group including one or more selected from the group consisting of a hydroxyl group, a carboxyl group, and an oxyalkylene chain.

2. The coating composition according to claim 1, wherein R in the formula (b) B It represents a monovalent group containing an oxyalkylene chain.

3. The coating composition according to claim 1 or 2, wherein the monomer (a) is at least one selected from the group consisting of a monomer (a1) 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 7] In formula (I'), R 31 represents a hydrogen atom or a methyl group, a, b, m, n and R 1 ~R 5 Means the same as above; [Chemical formula 8] In formula (II'), R 32 represents a hydrogen atom or a methyl group, c, d, p and R 6 ~R 8 Means the same as above; [Chemical formula 9] In formula (III'), R 33 and R 34 Each independently represents a hydrogen atom or a methyl group, and e, f, g, h, q, r, s and R 9 ~R 12 Means the same as above; [Chemical formula 10] In formula (IV'), R 35 and R 36 Each independently represents a hydrogen atom or a methyl group, and i, j, k, l, t, u, v, w and R 13 ~R 22 Means the same as above. 4 . The coating composition according to claim 1 , further comprising a structural unit (D) derived from a monomer (d) having a triorganosiloxycarbonyl group.

5. The coating composition according to claim 4, wherein the monomer (d) is a monomer (d1) represented by the following formula (VII'); [Chemical formula 11] In formula (VⅡ'), R 43 represents a hydrogen atom or a methyl group, R 40 , R 41 and R 42 The same or different groups represent a hydrocarbon group having 1 to 20 carbon atoms. 6 . The coating composition according to claim 1 , wherein a content of the structural unit (B) is 1% by mass or more and 30% by mass or less of all structural units contained in the silicon atom-containing resin. 7 . The coating composition according to claim 1 , wherein the solubility parameter SP of the homopolymer of the monomer (b) is 10.0 or more.

8. The coating composition according to claim 1 or 2, further comprising at least one selected from a defoaming agent and an anti-sagging agent.

9. The coating composition according to claim 1 or 2, wherein the silicon atom-containing resin further comprises a structural unit (E) derived from a monomer (e), wherein the monomer (e) comprises at least one metal atom-containing group selected from a group represented by the following formula (V) and a group represented by the following formula (VI); [Chemical formula 12] In formula (V), M represents a divalent metal atom, R 30 represents an organic acid residue or an alcohol residue; [Chemical formula 13] In formula (VI), M represents a divalent metal atom.

10. The coating composition according to claim 9, wherein the monomer (e) is at least one selected from the group consisting of a monomer (e1) represented by the following formula (V') and a monomer (e2) represented by the following formula (VI'); [Chemical formula 14] In formula (V'), R 37 Represents a hydrogen atom or a methyl group, M and R 30 Means the same as above; [Chemical formula 15] In formula (VI'), R 38 and R 39 Each independently represents a hydrogen atom or a methyl group, and M has the same meaning as above.

11. A coating film formed from the coating composition according to claim 1.

12. A composite coating film comprising: a primer coating film formed of an anti-rust paint; and a coating film formed of the coating composition according to claim 1 laminated on the primer coating film.

13. A ship having the coating film according to claim 11 or the composite coating film according to claim 12.

14. An underwater structure having the coating film according to claim 11 or the composite coating film according to claim 12.

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