Antifouling coating composition and antifouling coating film

Abstract

To provide an antifouling coating composition capable of forming an antifouling coating film having excellent antifouling performance and excellent crack resistance.SOLUTION: Provided is an antifouling coating composition which contains a silicon atom-containing resin and a thermoplastic resin other than the silicon atom-containing resin. The silicon atom-containing resin contains a constituent unit (A) having at least one silicon atom-containing group selected from the group consisting of a group represented by the following formula (I), a group represented by the following formula (II), and the like. The thermoplastic resin contains a thermoplastic resin having a weight average molecular weight of 1,000 or more. The content of the thermoplastic resin having a weight average molecular weight of 1,000 or more is 6.0 pts.mass or more and 11.0 pts.mass or less based on 100 pts.mass of the silicon atom-containing resin.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] In ships, the adhesion of organisms such as barnacles, mussels, and algae to the parts of the ship that come into contact with seawater hinders efficient operation and causes problems such as fuel waste. Conventionally, in order to prevent the adhesion of organisms, an antifouling paint composition has been applied to the surface of the ship. For example, International Publication No. 2011 / 046086 (Patent Document 1) discloses an antifouling paint composition that contains a silicon atom-containing resin as a vehicle and a thermoplastic resin and / or a plasticizer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2011 / 046086 Summary of the Invention [Problem to be solved by the invention]

[0004] The antifouling coating film formed from the antifouling coating composition is required to exhibit excellent antifouling performance for a long period of time when immersed in water (seawater), and is also required to have excellent crack resistance, i.e., to be less susceptible to cracking even in an environment where drying and wetting are repeated.

[0005] The object of the present invention is to provide an antifouling coating composition capable of forming an antifouling coating film having excellent antifouling performance and excellent crack resistance. Another object of the present invention is to provide an antifouling coating film formed from the antifouling coating composition, a composite coating film having the antifouling coating film, and a ship or underwater structure having the antifouling coating film or the composite coating film. [Means for solving the problem]

[0006] The present invention provides the following antifouling coating composition, antifouling coating film, composite coating film, ship, and underwater structure. [1] An antifouling coating composition comprising a silicon atom-containing resin and a thermoplastic resin other than the silicon atom-containing resin, The silicon atom-containing resin contains a structural unit (A) having at least one silicon atom-containing group selected from the group consisting of a group represented by the following formula (I), a group represented by the following formula (II), a group represented by the following formula (III), and a group represented by the following formula (IV), The thermoplastic resin includes a thermoplastic resin having a weight average molecular weight of 1,000 or more, An antifouling coating composition, wherein the content of the thermoplastic resin having a weight average molecular weight of 1,000 or more is 6.0 parts by mass or more and 11.0 parts by mass or less per 100 parts by mass of the silicon atom-containing resin. [ka] [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. [ka] 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 are each independently an alkyl group, R a or R b Represents. R a teeth, [ka] (In the formula, x represents an integer of 0 to 200. 23 ~R 27 are the same or different and each represents an alkyl group; R b teeth, [ka] (In the formula, y represents an integer of 1 to 200. 28 and R 29 are the same or different and each represents an alkyl group. [ka] [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. [ka] [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 are the same or different and represent an alkyl group. [2] The antifouling coating composition according to [1], wherein the silicon atom-containing resin further comprises a structural unit (B) having a triorganosilyloxycarbonyl group. [3] The antifouling coating composition according to [1] or [2], wherein the silicon atom-containing resin further has a structural unit (C) derived from a monomer (c) which is a monofunctional (meth)acrylic acid ester represented by the following formula (c): CH2=C(R A )(COOR B ) (c) [In formula (c), R A R represents a hydrogen atom or a methyl group. B represents a monovalent group containing one or more groups selected from the group consisting of a hydroxyl group, a carboxy group, and an oxyalkylene chain. [4] The antifouling coating composition according to any one of [1] to [3], wherein the silicon atom-containing resin further has a structural unit (D) having at least one metal atom-containing group selected from the group consisting of a group represented by the following formula (V) and a group represented by the following formula (VI): [ka] [In formula (V), M represents a divalent metal atom, R 30 represents an organic acid residue or an alcohol residue. [ka] [In formula (VI), M represents a divalent metal atom.] [5] The antifouling coating composition according to any one of [1] to [4], wherein the content of the structural unit (A) is 20 mass % or more of all structural units contained in the silicon atom-containing resin. [6] The antifouling coating composition according to any one of [1] to [5], which does not contain an antifouling agent. [7] The antifouling coating composition according to any one of [1] to [5], further comprising an antifouling agent. [8] The antifouling coating composition according to [7], wherein the antifouling agent is at least one selected from the group consisting of cuprous oxide, a pyrithione metal salt, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and medetomidine. [9] An antifouling coating film formed from the antifouling coating composition according to any one of [1] to [8].

[10] A composite coating film having an undercoat coating film formed from an anticorrosive coating composition, and an antifouling coating film formed from the antifouling coating composition according to any one of [1] to [8] and laminated on the undercoat coating film.

[11] A ship having the antifouling coating film according to [9] or the composite coating film according to

[10] .

[12] An underwater structure having the antifouling coating film according to [9] or the composite coating film according to

[10] . Effect of the Invention

[0007] It is possible to provide an antifouling coating composition capable of forming an antifouling coating film having excellent antifouling performance and excellent crack resistance. It is also possible to provide an antifouling coating film formed from the antifouling coating composition, a composite coating film having the antifouling coating film, and a ship or underwater structure having the antifouling coating film or the composite coating film. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a schematic top view illustrating a method for evaluating the antifouling properties of a coating film. [Diagram 2] FIG. 2 is a schematic cross-sectional view illustrating a method for evaluating the antifouling properties of a coating film. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] <Antifouling paint composition> The antifouling coating composition according to the present invention (hereinafter, simply referred to as the "coating composition") contains a specific silicon atom-containing resin described below and a thermoplastic resin other than the silicon atom-containing resin. The thermoplastic resin contains a thermoplastic resin having a weight-average molecular weight of 1,000 or more, and the content of the thermoplastic resin having a weight-average molecular weight of 1,000 or more is 6.0 parts by mass or more and 11.0 parts by mass or less per 100 parts by mass of the silicon atom-containing resin.

[0010] According to the coating composition of the present invention, it is possible to form an antifouling coating film (hereinafter, also simply referred to as a "coating film") that can exhibit excellent antifouling performance for a long period of time when immersed in water (seawater). When the coating film of the present invention is formed on the surface of an underwater moving body such as a ship, the coating film can exhibit excellent antifouling performance even while the underwater moving body is moving in seawater. Conventional antifouling coating films tend to have a decrease in antifouling performance in the latter period when the underwater moving body moves in seawater for a long period of time, but the coating film of the present invention can maintain excellent antifouling performance even in the latter period.

[0011] Furthermore, the coating composition according to the present invention can form a coating film that exhibits excellent crack resistance for a long period of time when immersed in water (seawater). Conventional antifouling coating films tend to show a decrease in crack resistance in the later period when an underwater mobile body is immersed in seawater for a long period of time. The decrease in crack resistance promotes the decrease in antifouling performance. The coating film according to the present invention can maintain excellent crack resistance even in the later period. Furthermore, the coating film according to the present invention can maintain excellent crack resistance even when exposed to an environment in which the state of being immersed in seawater and the state of not being immersed in seawater are repeated after being left stationary for a certain period of time.

[0012] The coating composition according to the present invention can be suitably used as an antifouling coating composition to be applied to underwater moving bodies such as ships or underwater structures, and is particularly suitable as an antifouling coating composition to be applied to underwater moving bodies such as ships. The components that are or may be contained in the coating composition are described in detail below.

[0013] (1) Silicon atom-containing resin The silicon atom-containing resin contained in the coating composition contains a structural unit (A). The structural unit (A) is a structural unit having at least one silicon atom-containing group selected from the group consisting of a group represented by formula (I), a group represented by formula (II), a group represented by formula (III), and a group represented by formula (IV). The structural unit (A) may be a structural unit derived from a monomer (a) having at least one silicon atom-containing group selected from the above group.

[0014] The silicon atom-containing resin may contain a structural unit other than the structural unit (A). Examples of the structural unit include: A structural unit (B) having a triorganosilyloxycarbonyl group, A structural unit (C) derived from a monomer (c) which is a monofunctional (meth)acrylic acid ester represented by formula (c), and A structural unit (D) having at least one metal atom-containing group selected from the group consisting of a group represented by formula (V) and a group represented by formula (VI): etc.

[0015] In this specification, "(meth)acryloyl" refers to at least one of methacryloyl and acryloyl, "(meth)acrylic" refers to at least one of methacryl and acrylic, and "(meth)acrylate" refers to at least one of methacrylate and acrylate.

[0016] (1-1) Silicon atom-containing group The silicon atom-containing group is at least one selected from the group consisting of a group represented by formula (I), a group represented by formula (II), a group represented by formula (III), and a group represented by formula (IV).

[0017] 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 5each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.

[0018] 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 are each independently an alkyl group, R a or R b Represents. R a In the formula, x represents an integer of 0 to 200. 23 ~R 27 are the same or different and represent an alkyl group. R b In the formula, y represents an integer of 1 to 200. 28 and R 29 are the same or different and represent an alkyl group.

[0019] 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.

[0020] 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 are the same or different and represent an alkyl group.

[0021] The silicon atom-containing resin may have two or more silicon atom-containing groups selected from the group consisting of a group represented by formula (I), a group represented by formula (II), a group represented by formula (III), and a group represented by formula (IV). In this case, the resin may have two or more types of groups represented by formula (I), two or more types of groups represented by formula (II), two or more types of groups represented by formula (III), and / or two or more types of groups represented by formula (IV).

[0022] (1-2) Monomer (a) The structural unit (A) may be a structural unit derived from a monomer (a) having at least one silicon atom-containing group selected from the group consisting of a group represented by formula (I), a group represented by formula (II), a group represented by formula (III), and a group represented by formula (IV).

[0023] The monomer (a) is preferably at least one selected from the group consisting of the monomer (a1) represented by formula (I'), the monomer (a2) represented by formula (II'), the monomer (a3) ​​represented by formula (III') and the monomer (a4) represented by formula (IV'). The monomer (a1) represented by formula (I'), the monomer (a2) represented by formula (II'), the monomer (a3) ​​represented by formula (III') and the monomer (a4) represented by formula (IV') are silicon atom-containing polymerizable monomers having a group represented by formula (I), a group represented by formula (II), a group represented by formula (III) and a group represented by formula (IV), respectively.

[0024] [ka] [In formula (I'), R 31 represents a hydrogen atom or a methyl group, and a, b, m, n and R 1 ~R 5 has the same meaning as above.] [ka] [In formula (II'), R 32 represents a hydrogen atom or a methyl group, and c, d, p and R 6~R 8 has the same meaning as above.] [ka] [In formula (III'), R 33 and R 34 each independently represents a hydrogen atom or a methyl group; e, f, g, h, q, r, s, and R 9 ~R 12 has the same meaning as above.] [ka] [In formula (IV'), R 35 and R 36 each independently represents a hydrogen atom or a methyl group; i, j, k, l, t, u, v, w and R 13 ~R 22 has the same meaning as above.]

[0025] By polymerization of the monomer composition containing the monomer (a) as described above, a silicon atom-containing resin is obtained, which is a (meth)acrylic resin containing a structural unit (A) derived from the monomer (a) selected from the group consisting of the monomer (a1), the monomer (a2), the monomer (a3) ​​and the monomer (a4). This silicon atom-containing resin has at least one silicon atom-containing group selected from the group consisting of the group represented by the formula (I), the group represented by the formula (II), the group represented by the formula (III) and the group represented by the formula (IV). The silicon atom-containing resin may contain two or more types of structural units (A) derived from the monomer (a).

[0026] Monomer (a) may be a combination of two or more monomers belonging to monomer (a). The two or more monomers may have different molecular weights.

[0027] The monomer (a1) is represented by the formula (I'). By using the monomer (a1) as the monomer (a), a silicon atom-containing resin, which is a (meth)acrylic resin having a silicon atom-containing group represented by the formula (I) in a side chain, can be obtained. The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a1).

[0028] In formula (I') (the same applies to formula (I)), a is preferably 2 or 3. b is preferably 2 or 3. From the viewpoint of the water resistance of the coating film, adhesion to the base, etc., m is preferably 0 or more and 25 or less, more preferably 0 or more and 20 or less. m may be 3 or more or 5 or more, and may be 10 or less or 8 or less. From the viewpoint of the antifouling performance of the coating film and solubility in general organic solvents, n is usually 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, and even more preferably 45 or more and 160 or less. R 1 ~R 5 The substituents of the substituted phenyl group and the substituted phenoxy group in the above formula are, for example, an alkyl group and a halogen atom. R 1 ~R 5 is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group, and particularly preferably a methyl group or an ethyl group.

[0029] As the monomer (a1), a commercially available product may be used. Examples of the commercially available product include JNC Corporation's "FM-0711" (one-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,000), "FM-0721" (one-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5,000), and "FM-0725" (one-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 10,000), Shin-Etsu Chemical Co., Ltd.'s "X-22-2404" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 420), "X-22-174ASX" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 900), "X-22-174BX" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 2,300), "KF-2012" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 4,600), and "X-22-2426" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 12,000) etc.

[0030] The monomer (a2) is represented by the formula (II'). By using the monomer (a2) as the monomer (a), a silicon atom-containing resin, which is a (meth)acrylic resin having a silicon atom-containing group represented by the formula (II) in a side chain, can be obtained. The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a2).

[0031] In formula (II') (the same applies to formula (II)), c is preferably 2 or 3. d is preferably 2 or 3. From the viewpoints of the water resistance of the coating film, adhesion to the base, etc., p is preferably 0 or more and 25 or less, more preferably 0 or more and 20 or less. p may be 3 or more or 5 or more, and may be 10 or less or 8 or less.

[0032] From the viewpoint of solubility in general 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. From the viewpoint of solubility in general 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. R 6 ~R 8 and R 23 ~R 29The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group, and even more preferably a methyl group or an ethyl group. R 6 ~R 8 is preferably an alkyl group.

[0033] As the monomer (a2), a commercially available product may be used, for example, "TM-0701T" (one-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 423) manufactured by JNC Corporation.

[0034] The monomer (a3) ​​is represented by the formula (III'). By using the monomer (a3) ​​as the monomer (a), a silicon atom-containing resin, which is a (meth)acrylic resin having a silicon atom-containing group represented by the formula (III) (this silicon atom-containing group is a cross-linking group that cross-links between polymer main chains), can be obtained. The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a3).

[0035] In formula (III') (the same applies to formula (III)), e and h are preferably 2 or 3, respectively. f and g are preferably 2 or 3, respectively. From the viewpoint of the water resistance of the coating film, adhesion to the base, etc., q and s are each preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, and even more preferably 0 or more and 20 or less. q and s may each be 3 or more or 5 or more, or 10 or less or 8 or less. From the viewpoints of the antifouling performance of the coating film, solubility in general organic solvents, etc., r is usually 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, and even more preferably 45 or more and 160 or less. R 9 ~R 12The substituents of the substituted phenyl group and the substituted phenoxy group in the above formula are, for example, an alkyl group and a halogen atom. R 9 ~R 12 is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group, and particularly preferably a methyl group or an ethyl group.

[0036] As the monomer (a3), a commercially available product may be used. Examples of the commercially available product include JNC Corporation's "FM-7711" (both-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,000), "FM-7721" (both-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5,000), and "FM-7725" (both-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 10,000), Shin-Etsu Chemical Co., Ltd.'s "X-22-164" (organopolysiloxane modified with methacryloyloxyalkyl at both ends, molecular weight: 380), "X-22-164AS" (organopolysiloxane modified with methacryloyloxyalkyl at both ends, molecular weight: 900), "X-22-164A" (organopolysiloxane modified with methacryloyloxyalkyl at both ends, molecular weight: 1,720), and "X-22-164B" (organopolysiloxane modified with methacryloyloxyalkyl at both ends, molecular weight: 1,720) were used. "X-22-2445" (both terminal acryloyloxyalkyl modified organopolysiloxane, molecular weight: 3,200), "X-22-164C" (both terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4,800), "X-22-164E" (both terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 7,800) etc.

[0037] Monomer (a4) is represented by formula (IV'). By using monomer (a4) as monomer (a), a silicon atom-containing resin, which is a (meth)acrylic resin having a silicon atom-containing group represented by formula (IV) (this silicon atom-containing group is a cross-linking group that cross-links between polymer main chains), can be obtained. Commercially available products may be used as monomer (a4). The silicon atom-containing resin may contain structural units derived from two or more types of monomers (a4).

[0038] In formula (IV') (the same applies to formula (IV)), i and l are preferably 2 or 3, respectively. j and k are preferably 2 or 3, respectively. From the viewpoints of the water resistance of the coating film, adhesion to the base, etc., t and u are each preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, and even more preferably 0 or more and 20 or less. q and s may each be 3 or more or 5 or more, and 10 or less or 8 or less. From the viewpoints of the antifouling performance of the coating film, solubility in general organic solvents, etc., 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. R 13 ~R 22 The alkyl group in the formula (I) is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, or a tert-butyl group, and even more preferably a methyl group or an ethyl group.

[0039] From the viewpoint of enhancing the antifouling performance of the resulting coating film, the molecular weight of the monomer (a) is preferably 400 or more, more preferably 500 or more, even more preferably 1,000 or more, even more preferably 2,000 or more, particularly preferably 2,500 or more, even more particularly preferably 3,000 or more, most preferably 4,000 or more or 5,000 or more, and may be 10,000 or more. The molecular weight of the monomer (a) is usually 20,000 or less, preferably 18,000 or less, more preferably 15,000 or less, and even more preferably 12,000 or less. If the molecular weight of the monomer (a) is too large, the coating film formed from the coating composition is likely to be non-uniform in its components due to the incompatibility between monomers in the monomer composition, which is a mixture of monomers used to prepare the silicon atom-containing resin, or the incompatibility between polymers produced by polymerization of the monomer composition.

[0040] The molecular weight of the monomer (a) may be a number average molecular weight. The number average molecular weight of the monomer (a) is a number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0041] The content of the structural unit (A) is preferably 20% by mass or more, more preferably 21% by mass or more, and even more preferably 25% by mass or more, and may be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 50% by mass or more, in terms of improving the antifouling performance of the coating film, in all structural units contained in the silicon atom-containing resin. By having the content of the structural unit (A) of 20% by mass or more, a coating composition that exhibits sufficient antifouling performance can be obtained even when an antifouling agent is not separately contained. In addition, in terms of the coating film properties and the above-mentioned uniformity of the coating film, the content of the structural unit (A) is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, and particularly preferably 60% by mass or less, in all structural units contained in the silicon atom-containing resin.

[0042] (1-3) Monomer (b) The silicon atom-containing resin may further have a structural unit (B) having a triorganosilyloxycarbonyl group. The structural unit (B) may be a structural unit derived from a monomer (b) having a triorganosilyloxycarbonyl group. By the silicon atom-containing resin further having the structural unit (B), the antifouling performance of the coating film can be further improved.

[0043] The triorganosilyloxycarbonyl group includes a group represented by the formula (VII). [ka] [In formula (VII), R 40 , R 41 and R 42 are the same or different and represent a hydrocarbon residue having 1 to 20 carbon atoms.]

[0044] The monomer (b) is preferably a monomer (b1) represented by the formula (VII'). [ka] [In formula (VII'), R 43 represents a hydrogen atom or a methyl group, R 40 , R 41 and R 42 are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms.]

[0045] By polymerization of a monomer composition containing the monomer (b1), a silicon atom-containing resin, which is a (meth)acrylic resin containing a structural unit (B) derived from the monomer (b1), is obtained. This silicon atom-containing resin has a triorganosilyloxycarbonyl group represented by -C(=O)-O-SiR 40 R 41 R 42 has. The silicon atom-containing resin may contain two or more types of structural units (B). For example, the silicon atom-containing resin may contain two or more types of structural units (B) having different triorganosilyloxycarbonyl groups.

[0046] R in formula (VII') (the same applies to formula (VII)). 40 , R 41 and R 42 are the same or different and represent a hydrocarbon residue (monovalent hydrocarbon group) having 1 to 20 carbon atoms. Examples of the hydrocarbon residue having 1 to 20 carbon atoms include a linear or branched alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, or a tetradecyl group; a cyclic alkyl group which may have a substituent, such as a cyclohexyl group or a substituted cyclohexyl group; or an aryl group which may have a substituent, such as an aryl group or a substituted aryl group.

[0047] Examples of substituted cyclic alkyl groups include cyclic alkyl groups substituted with halogens, alkyl groups having up to about 18 carbon atoms, acyl groups, nitro groups, amino groups, etc. Examples of substituted aryl groups include aryl groups substituted with halogens, alkyl groups having up to about 18 carbon atoms, acyl groups, nitro groups, amino groups, etc.

[0048] Among them, R is the most popular because it tends to maintain the antifouling performance of the coating film stably for a long period of time. 40 , R 41 and R 42 Preferably, at least one of R is an isopropyl group. 40 , R 41 and R 42 More preferably, all of are isopropyl groups.

[0049] When the silicon atom-containing resin contains the structural unit (B), the content of the structural unit (B) is, from the viewpoint of the antifouling performance of the coating film, preferably from 2 mass% to 50 mass% of all structural units contained in the silicon atom-containing resin, more preferably from 3 mass% to 40 mass%. Even more preferably from 5 mass% to 35 mass% and still more preferably from 5 mass% to 25 mass%.

[0050] When the silicon atom-containing resin contains the structural unit (B), the ratio of the content of the structural unit (B) to the content of the structural unit (A) is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 90 parts by mass or less, and even more preferably 10 parts by mass or more and 80 parts by mass or less, per 100 parts by mass of the structural unit (A), and may be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less.

[0051] (1-4) Monomer (c) The silicon atom-containing resin may further have a structural unit (C) derived from a monomer (c). The monomer (c) is a monofunctional (meth)acrylic acid ester represented by formula (c). When the silicon atom-containing resin further has the structural unit (C), the antifouling performance of the coating film can be further improved. Furthermore, by including the structural unit (C), the coating film wear rate can be appropriately increased. CH2=C(R A )(COOR B ) (c)

[0052] In formula (c), R A R represents a hydrogen atom or a methyl group. B represents a monovalent group containing one or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, and an oxyalkylene chain. The silicon atom-containing resin may contain structural units derived from two or more types of monomers (c). The monomer (c) may be a monomer having two or more groups selected from the group consisting of a hydroxyl group, a carboxyl group, and an oxyalkylene chain.

[0053] From the viewpoint of enhancing the antifouling performance of the coating film, R BIt is preferable that the alkylene group contains at least an oxyalkylene chain. The alkylene group contained in the oxyalkylene chain may be linear or branched, and the number of carbon atoms in 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 -CH2-, -(CH2)2-, -(CH2)3-, -CH(CH3)CH2-, -CH2CH(CH3)-, and the like.

[0054] Examples of the monomer (c) include hydroxyl group-containing (meth)acrylic acid alkyl esters having an ester moiety of 1 to 20 carbon atoms, 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 (meth)acrylic acid alkyl esters having an ester moiety of 1 to 20 carbon atoms; alkoxyalkyl (meth)acrylates having an ester moiety of 1 to 20 carbon atoms, such as methoxyethyl (meth)acrylate; and methoxypolyethylene glycol (meth)acrylates (the number of repetitions of -OC2H4- is, for example,

[0043] Examples of such (meth)acrylic acid esters include (meth)acrylic acid esters in which the ester moiety contains a polyalkylene glycol chain, such as (meth)acryloyloxyethyl succinate, (meth)acryloyloxyethyl phthalate, (meth)acryloyloxyethyl hexahydrophthalate, (meth)acryloyloxypropyl phthalate, and (meth)acryloyloxypropyl hexahydrophthalate.

[0055] Among the above, the monomer (c) is preferably an alkoxyalkyl (meth)acrylate having an ester moiety with 1 to 20 carbon atoms, a (meth)acrylic acid ester having an ester moiety containing a polyalkylene glycol chain, and / or a (meth)acrylic acid ester having an ester moiety containing a polyalkylene glycol chain and a carboxy group.

[0056] When the silicon atom-containing resin contains the structural unit (C), the content of the structural unit (C) is, from the viewpoint of the antifouling performance of the coating film, preferably from 0.1 to 40 mass%, more preferably from 0.5 to 35 mass%, and even more preferably from 1 to 30 mass%, of all structural units contained in the silicon atom-containing resin, and may be 25 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less.

[0057] When the silicon atom-containing resin contains the structural unit (C), the ratio of the content of the structural unit (C) to the content of the structural unit (A) is preferably 0.5 parts by mass or more and 80 parts by mass or less, more preferably 1 part by mass or more and 70 parts by mass or less, even more preferably 1 part by mass or more and 60 parts by mass or less, and still more preferably 2 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the structural unit (A), and may be 45 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, or 20 parts by mass or less.

[0058] (1-5) Monomer (d) The silicon atom-containing resin may further have a structural unit (D) having at least one metal atom-containing group selected from the group consisting of a group represented by formula (V) and a group represented by formula (VI). The structural unit (D) may be a structural unit derived from a monomer (d) having at least one metal atom-containing group selected from the above group. By the silicon atom-containing resin further having the structural unit (D), the antifouling performance of the coating film can be further improved. The silicon atom-containing resin may have both a group represented by formula (V) and a group represented by formula (VI).

[0059] The monomer (d) is preferably at least one selected from the group consisting of a monomer (d1) represented by formula (V') and a monomer (d2) represented by formula (VI'). [ka] [In formula (V'), R 37 represents a hydrogen atom or a methyl group, and M and R 30 has the same meaning as above.] [ka] [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 defined above.

[0060] By polymerization of the monomer composition containing the monomer (d) as described above, a silicon atom-containing resin is obtained, which is a (meth)acrylic resin containing a structural unit (D) derived from the monomer (d) selected from the group consisting of the monomer (d1) and the monomer (d2). This silicon atom-containing resin has at least one metal atom-containing group selected from the group consisting of the group represented by the formula (V) and the group represented by the formula (VI). The silicon atom-containing resin may contain two or more types of structural units (D).

[0061] The divalent metal atom M in formula (V') (the same applies to formula (V)) and formula (VI') (the same applies to formula (VI)) may include Mg, Zn, Cu, etc., and is preferably Zn or Cu. R in formula (V') (the same applies to formula (V)). 30 is preferably an organic acid residue.

[0062] The monomer (d1) is represented by the formula (V'). By using the monomer (d1) as the monomer (d), a silicon atom-containing resin, which is a (meth)acrylic resin further having a metal atom-containing group represented by the formula (V), can be obtained.

[0063] R 30 In the above, examples of the organic acid that forms the organic acid residue include monobasic organic acids such as acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexyl acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotinic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, ricinoelaidic acid, brassidic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, and pulvinic acid.

[0064] Among them, when the organic acid residue is a fatty acid residue, it is preferred since it tends to maintain a coating film free from cracks and peeling for a long period of time. In particular, zinc oleate (meth)acrylate or zinc versatate (meth)acrylate, which have high plasticity, are preferably used as the monomer (d1).

[0065] Other preferred organic acids include monobasic cyclic organic acids other than aromatic organic acids. Examples of the monobasic cyclic organic acids include organic acids having a cycloalkyl group such as naphthenic acid, resin acids such as tricyclic resin acids, and salts thereof.

[0066] 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 an abietane, pimarane, isopimaran, and labdane skeleton. More specifically, examples of the monobasic acids include abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, palustric acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, and salts thereof. Among them, from the viewpoint of the antifouling performance of the coating film, abietic acid, hydrogenated abietic acid, and salts thereof are preferred.

[0067] As the monobasic cyclic organic acid, for example, rosin, pine resin acid, etc. can be used. Examples of such acids include rosins, hydrogenated rosins, disproportionated rosins, naphthenic acid, etc. Rosins include gum rosin, wood rosin, tall oil rosin, etc. Rosins, hydrogenated rosins, and disproportionated rosins are preferred in that they are inexpensive, easily available, have excellent handleability, and are easy to improve antifouling performance.

[0068] The acid value of the monobasic cyclic organic acid is preferably 100 mgKOH / g or more and 220 mgKOH / g or less, more preferably 120 mgKOH / g or more and 190 mgKOH / g or less, and even more preferably 140 mgKOH / g or more and 185 mgKOH / g or less. R 30 When the monobasic cyclic organic acid forming the compound having an acid value within the above range is used, the excellent stain-proofing performance of the coating film tends to be maintained for a longer period of time. The organic acid residue contained in the monomer (d1) may be formed from one type of organic acid, or may be formed from two or more types of organic acids.

[0069] R 30 A method for producing the monomer (d1) having an organic acid residue as a monomer unit may include, for example, a method of reacting an inorganic metal compound, a carboxyl group-containing radical polymerizable monomer such as (meth)acrylic acid, and a non-polymerizable organic acid (an organic acid constituting the organic acid residue) in an organic solvent containing an alcohol compound. The structural unit (D) derived from the monomer (d1) can also be formed by a method of reacting a resin obtained by polymerizing a monomer composition containing a carboxyl group-containing radically polymerizable monomer such as (meth)acrylic acid with a metal compound and a non-polymerizable organic acid (an organic acid that constitutes the above-mentioned organic acid residue).

[0070] The monomer (d2) is represented by the formula (VI'). By using the monomer (d2) as the monomer (d), a silicon atom-containing resin, which is a (meth)acrylic resin further having a metal atom-containing group represented by the formula (VI) (this metal atom-containing group is a cross-linking group that cross-links between polymer main chains), can be obtained.

[0071] Examples of the monomer (d2) include magnesium acrylate [(CH2=CHCOO)2Mg], magnesium methacrylate [(CH2=C(CH3)COO)2Mg], zinc acrylate [(CH2=CHCOO)2Zn], zinc methacrylate [(CH2=C(CH3)COO)2Zn], copper acrylate [(CH2=CHCOO)2Cu], copper methacrylate [(CH2=C(CH3)COO)2Cu], etc. These may be used alone or in combination of two or more as required.

[0072] The method for producing the monomer (d2) may be, for example, a method in which a polymerizable unsaturated organic acid such as (meth)acrylic acid is reacted with a metal compound together with water in an organic solvent containing an alcohol-based compound. In this case, it is preferable to adjust the water content in the reaction product to 0.01% by mass or more and 30% by mass or less.

[0073] The silicon atom-containing resin may contain both a structural unit derived from the monomer (d1) and a structural unit derived from the monomer (d2).

[0074] When the silicon atom-containing resin contains the structural unit (D), the content of the structural unit (D) is preferably from 1 mass % to 30 mass %, more preferably from 2 mass % to 25 mass %, and even more preferably from 4 mass % to 20 mass %, of all structural units contained in the silicon atom-containing resin, from the viewpoint of the antifouling performance of the coating film, etc.

[0075] When the silicon atom-containing resin contains the structural unit (D), the ratio of the content of the structural unit (D) to the content of the structural unit (A) is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, even more preferably 2 parts by mass or more and 35 parts by mass or less, and still more preferably 5 parts by mass or more and 30 parts by mass or less, and may be 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less, per 100 parts by mass of the structural unit (A).

[0076] (1-6) Monomer (e) The silicon atom-containing resin may further have a structural unit (E) derived from a monomer (e) that is a polyfunctional (meth)acrylic acid ester having two or more (meth)acryloyl groups. By the silicon atom-containing resin further having the structural unit (E), the dynamic antifouling property and / or crack resistance of the coating film can be further improved. The silicon atom-containing resin may contain two or more types of structural units (E) derived from the monomer (e).

[0077] Examples of the monomer (b) include difunctional (meth)acrylates having two (meth)acryloyloxy groups in the molecule, and trifunctional or higher functional (meth)acrylates having three or more (meth)acryloyloxy groups in the molecule.

[0078] An example of the bifunctional (meth)acrylate is a compound (e-1) represented by the formula (e-1). [ka] [In the formula, R C R each independently represents a hydrogen atom or a methyl group. D represents a divalent hydrocarbon group which may have a substituent, and at least one -CH2- in the hydrocarbon group may be replaced by -O- or -C(=O)-.

[0079] R C is preferably a methyl group. RD Examples of the alkylene group include, but are not limited to, an alkylene group, a poly(oxyalkylene) group, etc. The number of carbon atoms in the alkylene group may be, for example, 1 to 20, 2 to 12, or 3 to 10. The alkylene group may be linear, branched, or cyclic.

[0080] The poly(oxyalkylene) group is -(oxyalkylene group). x -. x represents the number of repetitions of the oxyalkylene group and may be, for example, 1 to 50, 1 to 23, 2 to 23, 2 to 20, 2 to 12, or 2 to 10. The number of carbon atoms in the alkylene group in the oxyalkylene group may be, for example, 2 to 6, 2 to 4, or 2 to 3.

[0081] Specific examples of bifunctional (meth)acrylates include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and the like. Examples of the di(meth)acrylate include acrylate, tricyclodecane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (the number of repeating oxyalkylene groups is, for example, 4 or more and 23 or less), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate (the number of repeating oxyalkylene groups is, for example, 4 or more and 23 or less).

[0082] Examples of the trifunctional or higher (meth)acrylates include glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, and ethylene glycol modified trimethylolpropane tri(meth)acrylate. acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, and the like.

[0083] The tri- or higher functional (meth)acrylate is preferably tri- to hexafunctional, and more preferably tri- or tetrafunctional.

[0084] When the silicon atom-containing resin contains the structural unit (E), the content of the structural unit (E) derived from the monomer (e) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and may be 2% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more, in terms of further improving the crack resistance, in the total structural units contained in the silicon atom-containing resin. The content of the structural unit (E) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. If the content of the structural unit (E) is too large, the silicon atom-containing resin tends to gel when it is prepared.

[0085] When the silicon atom-containing resin contains the structural unit (E), the ratio of the content of the structural unit (E) to the content of the structural unit (A) is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, and even more preferably 2 parts by mass or more and 30 parts by mass or less, per 100 parts by mass of the structural unit (A).

[0086] (1-7) Other monomers The silicon atom-containing resin may contain a structural unit (F) derived from a monomer (f) other than the above. The silicon atom-containing resin may contain two or more types of structural units (F).

[0087] The other monomer (f) is not particularly limited as long as it is an unsaturated monomer copolymerizable with the monomers (a) to (e), and examples thereof include Methyl (meth)acrylate, ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethylhexaoxy)ethyl (meth)acrylate, 1-methyl-2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate, m-methoxyphenyl (meth)acrylate, p-methoxyphenyl (meth)acrylate, o-methoxyphenylethyl (meth)acrylate, m-methoxyphenylethyl (meth)acrylate, p (meth)acrylic acid ester monomers not belonging to monomers (c) and (e), such as -methoxyphenylethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, and glycidyl (meth)acrylate; Primary or secondary amino group-containing vinyl monomers such as butylaminoethyl (meth)acrylate and (meth)acrylamide; Tertiary amino group-containing vinyl monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylamide, and dimethylaminopropyl (meth)acrylamide; Heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine, and vinylcarbazole; Other vinyl monomers such as styrene, vinyl toluene, α-methylstyrene, (meth)acrylonitrile, vinyl acetate, and vinyl propionate etc. The silicon atom-containing resin preferably contains methyl methacrylate.

[0088] When the silicon atom-containing resin contains the structural unit (F), the content of the structural unit (F) is usually 0.1% by mass or more and 85% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 75% by mass or less, even more preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 70% by mass or less, based on the total structural units contained in the silicon atom-containing resin. By making the content of the structural unit (F) 0.1% by mass or more, it is possible to balance the various properties of the resulting coating composition and coating film. By making the content of the structural unit (F) 85% by mass or less, a coating film that exhibits sufficient antifouling performance can be formed even without separately containing an antifouling agent.

[0089] (1-8) Molecular weight of silicon atom-containing resin The number average molecular weight of the silicon atom-containing resin is usually 2,000 or more and 100,000 or less, preferably 3,000 or more and 50,000 or less, more preferably 5,000 or more and 30,000 or less. When the number average molecular weight of the silicon atom-containing resin is 2,000 or more, the coating film formed from the coating composition tends to exhibit antifouling performance. When the number average molecular weight of the silicon atom-containing resin is 100,000 or less, the silicon atom-containing resin tends to be easily dispersed uniformly in the coating composition. The number average molecular weight of the silicon atom-containing resin is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0090] (1-9) Method for producing silicon atom-containing resin The method for producing the silicon atom-containing resin is not particularly limited, but for example, the resin can be produced by reacting a monomer composition obtained by mixing the above-mentioned 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 may be appropriately adjusted.

[0091] Examples of the radical initiator include 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylvaleronitrile), 2,2-azobis(2-methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-tert-butyl peroxide, and tert-butylperoxy-2-ethylhexanoate.

[0092] The polymerization method may be a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, etc., which are carried out in an organic solvent. From the viewpoint of the production efficiency of the silicon atom-containing resin, the solution polymerization method is preferable. The organic solvent may be a general organic solvent such as toluene, xylene, methyl isobutyl ketone, or n-butyl acetate.

[0093] (1-10) Silicon atom-containing resin content The content of the silicon atom-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 98% by mass or less, and even more preferably 35% by mass or more and 97% by mass or less, and may be 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the solid content contained in the coating composition. If the content of the silicon atom-containing resin is less than 25% by mass, the antifouling property and the adhesion of the coating film to the base tend to decrease. The solid content contained in the coating composition refers to the total of the components other than the solvent contained in the coating composition.

[0094] (1-11) Silicon Atom-Containing Resin Preferred embodiments of the silicon atom-containing resin are exemplified below. (i) A silicon atom-containing resin having constitutional units derived from a monomer (a) and a monomer (b). (ii) A silicon atom-containing resin having constitutional units derived from the monomer (a) and the monomer (c). (iii) A silicon atom-containing resin having constitutional units derived from the monomer (a) and the monomer (e). (iv) A silicon atom-containing resin having constitutional units derived from the monomer (a), the monomer (b) and the monomer (e). (v) A silicon atom-containing resin having constitutional units derived from the monomer (a) and the monomer (d). (vi) A silicon atom-containing resin having constitutional units derived from the monomer (a), the monomer (b) and the monomer (d). (vii) A silicon atom-containing resin in any one of the above (i), (iii) to (vi), further comprising a structural unit derived from a monomer (c).

[0095] From the viewpoints of dynamic antifouling properties and crack resistance, the silicon atom-containing resin preferably has a structural unit derived from at least one monomer selected from monomer (b) and monomer (d), and more preferably has a structural unit derived from monomer (b). From the viewpoints of dynamic antifouling properties and crack resistance, the silicon atom-containing resin preferably has a structural unit derived from monomer (e), and more preferably has a structural unit derived from monomer (b) and monomer (e). When the silicon atom-containing resin has a structural unit derived from a monomer (d), the metal atom M contained in the monomer (d) is preferably Zn or Cu from the viewpoints of dynamic antifouling property and crack resistance, and more preferably Zn from the viewpoint of crack resistance. When the silicon atom-containing resin further contains a structural unit derived from the monomer (c), the dynamic antifouling property tends to be further improved.

[0096] (2)Thermoplastic resin The coating composition contains a thermoplastic resin other than the silicon atom-containing resin, and the thermoplastic resin contains a thermoplastic resin having a weight average molecular weight of 1,000 or more. Hereinafter, the thermoplastic resin having a weight average molecular weight of 1,000 or more is also referred to as a "high molecular weight thermoplastic resin." The content of the high molecular weight thermoplastic resin in the coating composition is 6.0 parts by mass or more and 11.0 parts by mass or less per 100 parts by mass of the silicon atom-containing resin. The coating composition may contain two or more high molecular weight thermoplastic resins.

[0097] According to the coating composition of the present invention, which contains a predetermined amount of a high molecular weight thermoplastic resin in addition to a silicon atom-containing resin, the coating film formed from it can achieve both excellent antifouling performance (dynamic antifouling property) and excellent crack resistance at a remarkably high level.

[0098] The weight average molecular weight of the high molecular weight thermoplastic resin is preferably 2,000 or more, more preferably 2,500 or more, even more preferably 3,000 or more, and even more preferably 4,000 or more, from the viewpoint of improving the crack resistance of the coating film or further improving the dynamic antifouling property. From the viewpoint of improving the dynamic antifouling property and / or the crack resistance, the weight average molecular weight of the high molecular weight thermoplastic resin is preferably 200,000 or less, more preferably 150,000 or less, even more preferably 100,000 or less, even more preferably 50,000 or less, particularly preferably 25,000 or less, even more particularly preferably 10,000 or less, even more particularly preferably 9,000 or less, and most preferably 6,000 or less or 5,000 or less. The weight average molecular weight of the thermoplastic resin is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0099] Examples of high molecular weight thermoplastic resins include chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; partially hydrogenated terphenyls; polyvinyl acetate; (meth)acrylic resins; 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 and fats, and refined products thereof.

[0100] Examples of the (meth)acrylic resin include homopolymers or copolymers formed from a monomer selected from the (meth)acrylic acid ester monomers exemplified above as examples of the other monomer (f). More specific examples include poly(meth)acrylic acid alkyl esters such as methyl (meth)acrylate-based copolymers, ethyl (meth)acrylate-based copolymers, propyl (meth)acrylate-based copolymers, butyl (meth)acrylate-based copolymers, and cyclohexyl (meth)acrylate-based copolymers.

[0101] The (meth)acrylic resin may contain at least one type of structural unit selected from the group consisting of the structural unit (B), the structural unit (C), and the structural unit (D).

[0102] In particular, from the viewpoint of achieving both excellent antifouling performance and excellent crack resistance at a significantly high level, the high molecular weight thermoplastic resin is preferably selected from polyvinyl ether, vinyl chloride-isobutyl vinyl ether copolymer, poly(alkyl(meth)acrylate), and a (meth)acrylic resin containing the structural unit (D).

[0103] From the viewpoint of achieving a high degree of compatibility between dynamic soiling resistance and crack resistance, the content of the high molecular weight thermoplastic resin is 6.0 parts by mass or more and 11.0 parts by mass or less, preferably 6.5 parts by mass or more and 10.5 parts by mass or less, and more preferably 7.0 parts by mass or more and 10.0 parts by mass or less, per 100 parts by mass of the silicon atom-containing resin.

[0104] The coating composition may contain a thermoplastic resin having a weight-average molecular weight of less than 1,000. By further containing such a thermoplastic resin, the antifouling performance and / or crack resistance of the coating film can be adjusted. Examples of the thermoplastic resin having a weight-average molecular weight of less than 1,000 include chlorinated paraffin, rosin, hydrogenated rosin, naphthenic acid, fatty acid, and divalent metal salts thereof. In addition, examples of the thermoplastic resin having a weight-average molecular weight of less than 1,000 include the thermoplastic resins listed as examples of high molecular weight thermoplastic resins, which have a weight-average molecular weight of less than 1,000.

[0105] The content of the thermoplastic resin having a weight average molecular weight of less than 1,000 is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and may be 15 parts by mass or less, or even 10 parts by mass or less, or may be 1 part by mass or more, or 2 parts by mass or more, relative to 100 parts by mass of the silicon atom-containing resin.

[0106] (3) Other components that may be contained in the coating composition The coating composition may contain one or more other components other than the silicon atom-containing resin and the thermoplastic resin. Examples of the other components include additives such as defoamers, anti-sagging agents, plasticizers, antifouling agents, water binding agents, color separation inhibitors, anti-settling agents, coating wear regulators, ultraviolet absorbers, surface regulators, viscosity regulators, leveling agents, pigment dispersants, pigments, and solvents. These additives, pigments, and solvents may each be used alone or in combination of two or more.

[0107] The defoaming agent is an agent that has the effect of making the surface of the foam to be formed uneven and suppressing the formation of foam, or an agent that has the effect of locally thinning the surface of the formed foam and breaking the foam. Examples of the defoaming agent include silicon-based defoaming agents and non-silicon-based defoaming agents. The silicon-based defoaming agent is a defoaming agent containing a polysiloxane having surface activity or a modified product thereof, and the non-silicon-based defoaming agent is a defoaming agent other than the silicon-based defoaming agent (a defoaming agent that does not contain a polysiloxane or a modified product thereof). The silicon-based defoaming agent may be a fluorine-modified silicon-based defoaming agent. The fluorine-modified silicon-based defoaming agent is a defoaming agent containing a fluorine-modified polysiloxane.

[0108] Examples of non-silicon-based defoamers include higher alcohol-based, higher alcohol derivative-based, fatty acid-based, fatty acid derivative-based, paraffin-based, (meth)acrylic polymer-based, mineral oil-based, etc. Examples of silicone-based defoamers include oil-based, compound-based, self-emulsifying, emulsion-based, etc.

[0109] As the defoaming agent, a commercially available product may be used. Examples of commercially available non-silicon-based defoaming agents include mineral oil-based defoaming agents such as "BYK-030" manufactured by BYK Co., Ltd.; polymer-based defoaming agents such as "Disparlon OX68" manufactured by Kusumoto Chemical Co., Ltd. and "BYK-1790" manufactured by BYK Co., Ltd., and the like. Examples of commercially available silicone-based defoaming agents other than fluorine-modified silicone-based defoaming agents include silicone oil-based defoaming agents such as "KF-96" manufactured by Shin-Etsu Chemical Co., Ltd. and "BYK-081" manufactured by BYK Co., Ltd., and the like. Examples of commercially available fluorine-modified silicone-based defoaming agents include fluorosilicone oil-based defoaming agents such as "BYK-063", "BYK-065", and "BYK-066N" manufactured by BYK Co., Ltd. and "FA-630" manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0110] From the viewpoint of improving defoaming properties, the content of the defoaming agent is, relative to 100 parts by mass of the silicon atom-containing resin, 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, even more preferably 0.01 parts by mass or more and 0.40 parts by mass or less, and even more preferably 0.01 parts by mass or more and 0.20 parts by mass or less.

[0111] The anti-sagging agent is an agent that has the effect of suppressing the occurrence of sagging of the coating composition that may occur between the application of the coating composition to the substrate and the completion of drying of the coating film. Examples of the anti-sagging agent include amide-based anti-sagging agents, bentonite-based anti-sagging agents, polyethylene wax such as oxidized polyethylene wax, hydrogenated castor oil wax, long-chain fatty acid ester-based polymers, polycarboxylic acids, silica microparticle-based anti-sagging agents, and mixtures of two or more of these.

[0112] Examples of the amide-based anti-sagging agent include amide wax-based anti-sagging agents such as fatty acid amide wax, polyamide wax, etc. Examples of the fatty acid amide wax include stearic acid amide wax, oleic acid amide wax, etc.

[0113] Commercially available products may be used as the sagging prevention agent. Commercially available amide wax-based sagging prevention agents include, for example, "Tallen 7200-20" manufactured by Kyoeisha Chemical Co., Ltd., "Disparlon 6900-20X" and "Disparlon RE-8000" manufactured by Kusumoto Chemical Co., Ltd., and "Monoral 3300" manufactured by HS CHEM. Other commercially available sagging prevention agents include, for example, organic bentonite-based sagging prevention agents such as "Benton 38" manufactured by Elementis Japan Co., Ltd. and "TIXOGEL" manufactured by BYK.

[0114] From the viewpoint of improving sagging prevention properties, the content of the anti-drooping agent is, relative to 100 parts by mass of the silicon atom-containing resin, 0.1 parts by mass or more and 6.0 parts by mass or less, more preferably 0.2 parts by mass or more and 5.0 parts by mass or less, and even more preferably 0.25 parts by mass or more and 4.0 parts by mass or less.

[0115] The coating composition may contain a plasticizer. By further containing a plasticizer, the antifouling performance and / or crack resistance of the coating film may be adjusted. Examples of the plasticizer include phthalates such as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate (DIDP); aliphatic dibasic acid esters such as isobutyl adipate and dibutyl sebacate; glycol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; phosphate esters such as tricresyl phosphoric acid (tricresyl phosphate), triaryl phosphoric acid (triaryl phosphate), and trichloroethyl phosphoric acid; epoxy compounds such as epoxy soybean oil and epoxy octyl stearate; organic tin compounds such as dioctyl tin laurate and dibutyl tin laurate; trioctyl trimellitate, triacetylene, and the like.

[0116] The content of the plasticizer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, and may be 15 parts by mass or less, or even 10 parts by mass or less, or may be 1 part by mass or more, or 2 parts by mass or more, relative to 100 parts by mass of the silicon atom-containing resin.

[0117] The coating film formed from the coating composition of the present invention can exhibit good antifouling performance due to the antifouling effect based on the silicon atom-containing resin, so it is not necessary to contain an antifouling agent separately from the silicon atom-containing resin. However, in order to further improve the antifouling performance or to further improve the long-term durability of the antifouling performance, the coating composition may contain an antifouling agent as necessary. As the antifouling agent, a known one can be used, for example, an inorganic compound, an organic compound containing a metal, and an organic compound not containing a metal.

[0118] Examples of antifouling agents include zinc oxide, cuprous oxide, manganese ethylene bisdithiocarbamate, zinc dimethyl dithiocarbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyldichlorophenylurea, zinc ethylene bisdithiocarbamate, copper rhodanide (cuprous thiocyanate), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5,-dichloro-2- n-Octyl-3(2H)isothiazolone;N-(Fluorodichloromethylthio)phthalimide;N,N'-Dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide;Metal pyrithione salts such as zinc pyrithione or copper pyrithione of 2-pyridinethiol-1-oxide;Tetramethylthiuram disulfide;2,4,6-Trichlorophenylmaleimide;2,3,5,6-Tetrachloro-4-(methylsulfonyl)pyridine;3-Iodo-2-propylbutyl Carbamates;Diiodomethyl-p-trisulfone;Phenyl(bispyridyl)bismuth dichloride;2-(4-Thiazolyl)-benzimidazole;Triphenylboron pyridine salt;Stearylamine-triphenylboron;Laurylamine-triphenylboron;Bisdimethyldithiocarbamoylzinc ethylene bisdithiocarbamate;1,1-Dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfenamide;1,1-Dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfenamide N'-(3,4-dichlorophenyl)-N,N'-dimethylurea; N'-t-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 (generic name: medetomidine).

[0119] Among them, the antifouling agent is preferably at least one selected from the group consisting of cuprous oxide, pyrithione metal salts, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and medetomidine.

[0120] When the coating composition contains an antifouling agent, the content of the antifouling agent in the coating composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass, and may be 0.5 parts by mass or more, 1 part by mass or more, or 5 parts by mass or more, relative to 100 parts by mass of the silicon atom-containing resin. The content of the antifouling agent in the coating composition is preferably 150 parts by mass or less, more preferably 120 parts by mass or less, and even more preferably 100 parts by mass or less, relative to 100 parts by mass of the silicon atom-containing resin, and may be 80 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, 40 parts by mass or less, 30 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less. By having the content of the antifouling agent within the above range, it is possible to further improve the antifouling performance and further improve the long-term durability of the antifouling performance without adversely affecting the performance of the obtained coating film.

[0121] Examples of pigments include extender pigments such as precipitated barium, talc, clay, chalk, silica white, alumina white, bentonite, calcium carbonate, magnesium carbonate, silicic acid, silicates, aluminum oxide hydrate, and calcium sulfate; and color pigments such as titanium oxide, zirconium oxide, basic lead sulfate, tin oxide, carbon black, white lead, graphite, zinc sulfide, zinc oxide, chromium oxide, yellow nickel titanium, yellow chromium titanium, yellow iron oxide, red iron oxide (red oxide), black iron oxide, azo-based red and yellow pigments, chrome yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, and quinacridone.

[0122] Examples of the solvent include hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, and white spirit; 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 propyl alcohol.

[0123] (4) Preparation of coating composition The coating composition can be prepared, for example, by adding a high molecular weight thermoplastic resin and, if necessary, other components 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 mixing them using a mixer such as a ball mill, a pebble mill, a roll mill, a sand grind mill, or a high-speed disperser.

[0124] It is preferable that the coating composition has a low VOC. VOC is an abbreviation for volatile organic compounds, and is calculated by dividing the non-volatile content (solid content, unit: mass %) of the coating composition by the specific gravity (unit: g / cm 3 ) and calculate the value by substituting it into the following formula (unit: g / L). Generally, if the VOC is high, the non-volatile content in the paint composition will be low, and if the VOC is low, the non-volatile content will be high. VOC = 1,000 x specific gravity of paint composition x (1 - non-volatile content of paint composition / 100) The VOC of the coating composition is, for example, 570 or less or 550 or less, and preferably 500 or less.

[0125] <Anti-fouling coating film and composite coating film> The antifouling coating film according to the present invention (hereinafter, also simply referred to as "coating film") is a coating film formed from the antifouling paint composition according to the present invention. The coating film is an antifouling coating film having antifouling performance. Since the coating film is formed from the antifouling paint composition according to the present invention, it is possible to achieve both excellent antifouling performance and excellent crack resistance at a remarkably high level.

[0126] The coating film can be formed by applying the coating composition to the surface of the substrate in a conventional manner, and then volatilizing and removing the solvent at room temperature or under heating as necessary. Examples of the coating composition application method include conventionally known methods such as immersion, spraying, brush coating, 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, and preferably 100 μm or more and 400 μm or less.

[0127] Examples of the object to be coated include underwater moving bodies such as ships and underwater structures. Examples of the underwater structures include various fishing nets such as fish farming nets and other fishing gear, port facilities, oil fences, water intake facilities such as power plants, piping such as cooling water pipes, bridges, buoys, industrial water system facilities, and undersea bases. The object to be coated is preferably an underwater moving body, and examples of the underwater moving body include ships, fishing nets, and fishing gear.

[0128] The coating surface of the above-mentioned substrate may be pretreated as necessary, or a coating film formed from the coating composition of the present invention may be formed on an undercoat coating film formed on the substrate from another coating composition such as an anti-rust coating composition (anti-corrosion coating composition) to form a composite coating film.

[0129] According to the coating composition of the present invention, since the vehicle, the silicon-containing resin, itself exhibits good antifouling properties, it is possible to eliminate the need for a separate antifouling agent or to reduce the amount of such agent added. Therefore, according to the coating composition of the present invention, it is possible to form a clear (highly transparent) antifouling coating film.

[0130] For example, in a composite coating film having an undercoat coating film formed by an anti-rust paint composition or the like and the coating film of the present invention formed on the undercoat coating film, by making the coating film of the present invention a clear antifouling coating film and using anti-rust paint compositions of various hues, it is possible to provide a coated object such as a ship having an unprecedented hue on the surface on which the composite coating film is formed while maintaining antifouling performance. Also, by forming an intermediate coating film formed by a paint having various hues between the undercoat coating film formed by the anti-rust paint composition or the like and the clear antifouling coating film, it is possible to provide a coated object having an unprecedented hue.

[0131] Examples of the coating composition that forms the intermediate coating film include various coating compositions such as an antifouling coating composition, an epoxy resin-based coating composition, a urethane resin-based coating composition, a (meth)acrylic resin-based coating composition, a chlorinated rubber-based coating composition, an alkyd resin-based coating composition, a silicone resin-based coating composition, and a fluororesin-based coating composition. The antifouling coating composition that forms the intermediate coating film may be the coating composition according to the present invention, or may be another antifouling coating composition such as a conventional antifouling coating composition containing a relatively large amount of an antifouling agent.

[0132] The intermediate coating film may be formed on the entire surface of the undercoat coating film, or may be formed on a part of the surface. The intermediate coating film and the undercoat coating film may be old coating films that have been used. In this case, the coating composition of the present invention and the coating film formed therefrom may be used for repairing the old coating film. EXAMPLES

[0133] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these.

[0134] <Resin Production Example 1: Production of Silicon Atom-Containing Resin (S1)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as a solvent and kept at 100° C. A mixture of 40.0 parts by mass of FM-0721 as monomer (a), 14.2 parts by mass of TIPSMA as monomer (b), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, and 20.0 parts by mass of EA as monomer (f), and 2.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel and dropped at a constant rate into the four-neck flask over a period of 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropping. Thereafter, a mixed liquid consisting of 24.0 parts by mass of xylene, 24 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and after completion of the addition, the mixture was kept warm for 1.5 hours to obtain a resin composition (solution) containing a silicon atom-containing resin (S1).

[0135] <Resin Production Example 2: Production of Silicon Atom-Containing Resin (S2)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as a solvent and kept at 100° C. A mixture of 40.0 parts by mass of FM-0721 as monomer (a), 10.0 parts by mass of EHMA, 30.0 parts by mass of MMA, and 20.0 parts by mass of EA as monomer (f), and 2.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 30 minutes after the completion of the dropping. Thereafter, a mixture of 15.0 parts by mass of xylene, 15.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S2).

[0136] <Resin Production Example 3: Production of Silicon Atom-Containing Resin (S3)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as a solvent and kept at 100° C. A mixture of 40.0 parts by mass of FM-0721 as monomer (a), 14.2 parts by mass of TIPSMA as monomer (b), 5.0 parts by mass of CB-1 as monomer (c), 10.0 parts by mass of EHMA, 10.8 parts by mass of MMA, and 20.0 parts by mass of EA as monomer (f), and 2.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this was dropped into the four-neck flask at a constant speed over 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropwise addition. Thereafter, a mixture of 18.0 parts by mass of xylene, 18.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S3).

[0137] <Resin Production Example 4: Production of Silicon Atom-Containing Resin (S4)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as a solvent and kept at 100° C. A mixture of 40.0 parts by mass of FM-0721 as monomer (a), 14.2 parts by mass of TIPSA as monomer (b), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, and 20.0 parts by mass of EA as monomer (f), and 2.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this was dropped into the four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropwise addition. Thereafter, a mixture of 4.0 parts by mass of xylene, 4.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S4).

[0138] <Resin Production Example 5: Production of Silicon Atom-Containing Resin (S5)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as a solvent and kept at 100° C. A mixture of 40.0 parts by mass of FM-0721 as monomer (a), 14.2 parts by mass of TIPSA as monomer (b), 1.0 parts by mass of NPG as monomer (e), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, and 19.0 parts by mass of EA as monomer (f), and 2.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this was dropped into the four-neck flask at a constant speed over 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropwise addition. Thereafter, a mixture of 4.0 parts by mass of xylene, 4.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S5).

[0139] <Resin Production Example 6: Production of Silicon Atom-Containing Resin (S6)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 80.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 40.0 parts by mass of KF-2012 as monomer (a), 15.0 parts by mass of TIPSA as monomer (b), 5.0 parts by mass of CB-1 as monomer (c), 1.0 parts by mass of NPG as monomer (e), 20.0 parts by mass of t-BMA, 8.0 parts by mass of n-BMA, 5.5 parts by mass of MMA, and 5.5 parts by mass of EA as monomer (f), and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this was dropped into the four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 60 minutes after the end of the dropwise addition. Thereafter, a mixture of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S6).

[0140] <Resin Production Example 7: Production of Silicon Atom-Containing Resin (S7)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 21.0 parts by mass of FM-0721 as monomer (a), 4.0 parts by mass of M-40G and 1.0 part by mass of HEMA as monomer (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 5.0 parts by mass of EHMA, and 39.0 parts by mass of MMA as monomer (f), 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel and dropped at a constant rate into the four-neck flask over 3 hours, and the mixture was kept warm for 80 minutes after the end of the dropping. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S7).

[0141] <Resin Production Example 8: Production of Silicon Atom-Containing Resin (S8)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 21.0 parts by mass of FM-0711 as monomer (a), 4.0 parts by mass of M-40G and 1.0 parts by mass of HEMA as monomer (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 5.0 parts by mass of EHMA, and 39.0 parts by mass of MMA as monomer (f), 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel, and this was dropped into the four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 80 minutes after the end of the dropping. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S8).

[0142] <Resin Production Example 9: Production of Silicon Atom-Containing Resin (S9)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 21.0 parts by mass of TM-0701T as monomer (a), 4.0 parts by mass of M-40G and 1.0 parts by mass of HEMA as monomer (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 5.0 parts by mass of EHMA, and 39.0 parts by mass of MMA as monomer (f), 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, was added to the dropping funnel and dropped at a constant rate into the four-neck flask over a period of 3 hours, and the mixture was kept warm for 80 minutes after the end of the dropping. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a silicon atom-containing resin (S9).

[0143] <Resin Production Example 10: Production of Silicon Atom-Containing Resin (S10)> (1) Preparation of Metal Atom-Containing Polymerizable Monomer Mixture (M1): Monomer (d) In a four-neck flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, 85.4 parts by mass of PGM (propylene glycol methyl ether) and 40.7 parts by mass of zinc oxide were charged and heated to 75°C while stirring. Next, a mixture consisting of 43.1 parts by mass of MAA (methacrylic acid), 36.1 parts by mass of AA (acrylic acid) and 5.0 parts by mass of water was dropped at a constant rate from the dropping funnel over 3 hours. After stirring for another 2 hours, 36.0 parts by mass of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture (M1) (solid content concentration: 44.8 parts by mass). This metal atom-containing polymerizable monomer mixture (M1) contains zinc (meth)acrylate belonging to the monomer (d2) represented by the above formula (VI').

[0144] (2) Production of silicon atom-containing resin (S10) Into a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 15.0 parts by mass of PGM as a solvent, 65.0 parts by mass of xylene, and 4.0 parts by mass of EA as monomer (f) were charged, and the temperature was raised with stirring and maintained at 100°C. A mixture obtained by previously mixing 40.0 parts by mass of FM-0711 (monomer (a)), 21.7 parts by mass of the metal atom-containing polymerizable monomer mixture (M1) (monomer (d)) produced in (1) above, and 20.4 parts by mass of MMA and 13.9 parts by mass of EA (monomer (f)), 10.0 parts by mass of xylene, 1.2 parts by mass of a chain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of azobisisobutyronitrile (AIBN), and 0.8 parts by mass of azobismethylbutyronitrile (AMBN) was placed in the dropping funnel and added dropwise to the four-neck flask at a constant rate over 6 hours. Then, 0.5 parts by mass of t-butyl peroctoate and 10.0 parts by mass of xylene were added dropwise over 30 minutes, and the mixture was stirred for another 1 hour and 30 minutes, after which 10.1 parts by mass of xylene was added to obtain a resin composition (solution) containing a silicon atom-containing resin (S10).

[0145] <Resin Production Example 11: Production of Silicon Atom-Containing Resin (S11)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 30.0 parts by mass of FM-0725 as monomer (a), 6.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 30.0 parts by mass of MMA, and 10.0 parts by mass of EA, 14.0 parts by mass of AA, 10.0 parts by mass of xylene as monomer (f), and 1.2 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel, and this was dropped into the four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropping. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.0 hour after completion of the addition to obtain a resin composition (solution) containing a resin having a carboxyl group.

[0146] Next, 100 parts by mass of the resin composition, 18.6 parts by mass of zinc acetate (II), 33.2 parts by mass of naphthenic acid (NA-165), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours while removing the mixture of acetic acid, water, and solvent that was distilled, and replenishing the same amount of xylene. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, n-butanol and xylene were added so that the solid content concentration of the resin composition was 50.2% by mass, to obtain a resin composition (solution) containing resin (S11). Resin (S11) is a resin having a carboxyl group, in which the carboxyl group of the resin having a carboxyl group is -COO-Zn 2+ ( - OOC-Y), where Y is the non-carboxyl portion of naphthenic acid.

[0147] <Resin Production Example 12: Production of Silicon Atom-Containing Resin (S12)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as a solvent and kept at 100° C. A mixture of 40.0 parts by mass of FM-0711 as monomer (a), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, 20.0 parts by mass of EA, and 14.2 parts by mass of AA as monomer (f), and 2.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and dropped at a constant rate into the four-neck flask over a period of 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropping. Thereafter, a mixture of 25.0 parts by mass of xylene, 25.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after completion of the addition to obtain a resin composition (solution) containing a resin having a carboxyl group.

[0148] Next, 100 parts by mass of the resin composition, 19.6 parts by mass of copper (II) acetate, 27.5 parts by mass of naphthenic acid (NA-200), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours while removing the mixture of acetic acid, water, and solvent that was distilled, and replenishing the same amount of xylene. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, xylene was added so that the solid content concentration of the resin composition was 46.4% by mass, to obtain a resin composition (solution) containing resin (S12). Resin (S12) is a resin having the above carboxyl group, in which the carboxyl group of the resin having the carboxyl group is -COO-Cu. 2+ ( - OOC-Y), where Y is the non-carboxyl portion of naphthenic acid.

[0149] <Resin Production Example 13: Production of Silicon Atom-Containing Resin (S13)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 35.0 parts by mass of FM-0721 as monomer (a), 19.0 parts by mass of TIPSA as monomer (b), 1.0 parts by mass of M-230G as monomer (c), 10.0 parts by mass of n-BA and 26.0 parts by mass of MMA, 9.0 parts by mass of AA, 10 parts by mass of xylene, and 1.5 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, which was previously mixed, was placed in the dropping funnel, and this was dropped into the four-neck flask at a constant speed over 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropwise addition. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after the completion of the addition to obtain a resin composition (solution) containing a resin having a carboxyl group.

[0150] Next, 100 parts by mass of the resin composition, 13.1 parts by mass of copper (II) acetate, 22.1 parts by mass of hydrogenated rosin (Hyper CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours while removing the mixture of acetic acid, water, and solvent that was distilled, and replenishing the same amount of xylene. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, xylene was added so that the solid content concentration of the resin composition was 50.5% by mass, to obtain a resin composition (solution) containing resin (S13). Resin (S13) is a resin having the above carboxyl group, in which the carboxyl group of the resin is -COO-Cu 2+ ( - OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0151] <Resin Production Example 14: Production of Silicon Atom-Containing Resin (S14)> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 35.0 parts by mass of FM-0721 as monomer (a), 19.0 parts by mass of TIPSA as monomer (b), 1.0 parts by mass of M-230G as monomer (c), 10.0 parts by mass of n-BA and 26.0 parts by mass of MMA, 9.0 parts by mass of AA, 10 parts by mass of xylene, and 1.5 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, which was previously mixed, was placed in the dropping funnel, and this was dropped into the four-neck flask at a constant speed over 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropwise addition. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.5 hours after the completion of the addition to obtain a resin composition (solution) containing a resin having a carboxyl group.

[0152] Next, 100 parts by mass of the resin composition, 13.1 parts by mass of zinc acetate (II), 22.1 parts by mass of hydrogenated rosin (Hyper CH) and 60.0 parts by mass of xylene were added to the same reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours while removing the mixture of acetic acid, water and solvent that was distilled and replenishing the same amount of xylene. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, n-butanol and xylene were added so that the solid content concentration of the resin composition was 50.7% by mass, and a resin composition (solution) containing resin (S14) was obtained. Resin (S14) is a resin having a carboxyl group, in which the carboxyl group of the resin having a carboxyl group is -COO-Zn 2+ ( - OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0153] <Resin Production Example 15: Production of Silicon Atom-Containing Resin (S15)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 70.0 parts by mass of xylene and 30.0 parts by mass of n-butanol were added as solvents and maintained at 105°C. A mixture of 10.0 parts by mass of FM-0711, 10.0 parts by mass of FM-0721, and 10.0 parts by mass of X-22-164C, which are monomers (a), 30.0 parts by mass of TIPSA, which is monomer (b), 5.0 parts by mass of M-90G, which is monomer (c), 10.0 parts by mass of EHMA, 8.6 parts by mass of MMA, 10.0 parts by mass of EA, and 6.4 parts by mass of AA, which are monomers (f), and 2.0 parts by mass of azobisisobutyronitrile as a radical polymerization initiator, was placed in the dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the dropping, the mixture was kept warm for 60 minutes, thereby obtaining a resin composition (solution) containing a resin having a carboxyl group.

[0154] Next, 100 parts by mass of the resin composition, 9.3 parts by mass of copper (II) acetate, 27.5 parts by mass of naphthenic acid (NA-200), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours while removing the mixture of acetic acid, water, and solvent that was distilled, and replenishing the same amount of xylene. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, xylene was added so that the solid content concentration of the resin composition became 51.8% by mass, to obtain a resin composition (solution) containing resin (S15). Resin (S15) is a resin having a carboxyl group, in which the carboxyl group of the resin having a carboxyl group is -COO-Cu. 2+ ( - OOC-Y), where Y is the non-carboxyl portion of naphthenic acid.

[0155] Tables 1 and 2 show the monomers and their amounts (parts by mass) used in each resin production example, except for resin production examples 11 to 15, which show the monomers and their amounts used in the production of the resins having a carboxyl group.

[0156] The number average molecular weights (Mn) of the resulting resins (S1) to (S15) and the solid content concentrations of the resulting resin compositions were measured. The results are shown in Tables 1 and 2. The measurement methods were as follows. In Table 2, the number average molecular weights (Mn) shown in Resin Production Examples 11 to 15 are for resins having a carboxyl group (a carboxyl group is replaced by -COO-Me 2+ ( - Mn is measured for the resin before the reaction to convert it into OOC-Y is carried out. Me is Cu or Zn.

[0157] [i] Number average molecular weight (Mn) The number average molecular weight (Mn) of the obtained resin and monomer (a) is a polystyrene-equivalent number average molecular weight measured by GPC under the following measurement conditions. Equipment: Tosoh Corporation "HLC-8220GPC" Column: TSKgel SuperHZM-M x 2 Eluent: Tetrahydrofuran Measurement temperature: 35℃ Detector: RI

[0158] [ii] Solid content concentration The solids concentration of the resin composition was calculated according to the following formula. Solid content concentration (mass%)=100×(total mass of raw materials used in preparing the resin composition excluding the solvent) / (mass of the obtained resin composition)

[0159] [Table 1]

[0160] [Table 2]

[0161] Details of the abbreviations of the various monomers shown in Tables 1 and 2 and other components used in the resin production examples are as follows:

[0162] [Monomer (a)] FM-0711: Manufactured by JNC Corporation; one-terminated methacryloyloxyalkyl-modified organopolysiloxane; in the formula (I'), m = 0, b = 3, n = 10, R 1 ~R 4 and R 31 is a methyl group, R 5 Monomer with n-butyl group, molecular weight: 1,000 FM-0721: Manufactured by JNC Corporation; one-terminated methacryloyloxyalkyl-modified organopolysiloxane; in the formula (I'), m = 0, b = 3, n = 65, R 1 ~R 4 and R 31 is a methyl group, R 5 Monomer with n-butyl group, molecular weight: 5,000 FM-0725: Manufactured by JNC Corporation; one-terminated methacryloyloxyalkyl-modified organopolysiloxane; in the formula (I'), m = 0, b = 3, n = 132, R 1 ~R 4 and R 31 is a methyl group, R5 Monomer with n-butyl group, molecular weight: 10,000 KF-2012: Manufactured by Shin-Etsu Chemical Co., Ltd., one-terminated methacryloyloxyalkyl-modified organopolysiloxane, in formula (I'), m = 0, R 1 ~R 5 and R 31 is a methyl group, molecular weight: 4,600 TM-0701T: Manufactured by JNC Corporation; one-terminated methacryloyloxyalkyl-modified organopolysiloxane; in the formula (II'), p=0, d=3, R 6 ~R 8 and R 32 is a methyl group, molecular weight: 423 X-22-164C: manufactured by Shin-Etsu Chemical Co., Ltd. In the above general formula (III'), q and s = 0, f and g = 3, R 9 ~R 12 , R 33 and R 34 Silicon-containing polymerizable monomer with methyl group, molecular weight: 10,000

[0163] [Monomer (b)] TIPSA: Triisopropylsilyl acrylate, manufactured by Shin-Etsu Chemical Co., Ltd. TIPSMA: Triisopropylsilyl methacrylate, manufactured by Shin-Etsu Chemical Co., Ltd.

[0164] [Monomer (c)] M-40G: Methacrylic acid methoxypolyethylene glycol ester (oxyethylene chain repeat number = 4), manufactured by Shin-Nakamura Chemical Co., Ltd. M-90G: Methacrylic acid methoxypolyethylene glycol ester (oxyethylene chain repeat number = 9), manufactured by Shin-Nakamura Chemical Co., Ltd. M-230G: Methacrylic acid methoxypolyethylene glycol ester (oxyethylene chain repeat number = 23), manufactured by Shin-Nakamura Chemical Co., Ltd. CB-1: Methacryloyloxyethyl phthalate, manufactured by Shin-Nakamura Chemical Co., Ltd. HEMA: 2-hydroxyethyl methacrylate, manufactured by Mitsubishi Chemical Corporation

[0165] [Monomer (e)] NPG: Neopentyl glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

[0166] [Monomer (f)] t-BMA: t-butyl methacrylate, manufactured by Mitsubishi Chemical Corporation n-BMA: n-butyl methacrylate, manufactured by Mitsubishi Gas Chemical Company, Inc. n-BA: n-butyl acrylate, manufactured by Toagosei Co., Ltd. EHMA: 2-Ethylhexyl methacrylate, manufactured by Mitsubishi Chemical Corporation MMA: Methyl methacrylate, manufactured by Mitsubishi Gas Chemical Company EA: Ethyl acrylate, manufactured by Toagosei Co., Ltd.

[0167] [Other monomers] AA: Acrylic acid, manufactured by Osaka Organic Chemical Industry Co., Ltd. ·MAA: Methacrylic acid, manufactured by Kuraray

[0168] [Other ingredients] Zinc oxide: Sakai Chemical Industry Co., Ltd. Zinc acetate (II): manufactured by Nippon Chemical Industries Co., Ltd. Copper(II) acetate: manufactured by Nippon Chemical Industries Co., Ltd. NA-165: Naphthenic acid, acid value: 165mgKOH / g, manufactured by Yamato Oil Industries Co., Ltd. NA-200: Naphthenic acid, acid value: 200mgKOH / g, manufactured by Yamato Oil Industries Co., Ltd. Hyperpale CH: Hydrogenated rosin, acid value: 160mgKOH / g, manufactured by Arakawa Chemical Industries Co., Ltd. Chain transfer agents; α-Methylstyrene dimer, manufactured by Mitsui Chemicals Radical polymerization initiators; tert-Butyl peroxy-2-ethylhexanoate, manufactured by Kahaku Akzo Co., Ltd. AIBN: Azobisisobutyronitrile, manufactured by Otsuka Chemical Co., Ltd. AMBN: Azobismethylbutyronitrile, manufactured by Otsuka Chemical Co., Ltd. Organic solvents; Xylene: JFE Chemical Corporation n-Butanol: JNC PGM: Propylene glycol methyl ether: Dow Chemical

[0169] <Example 1> (1) Preparation of antifouling paint composition 1 83.20 parts by mass of the silicon-containing resin (S1) obtained above, 6.74 parts by mass of a (meth)acrylic resin containing structural unit (D) as thermoplastic resin 6, 0.30 parts by mass of Typec CR-50 as pigment 1, 3.40 parts by mass of Bayferox 130 as pigment 2, and 6.36 parts by mass of xylene as solvent 1 were mixed and dispersed using a disper (2,000 rpm) to prepare antifouling coating composition 1. The blending amount means the amount (parts by mass) as it is, including volatile matter such as solvent. The VOC value of antifouling coating composition 1 is shown in Table 3.

[0170] (2) Preparation of coating film Antifouling paint composition 1 was spray-applied to an SPCC steel plate (150 mm x 70 mm x 3.2 mm) on which an anti-rust coating film made of an anti-rust paint composition (epoxy-based anticorrosive paint: NIPPON E-MARINE A / C, manufactured by Nippon Paint Marine Co., Ltd.) had previously been formed, so that the dry film thickness was 300 μm, and the plate was left to dry indoors for two days and nights to obtain a test plate with an antifouling coating film.

[0171] <Examples 2 to 32 and Comparative Examples 1 to 6> Antifouling coating compositions 2 to 32 and comparative antifouling coating compositions 1 to 6 were prepared in the same manner as in the preparation of antifouling coating composition 1 in Example 1, except that the types and amounts of each blended component were changed as shown in Tables 3 to 8. Test panels having antifouling coating films were obtained in the same manner as in Example 1, except that antifouling coating compositions 2 to 32 and comparative antifouling coating compositions 1 to 6 were used, respectively. The VOC values ​​of antifouling coating compositions 2 to 32 and comparative antifouling coating compositions 1 to 6 are shown in Tables 3 to 8.

[0172] The details of each compounding component shown in Tables 3 to 8 are as follows. Thermoplastic resin 1: Chlorinated paraffin (Tosoh Corporation's "Toyoparax A50", solid content concentration: 100% by mass, weight average molecular weight: 750 ·Thermoplastic resin 2: Rosin (“WW Rosin” manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration: 100% by mass, weight average molecular weight: 350 Thermoplastic resin 3: Polyvinyl ethyl ether, BASF "Lutnar A25", solid content: 95% by mass, weight average molecular weight: 4,500 Thermoplastic resin 4: Vinyl chloride-isobutyl vinyl ether copolymer (BASF JAPAN "LALOFLEX MP25", solid content: 100% by mass, weight average molecular weight: 28,000 Thermoplastic resin 5: Acrylic resin, BASF "Dianal BR-106", solid content concentration: 100% by mass, weight average molecular weight: 55,000 Thermoplastic resin 6: a (meth)acrylic resin containing a structural unit (D) produced by the method described below, solid content concentration: 46.0% by mass, weight average molecular weight: 8,000 Antifouling agent 1: Cuprous oxide, manufactured by Furukawa Chemicals Antifouling agent 2: Zinc pyrithione, Arch Chemical's "Zinc Omadine" Antifouling agent 3: Copper pyrithione, Arch Chemical's "Copper Omadine" Antifouling agent 4: Seanine 211, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-3(2H)isothiazolone), Rohm and Haas "Seanine 211" Antifouling agent 5: Irgarol, N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, manufactured by Ciba Specialty Chemicals, Inc. "Irgarol 1051" Antifouling agent 6: Econair, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, Janssen PMP "Econair" Antifouling agent 7: Medetomidine, "Selektope" manufactured by I-TECH AB Pigment 1: Titanium oxide, Ishihara Sangyo Kaisha "Tipaque CR-50" Pigment 2: Iron oxide, LANXESS "Bayferox 130"

[0173] <Thermoplastic Resin Production Example 1: Production of Thermoplastic Resin 6> A four-neck flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 50.0 parts by mass of xylene as a solvent and kept at 95° C. A mixture of 58.3 parts by mass of EA, 25.0 parts by mass of CHA (cyclohexyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 16.7 parts by mass of AA, 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and dropped at a constant rate into the four-neck flask over a period of 3 hours, and the mixture was kept warm for 30 minutes after the end of the dropping. Thereafter, a mixture of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate over a period of 30 minutes to the four-neck flask, and the mixture was then kept warm for 1.0 hour after completion of the addition to obtain a resin composition (solution) containing a resin having a carboxyl group.

[0174] Next, 100.0 parts by mass of the resin composition, 18.6 parts by mass of zinc acetate (II), 33.2 parts by mass of naphthenic acid (NA-165) and 60.0 parts by mass of xylene were added to the same reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours while removing the mixture of acetic acid, water and solvent that was distilled, and replenishing the same amount of xylene. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled solvent. After cooling the reaction solution, the same masses of n-butanol and xylene were added so that the solid content concentration of the resin composition was 46.0% by mass to obtain a resin composition (solution) containing thermoplastic resin 6.

[0175] The weight average molecular weight (Mw) of each of the thermoplastic resins 1 to 6 is a weight average molecular weight in terms of polystyrene measured by GPC, and the measurement conditions were as follows. Equipment: Tosoh Corporation "HLC-8220GPC" Column: TSKgel SuperHZM-M x 2 Eluent: Tetrahydrofuran Measurement temperature: 35℃ Detector: RI

[0176] (Evaluation of Antifouling Paint Compositions) [a] Antifouling properties of coating film (dynamic antifouling test) A metal water channel 10 was prepared as shown in Figures 1 and 2. The width of the groove in the water channel 10 was 450 mm, and the depth was 200 mm. As shown in the figures, the test plates 20 obtained in the examples and comparative examples were placed on the bottom of the groove with the antifouling coating film facing upward.

[0177] The waterway 10 with the test plate 20 installed was placed indoors in the sunlight of the coastal evaluation technology center of Nippon Paint Marine Co., Ltd. in Tamano City, Okayama Prefecture. In this case, the waterway 10 was arranged along a north-south direction in order to maximize the time that the test plate 20 was exposed to sunlight (Figure 1). Natural seawater continuously drawn up from the Seto Inland Sea was continuously flowed into the waterway 10. The flow direction 30 of the natural seawater was from north to south. The water level of the natural seawater flowing in the waterway 10 was changed from 40 mm to 200 mm in a 12-hour cycle to mimic the tide level in nature. The flow speed of the natural seawater flowing in the waterway 10 was set to about 30 cm / sec (when the water level was at its lowest) to about 10 cm / sec (when the water level was at its highest) according to the water level.

[0178] A test was conducted for 12 months in which natural seawater was continuously flowed into the waterway 10, and the adhesion area of ​​marine organisms was determined and evaluated according to the following criteria. The evaluation results after 6 and 12 months of the test are shown in Tables 3 to 8. The evaluation result is preferably 3 or higher. 5: The area of ​​the surface area of ​​marine organisms attached is between 0% and 5% 4: The area of ​​the surface area where marine organisms are attached is between 5% and 10% 3: The area of ​​the surface area covered by marine organisms is between 10% and 15% 2: The area of ​​the surface area where marine organisms are attached is between 15% and 30% 1: The surface area of ​​the surface with marine organisms attached is 30% or more.

[0179] [b] Crack resistance of coating film (crack resistance test in a repeated dry and wet environment after static immersion) Sodium hydroxide was added to natural seawater collected from the Nippon Paint Marine Research and Development Center in Tamano, Okayama Prefecture, to adjust the pH to 9 (general seawater is about 8.2) to prepare adjusted seawater. The test plates obtained in the examples and comparative examples were immersed in the adjusted seawater at 30° C. for one month. During the one-month immersion, the adjusted seawater was replaced with new seawater every few days.

[0180] The test plate 20 after the one-month immersion was immersed in natural seawater at 40°C for one week, and then dried indoors for one week. This was considered as one cycle, and a wet-dry alternating test was carried out up to 20 cycles, and the state of the coating film on the test plate was observed. If cracks occurred in the coating film during the test, the test was stopped at the time when the cracks occurred, and the number of cycles at that time was used as an index of crack resistance. The numbers listed in the table are the number of cycles at which cracks first occurred. Note that if no cracks occurred even after 20 cycles, it was rated as 20<. The evaluation result is preferably 15 or more.

[0181] In Examples 1 to 32, both excellent antifouling performance and excellent crack resistance were achieved at a remarkably high level.

[0182] Comparative Examples 1 to 4 are examples in which the content of the thermoplastic resin was outside the prescribed range, and no coating film satisfying both the antifouling property and the crack resistance was obtained. Comparative Examples 5 and 6 are examples in which only thermoplastic resins having a weight average molecular weight of less than 1,000 were blended, and no coating film satisfying both the stain resistance and crack resistance was obtained.

[0183] [Table 3]

[0184] [Table 4]

[0185] [Table 5]

[0186] [Table 6]

[0187] [Table 7]

[0188] [Table 8] [Industrial Applicability]

[0189] The antifouling coating composition according to the present invention can form a coating film having both excellent antifouling performance (particularly dynamic antifouling property) and excellent crack resistance at a remarkably high level. The antifouling coating composition according to the present invention can be suitably used as an antifouling coating composition applied to underwater moving bodies such as ships or underwater structures. [Explanation of symbols]

[0190] 10 waterway, 20 test plate, 25 second adhesive layer, 30 flow direction of natural seawater.

Claims

1. An antifouling coating composition comprising a silicon atom-containing resin and a thermoplastic resin other than the silicon atom-containing resin, The silicon atom-containing resin contains a structural unit (A) having at least one silicon atom-containing group selected from the group consisting of a group represented by the following formula (I), a group represented by the following formula (II), a group represented by the following formula (III), and a group represented by the following formula (IV): The thermoplastic resin includes a thermoplastic resin having a weight average molecular weight of 1,000 or more, an antifouling coating composition, wherein the content of the thermoplastic resin having a weight average molecular weight of 1,000 or more is 6.0 parts by mass or more and 11.0 parts by mass or less per 100 parts by mass of the silicon atom-containing resin; 【Chemistry 1】 [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. 【Chemistry 2】 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 are each independently an alkyl group, R ａ Or R ｂ Represents. R ａ teeth, 【Chemistry 3】 (In the formula, x represents an integer of 0 to 200. R ２３ ~R ２７ are the same or different and each represents an alkyl group; R ｂ teeth, 【Chemistry 4】 (In the formula, y represents an integer of 1 to 200. R ２８ and R ２９ are the same or different and each represents an alkyl group. 【Chemistry 5】 [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. 【Chemistry 6】 [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 are the same or different and represent an alkyl group.

2. 2. The antifouling coating composition according to claim 1, wherein the silicon atom-containing resin further comprises a structural unit (B) having a triorganosilyloxycarbonyl group.

3. 3. The antifouling coating composition according to claim 1, wherein the silicon atom-containing resin further comprises a structural unit (C) derived from a monomer (c) which is a monofunctional (meth)acrylic acid ester represented by the following formula (c): CH ２ =C(R Ａ )(COOR Ｂ ) (c) [In formula (c), R Ａ represents a hydrogen atom or a methyl group. Ｂ represents a monovalent group containing one or more selected from the group consisting of a hydroxyl group, a carboxy group, and an oxyalkylene chain.

4. 3. The antifouling coating composition according to claim 1, wherein the silicon atom-containing resin further comprises a structural unit (D) having at least one metal atom-containing group selected from the group consisting of a group represented by the following formula (V) and a group represented by the following formula (VI): 【Chemistry 7】 [In formula (V), M represents a divalent metal atom, R ３０ represents an organic acid residue or an alcohol residue. 【Chemistry 8】 [In formula (VI), M represents a divalent metal atom.]

5. 3. The antifouling coating composition according to claim 1, wherein the content of the structural unit (A) is 20 mass % or more of all structural units contained in the silicon atom-containing resin.

6. 3. The antifouling coating composition according to claim 1 or 2, which does not contain an antifouling agent.

7. The antifouling coating composition according to claim 1 or 2, further comprising an antifouling agent.

8. The antifouling coating composition according to claim 7, wherein the antifouling agent is at least one selected from the group consisting of cuprous oxide, pyrithione metal salts, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and medetomidine.

9. An antifouling coating film formed by the antifouling coating composition according to claim 1.

10. A composite coating film comprising an undercoat coating film formed from an anticorrosive coating composition, and an antifouling coating film formed from the antifouling coating composition according to claim 1 laminated on the undercoat coating film.

11. A ship having the antifouling coating film according to claim 9 or the composite coating film according to claim 10.

12. An underwater structure having the antifouling coating film according to claim 9 or the composite coating film according to claim 10.

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