Coating composition and coating film

Abstract

To provide a coating composition capable of forming a coating film having excellent crack resistance even in an environment where the temperature of seawater in which the coating film is immersed changes drastically and drying and wetting are repeated. [Solution] A coating composition is provided which comprises a thermoplastic resin (X) and a thermoplastic resin (Y), wherein the thermoplastic resin (X) has a weight-average molecular weight of 5,000 or more and has one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group, and does not contain the following structural unit (A); the thermoplastic resin (Y) has a weight-average molecular weight of 5,000 or more and contains a structural unit (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), and the total content of the thermoplastic resin (C) having a weight-average molecular weight of less than 5,000 and the plasticizer is less than 1.0 mass% in the coating composition.

Description

[Technical Field]

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

[0002] In ships, the adhesion of organisms such as barnacles, mussels, and algae to parts that come into contact with seawater hinders efficient operation and causes problems such as fuel waste. Conventionally, to prevent the adhesion of organisms, an antifouling coating composition has been applied to the surface of the ship. For example, WO 2011 / 046086 (Patent Document 1) discloses an antifouling coating composition containing a hydrolyzable resin 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] Coating films formed from coating compositions are required to have excellent crack resistance, i.e., they are less likely to crack (crack or fissure) even when immersed in seawater. However, coating films formed from conventional coating compositions, even those that are considered to have relatively good crack resistance, can still crack when immersed in seawater under harsh environments, leaving room for further improvement. A harsh environment is one in which the temperature of the seawater in which the coating film is immersed changes drastically and the coating film alternates between being immersed in seawater and not being immersed in seawater (dry and wet).

[0005] An object of the present invention is to provide a coating composition that can form a coating film having excellent crack resistance even in an environment where the seawater in which the coating film is immersed experiences drastic temperature changes and where drying and wetting are repeated. Another object of the present invention is to provide a coating film formed from the coating composition, a composite coating film having said coating film, and a ship or underwater structure having said coating film or said composite coating film. [Means for solving the problem]

[0006] The present invention provides the following coating composition, coating film, composite coating film, ship and underwater structure. [1] A coating composition comprising a thermoplastic resin (X) and a thermoplastic resin (Y), The thermoplastic resin (X) is The weight average molecular weight is 5,000 or more, has one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group, and Does not contain the following structural unit (A): The thermoplastic resin (Y) is The weight average molecular weight is 5,000 or more, The polymerizable composition includes a structural unit (A) derived from a monomer (a) having at least one silicon atom-containing group selected from the group consisting of a group represented by the following formula (I), a group represented by the following formula (II), a group represented by the following formula (III), and a group represented by the following formula (IV), A coating composition, wherein the total content of the thermoplastic resin (Z) having a weight-average molecular weight of less than 5,000 and the plasticizer is less than 1.0 mass % in the coating composition. [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. R 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. [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. R 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. R 23 ~R 27 are the same or different and represent an alkyl group; R b teeth, [ka] (In the formula, y represents an integer of 1 to 200. R 28 and R 29 are the same or different and represent 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. R 9 ~R 12 each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group. [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. R 13 ~R 22 are the same or different and represent an alkyl group. [2] The coating composition according to [1], wherein the content of the thermoplastic resin (Y) is 900 parts by mass or less per 100 parts by mass of the thermoplastic resin (X). [3] The coating composition according to [2], wherein the content of the thermoplastic resin (Y) is 100 parts by mass or less per 100 parts by mass of the thermoplastic resin (X). [4] The coating composition according to any one of [1] to [3], wherein the thermoplastic resin (X) has the metal atom-containing group. [5] The coating composition according to any one of [1] to [4], wherein the thermoplastic resin (Y) further has one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group. [6] The coating composition according to any one of [1] to [5], wherein the content of the pigment is 20 parts by mass or more and 390 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (X) and the thermoplastic resin (Y). [7] The coating composition according to any one of [1] to [6], wherein the monomer (a) has a molecular weight of 25,000 or less. [8] The coating composition according to any one of [1] to [7], further comprising an antifouling agent. [9] The coating composition according to [8], 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.

[10] A coating film formed from the coating composition according to any one of [1] to [9].

[11] A composite coating film having an undercoat coating film formed from an anticorrosive coating composition and a coating film formed from the coating composition according to any one of [1] to [9] laminated on the undercoat coating film.

[12] A ship having the coating film according to

[10] or the composite coating film according to

[11] .

[13] An underwater structure having the coating film according to

[10] or the composite coating film according to

[11] . [Effects of the Invention]

[0007] It is possible to provide a coating composition that can form a coating film with excellent crack resistance even in an environment where the seawater in which the coating film is immersed experiences drastic temperature changes and where drying and wetting are repeated.It is also possible to provide a coating film formed from the coating composition, a composite coating film having such a coating film, and a ship or underwater structure having such a coating film or such a composite coating film. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Paint composition> The coating composition according to the present invention (hereinafter simply referred to as the "coating composition") contains a thermoplastic resin (X) and a thermoplastic resin (Y) described below. The coating composition contains a thermoplastic resin (Z) having a weight-average molecular weight (Mw) of less than 5,000 and a plasticizer in an amount of less than 1.0 mass%.

[0009] The coating composition of the present invention uses a combination of thermoplastic resin (X) and thermoplastic resin (Y) as the vehicle resin, and the total content of thermoplastic resin (Z) and plasticizer is as described above, so that a coating film having excellent crack resistance can be formed even in harsh environments such as those in which the seawater in which the coating film is immersed experiences drastic temperature changes and is subject to repeated drying and wetting. The coating composition of the present invention makes it possible to form a coating film that exhibits excellent crack resistance for a long period of time.

[0010] The coating composition of the present invention is suitable for application to the surface of, for example, a ship or underwater structure. When the coating composition is applied to, for example, a ship, a coating film formed from the coating composition may be exposed to drastic temperature changes during immersion in water due to factors such as the temperature difference between day and night in the immersed water (e.g., seawater). Furthermore, the coating film is exposed to an alternating wet-dry environment at or near the ship's waterline, where the state of being immersed in water and the state of not being immersed are repeated, or may be exposed to an alternating wet-dry environment due to the influence of waves. Furthermore, after a period of sailing, a ship bearing the coating film is landed at a dock for repairs, etc. In this case, the coating film is also exposed to an alternating wet-dry environment. The same can be said for underwater structures. The coating composition of the present invention can form a coating film with excellent crack resistance, even when exposed to such harsh conditions.

[0011] When cracks occur in a coating film, the antifouling performance of the coating film (its ability to inhibit adhesion of aquatic organisms) tends to decrease. Therefore, excellent crack resistance of the coating film is advantageous in terms of imparting excellent antifouling performance to the coating film.

[0012] An antifouling coating film formed from an antifouling coating composition is required to exhibit excellent antifouling performance when immersed in water (seawater). According to one embodiment of the coating composition of the present invention, it is possible to form a coating film (antifouling coating film) that has excellent crack resistance and exhibits excellent antifouling performance even under the above-mentioned harsh environment. The coating film can exhibit excellent antifouling performance for a long period of time.

[0013] In particular, one embodiment of the coating composition according to the present invention can form an antifouling coating film that exhibits excellent antifouling performance even when exposed to an environment with drastic temperature changes. Furthermore, one embodiment of the coating composition according to the present invention can form a coating film that, when formed on the surface of an underwater vehicle such as a ship, can exhibit excellent antifouling performance for a long period of time, even when the underwater vehicle is exposed to an environment with drastic temperature changes while moving underwater. Hereinafter, the antifouling performance while moving is also referred to as "dynamic antifouling property."

[0014] The coating composition according to the present invention can be suitably used as a 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 can be contained in the coating composition are described in detail below. In this specification, "(meth)acryloyl" refers to at least one of methacryloyl and acryloyl, "(meth)acrylic" refers to at least one of methacrylic and acrylic, and "(meth)acrylate" refers to at least one of methacrylate and acrylate.

[0015] (1) Thermoplastic resin (X) The thermoplastic resin (X) is a resin having a weight average molecular weight (Mw) of 5,000 or more, having one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group, and not containing the structural unit (A) described below.

[0016] The Mw of the thermoplastic resin (X) is set to 5,000 or more so that it can exhibit excellent crack resistance even under the above-mentioned harsh environments, and from the same viewpoint, it is preferably 6,000 or more, more preferably 7,000 or more, even more preferably 8,000 or more, and still more preferably 9,000 or more. Furthermore, from the viewpoint of crack resistance and stain resistance, particularly dynamic stain resistance, the Mw of the thermoplastic resin (X) is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, still more preferably 50,000 or less, particularly preferably 40,000 or less, and even more particularly preferably 35,000 or less.

[0017] The thermoplastic resin (X) has one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group. The presence of such groups in the thermoplastic resin (X) is advantageous in imparting good antifouling properties to the coating film, and is also advantageous in imparting excellent crack resistance even under the above-mentioned harsh environments.

[0018] The thermoplastic resin (X) may be: a thermoplastic resin (X1) that contains a structural unit (D) having a metal atom-containing group that contains a divalent metal atom, but does not contain a structural unit (B) that has a triorganosilyloxycarbonyl group; a thermoplastic resin (X2) containing the structural unit (B) but not containing the structural unit (D); A thermoplastic resin (X3) containing the structural unit (B) and the structural unit (D). Examples include: From the viewpoint of providing a coating composition that exhibits excellent crack resistance even under the above-mentioned harsh environments, the coating composition preferably contains a thermoplastic resin (X1).

[0019] When the thermoplastic resin (X) contains the structural unit (D), it can contain one or more types of said structural unit.When the thermoplastic resin (X) contains the structural unit (B), it can contain one or more types of said structural unit.

[0020] The structural unit (D) may be a structural unit derived from a monomer (d) having a metal atom-containing group containing a divalent metal atom, and the structural unit (B) may be a structural unit derived from a monomer (b) having a triorganosilyloxycarbonyl group.

[0021] (1-1) Monomer (d) The structural unit (D) is preferably a structural unit 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): The thermoplastic resin (X) may have both a group represented by the formula (V) and a group represented by the formula (VI). [ka] [In formula (V), M represents a divalent metal atom, and R 30 represents an organic acid residue or an alcohol residue.] [ka] [In formula (VI), M represents a divalent metal atom.]

[0022] 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.

[0023] Polymerization of the monomer composition containing the above-mentioned monomer (d) produces a thermoplastic resin (X), which is a (meth)acrylic resin containing a structural unit (D) derived from the monomer (d) selected from the group consisting of monomer (d1) and monomer (d2). This thermoplastic resin (X) has 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).

[0024] 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 from the viewpoint of providing a coating composition that exhibits excellent crack resistance even in the above-mentioned harsh environments, Zn or Cu is preferred, and Zn is more preferred. R in formula (V') (similar to formula (V)) 30 is preferably an organic acid residue.

[0025] The monomer (d1) is represented by the formula (V'): By using the monomer (d1) as the monomer (d), a thermoplastic resin (X) which is a (meth)acrylic resin having a metal atom-containing group represented by the formula (V) can be obtained.

[0026] 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-ethylhexylic acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotic 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.

[0027] Furthermore, other organic acids that are preferable from the viewpoint of crack resistance, etc. include monobasic cyclic organic acids other than aromatic organic acids. Examples of 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.

[0028] 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, or labdane skeleton. More specifically, examples 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 these, abietic acid, hydrogenated abietic acid, and salts thereof are preferred from the viewpoint of the antifouling performance of the coating film.

[0029] As the monobasic cyclic organic acid, for example, rosin, pine resin acid, etc. can also 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 because they are inexpensive, easily available, easy to handle, and can easily improve crack resistance and stain resistance.

[0030] 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 a monobasic cyclic organic acid having an acid value within the above range is used as the monobasic cyclic organic acid forming the formula (I), the good antifouling 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 kind of organic acid, or may be formed from two or more kinds of organic acids.

[0031] R 30 Examples of a method for producing the monomer (d1) having an organic acid residue as a monomer include 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).

[0032] The monomer (d2) is represented by formula (VI'): By using the monomer (d2) as the monomer (d), a thermoplastic resin (X) is obtained, which is a (meth)acrylic resin further having a metal atom-containing group represented by formula (VI) (this metal atom-containing group is a crosslinking group that crosslinks between polymer main chains).

[0033] 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 needed.

[0034] The monomer (d2) can be produced, for example, by reacting a polymerizable unsaturated organic acid such as (meth)acrylic acid with a metal compound together with water in an organic solvent containing an alcoholic compound. In this case, it is preferable to adjust the water content in the reaction mixture to 0.01% by mass or more and 30% by mass or less.

[0035] The thermoplastic resin (X) may contain both a structural unit derived from the monomer (d1) and a structural unit derived from the monomer (d2).

[0036] When the thermoplastic resin (X) contains the structural unit (D), the content of the structural unit (D) is preferably from 1 to 30% by mass, more preferably from 2 to 25% by mass, and even more preferably from 4 to 20% by mass, of all structural units contained in the thermoplastic resin (X), from the viewpoint of the crack resistance and stain resistance of the coating film.

[0037] (1-2) Monomer (b) The structural unit (B) may be a structural unit derived from a monomer (b) having a triorganosilyloxycarbonyl group. Examples of the triorganosilyloxycarbonyl group include a group represented by 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.

[0038] The monomer (b) is preferably a monomer (b1) represented by formula (VII'). [ka] [In formula (VII'), R 43 represents a hydrogen atom or a methyl group, and R 40 , R 41 and R 42 are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms.

[0039] By polymerizing a monomer composition containing the monomer (b1), a thermoplastic resin (X) is obtained, which is a (meth)acrylic resin containing a structural unit (B) derived from the monomer (b1). This thermoplastic resin (X) contains a triorganosilyloxycarbonyl group in the form of -C(=O)-O-SiR 40 R 41 R 42 It has. The thermoplastic resin (X) may contain two or more types of structural units (B). For example, the thermoplastic resin (X) may contain two or more types of structural units (B) having different triorganosilyloxycarbonyl groups.

[0040] R in formula (VII') (similar to formula (VII)) 40 , R 41 and R 42are 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 isopropyl group, an n-butyl group, an isobutyl 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, and a tetradecyl group; a cyclic alkyl group which may have a substituent, such as a cyclohexyl group or a substituted cyclohexyl group; and an aryl group which may have a substituent, such as an aryl group or a substituted aryl group.

[0041] Examples of substituted cyclic alkyl groups include cyclic alkyl groups substituted with halogen, 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 halogen, alkyl groups having up to about 18 carbon atoms, acyl groups, nitro groups, amino groups, etc.

[0042] Among them, from the viewpoint of crack resistance and antifouling performance of the coating film, R 40 , R 41 and R 42 Preferably, one or more of R 40 , R 41 and R 42 It is more preferable that all of the groups are isopropyl groups.

[0043] When the thermoplastic resin (X) contains the structural unit (B), the content of the structural unit (B) is preferably from 10% by mass to 90% by mass, more preferably from 20% by mass to 80% by mass, even more preferably from 30% by mass to 70% by mass, and still more preferably from 40% by mass to 60% by mass, of all structural units contained in the thermoplastic resin (X), from the viewpoint of the crack resistance and antifouling performance of the coating film.

[0044] When the thermoplastic resin (X) is a thermoplastic resin (X3) containing the structural unit (B) and the structural unit (D), the total content of the structural unit (B) and the structural unit (D) may be 2% by mass or more, 3% by mass or more, 4% by mass or more, or 5% by mass or more, and may be 65% by mass or less, 60% by mass or less, 55% by mass or less, or 50% by mass or less, from the viewpoint of the crack resistance and stain resistance of the coating film. From the same viewpoint, the total content of the structural unit (B) and the structural unit (D) is preferably 2% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 40% by mass or less, even more preferably 5% by mass or more and 35% by mass or less, and even more preferably 5% by mass or more and 25% by mass or less, of all the structural units contained in the thermoplastic resin (X).

[0045] In one preferred embodiment, the thermoplastic resin (X) is a (meth)acrylic resin containing one or more structural units selected from the group consisting of: a structural unit (D) derived from a monomer (d1) represented by formula (V'), wherein M in formula (V') is divalent Zn; a structural unit (D) derived from a monomer (d1) represented by formula (V'), wherein M in formula (V') is divalent Cu; and a structural unit (B) derived from a monomer (b1) represented by formula (VII'). In this embodiment, from the viewpoint of improving the crack resistance and antifouling performance of the coating film under the above-mentioned harsh environments, the thermoplastic resin (X) is preferably a (meth)acrylic resin containing one or more structural units selected from the group consisting of structural unit (D) derived from monomer (d1) represented by formula (V'), where M in formula (V') is divalent Zn, and structural unit (B) derived from monomer (b1) represented by formula (VII'), and more preferably a (meth)acrylic resin containing structural unit (D) derived from monomer (d1) represented by formula (V'), where M in formula (V') is divalent Zn.

[0046] (1-3) Monomer (c) The thermoplastic resin (X) may further contain a structural unit (C) derived from a monomer (c). The monomer (c) is a monofunctional (meth)acrylic acid ester represented by formula (c). The presence of the structural unit (C) in the thermoplastic resin (X) is advantageous in improving the antifouling performance of the coating film. Furthermore, the inclusion of the structural unit (C) can moderately increase the coating film wear rate. CH2=C(R A )(COOR B ) (c)

[0047] In formula (c), R A 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 thermoplastic resin (X) may contain structural units derived from two or more types of monomers (c). Furthermore, the monomer (c) may be a monomer containing two or more types of groups selected from the group consisting of a hydroxyl group, a carboxyl group, and an oxyalkylene chain.

[0048] In order to improve the antifouling performance of the coating film, the R B It 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 even more preferably 2 or 3. Examples of the alkylene group include -CH-, -(CH)-, -(CH)-, -CH(CH)CH-, -CHCH(CH)-, and the like.

[0049] Examples of the monomer (c) include hydroxyl group-containing (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms in the ester moiety, 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; carboxy group-containing (meth)acrylic acid alkyl esters having 1 to 20 carbon atoms in the ester moiety; alkoxyalkyl (meth)acrylates having 1 to 20 carbon atoms in the ester moiety, such as methoxyethyl (meth)acrylate; and methoxypolyethylene glycol (meth)acrylates (wherein the number of repeating groups of -OC2H4- is, for example, 100 to 200).

[0049] (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.

[0050] 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.

[0051] When the thermoplastic resin (X) 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% by mass to 40% by mass, more preferably from 0.5% by mass to 35% by mass, and even more preferably from 1% by mass to 30% by mass, and may be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, of all structural units contained in the thermoplastic resin (X).

[0052] (1-4) Monomer (e) The thermoplastic resin (X) may further contain a structural unit (E) derived from a monomer (e) that is a polyfunctional (meth)acrylic acid ester having two or more (meth)acryloyl groups. When the thermoplastic resin (X) further contains the structural unit (E), the dynamic stain resistance and / or crack resistance of the coating film can be further improved. The thermoplastic resin (X) may contain two or more types of structural units (E) derived from the monomer (e).

[0053] Examples of the monomer (e) include bifunctional (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.

[0054] An example of the bifunctional (meth)acrylate is a compound (e-1) represented by 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 —CH— in the hydrocarbon group may be replaced with —O— or —C(═O)—.

[0055] R C is preferably a methyl group. R DExamples 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.

[0056] The poly(oxyalkylene) group is -(oxyalkylene group) x -. x represents the number of repeating oxyalkylene groups 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.

[0057] 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, and 1,10-decanediol di(meth)acrylate. acrylate, tricyclodecane dimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (the number of repetitions of the oxyalkylene group 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, polypropylene glycol di(meth)acrylate (the number of repetitions of the oxyalkylene group is, for example, 4 or more and 23 or less).

[0058] Examples of 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.

[0059] The tri- or higher functional (meth)acrylate is preferably tri- to hexa-functional, and more preferably tri- or tetra-functional.

[0060] When the thermoplastic resin (X) contains the structural unit (E), the content of the structural unit (E) derived from the monomer (e) is, from the viewpoint of further improving crack resistance, 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, based on the total structural units contained in the thermoplastic resin (X). 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 high, the thermoplastic resin (X) tends to gel easily during preparation.

[0061] (1-5) Monomer (f) The thermoplastic resin (X) may contain a structural unit (F) derived from a monomer (f) other than those mentioned above. The thermoplastic resin (X) may contain two or more types of structural units (F).

[0062] The monomer (f) is not particularly limited as long as it is an unsaturated monomer copolymerizable with other monomers that form the thermoplastic resin (X), and examples thereof include: Methyl (meth)acrylate, ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethylhexoxy)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-methyl styrene, (meth)acrylonitrile, vinyl acetate, vinyl propionate, and (meth)acrylic acid etc.

[0063] When the thermoplastic resin (X) contains the structural unit (F), the content of the structural unit (F) is typically 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 thermoplastic resin (X). A structural unit (F) content of 0.1% by mass or more makes it possible to achieve a good balance of the properties of the resulting coating composition and coating film. A structural unit (F) content of 85% by mass or less makes it possible to form a coating film that exhibits good crack resistance and antifouling performance.

[0064] (1-6) Method for producing thermoplastic resin (X) The method for producing the thermoplastic resin (X) is not particularly limited, but it can be produced, for example, 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 adjusted appropriately. The thermoplastic resin (Y) described below can also be produced in the same manner as the thermoplastic resin (X). Furthermore, the thermoplastic resin (X) containing the structural unit (D) derived from the monomer (d1) can be prepared by polymerizing a carboxyl group-containing resin obtained by polymerizing a monomer composition containing a carboxyl group-containing radically polymerizable monomer such as (meth)acrylic acid in the same manner as described above, a metal compound, and a non-polymerizable organic acid (the above-mentioned R 30 By reacting with the organic acid constituting the resin, the carboxyl group of the carboxyl group-containing resin is converted to -COO-MR 30 It can also be formed by a method of converting

[0065] 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.

[0066] Examples of the polymerization method include solution polymerization, emulsion polymerization, and suspension polymerization carried out in an organic solvent. From the viewpoint of the production efficiency of the thermoplastic resin (X), the solution polymerization method is preferred. Examples of the organic solvent include common organic solvents such as toluene, xylene, methyl isobutyl ketone, and n-butyl acetate.

[0067] (1-7) Thermoplastic resin (X) content The content of the thermoplastic resin (X) in the coating composition is preferably 0.1% by mass or more and 80% by mass or less, more preferably 0.5% by mass or more and 70% by mass or less, even more preferably 2% by mass or more and 60% by mass or less, even more preferably 4% by mass or more and 60% by mass or less, particularly preferably 8% by mass or more and 55% by mass or less, and even more particularly preferably 12% by mass or more and 50% by mass or less, based on the solid content of the coating composition. When the content of the thermoplastic resin (X) is within the above range, excellent crack resistance tends to be easily obtained even under the above-mentioned harsh environments, and excellent antifouling performance also tends to be easily obtained. The solid content contained in the coating composition refers to the total of all components other than the solvent contained in the coating composition.

[0068] (2) Thermoplastic resin (Y) The thermoplastic resin (Y) has a weight-average molecular weight (Mw) of 5,000 or more and 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). More specifically, the structural unit (A) is a structural unit derived from a monomer (a) having at least one silicon atom-containing group selected from the above group.

[0069] The Mw of the thermoplastic resin (Y) is set to 5,000 or more so that it can exhibit excellent crack resistance even under the above-mentioned harsh environments, and from the same viewpoint, it is preferably 8,000 or more, more preferably 10,000 or more, even more preferably 12,000 or more, and may be 20,000 or more or 30,000 or more. Furthermore, from the viewpoint of crack resistance and stain resistance, particularly dynamic stain resistance, the Mw of the thermoplastic resin (Y) is preferably 100,000 or less, more preferably 80,000 or less, even more preferably 60,000 or less, and still more preferably 50,000 or less.

[0070] The thermoplastic resin (Y) may contain a structural unit other than the structural unit (A). Although not particularly limited, examples of such a structural unit include: a structural unit (B) having a triorganosilyloxycarbonyl group, A structural unit (C) derived from a monomer (c) that is a monofunctional (meth)acrylic acid ester represented by the formula (c) described below, and Structural unit (D) having a metal atom-containing group containing a divalent metal atom etc. The thermoplastic resin (Y) may contain one or more structural units other than the structural unit (A). From the viewpoint of crack resistance and stain resistance, particularly dynamic stain resistance, the thermoplastic resin (Y) preferably further contains one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group, and more preferably further contains a metal atom-containing group containing a divalent metal atom.

[0071] (2-1) Monomer (a) The silicon atom-containing group contained in the monomer (a) 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).

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] Monomer (a) 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, monomer (a) 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).

[0077] The monomer (a) is preferably at least one selected from the group consisting of a monomer (a1) represented by formula (I'), a monomer (a2) represented by formula (II'), a monomer (a3) ​​represented by formula (III'), and a 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.

[0078] [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 34each independently represents a hydrogen atom or a methyl group, and 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, and i, j, k, l, t, u, v, w and R 13 ~R 22 has the same meaning as above.]

[0079] Polymerization of a monomer composition containing the above-described monomer (a) produces a thermoplastic resin (Y), which is a (meth)acrylic resin containing a structural unit (A) derived from the monomer (a) selected from the group consisting of monomers (a1), (a2), (a3), and (a4). The thermoplastic resin (Y) contains 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 thermoplastic resin (Y) may contain two or more types of structural units (A) derived from the monomer (a).

[0080] Monomer (a) may be a combination of two or more monomers belonging to monomer (a), and the two or more monomers may have different molecular weights.

[0081] The monomer (a1) is represented by formula (I'): By using the monomer (a1) as the monomer (a), a thermoplastic resin (Y) is obtained, which is a (meth)acrylic resin having a silicon atom-containing group represented by formula (I) in its side chain. The thermoplastic resin (Y) may contain structural units derived from two or more types of monomers (a1).

[0082] 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 substrate, etc., m is preferably from 0 to 25, more preferably from 0 to 20. m may be 3 or more or 5 or more, or may be 10 or less or 8 or less. From the viewpoint of the antifouling performance of the coating film and solubility in common 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 or 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 isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, and particularly preferably a methyl group or an ethyl group.

[0083] Commercially available products may be used as the monomer (a1). Examples of commercially available products include: JNC Corporation's "FM-0711" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,000), "FM-0721" (single-terminated methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5,000), and "FM-0725" (single-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.

[0084] The monomer (a2) is represented by formula (II'): By using the monomer (a2) as the monomer (a), a thermoplastic resin (Y) is obtained, which is a (meth)acrylic resin having a silicon atom-containing group represented by formula (II) in its side chain. The thermoplastic resin (Y) may contain structural units derived from two or more types of monomers (a2).

[0085] In formula (II') (the same applies to formula (II)), c is preferably 2 or 3. d is preferably 2 or 3. From the viewpoint of the water resistance of the coating film, adhesion to the substrate, 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, or may be 10 or less or 8 or less.

[0086] From the viewpoint of solubility in common organic solvents, x is usually 0 or more and 200 or less, preferably 10 or more and 150 or less, and more preferably 20 or more and 125 or less. From the viewpoint of solubility in common organic solvents, y is usually 1 or more and 200 or less, preferably 10 or more and 150 or less, and more preferably 20 or more and 125 or less. 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 isopropyl group, an n-butyl group, an isobutyl 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 are preferably all alkyl groups.

[0087] Monomer (a2) may be a commercially available product, such as "TM-0701T" (one-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 423) manufactured by JNC Corporation.

[0088] The monomer (a3) ​​is represented by formula (III'): By using the monomer (a3) ​​as the monomer (a), a thermoplastic resin (Y) is obtained, which is a (meth)acrylic resin having a silicon atom-containing group represented by formula (III) (this silicon atom-containing group is a crosslinking group that crosslinks between polymer main chains). The thermoplastic resin (Y) may contain structural units derived from two or more types of monomers (a3).

[0089] 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 substrate, etc., q and s are each preferably from 0 to 30, more preferably from 0 to 25, and even more preferably from 0 to 20. q and s may each be 3 or more or 5 or more, or 10 or less or 8 or less. From the viewpoint of the antifouling performance of the coating film, solubility in common organic solvents, etc., r is usually from 3 to 270, preferably from 35 to 245, more preferably from 45 to 205, and even more preferably from 45 to 160. 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 or 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 isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, and particularly preferably a methyl group or an ethyl group.

[0090] Commercially available products may be used as the monomer (a3). Examples of commercially available products include: JNC Corporation's "FM-7711" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,000), "FM-7721" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5,000), and "FM-7725" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 10,000), Shin-Etsu Chemical Co., Ltd.'s "X-22-164" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 380), "X-22-164AS" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 900), "X-22-164A" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,720), and "X-22-164B" (both-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,720). "X-22-2445" (acryloyloxyalkyl-modified organopolysiloxane at both ends, molecular weight: 3,200), "X-22-164C" (methacryloyloxyalkyl-modified organopolysiloxane at both ends, molecular weight: 4,800), "X-22-164E" (methacryloyloxyalkyl-modified organopolysiloxane at both ends, molecular weight: 7,800) etc.

[0091] The monomer (a4) is represented by formula (IV'). By using the monomer (a4) as the monomer (a), a thermoplastic resin (Y) is obtained, which is a (meth)acrylic resin having a silicon atom-containing group represented by formula (IV) (this silicon atom-containing group is a crosslinking group that crosslinks between polymer main chains). A commercially available product may be used as the monomer (a4). The thermoplastic resin (Y) may contain structural units derived from two or more types of monomers (a4).

[0092] 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 viewpoint of the water resistance of the coating film, adhesion to the substrate, etc., t and u are each preferably from 0 to 30, more preferably from 0 to 25, and even more preferably from 0 to 20. q and s may each be 3 or more or 5 or more, or 10 or less or 8 or less. From the viewpoint of the antifouling performance of the coating film, solubility in common organic solvents, etc., v and w are each 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 isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group, and even more preferably a methyl group or an ethyl group.

[0093] From the viewpoint of improving the crack resistance and antifouling performance of the coating film under severe environments, the molecular weight of the monomer (a) is preferably 400 or more, more preferably 500 or more, even more preferably 1,000 or more, still more preferably 2,000 or more, particularly preferably 2,500 or more, even more particularly preferably 3,000 or more, and most preferably 4,000 or more or 5,000 or more, and may even be 10,000 or more. The molecular weight of the monomer (a) is usually 25,000 or less, preferably 20,000 or less, more preferably 18,000 or less, even 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 incompatibility between the monomers in the monomer composition, which is a mixture of monomers used to prepare the silicon atom-containing resin, or incompatibility between the polymers produced by polymerization of the monomer composition. If the coating film is non-uniform in its components, this may adversely affect the crack resistance and stain resistance of the coating film in harsh environments.

[0094] The molecular weight of the monomer (a) may be a weight average molecular weight (Mw). The weight average molecular weight of the monomer (a) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0095] From the viewpoint of improving the crack resistance and antifouling performance of the coating film under harsh environments, the content of the structural unit (A) is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and may even be 35% by mass or more or 40% by mass or more, of all structural units contained in the thermoplastic resin (Y). A content of the structural unit (A) of 20% by mass or more can result in a coating composition that exhibits sufficient crack resistance and antifouling performance even under the above-mentioned harsh environments. Furthermore, from the viewpoint of the coating film physical properties and the above-mentioned coating film uniformity, 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, of all structural units contained in the thermoplastic resin (Y).

[0096] (2-2) Monomer (b) In one preferred embodiment, the thermoplastic resin (Y) contains the structural unit (B). The structural unit (B) may be a structural unit derived from a monomer (b) having a triorganosilyloxycarbonyl group. The structural unit (B), the monomer (b), and the triorganosilyloxycarbonyl group are described above. The monomer (b) is preferably a monomer (b1) represented by formula (VII').

[0097] The thermoplastic resin (Y) may contain two or more types of structural units (B). For example, the thermoplastic resin (Y) may contain two or more types of structural units (B) having different triorganosilyloxycarbonyl groups.

[0098] From the viewpoint of crack resistance and antifouling performance of the coating film, R in formula (VII) and formula (VII') 40 , R 41 and R 42 Preferably, one or more of R 40 , R 41 and R 42 It is more preferable that all of the groups are isopropyl groups.

[0099] When the thermoplastic resin (Y) contains the structural unit (B), the content of the structural unit (B) is, from the viewpoint of the crack resistance and antifouling performance of the coating film, preferably from 2 to 50% by mass, more preferably from 3 to 40% by mass, even more preferably from 5 to 35% by mass, still more preferably from 5 to 25% by mass, and may even be from 5 to 20% by mass, of all structural units contained in the thermoplastic resin (Y).

[0100] When the thermoplastic resin (Y) contains the structural unit (B), the ratio of the content of the structural unit (B) to the content of the structural unit (A), from the viewpoint of the crack resistance and antifouling performance of the coating film, 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, 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, per 100 parts by mass of the structural unit (A).

[0101] (2-3) Monomer (d) In one preferred embodiment, the thermoplastic resin (Y) contains the above-mentioned structural unit (D). The structural unit (D) may be a structural unit derived from a monomer (d) having a metal atom-containing group containing a divalent metal atom. The structural unit (D) is preferably a structural unit 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 thermoplastic resin (Y) may have both a group represented by formula (V) and a group represented by formula (VI). The above descriptions are for the structural unit (D) and the monomer (d). 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'). The thermoplastic resin (Y) may contain both a structural unit derived from a monomer (d1) and a structural unit derived from a monomer (d2). The same applies to formula (V') [the same applies to formula (V)]. The divalent metal atom M in formula (VI') [the same applies to formula (VI)] may include Mg, Zn, Cu, etc., and from the viewpoint of providing a coating composition that exhibits excellent crack resistance even in the above-mentioned harsh environments, it is preferably Zn or Cu, and more preferably Zn.

[0102] When the thermoplastic resin (Y) contains the structural unit (D), the content of the structural unit (D) is preferably from 1 to 30% by mass, more preferably from 2 to 25% by mass, and even more preferably from 4 to 23% by mass, of all structural units contained in the thermoplastic resin (Y), from the viewpoint of the crack resistance and antifouling performance of the coating film.

[0103] When the thermoplastic resin (Y) contains the structural unit (B) and the structural unit (D), the total content of the structural unit (B) and the structural unit (D) is, from the viewpoint of the crack resistance and antifouling performance of the coating film, preferably from 2 to 50% by mass, more preferably from 3 to 40% by mass, even more preferably from 5 to 35% by mass, and still more preferably from 5 to 25% by mass, of all the structural units contained in the thermoplastic resin (Y).

[0104] When the thermoplastic resin (Y) contains the structural unit (D), the ratio of the content of the structural unit (D) to the content of the structural unit (A), from the viewpoint of the crack resistance and antifouling performance of the coating film, is preferably from 0.5 to 70 parts by mass, more preferably from 1 to 60 parts by mass, even more preferably from 2 to 55 parts by mass, and even more preferably from 5 to 55 parts by mass, per 100 parts by mass of the structural unit (A), and may be 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 15 parts by mass or less.

[0105] In one preferred embodiment, the thermoplastic resin (Y) is a (meth)acrylic resin containing the structural unit (A) and one or more structural units selected from the group consisting of a structural unit (D) derived from a monomer (d1) represented by formula (V'), wherein M in formula (V') is divalent Zn, a structural unit (D) derived from a monomer (d1) represented by formula (V'), wherein M in formula (V') is divalent Cu, and a structural unit (B) derived from a monomer (b1) represented by formula (VII'). In this embodiment, from the viewpoint of improving the crack resistance and antifouling performance of the coating film in the aforementioned harsh environments, the thermoplastic resin (Y) is preferably a (meth)acrylic resin containing the structural unit (A) and one or more structural units selected from the group consisting of the structural unit (D) derived from the monomer (d1) represented by the formula (V'), where M in the formula (V') is divalent Zn, and the structural unit (B) derived from the monomer (b1) represented by the formula (VII'), and more preferably a (meth)acrylic resin containing the structural unit (A) and the structural unit (D) derived from the monomer (d1) represented by the formula (V'), where M in the formula (V') is divalent Zn.

[0106] From the viewpoint of improving the crack resistance of the coating film under the above-mentioned harsh environments, it is preferable that the thermoplastic resin (Y) has the same type of group (a group selected from a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group) as the functional group possessed by the thermoplastic resin (X). For example, when the thermoplastic resin (X) contains a structural unit (D) derived from a monomer (d1) represented by formula (V') in which M is divalent Zn, it is preferable that the thermoplastic resin (Y) also contains a structural unit (D) derived from a monomer (d1) represented by formula (V') in which M is divalent Zn.

[0107] (2-4) Monomer (c) The thermoplastic resin (Y) may further contain a structural unit (C) derived from the monomer (c). The structural unit (C) and the monomer (c) are described above. The presence of the structural unit (C) in the thermoplastic resin (Y) is advantageous in improving the antifouling performance of the coating film. Furthermore, the inclusion of the structural unit (C) can appropriately increase the coating film wear rate. The thermoplastic resin (Y) may contain structural units derived from two or more types of monomers (c).

[0108] When the thermoplastic resin (Y) 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% by mass to 40% by mass, more preferably from 0.5% by mass to 35% by mass, and even more preferably from 1% by mass to 30% by mass, and may be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less, of all structural units contained in the thermoplastic resin (Y).

[0109] When the thermoplastic resin (Y) contains the structural unit (C), the ratio of the content of the structural unit (C) to the content of the structural unit (A), from the viewpoint of the antifouling performance of the coating film, is preferably from 0.5 to 80 parts by mass, more preferably from 1 to 70 parts by mass, even more preferably from 1 to 60 parts by mass, and still more preferably from 2 to 50 parts by mass, 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.

[0110] (2-5) Monomer (e) The thermoplastic resin (Y) may further contain a structural unit (E) derived from a monomer (e), which is a polyfunctional (meth)acrylic acid ester having two or more (meth)acryloyl groups. The above description of the structural unit (E) and the monomer (e) is cited. When the thermoplastic resin (Y) further contains the structural unit (E), the dynamic stain resistance and / or crack resistance of the coating film can be further improved. The thermoplastic resin (Y) may contain two or more types of structural units (E) derived from the monomer (e).

[0111] When the thermoplastic resin (Y) contains the structural unit (E), the content of the structural unit (E) derived from the monomer (e) is, from the viewpoint of further improving crack resistance, 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, or 5% by mass or more, based on the total structural units contained in the thermoplastic resin (Y). 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 high, the thermoplastic resin (Y) tends to gel easily during preparation.

[0112] When the thermoplastic resin (Y) contains the structural unit (E), the ratio of the content of the structural unit (E) to the content of the structural unit (A), from the viewpoint of crack resistance, 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, even more preferably 2 parts by mass or more and 30 parts by mass or less, and still more preferably 2 parts by mass or more and 20 parts by mass or less, per 100 parts by mass of the content of the structural unit (A).

[0113] (2-6) Monomer (f) The thermoplastic resin (Y) may contain a structural unit (F) derived from a monomer (f) other than those described above. The structural unit (F) and the monomer (f) are described above. The thermoplastic resin (Y) may contain two or more types of structural unit (F).

[0114] When the thermoplastic resin (Y) contains the structural unit (F), the content of the structural unit (F) is typically 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 thermoplastic resin (Y). A structural unit (F) content of 0.1% by mass or more makes it possible to achieve a good balance of the properties of the resulting coating composition and coating film. A structural unit (F) content of 85% by mass or less makes it possible to form a coating film that exhibits good crack resistance and antifouling performance.

[0115] (2-7) Thermoplastic resin (Y) content The content of thermoplastic resin (Y) in the coating composition is preferably 1% by mass to 65% by mass, more preferably 2% by mass to 60% by mass, even more preferably 4% by mass to 55% by mass, still more preferably 10% by mass to 55% by mass, particularly preferably 20% by mass to 55% by mass, and even more particularly preferably 25% by mass to 50% by mass. When the content of thermoplastic resin (Y) is within the above range, excellent crack resistance tends to be easily obtained even in the above-mentioned harsh environments, and excellent antifouling performance also tends to be easily obtained.

[0116] The content of thermoplastic resin (Y) in the coating composition is preferably 900 parts by mass or less, more preferably 500 parts by mass or less, even more preferably 300 parts by mass or less, and even more preferably 100 parts by mass or less, per 100 parts by mass of thermoplastic resin (X). More specifically, the content of thermoplastic resin (Y) in the coating composition is preferably 1 part by mass or more and 900 parts by mass or less, more preferably 5 parts by mass or more and 500 parts by mass or less, even more preferably 10 parts by mass or more and 300 parts by mass or less, even more preferably 15 parts by mass or more and 100 parts by mass or less, particularly preferably 15 parts by mass or more and 80 parts by mass or less, and even more particularly preferably 15 parts by mass or more and 60 parts by mass or less, per 100 parts by mass of thermoplastic resin (X). When the content of thermoplastic resin (Y) is within the above range, excellent crack resistance tends to be easily obtained even under the above-mentioned harsh environments, and excellent antifouling performance also tends to be easily obtained.

[0117] (2-8) Embodiments of Thermoplastic Resin (Y) Preferred embodiments of the thermoplastic resin (Y) are exemplified below. (i) A thermoplastic resin (Y) having structural units derived from a monomer (a) and a monomer (b). (ii) A thermoplastic resin (Y) having structural units derived from the monomer (a) and the monomer (c). (iii) A thermoplastic resin (Y) having structural units derived from the monomer (a) and the monomer (e). (iv) A thermoplastic resin (Y) having structural units derived from the monomer (a), the monomer (b) and the monomer (e). (v) A thermoplastic resin (Y) having structural units derived from the monomer (a) and the monomer (d). (vi) A thermoplastic resin (Y) having structural units derived from the monomer (a), the monomer (b) and the monomer (d). (vii) A thermoplastic resin (Y) in any one of the above (i), (iii) to (vi), further having a structural unit derived from the monomer (c).

[0118] From the viewpoint of crack resistance and antifouling performance, the thermoplastic resin (Y) preferably has, in addition to the structural unit (A), a structural unit derived from at least one monomer selected from the monomer (b) and the monomer (d). When the thermoplastic resin (Y) has a structural unit derived from the monomer (d), the metal atom M contained in the monomer (d) is preferably Zn or Cu from the viewpoint of crack resistance and antifouling performance, and more preferably Zn from the viewpoint of crack resistance. When the thermoplastic resin (Y) further contains a structural unit derived from the monomer (c), the dynamic soil resistance tends to be further improved.

[0119] (3) Total content of thermoplastic resin (Z) and plasticizer The total content of the thermoplastic resin (Z) and plasticizer in the coating composition is less than 1.0% by mass, preferably 0.5% by mass or less, more preferably 0.2% by mass or less, even more preferably 0.1% by mass, and may even be 0% by mass. By having the total content less than 1.0% by mass, it is possible to form a coating film that exhibits excellent crack resistance even under the above-mentioned harsh environments. The thermoplastic resin (Z) refers to a thermoplastic resin having an Mw of less than 5,000.

[0120] Conventional antifouling coating compositions sometimes contain thermoplastic resins and / or plasticizers with relatively small molecular weights to improve the crack resistance of the coating film. However, coating films formed from such antifouling coating compositions tend to be unable to exhibit sufficient crack resistance under the above-mentioned harsh environments. This is presumably because, as the coating film repeatedly expands and contracts under the above-mentioned harsh environments, at least a portion of the thermoplastic resin and / or plasticizer bleeds out of the coating film, causing changes in the properties or composition of the coating film.

[0121] The thermoplastic resin (Z) can contain one or more structural units selected from the structural units (A) to (F) above, so long as its Mw is less than 5,000. The thermoplastic resin (Z) does not necessarily contain any of the structural units (A) to (F). The thermoplastic resin (Z) may be a (meth)acrylic resin, a polyester resin, or the like.

[0122] Plasticizers are agents that can impart flexibility to coating films and generally have low molecular weights. Examples of plasticizers 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 phosphate (tricresyl phosphate), triaryl phosphate (triaryl phosphate), and trichloroethyl phosphate; 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 and triacetylene.

[0123] (4) Measurement of weight average molecular weight (Mw) of thermoplastic resin The Mw of the thermoplastic resins such as the thermoplastic resin (X), the thermoplastic resin (Y), and the thermoplastic resin (Z) is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC). Specific measurement conditions for GPC are as described in the Examples section below.

[0124] (5) Other components that may be contained in the coating composition The coating composition may contain one or more other components in addition to those described above. Examples of such other components include additives such as antifouling agents, antifoaming agents, anti-sagging agents, water binding agents, color-flux inhibitors, anti-settling agents, coating wear regulators, UV absorbers, surface conditioners, viscosity modifiers, leveling agents, and pigment dispersants, as well as thermoplastic resins other than the thermoplastic resins (X) and (Y) that have a weight-average molecular weight of 5,000 or more, pigments, and solvents. These additives, thermoplastic resins, pigments, and solvents may each be used alone or in combination of two or more.

[0125] The coating composition preferably contains an antifouling agent to enhance the antifouling performance, particularly the dynamic antifouling performance, of the coating film. Known antifouling agents can be used, including, for example, inorganic compounds, organic compounds containing metal atoms, and organic compounds not containing metal atoms. The coating composition can contain one or more antifouling agents.

[0126] Examples of antifouling agents include 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-4-isothiazolin-3-one). Thiyl-3(2H)isothiazolone; N-(Fluorodichloromethylthio)phthalimide; N,N'-Dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide; Pyrithione metal salts such as zinc pyrithione or copper pyrithione (2-pyridinethiol-1-oxide); Tetramethylthiuram disulfide; 2,4,6-Trichlorophenylmaleimide; 2,3,5,6-Tetrachloro-4-(methylsulfonyl)pyridine; 3-Iodo-2-propylbutylcarba mate;Diiodomethyl-para-trisulfone;Phenyl(bispyridyl)bismuth dichloride;2-(4-Thiazolyl)-benzimidazole;Triphenylboron pyridine salt;Stearylamine-triphenylboron;Laurylamine-triphenylboron;Bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate;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; and 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (generic name: medetomidine).

[0127] Among these, the antifouling agent is preferably at least one selected from the group consisting of cuprous oxide, 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.

[0128] In one embodiment, the coating composition contains one or more antifouling agents that are organic compounds. In this embodiment, the antifouling agent may be an organic compound that contains a metal atom, or an organic compound that does not contain a metal atom. Preferably, the antifouling agent contains an organic compound that does not contain a metal atom. By using an antifouling agent that is an organic compound, the amount of antifouling agent added can be reduced compared to when an antifouling agent that is an inorganic compound is used.

[0129] In the above embodiment, an organic compound containing no metal atoms can be expected to achieve a high level of antifouling properties even in a smaller amount than an organic compound containing a metal atom, and is preferably an organic compound having a heterocycle. Suitable examples of the antifouling agent that is an organic compound having a heterocycle include 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-3(2H)isothiazolone), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and medetomidine.

[0130] 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, per 100 parts by mass of the total content of the thermoplastic resin (X) and the thermoplastic resin (Y). The content of the antifouling agent in the coating composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, even more preferably 60 parts by mass or less, and even more preferably 50 parts by mass or less, and may be 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, per 100 parts by mass of the total content of the thermoplastic resin (X) and the thermoplastic resin (Y). An excessively high content of the antifouling agent may adversely affect the antifouling properties of the coating film and may also reduce the crack resistance of the coating film.

[0131] 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; iron oxides 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 iron oxide), and black iron oxide; azo-based red and yellow pigments; color pigments such as chrome yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, and quinacridone. The coating composition can contain one or more pigments.

[0132] When the coating composition contains a pigment, the content of the pigment in the coating composition is preferably 1 to 450 parts by mass, more preferably 10 to 420 parts by mass, even more preferably 15 to 400 parts by mass, even more preferably 35 to 150 parts by mass, and particularly preferably 45 to 120 parts by mass, per 100 parts by mass of the total content of thermoplastic resin (X) and thermoplastic resin (Y). When the coating composition of the present invention contains a pigment, the ratio of the pigment content to the total content of thermoplastic resin (X) and thermoplastic resin (Y) can affect the crack resistance and stain resistance of the coating film. When the pigment content is within the above range, good crack resistance and stain resistance tend to be easily obtained.

[0133] An antifoaming agent is an agent that has the effect of making the surface of foam that is about to be formed uneven and suppressing foam formation, or an agent that has the effect of locally thinning the surface of formed foam and breaking the foam. Examples of antifoaming agents include silicon-based antifoaming agents and non-silicon-based antifoaming agents. Silicon-based antifoaming agents are antifoaming agents containing surface-active polysiloxane or modified products thereof, and non-silicon-based antifoaming agents are antifoaming agents other than silicon-based antifoaming agents (antifoaming agents that do not contain polysiloxane or modified products thereof). Silicon-based antifoaming agents may be fluorine-modified silicon-based antifoaming agents. Fluorine-modified silicon-based antifoaming agents are antifoaming agents containing fluorine-modified polysiloxane. The coating composition may contain one or more antifoaming agents.

[0134] Non-silicon-based defoaming agents 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. Silicon-based defoaming agents include oil-based, compound-based, self-emulsifying-type, emulsion-based, etc.

[0135] Commercially available products may be used as the defoaming agent. Examples of commercially available non-silicone defoaming agents include mineral oil-based defoamers such as "BYK-030" manufactured by BYK; and polymer-based defoamers such as "Disparlon OX68" manufactured by Kusumoto Chemical Co., Ltd. and "BYK-1790" manufactured by BYK. Examples of commercially available silicone-based defoaming agents other than fluorine-modified silicone-based defoaming agents include silicone oil-based defoamers such as "KF-96" manufactured by Shin-Etsu Chemical Co., Ltd. and "BYK-081" manufactured by BYK. Examples of commercially available fluorine-modified silicone-based defoaming agents include fluorosilicone oil-based defoamers such as "BYK-063," "BYK-065," and "BYK-066N" manufactured by BYK, and "FA-630" manufactured by Shin-Etsu Chemical Co., Ltd.

[0136] From the viewpoint of improving defoaming properties, the content of the antifoaming agent is, relative to 100 parts by mass of the total content of the thermoplastic resin (X) and the thermoplastic resin (Y), 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 still more preferably 0.01 parts by mass or more and 0.20 parts by mass or less.

[0137] Anti-sagging agents are agents that have the effect of suppressing sagging of the coating composition, which may occur between the application of the coating composition to the substrate and the completion of drying of the coating film. Examples of anti-sagging agents include amide-based anti-sagging agents; bentonite-based anti-sagging agents; polyethylene waxes such as oxidized polyethylene wax; hydrogenated castor oil wax; long-chain fatty acid ester polymers; polycarboxylic acids; silica microparticle-based anti-sagging agents; and mixtures of two or more of these. The coating composition can contain one or more anti-sagging agents.

[0138] Examples of the amide-based anti-sagging agent include amide wax-based anti-sagging agents such as fatty acid amide wax and polyamide wax. Examples of the fatty acid amide wax include stearic acid amide wax and oleic acid amide wax.

[0139] Commercially available products may be used as the anti-sagging agent. Examples of commercially available amide wax-based anti-sagging agents include "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 anti-sagging agents include, for example, "Benton 38" manufactured by Elementis Japan Co., Ltd. and organic bentonite-based anti-sagging agents such as "TIXOGEL" manufactured by BYK.

[0140] From the viewpoint of improving sagging prevention properties, the content of the anti-sagging agent is 0.1 parts by mass or more and 6.0 parts by mass or less, more preferably 0.2 parts by mass or more and 5.0 parts by mass or less, and even more preferably 0.25 parts by mass or more and 4.0 parts by mass or less, relative to 100 parts by mass of the total content of the thermoplastic resin (X) and the thermoplastic resin (Y).

[0141] Examples of solvents 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. The coating composition can contain one or more solvents.

[0142] (6) Preparation of coating composition The coating composition can be prepared, for example, by mixing the thermoplastic resin (X) or a resin composition containing it (for example, a solution or dispersion containing the thermoplastic resin (X)), the thermoplastic resin (Y) or a resin composition containing it (for example, a solution or dispersion containing the thermoplastic resin (Y)), and other components added as needed, using a mixer such as a ball mill, a pebble mill, a roll mill, a sand grind mill, or a high-speed disperser.

[0143] <Anti-fouling coating film and composite coating film> The coating film according to the present invention is a coating film formed from the coating composition according to the present invention. The coating film is preferably an antifouling coating film having antifouling properties. The coating composition according to the present invention makes it possible to form an antifouling coating film that has excellent crack resistance even in the above-mentioned harsh environments and exhibits excellent antifouling properties (particularly dynamic antifouling properties) even when exposed to environments with rapid temperature changes.

[0144] 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 heat as necessary. Examples of methods for applying the coating composition include conventionally known methods such as dipping, spraying, brushing, roller coating, electrostatic coating, and electrodeposition coating. The thickness of the coating film is, for example, from 50 μm to 500 μm, and preferably from 100 μm to 400 μm.

[0145] Examples of the object to be coated include underwater moving bodies and underwater structures such as ships, various fishing nets such as aquaculture nets, and other fishing gear. Examples of the underwater structures include port facilities, oil fences, water intake facilities for power plants, etc., 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.

[0146] The coated surface of the above-mentioned substrate may be pretreated as necessary, or a composite coating film may be formed by forming a coating film formed from the coating composition of the present invention on an undercoat coating film formed on the substrate with another coating composition such as an anti-rust coating composition (anti-corrosion coating composition). The composite coating film may have an intermediate coating film between the undercoat coating film formed from the anti-rust coating composition or the like and the coating film formed from the coating composition of the present invention.

[0147] Examples of the coating composition that can be used to form 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.

[0148] The intermediate coating film may be formed on the entire surface of the primer coating film, or on only a portion of the surface. The intermediate coating film and the primer 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 to repair the old coating film. [Example]

[0149] EXAMPLES 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.

[0150] <Resin Manufacturing Example X1: Manufacturing of Thermoplastic Resin (X1)> A four-neck flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 50.0 parts by weight of xylene as a solvent and maintained at 105°C. A premixed mixture of 25.0 parts by weight of n-BA, 58.3 parts by weight of EA, and 16.7 parts by weight of AA as monomer (f), 20.0 parts by weight of xylene as a solvent, and 1.1 parts by weight of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours. After the addition, the mixture was kept warm for 60 minutes. A mixture of 30.0 parts by weight of xylene and 0.2 parts by weight of tert-butylperoxy-2-ethylhexanoate was then added dropwise to the four-neck flask at a constant rate over 30 minutes. After the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having carboxyl groups.

[0151] Next, 100 parts by mass of the resin composition, 25.4 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (X1) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (X1). The thermoplastic resin (X1) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0152] <Resin Manufacturing Example X2: Manufacturing of Thermoplastic Resin (X2)> A four-neck flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 50.0 parts by weight of xylene as a solvent and maintained at 105°C. A premixed mixture of 40.0 parts by weight of n-BA, 43.3 parts by weight of EA, and 16.7 parts by weight of AA as monomer (f), 20.0 parts by weight of xylene as a solvent, and 1.1 parts by weight of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours. After the addition, the mixture was kept warm for 60 minutes. A mixture of 30.0 parts by weight of xylene and 0.2 parts by weight of tert-butylperoxy-2-ethylhexanoate was then added dropwise to the four-neck flask at a constant rate over 30 minutes. After the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having carboxyl groups.

[0153] Next, 100 parts by mass of the resin composition, 25.4 parts by mass of zinc(II) acetate, 12.1 parts by mass of hydrogenated rosin (Hyper-Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (X2) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (X2). The thermoplastic resin (X2) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0154] <Resin Manufacturing Example X3: Manufacturing of Thermoplastic Resin (X3)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105° C. A premixed mixture containing 20 parts by mass of t-BMA, 13.3 parts by mass of n-BMA, 30.0 parts by mass of EHMA, 10.0 parts by mass of n-BA, 10.0 parts by mass of EA, and 16.7 parts by mass of AA as monomers (f), 20.0 parts by mass of xylene as a solvent, and 1.1 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. After completion of the addition, the mixture was kept warm for 60 minutes. Thereafter, a mixture of 30.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0155] Next, 100 parts by mass of the resin composition, 25.4 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (X3) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (X3). The thermoplastic resin (X3) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0156] <Resin Manufacturing Example X4: Manufacturing of Thermoplastic Resin (X4)> A four-neck flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 50.0 parts by weight of xylene as a solvent and maintained at 105°C. A premixed mixture of 15.0 parts by weight of t-BMA, 68.3 parts by weight of CHMA, and 16.7 parts by weight of AA as monomer (f), 20.0 parts by weight of xylene as a solvent, and 1.1 parts by weight of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours. After the addition, the mixture was kept warm for 60 minutes. A mixture of 30.0 parts by weight of xylene and 0.2 parts by weight of tert-butylperoxy-2-ethylhexanoate was then added dropwise to the four-neck flask at a constant rate over 30 minutes. After the addition, the mixture was kept warm for 1.0 hour, yielding a resin composition containing a resin having carboxyl groups.

[0157] Next, 100 parts by mass of the resin composition, 25.4 parts by mass of zinc(II) acetate, 12.1 parts by mass of hydrogenated rosin (Hyper-Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (X4) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (X4). The thermoplastic resin (X4) contained in this resin composition was obtained by adding a carboxyl group-containing resin to the resin (X4) in which the carboxyl group was -COO-Zn 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0158] <Resin production example X5: Production of thermoplastic resin (X5)> (1) Preparation of Metal Atom-Containing Polymerizable Monomer Mixture (M1) A four-neck flask equipped with a condenser, thermometer, dropping funnel, and stirrer was charged with 85.4 parts by weight of PGM (propylene glycol methyl ether) and 40.7 parts by weight of zinc oxide, and the mixture was heated to 75°C with stirring. Next, a mixture consisting of 43.1 parts by weight of MAA (methacrylic acid), 36.1 parts by weight of AA (acrylic acid), and 5.0 parts by weight of water was added dropwise from the dropping funnel at a constant rate over 3 hours. After stirring for an additional 2 hours, 36.0 parts by weight of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture (M1) (solids concentration: 44.8 parts by weight). This metal atom-containing polymerizable monomer mixture (M1) contains zinc (meth)acrylate, which belongs to the monomer (d2) represented by the above formula (VI').

[0159] (2) Manufacturing of thermoplastic resin (X5) A four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 15.0 parts by mass of PGM as a solvent, 25.0 parts by mass of xylene, and 4.0 parts by mass of EA as the monomer (f), and the temperature was raised with stirring and maintained at 100°C. A mixture prepared in advance from 8.3 parts by mass of TIPSA (monomer (b)), 21.7 parts by mass of the metal atom-containing polymerizable monomer mixture (M1) (monomer (d)) produced in (1) above, and 15.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 10.0 parts by mass of n-BA, 35.0 parts by mass of MMA, 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 a dropping funnel and added dropwise to the four-neck flask at a constant rate over 6 hours. Then, 0.5 parts by mass of tert-butylperoxy-2-ethylhexanoate and 10.0 parts by mass of xylene were added dropwise over 30 minutes, and after stirring for another 1 hour and 30 minutes, 10.1 parts by mass of xylene was added to obtain a resin composition (X5) (solid content: 50% by mass), which is a solution containing a thermoplastic resin (X5). The thermoplastic resin (X5) contained in this resin composition has a metal atom-containing group (crosslinking group) represented by the above formula (VI) (M is Zn).

[0160] <Resin production example X6: Production of thermoplastic resin (X6)> A four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 30.0 parts by mass of xylene as a solvent and maintained at 95° C. A premixed mixture of 10.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 25.0 parts by mass of CHMA, and 55.0 parts by mass of EA as monomers (f), 20.0 parts by mass of xylene as a solvent, and 1.1 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. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixture of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after completion of the addition to obtain a resin composition (X6) (solid concentration: 50% by mass) which is a solution containing a thermoplastic resin (X6).

[0161] <Resin Manufacturing Example X7: Manufacturing of Thermoplastic Resin (X7)> A four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 30.0 parts by mass of xylene as a solvent and maintained at 95° C. A premixed mixture of 20.0 parts by mass of t-BMA, 20.0 parts by mass of n-BMA, 20.0 parts by mass of EHMA, 30.0 parts by mass of CHMA, and 10.0 parts by mass of MMA as monomers (f), 20.0 parts by mass of xylene as a solvent, and 1.1 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. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixture of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after completion of the addition to obtain a resin composition (X7) (solid concentration: 50% by mass) which is a solution containing a thermoplastic resin (X7).

[0162] <Resin manufacturing example X8: Manufacturing of thermoplastic resin (X8)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105° C. A mixture of 5.0 parts by mass of t-BMA, 20.0 parts by mass of n-BMA, 10.0 parts by mass of EHMA, 18.0 parts by mass of n-BA, 15.0 parts by mass of CHMA, 15.3 parts by mass of MMA, and 16.7 parts by mass of AA as monomers (f), 20.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 60 minutes. Thereafter, a mixture of 30.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0163] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 parts by mass of hydrogenated rosin (Hyper Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (X8) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (X8). The thermoplastic resin (X8) contained in this resin composition was obtained by adding a carboxyl group-containing resin to a resin having a carboxyl group in the -COO-Cu structure. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0164] <Resin Manufacturing Example X9: Manufacturing of Thermoplastic Resin (X9)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105° C. A mixture of 5.0 parts by mass of t-BMA, 13.3 parts by mass of n-BMA, 25.0 parts by mass of EHMA, 10.0 parts by mass of n-BA, 10.0 parts by mass of CHMA, 5.0 parts by mass of MMA, 15.0 parts by mass of EA, and 16.7 parts by mass of AA, 20.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 60 minutes. Thereafter, a mixture of 30.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0165] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 parts by mass of hydrogenated rosin (Hyper-Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (X9) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (X9). The thermoplastic resin (X9) contained in this resin composition was obtained by adding a carboxyl group-containing resin in which the carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0166] <Resin Manufacturing Example X10: Manufacturing of Thermoplastic Resin (X10)> A four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 30.0 parts by mass of xylene as a solvent and maintained at 95° C. A premixed mixture containing 60.0 parts by mass of TIPSA as monomer (b), 10.0 parts by mass of t-BMA, 5.0 parts by mass of n-BMA, 10.0 parts by mass of n-BA, 10.0 parts by mass of MMA, and 5.0 parts by mass of EA as monomer (f), 20.0 parts by mass of xylene as a solvent, and 1.1 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. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixture of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the addition to obtain a resin composition (X10) (solid concentration: 50% by mass) which is a solution containing a thermoplastic resin (X10).

[0167] <Resin Manufacturing Example X11: Manufacturing of Thermoplastic Resin (X11)> A four-neck flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 30.0 parts by mass of xylene as a solvent and maintained at 95 ° C. A mixture of 50.0 parts by mass of TIPSMA as monomer (b), 10.0 parts by mass of t-BMA, 5.0 parts by mass of n-BMA, 10.0 parts by mass of EHMA, 5.0 parts by mass of n-BA, 5.0 parts by mass of CHMA, 10.0 parts by mass of MMA, 5.0 parts by mass of EA, 20.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixture of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the addition, thereby obtaining a resin composition (X11) (solid content: 50% by mass) which is a solution containing a thermoplastic resin (X11).

[0168] <Resin Production Example Y1: Production of Thermoplastic Resin (Y1)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105°C. A premixed mixture of 40.0 parts by mass of FM-0711 as monomer (a), 20.4 parts by mass of MMA, 17.9 parts by mass of EA, and 21.7 parts by mass of AA as monomer (f), 30.0 parts by mass of xylene as a solvent, and 1.1 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. After completion of the addition, the mixture was kept warm for 60 minutes. 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 to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0169] Next, 100 parts by mass of the resin composition, 7.8 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y1) (solid content concentration: 50% by mass) containing a thermoplastic resin (Y1). The thermoplastic resin (Y1) contained in this resin composition was obtained by adding a carboxyl group-containing resin to the resin (Y1) in which the carboxyl group was -COO-Zn. 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0170] <Resin Production Example Y2: Production of Thermoplastic Resin (Y2)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105°C. A mixture of 20.0 parts by mass of FM-0721, 10.0 parts by mass of FM-0725, and 5.0 parts by mass of TM-0701T as monomers (a), 5.0 parts by mass of t-BMA, 5.0 parts by mass of n-BMA, 25.0 parts by mass of MMA, 15.0 parts by mass of EA, and 15.0 parts by mass of AA as monomers (f), 30.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 60 minutes. 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 to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0171] Next, 100 parts by mass of the resin composition, 7.8 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y2) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y2). The thermoplastic resin (Y2) contained in this resin composition was obtained by adding a carboxyl group-containing resin to the resin (Y2) in which the carboxyl group was -COO-Zn. 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0172] <Resin Production Example Y3: Production of Thermoplastic Resin (Y3)> (1) Preparation of Metal Atom-Containing Polymerizable Monomer Mixture (M1) A four-neck flask equipped with a condenser, thermometer, dropping funnel, and stirrer was charged with 85.4 parts by weight of PGM (propylene glycol methyl ether) and 40.7 parts by weight of zinc oxide, and the mixture was heated to 75°C with stirring. Next, a mixture consisting of 43.1 parts by weight of MAA (methacrylic acid), 36.1 parts by weight of AA (acrylic acid), and 5.0 parts by weight of water was added dropwise from the dropping funnel at a constant rate over 3 hours. After stirring for an additional 2 hours, 36.0 parts by weight of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture (M1) (solids concentration: 44.8 parts by weight). This metal atom-containing polymerizable monomer mixture (M1) contains zinc (meth)acrylate, which belongs to the monomer (d2) represented by the above formula (VI').

[0173] (2) Production of thermoplastic resin (Y3) A four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller was charged with 15.0 parts by mass of PGM as a solvent, 25.0 parts by mass of xylene, and 4.0 parts by mass of EA as the monomer (f), and the temperature was raised with stirring and maintained at 100°C. A mixture prepared in advance from 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, 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 a dropping funnel and added dropwise to the four-neck flask at a constant rate over 6 hours. Then, 0.5 parts by mass of tert-butylperoxy-2-ethylhexanoate and 10.0 parts by mass of xylene were added dropwise over 30 minutes, and after stirring for another 1 hour and 30 minutes, 10.1 parts by mass of xylene was added to obtain a resin composition (Y3) (solid content: 50% by mass), which is a solution containing a thermoplastic resin (Y3). The thermoplastic resin (Y3) contained in this resin composition has a metal atom-containing group (crosslinking group) represented by the above formula (VI) (M is Zn).

[0174] <Resin Production Example Y4: Production of Thermoplastic Resin (Y4)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 50.0 parts by mass of xylene was added as a solvent, and the temperature was maintained at 105°C. A mixture of 40.0 parts by mass of KF-2012 as the monomer (a), 10.0 parts by mass of TIPSA as the monomer (b), 1.0 part by mass of M-90G, 1.0 part by mass of M-230G, 1.0 part by mass of CB-1, and 1.0 part by mass of HEMA as the monomer (c), 1.0 part by mass of NPG as the monomer (e), 10.0 parts by mass of EHMA, 10.0 parts by mass of CHMA, 10.0 parts by mass of MMA, and 10.0 parts by mass of EA as the monomer (f), 5.0 parts by mass of AA, 30.0 parts by mass of xylene as a solvent, and 1.1 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 over 3 hours. After completion of the dropping, the mixture was kept warm for 60 minutes. 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 to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0175] Next, 100 parts by mass of the resin composition, 7.8 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y4) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y4). The thermoplastic resin (Y4) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0176] <Resin Production Example Y5: Production of Thermoplastic Resin (Y5)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene as a solvent was added and maintained at 95°C. A pre-mixed mixture of 40.0 parts by mass of KF-2012 as the monomer (a), 15.0 parts by mass of TIPSA as the monomer (b), 5.0 parts by mass of CB-1 as the monomer (c), 1.0 part by mass of NPG as the 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 the monomer (f), 30.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this mixture was added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixed liquid consisting of 40.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition (Y5) (solid content: 50% by mass), which is a solution containing a thermoplastic resin (Y5).

[0177] <Resin Production Example Y6: Production of Thermoplastic Resin (Y6)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene was added as a solvent and maintained at 95°C. A mixture of 5.0 parts by mass of FM-0725 as the monomer (a), 5.0 parts by mass of X-22-164C as the monomer (b), 5.0 parts by mass of TIPSMA as the monomer (b), 1.0 part by mass of M-40G as the monomer (c), 1.0 part by mass of NPG as the monomer (e), 10.0 parts by mass of t-BMA, 8.0 parts by mass of n-BMA, 25.0 parts by mass of EHMA, 10.0 parts by mass of n-BA, 15.0 parts by mass of CHMA, and 15.0 parts by mass of MMA as the monomer (f), 30.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in a dropping funnel, and this mixture was added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixed liquid consisting of 40.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition (Y6) (solid concentration: 50% by mass) which is a solution containing a thermoplastic resin (Y6).

[0178] <Resin Production Example Y7: Production of Thermoplastic Resin (Y7)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene was added as a solvent and maintained at 95°C. A mixture of 25.0 parts by mass of FM-0721 and 5.0 parts by mass of TM-0701T as monomers (a), 1.0 part by mass of TIPSA and 1.0 part by mass of TIPSMA as monomers (b), 5.0 parts by mass of NPG as monomers (e), 10.0 parts by mass of n-BMA, 11.0 parts by mass of n-BA, 10.0 parts by mass of CHMA, 20.0 parts by mass of MMA, 5.0 parts by mass of EA, and 7.0 parts by mass of AA as monomers (f), 30.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in a dropping funnel, and this mixture was added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixed liquid consisting of 40.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition (Y7) (solid content: 50% by mass), which is a solution containing a thermoplastic resin (Y7).

[0179] <Resin Production Example Y8: Production of Thermoplastic Resin (Y8)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105°C. A mixture of 30.0 parts by mass of FM-0721 and 10.0 parts by mass of KF-2012 as monomers (a), 2.0 parts by mass of M-40G as monomers (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 6.3 parts by mass of MMA, and 21.7 parts by mass of AA as monomers (f), 30.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. 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 to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0180] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y8) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y8). The thermoplastic resin (Y8) contained in this resin composition was obtained by adding a carboxyl group-containing resin in which the carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0181] <Resin Production Example Y9: Production of Thermoplastic Resin (Y9)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 50.0 parts by mass of xylene as a solvent was added and maintained at 105°C. Thereto, 5.0 parts by mass of FM-0711, 10.0 parts by mass of TM-0701T, and 10.0 parts by mass of X-22-164C were added as monomers (a), 1.0 part by mass of M-230G and 1.0 part by mass of CB-1 were added as monomers (c), 1.0 part by mass of NPG was added as monomers (e), 10.0 parts by mass of t-BMA, 15.0 parts by mass of n-BMA, 10.0 parts by mass of EHMA, 5.0 parts by mass of n-BA, 10.0 parts by mass of CHMA, 7.0 parts by mass of EA, and 15.0 parts by mass of AA were added as monomers (f), 30.0 parts by mass of xylene as a solvent, and tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator. A premixed mixture of 1.1 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was placed in a dropping funnel and added dropwise to a four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 120 minutes after the addition. Subsequently, a mixture of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the addition, to obtain a resin composition containing a resin having a carboxyl group.

[0182] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 parts by mass of hydrogenated rosin (Hyper-Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y9) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y9). The thermoplastic resin (Y9) contained in this resin composition was a resin having a carboxyl group, in which the carboxyl group of the resin having a carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0183] <Resin Production Example Y10: Production of Thermoplastic Resin (Y10)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 50.0 parts by mass of xylene as a solvent was added and maintained at 105°C. A pre-mixed mixture of 40.0 parts by mass of FM-0725 as the monomer (a), 10.0 parts by mass of TIPSA as the monomer (b), 5.0 parts by mass of M-90G as the monomer (c), 10.0 parts by mass of EHMA, 10.0 parts by mass of CHMA, 10.0 parts by mass of MMA, 10.0 parts by mass of EA, and 5.0 parts by mass of AA, 30.0 parts by mass of xylene as a solvent, and 1.1 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this mixture was added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. 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 to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0184] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y10) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y10). The thermoplastic resin (Y10) contained in this resin composition was obtained by adding a carboxyl group-containing resin in which the carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0185] <Resin Production Example Y11: Production of Thermoplastic Resin (Y11)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105°C. A premixed mixture containing 40.0 parts by mass of FM-0711 as monomer (a), 20.4 parts by mass of MMA, 17.9 parts by mass of EA, and 21.7 parts by mass of AA as monomer (f), 40.0 parts by mass of xylene as a solvent, and 5.0 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. After completion of the addition, the mixture was kept warm for 60 minutes. Then, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after the addition was completed, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0186] Next, 100 parts by mass of the resin composition, 7.8 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y11) (solids concentration: 50% by mass) containing a thermoplastic resin (Y11). The thermoplastic resin (Y11) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0187] <Resin Production Example Y12: Production of Thermoplastic Resin (Y12)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105°C. A mixture of 20.0 parts by mass of FM-0721, 10.0 parts by mass of FM-0725, and 5.0 parts by mass of TM-0701T as monomers (a), 5.0 parts by mass of t-BMA, 5.0 parts by mass of n-BMA, 25.0 parts by mass of MMA, 15.0 parts by mass of EA, and 15.0 parts by mass of AA as monomers (f), 40.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 60 minutes. Then, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after the addition was completed, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0188] Next, 100 parts by mass of the resin composition, 7.8 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y12) (solid concentration: 50% by mass) containing a thermoplastic resin (Y12). The thermoplastic resin (Y12) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0189] <Resin Production Example Y13: Production of Thermoplastic Resin (Y13)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 50.0 parts by mass of xylene as a solvent was added and maintained at 105°C. A mixture of 40.0 parts by mass of KF-2012 as the monomer (a), 10.0 parts by mass of TIPSA as the monomer (b), 1.0 part by mass of M-90G, 1.0 part by mass of M-230G, 1.0 part by mass of CB-1, and 1.0 part by mass of HEMA as the monomer (c), 1.0 part by mass of NPG as the monomer (e), 10.0 parts by mass of EHMA, 10.0 parts by mass of CHMA, 10.0 parts by mass of MMA, 10.0 parts by mass of EA, and 5.0 parts by mass of AA, 40.0 parts by mass of xylene as a solvent, and 5.0 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 over 3 hours into the four-neck flask. After completion of the dropping, the mixture was kept warm for 60 minutes. Then, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after the addition was completed, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0190] Next, 100 parts by mass of the resin composition, 7.8 parts by mass of zinc(II) acetate, 12.1 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y13) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y13). The thermoplastic resin (Y13) contained in this resin composition was obtained by adding the carboxyl group of the resin having a carboxyl group to the -COO-Zn 2+ (-OOC-Y), where Y is the structural part of naphthenic acid other than the carboxyl group.

[0191] <Resin Production Example Y14: Production of Thermoplastic Resin (Y14)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene as a solvent was added and maintained at 95°C. A pre-mixed mixture of 40.0 parts by mass of KF-2012 as the monomer (a), 15.0 parts by mass of TIPSA as the monomer (b), 5.0 parts by mass of CB-1 as the monomer (c), 1.0 part by mass of NPG as the 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 the monomer (f), 60.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this mixture was added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after completion of the addition, thereby obtaining a resin composition (Y14) (solid concentration: 50% by mass) which is a solution containing a thermoplastic resin (Y14).

[0192] <Resin Production Example Y15: Production of Thermoplastic Resin (Y15)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene as a solvent was added and maintained at 95°C. A mixture of 5.0 parts by mass of FM-0725 as the monomer (a), 5.0 parts by mass of X-22-164C as the monomer (b), 5.0 parts by mass of TIPSMA as the monomer (b), 1.0 part by mass of M-40G as the monomer (c), 1.0 part by mass of NPG as the monomer (e), 10.0 parts by mass of t-BMA, 8.0 parts by mass of n-BMA, 25.0 parts by mass of EHMA, 10.0 parts by mass of n-BA, 15.0 parts by mass of CHMA, and 15.0 parts by mass of MMA as the monomer (f), 60.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was placed in a dropping funnel, and this mixture was added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after completion of the addition, thereby obtaining a resin composition (Y15) (solid content: 50% by mass) which is a solution containing a thermoplastic resin (Y15).

[0193] <Resin Production Example Y16: Production of Thermoplastic Resin (Y16)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene as a solvent was added and maintained at 95°C. A mixture of 25.0 parts by mass of FM-0721 and 5.0 parts by mass of TM-0701T as monomers (a), 1.0 part by mass of TIPSA and 1.0 part by mass of TIPSMA as monomers (b), 5.0 parts by mass of NPG as monomers (e), 10.0 parts by mass of n-BMA, 11.0 parts by mass of n-BA, 10.0 parts by mass of CHMA, 20.0 parts by mass of MMA, 5.0 parts by mass of EA, and 7.0 parts by mass of AA, 60.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator, was placed in a dropping funnel and added dropwise to the four-neck flask at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 120 minutes. Thereafter, a mixed liquid consisting of 10.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after completion of the addition, the mixture was kept warm for 1.0 hour to obtain a resin composition (Y16) (solid content: 50% by mass), which is a solution containing a thermoplastic resin (Y16).

[0194] <Resin Production Example Y17: Production of Thermoplastic Resin (Y17)> A four-neck flask equipped with a thermometer, a condenser, 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 maintained at 105°C. A mixture of 30.0 parts by mass of FM-0721 and 10.0 parts by mass of KF-2012 as monomers (a), 2.0 parts by mass of M-40G as monomers (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 6.3 parts by mass of MMA, and 21.7 parts by mass of AA as monomers (f), 40.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 60 minutes. Then, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after the addition was completed, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0195] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 parts by mass of hydrogenated rosin (Hyper-Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y17) (solid concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y17). The thermoplastic resin (Y17) contained in this resin composition was a resin having a carboxyl group, in which the carboxyl group of the resin having a carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0196] <Resin Production Example Y18: Production of Thermoplastic Resin (Y18)> To a four-neck flask equipped with a thermometer, a condenser, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 50.0 parts by mass of xylene as a solvent was added and maintained at 105°C. Thereto, 5.0 parts by mass of FM-0711, 10.0 parts by mass of TM-0701T, and 10.0 parts by mass of X-22-164C were added as monomers (a), 1.0 part by mass of M-230G and 1.0 part by mass of CB-1 were added as monomers (c), 1.0 part by mass of NPG was added as monomers (e), 10.0 parts by mass of t-BMA, 15.0 parts by mass of n-BMA, 10.0 parts by mass of EHMA, 5.0 parts by mass of n-BA, 10.0 parts by mass of CHMA, 7.0 parts by mass of EA, and 15.0 parts by mass of AA were added as monomers (f), 40.0 parts by mass of xylene as a solvent, and tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator. A premixed mixture of 5.0 parts by mass of xylene and 1.0 parts by mass of tert-butylperoxy-2-ethylhexanoate was placed in a dropping funnel and added dropwise to a four-neck flask at a constant rate over 3 hours, and the mixture was kept warm for 60 minutes after the addition. Subsequently, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the addition, to obtain a resin composition containing a resin having a carboxyl group.

[0197] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 parts by mass of hydrogenated rosin (Hyper-Pale CH), and 60.0 parts by mass of xylene were added to the same reaction vessel, and the mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y18) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y18). The thermoplastic resin (Y18) contained in this resin composition was obtained by adding a carboxyl group-containing resin in which the carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0198] <Resin Production Example Y19: Production of Thermoplastic Resin (Y19)> A four-neck flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. A mixture of 40.0 parts by mass of FM-0725 as monomer (a), 10.0 parts by mass of TIPSA as monomer (b), 5.0 parts by mass of M-90G as monomer (c), 10.0 parts by mass of EHMA, 10.0 parts by mass of CHMA, 10.0 parts by mass of MMA, 10.0 parts by mass of EA, and 5.0 parts by mass of AA, 40.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate over 3 hours. After completion of the addition, the mixture was kept warm for 60 minutes. Then, a mixture of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to the four-neck flask at a constant rate over 30 minutes, and after the addition was completed, the mixture was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0199] Next, 100 parts by mass of the resin composition, 6.5 parts by mass of copper(II) acetate, 12.5 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 mixture was heated to reflux temperature. The reaction was continued for 18 hours while removing the distilled mixture of acetic acid, water, and solvent 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 to obtain a resin composition (Y19) (solids concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y19). The thermoplastic resin (Y19) contained in this resin composition was a resin having a carboxyl group, in which the carboxyl group of the resin having a carboxyl group was -COO-Cu. 2+ (-OOC-Y), where Y is the structural portion of the hydrogenated rosin other than the carboxyl group.

[0200] Tables 1 to 6 show the monomers used in each resin production example and the amounts used (parts by mass). However, for resin production examples X1 to X4, X8, X9, Y1, Y2, Y4, Y8 to Y13, and Y17 to Y19, the monomers used in the production of intermediate resins having carboxyl groups and the amounts used are shown.

[0201] The weight average molecular weights (Mw) of the obtained thermoplastic resins (X1) to (X11) and (Y1) to (Y19) and the solid content concentrations of the obtained resin compositions were measured. The results are also shown in Tables 1 to 6. The measurement methods were as follows.

[0202] [i] Weight average molecular weight (Mw) The weight average molecular weights (Mw) of the thermoplastic resins obtained in the above Resin Production Examples, and the thermoplastic resins 1 to 4 and monomer (a) described below are polystyrene-equivalent weight average molecular weights measured by GPC under the following conditions. Apparatus: Gel permeation chromatography (GPC) (Tosoh Corporation, HLC-8220) Column: TSKgel α-M (Tosoh Corporation, 7.8 mm × 30 cm) and TSKguard column α (Tosoh Corporation, 6.0 mm × 4 cm) Eluent: DMF (N,N-dimethylformamide) Measurement temperature: 35℃ Detector: RI Calibration curve: Created using F288 / F128 / F80 / F40 / F20 / F2 / A1000 (Tosoh Corporation, standard polystyrene) and styrene monomer

[0203] [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)

[0204] [Table 1]

[0205] [Table 2]

[0206] [Table 3]

[0207] [Table 4]

[0208] [Table 5]

[0209] [Table 6]

[0210] Details of the abbreviations of the various monomers shown in Tables 1 to 6 and other components used in the resin production examples are as follows:

[0211] [Monomer (a)] FM-0711: Manufactured by JNC Corporation, one-terminated methacryloyloxyalkyl-modified organopolysiloxane, in 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 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 formula (I'), m = 0, b = 3, n = 132, R 1 ~R 4 and R 31 is a methyl group, R 5 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, b = 3, n = 66, R 1 ~R 4 and R 31 is a methyl group, R 5 Monomer with n-butyl group, molecular weight: 4,600 TM-0701T: Manufactured by JNC Corporation, one-terminated methacryloyloxyalkyl-modified organopolysiloxane, in 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=59, R 9 ~R 12 , R 33 and R 34 Silicon-containing polymerizable monomer with a methyl group, molecular weight: 4,800

[0212] [Monomer (b)] TIPSA: Triisopropylsilyl acrylate, manufactured by Shin-Etsu Chemical Co., Ltd. TIPSMA: Triisopropylsilyl methacrylate, manufactured by Shin-Etsu Chemical Co., Ltd.

[0213] [Monomer (c)] M-40G: Methoxy polyethylene glycol methacrylate (oxyethylene chain repeat number = 4), manufactured by Shin-Nakamura Chemical Co., Ltd. M-90G: Methoxy polyethylene glycol methacrylate (oxyethylene chain repeat number = 9), manufactured by Shin-Nakamura Chemical Co., Ltd. M-230G: Methoxy polyethylene glycol methacrylate (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

[0214] [Monomer (e)] NPG: Neopentyl glycol dimethacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.

[0215] [Monomer (f)] t-BMA: t-butyl methacrylate, manufactured by Mitsubishi Chemical Corporation n-BMA: n-butyl methacrylate, manufactured by Mitsubishi Gas Chemical Company, Inc. EHMA: 2-ethylhexyl methacrylate, manufactured by Mitsubishi Chemical Corporation n-BA: n-butyl acrylate, manufactured by Toagosei Co., Ltd. CHMA: Cyclohexyl methacrylate, manufactured by Mitsubishi Chemical Corporation MMA: Methyl methacrylate, manufactured by Mitsubishi Gas Chemical Company, Inc. EA: Ethyl acrylate, manufactured by Toagosei Co., Ltd.

[0216] [Other monomers] AA: Acrylic acid, manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0217] [Other ingredients] Zinc oxide: Sakai Chemical Industry Co., Ltd. Zinc(II) acetate: manufactured by Nippon Chemical Industry Co., Ltd. Copper(II) acetate: manufactured by Nippon Chemical Industry Co., Ltd. NA-165: Naphthenic acid, acid value: 165 mg KOH / g, manufactured by Yamato Oil & Fat Industries Co., Ltd. Hyper Pale CH: Hydrogenated rosin, acid value: 160 mg KOH / g, manufactured by Arakawa Chemical Industries, Ltd. α-Methylstyrene dimer: Chain transfer agent, manufactured by Mitsui Chemicals tert-Butylperoxy-2-ethylhexanoate: Radical polymerization initiator, manufactured by Kahaku Akzo Co., Ltd. AIBN: Azobisisobutyronitrile: Radical polymerization initiator manufactured by Otsuka Chemical Co., Ltd. AMBN: Azobismethylbutyronitrile: Radical polymerization initiator manufactured by Otsuka Chemical Co., Ltd. Xylene: Organic solvent, manufactured by JFE Chemical Corporation n-Butanol: organic solvent, manufactured by JNC PGM: Propylene glycol methyl ether: organic solvent, manufactured by The Dow Chemical Company

[0218] <Examples 1 to 37 and Comparative Examples 1 to 19> (1) Preparation of coating composition The components shown in Tables 7 to 18 were charged in the amounts shown in the tables, and mixed and dispersed using a disper (2,000 rpm) to prepare coating compositions 1 to 37 and coating compositions H1 to H19, respectively. The units of blending amounts are parts by mass. The blending amount of each component refers to the amount (parts by mass) in the original form, including volatile matters such as solvents.

[0219] (2) Preparation of coating film Each of the coating compositions obtained in (1) above was spray-coated onto 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 coating composition (epoxy anti-corrosion coating: 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 a coating film.

[0220] The details of each compounding component shown in Tables 7 to 18 are as follows. Thermoplastic resin 1: Chlorinated paraffin (Toyoparax A50 manufactured by Tosoh Corporation), solid content: 100% by mass, weight average molecular weight: 750 ·Thermoplastic resin 2: Rosin (“WW Rosin” manufactured by Arakawa Chemical Industries, Ltd.), solid content concentration: 100% by mass, weight average molecular weight: 350 Thermoplastic resin 3: Polyester polymer (Resonac "Teslac 2450"), solid content: 100% by mass, weight average molecular weight: 6,000 ·Thermoplastic resin 4: Versatic acid (neodecanoic acid) (manufactured by Tianjin Siyu Fine Chemicals Co., Ltd.), solid content concentration: 100% by mass, weight average molecular weight: 172 Antifouling agent 1: Cuprous oxide, manufactured by Furukawa Chemicals Antifouling agent 2: Zinc pyrithione, "Zinc Omadine" manufactured by Arch Chemicals Antifouling agent 3: Copper pyrithione, Arch Chemical's "Copper Omajin" Antifouling agent 4: Seenine 211, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-3(2H)isothiazolone), manufactured by Rohm and Haas. Antifouling agent 5: Econair, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, "Econair" manufactured by Janssen PMP Antifouling agent 6: Medetomidine, "Selektope" manufactured by I-TECH AB Pigment 1: Titanium oxide, Ishihara Sangyo Kaisha "Tipake CR-50" Pigment 2: Iron oxide, LANXESS "Bayferox 130" Pigment 3: Zinc oxide, Sakai Chemical Industry Co., Ltd. "Zinc oxide type 2" Anti-sagging agent: HS CHEM "Monoral 3300", non-volatile content: 20% by mass Antifoaming agent: BYK "BYK-066N", non-volatile content: 0.7% by mass Solvent 1: Xylene, manufactured by JFE Chemical Corporation Solvent 2: Methyl isobutyl ketone, manufactured by Mitsui Chemicals

[0221] (Evaluation of antifouling paint compositions) [a] Crack resistance of coating film under harsh environments Sodium hydroxide was added to natural seawater collected from the Nippon Paint Marine Research Center for Marine Technology in Tamano, Okayama Prefecture, to adjust the pH to 9 (common seawater has a pH of about 8.2) to prepare adjusted seawater. The test plates obtained in the examples and comparative examples were immersed in the adjusted seawater at a temperature of 20°C, and the following steps 1) to 4) were repeated 10 times. 1) The temperature of the adjusted seawater is raised from 20°C to 40°C over two hours. 2) Maintain at 40°C for 4 hours 3) The temperature of the adjusted seawater is lowered from 40°C to 20°C over two hours. 4) Keep at 20°C for 4 hours

[0222] The test plate was then removed from the conditioned seawater and allowed to stand for one week in a room at a temperature of 25°C. A maximum of 15 cycles of crack resistance tests were carried out, with the combination of the above-mentioned operations 1) to 4) and the subsequent one-week standing in the room being considered one cycle, and the condition of the coating film on the test plate was observed. If cracks appeared in the coating film during the test, the test was stopped at the time of crack appearance, and the number of cycles at that point was used as an index of crack resistance. The values ​​listed in Tables 7 to 18 are the number of cycles at which cracks first appeared. If no cracks appeared after 15 cycles, the rating was 15 or less. The evaluation result is preferably 10 or higher.

[0223] [b] Antifouling properties of coating film (dynamic antifouling test after static immersion in seawater under harsh conditions) Sodium hydroxide was added to natural seawater collected from the Nippon Paint Marine Research Center for Marine Technology in Tamano, Okayama Prefecture, to adjust the pH to 9 (common seawater has a pH of about 8.2) to prepare adjusted seawater. The test plates obtained in the examples and comparative examples were immersed in the adjusted seawater at a temperature of 20°C, and the following steps 1) to 4) were repeated 10 times. 1) The temperature of the adjusted seawater is raised from 20°C to 40°C over two hours. 2) Maintain at 40°C for 4 hours 3) The temperature of the adjusted seawater is lowered from 40°C to 20°C over two hours. 4) Keep at 20°C for 4 hours

[0224] The test plate was then removed from the conditioned seawater, attached to the side of a rotating cylinder, and rotated in natural seawater at a speed of approximately 10 knots per hour for 18 months. The area of ​​adhesion of marine organisms was determined and evaluated according to the following criteria. The evaluation results after 18 months of testing are shown in Tables 7 to 18. A rating of 3 or higher is preferred. 5: The area of ​​adhesion of marine organisms is between 0% and 5% 4: The area of ​​the surface where marine organisms are attached is 5% or more but less than 10% 3: The area of ​​the surface where marine organisms are attached is 10% or more but less than 15% 2: The area of ​​the surface where marine organisms are attached is 15% or more but less than 30% 1: The area of ​​the surface where marine organisms attach is 30% or more

[0225] [Table 7]

[0226] [Table 8]

[0227] [Table 9]

[0228] [Table 10]

[0229] [Table 11]

[0230] [Table 12]

[0231] [Table 13]

[0232] [Table 14]

[0233] [Table 15]

[0234] [Table 16]

[0235] [Table 17]

[0236] [Table 18] [Industrial Applicability]

[0237] The coating composition of the present invention can form a coating film having excellent crack resistance even in a harsh environment where the seawater in which the coating film is immersed experiences drastic temperature changes and where drying and wetting are repeated. The coating composition of the present invention can form a coating film that has excellent crack resistance even in the above-mentioned harsh environment and also exhibits excellent antifouling performance. The coating composition of the present invention can be suitably used as a coating composition, preferably an antifouling coating composition, to be applied to underwater vehicles such as ships or underwater structures.

Claims

1. A coating composition comprising a thermoplastic resin (X) and a thermoplastic resin (Y), The thermoplastic resin (X) is The weight average molecular weight is 5,000 or more, has one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group, and does not contain the following structural unit (A): The thermoplastic resin (Y) is The weight average molecular weight is 5,000 or more, The polymerizable composition includes a structural unit (A) derived from a monomer (a) having at least one silicon atom-containing group selected from the group consisting of a group represented by the following formula (I), a group represented by the following formula (II), a group represented by the following formula (III), and a group represented by the following formula (IV), A coating composition, wherein the total content of the thermoplastic resin (Z) having a weight-average molecular weight of less than 5,000 and the plasticizer is less than 1.0 mass% in the coating composition. 【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. R １ ~R ５ each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group. 【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. R ６ , R ７ and R ８ are each independently an alkyl group, R ａ or R ｂ Represents. R ａ teeth, 【Transformation 3】 (wherein x represents an integer of 0 to 200. R ２３ ~R ２７ are the same or different and represent an alkyl group; R ｂ teeth, 【Chemistry 4】 (wherein y represents an integer of 1 to 200. R ２８ and R ２９ are the same or different and represent an alkyl group. 【Transformation 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. R ９ ~R １２ each independently represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group. 【Transformation 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. R １３ ~R ２２ are the same or different and represent an alkyl group.

2. 2. The coating composition according to claim 1, wherein the content of the thermoplastic resin (Y) is 900 parts by mass or less per 100 parts by mass of the thermoplastic resin (X).

3. 3. The coating composition according to claim 2, wherein the content of the thermoplastic resin (Y) is 100 parts by mass or less per 100 parts by mass of the thermoplastic resin (X).

4. The coating composition according to claim 1 or 2, wherein the thermoplastic resin (X) has the metal atom-containing group.

5. 3. The coating composition according to claim 1, wherein the thermoplastic resin (Y) further has one or more groups selected from the group consisting of a metal atom-containing group containing a divalent metal atom and a triorganosilyloxycarbonyl group.

6. 3. The coating composition according to claim 1, wherein the content of the pigment is 20 parts by mass or more and 390 parts by mass or less per 100 parts by mass of the total content of the thermoplastic resin (X) and the thermoplastic resin (Y).

7. 3. The coating composition according to claim 1, wherein the monomer (a) has a molecular weight of 25,000 or less.

8. 3. The coating composition of claim 1 or 2, further comprising an antifouling agent.

9. The coating composition according to claim 8, wherein the antifouling agent is at least one selected from the group consisting of cuprous oxide, 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.

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

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

12. A vessel having the coating film according to claim 10 or the composite coating film according to claim 11.

13. An underwater structure having the coating film according to claim 10 or the composite coating film according to claim 11.

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