Paint composition and coating film

Abstract

The present invention provides a paint composition that can form a paint film with excellent crack resistance even in environments where the temperature of the seawater in which the paint film is immersed fluctuates drastically and where drying and wetting are repeated. [Solution] A paint composition is provided comprising 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 constituent unit (A); the thermoplastic resin (Y) has a weight-average molecular weight of 5,000 or more, and contains a constituent 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), which has a weight-average molecular weight of less than 5,000, and the plasticizer is less than 1.0% by mass in the paint composition.

Description

[Technical Field]

[0001] The present invention relates to a coating composition comprising 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 and underwater structure equipped with the coating film or the composite coating film. [Background technology]

[0002] In ships, the attachment of organisms such as barnacles, mussels, and algae to the parts that come into contact with seawater can hinder efficient operation and lead to problems such as wasted fuel. Conventionally, antifouling paint compositions have been applied to the surface of ships to prevent the attachment of organisms. For example, International Publication No. 2011 / 046086 (Patent Document 1) discloses an antifouling paint composition comprising 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 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] The coating film formed from the paint composition is required to have excellent crack resistance, meaning it is less likely to crack even when immersed in seawater. However, even coating films formed from conventional paint compositions that are considered to have relatively good crack resistance can crack when immersed in seawater under harsh conditions, leaving room for further improvement. Harsh conditions refer to environments where the temperature of the seawater into which the coating film is immersed fluctuates drastically, and where the coating film is repeatedly immersed in seawater and not immersed (wet and dry).

[0005] An object of the present invention is to provide a coating composition that can form a coating with excellent crack resistance even in environments where the temperature of the seawater in which the coating is immersed fluctuates drastically and where the seawater is repeatedly wet and dry. Another object of the present invention is to provide a coating formed from the coating composition, a composite coating having the coating, and a ship and underwater structure having the coating or the composite coating. [Means for solving the problem]

[0006] The present invention provides the following paint compositions, coatings, composite coatings, ships, and underwater structures. [1] A paint 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. It 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 Excluding the following constituent unit (A), The thermoplastic resin (Y) is The weight-average molecular weight is 5,000 or more. It comprises a constituent 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 paint composition in which the total content of a thermoplastic resin (Z) having a weight-average molecular weight of less than 5,000 and a plasticizer is less than 1.0% by mass in the paint composition. [ka] [In equation (I), a and b each independently represent an integer between 2 and 5, m represents an integer between 0 and 50, and n represents an integer between 3 and 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.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[10] A coating film formed by any of the coating compositions described in [1] to [9].

[11] A composite coating film having a primer coating film formed by a rust-preventive coating composition and a coating film formed by any of the coating compositions described in [1] to [9] which is laminated on the primer coating film.

[12] A ship having the coating described in

[10] or the composite coating described in

[11] .

[13] An underwater structure having the coating described in

[10] or the composite coating described in

[11] . [Effects of the Invention]

[0007] A paint composition can be provided that can form a paint film with excellent crack resistance even in environments where the temperature of the seawater in which the paint film is immersed fluctuates drastically and where the water is repeatedly wet and dry. Furthermore, a paint film formed from the paint composition, a composite paint film having said paint film, and a ship and underwater structure having said paint film or composite paint film can be provided. [Modes for carrying out the invention]

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

[0009] According to the paint composition of the present invention, a combination of thermoplastic resin (X) and thermoplastic resin (Y) is used as the vehicle resin, and the total content of thermoplastic resin (Z) and plasticizer is as described above. Therefore, a paint film with excellent crack resistance can be formed even in harsh environments such as those where the temperature of the seawater in which the paint film is immersed changes drastically and where drying and wetting are repeated. According to the paint composition of the present invention, it is possible to form a paint film that exhibits excellent crack resistance over a long period of time.

[0010] The coating composition according to the present invention is suitably applied to the surface of, for example, ships or underwater structures. When the coating composition is assumed to be applied to a ship, for example, the coating film formed from the coating composition may be exposed to severe temperature changes during immersion in water (seawater, etc.) due to the temperature difference between day and night. Furthermore, the coating film is exposed to alternating wet and dry conditions at or near the waterline of the ship, where it is repeatedly immersed in water and not immersed, or it may be exposed to alternating wet and dry conditions due to the influence of waves. Moreover, a ship with a coating film is brought ashore for repairs, etc., after sailing for a certain period of time. In this case as well, the coating film will be exposed to alternating wet and dry conditions. The same can be said for underwater structures. According to the coating composition according to the present invention, even when exposed to such harsh conditions as described above, a coating film with excellent crack resistance can be formed.

[0011] When cracks appear in a coating, the coating's antifouling performance (ability to inhibit the adhesion of aquatic organisms) tends to decrease. Therefore, having excellent crack resistance in the coating is advantageous in terms of providing the coating with excellent antifouling performance.

[0012] The antifouling coating film formed from the 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. This coating film can exhibit excellent antifouling performance over a long period of time.

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

[0014] The paint composition according to the present invention can be suitably used as a paint composition applied to underwater moving bodies such as ships or underwater structures, and is particularly suitable as an antifouling paint composition applied to underwater moving bodies such as ships. The components included in or potentially included in the paint 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) has a weight-average molecular weight (Mw) of 5,000 or more, and 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 does not contain the constituent unit (A) described later.

[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 harsh conditions described above. From this 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 antifouling properties, particularly dynamic antifouling properties, 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 still more preferably 50,000 or less, particularly preferably 40,000 or less, and still 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. Having such groups in the thermoplastic resin (X) is advantageous in providing good antifouling performance to the coating film, and is also advantageous in providing excellent crack resistance even under the harsh environment described above.

[0018] As for the thermoplastic resin (X), A thermoplastic resin (X1) containing a metal atom-containing unit (D) having a metal atom-containing group containing a divalent metal atom, and not containing a triorganosilyloxycarbonyl group (B), A thermoplastic resin (X2) that includes the above-mentioned constituent unit (B) but does not include the above-mentioned constituent unit (D), Thermoplastic resin (X3) containing the above-mentioned structural unit (B) and the above-mentioned structural unit (D) These are some examples. From the viewpoint of providing a paint composition that exhibits excellent crack resistance even under the harsh conditions described above, it is preferable that the paint composition contains a thermoplastic resin (X1).

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

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

[0021] (1-1) Monomer (d) The constituent unit (D) is preferably a constituent unit having at least one metal atom-containing group selected from the group consisting of the group represented by the following formula (V) and the group represented by the following formula (VI). The thermoplastic resin (X) may have both the group represented by formula (V) and the group represented by formula (VI). [ka] [In formula (V), M represents a divalent metal atom, and R 30 [This 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 monomer (d1) represented by formula (V') and monomer (d2) represented by formula (VI'). [ka] [In formula (V'), R 37 represents a hydrogen atom or a methyl group, and M and R represent hydrogen atoms or methyl groups. 30 This expresses the same meaning as above. [ka] [In formula (VI'), R 38 and R 39 Each of these independently represents either a hydrogen atom or a methyl group, and M has the same meaning as described above.

[0023] Polymerization of a monomer composition containing monomer (d) as described above yields a thermoplastic resin (X) which is a (meth)acrylic resin containing a constituent unit (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] Examples of divalent metal atoms M in formula (V') (the same applies to formula (V)) and formula (VI') (the same applies to formula (VI)) include Mg, Zn, Cu, etc. From the viewpoint of providing a paint composition that exhibits excellent crack resistance even under the harsh environment described above, Zn or Cu is preferred, and Zn is more preferred. In equation (V') [the same applies to equation (V)], R 30 Preferably, it is an organic acid residue.

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

[0026] R 30 Examples of organic acids that form organic acid residues include monobasic organic acids such as acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexyl acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, stearolic acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, and puruvic acid.

[0027] Furthermore, other preferred organic acids from the viewpoint of crack resistance and other factors include monobasic cyclic organic acids other than aromatic organic acids. Examples of monobasic cyclic organic acids include organic acids having cycloalkyl groups 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 abietane, pimaran, isopimaran, and compounds having a labdan skeleton. More specifically, examples include abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, palastic 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 a monobasic cyclic organic acid, for example, pine resin or pine resin acid can also be used. Examples of such substances include rosins, hydrogenated rosins, disproportionated rosins, and naphthenic acid. Rosins include gum rosin, wood rosin, and tall oil rosin. Rosins, hydrogenated rosins, and disproportionated rosins are preferred because they are inexpensive, readily available, easy to handle, and easily improve crack resistance and stain resistance.

[0030] The acid value of the monobasic cyclic organic acid is preferably 100 mg KOH / g or more and 220 mg KOH / g or less, more preferably 120 mg KOH / g or more and 190 mg KOH / g or less, and even more preferably 140 mg KOH / g or more and 185 mg KOH / g or less. R 30 When using a monobasic cyclic organic acid with an acid value within the above range as the forming agent, the good antifouling performance of the coating film tends to be maintained for a longer period of time. The organic acid residues in the monomer (d1) may be formed from one type of organic acid, or from two or more types of organic acids.

[0031] R 30 As a method for producing a monomer (d1) having an organic acid residue, for example, one method involves reacting an inorganic metal compound, a carboxyl group-containing radical polymerizable monomer such as (meth)acrylic acid, and a non-polymerizable organic acid (the organic acid constituting the above organic acid residue) in an organic solvent containing an alcohol-based compound. The constituent unit (D) derived from the monomer (d1) can also be formed by reacting a resin obtained by polymerizing a monomer composition containing a carboxyl group-containing radical 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] Monomer (d2) is represented by formula (VI'). By using monomer (d2) as 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 the polymer main chains).

[0033] Examples of monomers (d2) include magnesium acrylate [(CH2=CHCOO)2Mg], magnesium methacrylate [(CH2=C(CH3)COO)2Mg], zinc acrylate [(CH2=CHCOO)2Zn], zinc methacrylate [(CH2=C(CH3)COO)2Zn], copper acrylate [(CH2=CHCOO)2Cu], and copper methacrylate [(CH2=C(CH3)COO)2Cu]. One or more of these can be appropriately selected and used as needed.

[0034] One method for producing monomer (d2) is to react a polymerizable unsaturated organic acid, such as (meth)acrylic acid, with a metal compound in an organic solvent containing an alcohol-based compound and water. In this case, it is preferable to adjust the water content in the reactant to 0.01% by mass or more and 30% by mass or less.

[0035] The thermoplastic resin (X) may contain both constituent units derived from monomer (d1) and constituent units derived from monomer (d2).

[0036] When the thermoplastic resin (X) contains constituent units (D), the content of constituent units (D) is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 25% by mass or less, and even more preferably 4% by mass or more and 20% by mass or less, of the total constituent units contained in the thermoplastic resin (X), from the viewpoint of crack resistance and antifouling performance of the coating film.

[0037] (1-2) Monomer (b) The constituent unit (B) may be a constituent unit derived from monomer (b) having a triorganosilyloxycarbonyl group. An example of the triorganosilyloxycarbonyl group is the group represented by formula (VII). [ka] [In formula (VII), R 40 , R 41 and R 42 [This represents a hydrocarbon residue with 1 to 20 carbon atoms, which may be identical or different.]

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

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

[0040] The R in equation (VII') [and similarly for equation (VII)] 40 , R 41 and R 42This represents a hydrocarbon residue (monovalent hydrocarbon group) having 1 to 20 carbon atoms, either identical or different. Examples of hydrocarbon residues having 1 to 20 carbon atoms include linear or branched alkyl groups having 20 or fewer carbon atoms, such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, and tetradecyl group; cyclic alkyl groups which may have substituents, such as cyclohexyl group and substituted cyclohexyl group; and aryl groups which may have substituents, such as aryl group and substituted aryl group.

[0041] Examples of substituted cyclic alkyl groups include cyclic alkyl groups substituted with halogens, alkyl groups with up to approximately 18 carbon atoms, acyl groups, nitro groups, or amino groups. Examples of substituted aryl groups include aryl groups substituted with halogens, alkyl groups with up to approximately 18 carbon atoms, acyl groups, nitro groups, or amino groups.

[0042] In particular, from the viewpoint of crack resistance and stain resistance of the coating film, R 40 , R 41 and R 42 Preferably, one or more of them are iso-propyl groups, R 40 , R 41 and R 42 It is more preferable that all of them are iso-propyl groups.

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

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

[0045] In one preferred embodiment, the thermoplastic resin (X) is a (meth)acrylic resin comprising one or more constituent units selected from the group consisting of a constituent unit (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Zn, a constituent unit (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Cu, and a constituent 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 harsh environment described above, the thermoplastic resin (X) is preferably a (meth)acrylic resin containing one or more constituent units selected from the group consisting of constituent units (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Zn, and constituent units (B) derived from a monomer (b1) represented by formula (VII'). More preferably, it is a (meth)acrylic resin containing a constituent unit (D) derived from a 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 constituent unit (C) derived from monomer (c). Monomer (c) is a monofunctional (meth)acrylic acid ester represented by formula (c). The presence of constituent unit (C) in the thermoplastic resin (X) is advantageous in improving the antifouling performance of the coating film. Furthermore, by including constituent unit (C), the rate of coating film wear can be moderately increased. CH2=C(R A )(COOR B ) (c)

[0047] In formula (c), R A R represents a hydrogen atom or a methyl group. B This represents a monovalent group comprising one or more groups selected from the group consisting of hydroxyl groups, carboxyl groups, and oxyalkylene chains. The thermoplastic resin (X) may contain constituent units derived from two or more monomers (c). Monomer (c) may also be a monomer having two or more groups selected from the group consisting of hydroxyl groups, carboxyl groups, and oxyalkylene chains.

[0048] From the perspective of improving the antifouling performance of the coating film, the R possessed by monomer (c) B It is preferable that the mixture 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 -CH2-, -(CH2)2-, -(CH2)3-, -CH(CH3)CH2-, -CH2CH(CH3)-, etc.

[0049] Examples of monomers (c) include hydroxyl group-containing alkyl (meth)acrylates 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, where the ester portion has 1 to 20 carbon atoms; carboxyl group-containing alkyl (meth)acrylates where the ester portion has 1 to 20 carbon atoms; alkoxyalkyl (meth)acrylates such as methoxyethyl (meth)acrylate, where the ester portion has 1 to 20 carbon atoms; and methoxypolyethylene glycol (meth)acrylate, where the number of -OC2H4- repeating groups is, for example, Examples include (meth)acrylic acid esters in which the ester portion contains a polyalkylene glycol chain, such as methoxypolypropylene glycol (meth)acrylate [for example, the number of -OC3H6- repeating groups is 1 to 50, preferably 1 to 24, more preferably 2 to 14, and even more preferably 2 to 9]; and (meth)acrylic acid esters in which the ester portion contains a polyalkylene glycol chain and a carboxyl group, such as (meth)acryloyloxyethyl succinic acid, (meth)acryloyloxyethyl phthalic acid, (meth)acryloyloxyethyl hexahydrophthalic acid, (meth)acryloyloxypropyl phthalic acid, and (meth)acryloyloxypropyl hexahydrophthalic acid.

[0050] Among the above, monomer (c) is preferably an alkoxyalkyl (meth)acrylate having 1 to 20 carbon atoms in the ester portion, a (meth)acrylic acid ester in which the ester portion contains a polyalkylene glycol chain, and / or a (meth)acrylic acid ester in which the ester portion contains a polyalkylene glycol chain and a carboxyl group.

[0051] When the thermoplastic resin (X) contains constituent units (C), the content of constituent units (C) is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 35% by mass or less, and even more preferably 1% by mass or more and 30% by mass or less, from the viewpoint of the antifouling performance of the coating film, but may also be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

[0052] (1-4) Monomer (e) The thermoplastic resin (X) may further have constituent units (E) derived from a monomer (e) which is a polyfunctional (meth)acrylic acid ester having two or more (meth)acryloyl groups. By further having constituent units (E) in the thermoplastic resin (X), the dynamic antifouling and / or crack resistance of the coating film can be further improved. The thermoplastic resin (X) may contain two or more constituent units (E) derived from the monomer (e).

[0053] Examples of monomer (e) include difunctional (meth)acrylates having two (meth)acryloyloxy groups in the molecule, and trifunctional or more (meth)acrylates having three or more (meth)acryloyloxy groups in the molecule.

[0054] Examples of bifunctional (meth)acrylates include compound (e-1), represented by formula (e-1). [ka] [In the formula, R C Each of these independently represents either a hydrogen atom or a methyl group. D represents a divalent hydrocarbon group which may have substituents, and at least one -CH2- of the hydrocarbon group may be replaced by -O- or -C(=O)-.

[0055] R C The group is preferably a methyl group. R DThe group is not particularly limited, but examples include alkylene groups and poly(oxyalkylene) groups. 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 It can be represented by -. x represents the number of repeating oxyalkylene groups, which 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 within the oxyalkylene group may be, for example, 2 to 6, 2 to 4, or 2 to 3.

[0057] Specifically, difunctional (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. Examples include acrylates, tricyclodecanedimethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (for example, with 4 to 23 repeating oxyalkylene groups), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate (for example, with 4 to 23 repeating oxyalkylene groups).

[0058] Examples of (meth)acrylates with three or more functions 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. Examples include 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 succinate monoester, dipentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, and dipentaerythritol pentaacrylate maleate monoester.

[0059] The (meth)acrylate with three or more functionalities is preferably 3 to 6 functionalities, and more preferably 3 or 4 functionalities.

[0060] When the thermoplastic resin (X) contains constituent units (E), the content of constituent units (E) derived from monomers (e) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and may be 2% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more, from the viewpoint of further improving crack resistance. The content of constituent units (E) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. If the content of constituent units (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 constituent units (F) derived from other monomers (f) not mentioned above. The thermoplastic resin (X) may contain two or more types of constituent units (F).

[0062] The monomer (f) is not particularly limited as long as it is an unsaturated monomer that can copolymerize with other monomers that form the thermoplastic resin (X), for example, Methyl (meth)acrylate, ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethylhexaoxy)ethyl (meth)acrylate, 1-methyl-2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate, m-methoxyphenyl (meth)acrylate, p-methoxyphenyl (meth)acrylate, o-methoxyphenylethyl (meth)acrylate, m-methoxyphenylethyl (meth)acrylate, p (Meth)acrylic acid ester monomers that do not belong to monomers (c) and (e), such as -methoxyphenylethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (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, glycidyl (meth)acrylate, etc.; Vinyl monomers containing primary or secondary amino groups, 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; Styrene, vinyltoluene, α-methylstyrene, (meth)acrylonitrile, vinyl acetate, vinyl propionate, (meth)acrylic acid, and other vinyl monomers These are some examples.

[0063] When the thermoplastic resin (X) contains constituent units (F), the content of constituent units (F) is usually 0.1% by mass or more and 85% by mass or less of the total constituent units contained in the thermoplastic resin (X), 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 still more preferably 20% by mass or more and 70% by mass or less. By having a content of constituent units (F) of 0.1% by mass or more, it is possible to balance the various properties of the resulting paint composition and coating film. By having a content of constituent units (F) of 85% by mass or less, it is possible to form a coating film that exhibits good crack resistance and antifouling performance.

[0064] (1-6) Method of manufacturing thermoplastic resin (X) The method for producing thermoplastic resin (X) is not particularly limited, but for example, it can be produced by reacting a monomer composition obtained by mixing the above monomers in the presence of a radical initiator at a reaction temperature of 60 to 180°C for 5 to 14 hours. The conditions for the polymerization reaction may be adjusted as appropriate. Thermoplastic resin (Y), which will be described later, can also be produced in the same manner as thermoplastic resin (X). Furthermore, the thermoplastic resin (X) containing the constituent unit (D) derived from the monomer (d1) is a carboxyl group-containing resin obtained by polymerizing a monomer composition containing a carboxyl group-containing radical polymerizable monomer such as (meth)acrylic acid in the same manner as described above, a metal compound, and a non-polymerizable organic acid (R above). 30 By reacting it with organic acids (which constitute the compound), etc., the carboxyl groups of the carboxyl group-containing resin are converted to -COO-MR 30 It can also be formed by a method of conversion.

[0065] Examples of radical initiators 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-butyl peroxide-2-ethylhexanoate.

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

[0067] (1-7) Content of thermoplastic resin (X) The content of thermoplastic resin (X) in the paint composition is preferably 0.1% to 80% by mass, more preferably 0.5% to 70% by mass, even more preferably 2% to 60% by mass, even more preferably 4% to 60% by mass, particularly preferably 8% to 55% by mass, and most particularly preferably 12% to 50% by mass, based on the solid content of the paint composition. When the content of thermoplastic resin (X) is within the above range, excellent crack resistance tends to be obtained even under the harsh conditions described above, and furthermore, excellent antifouling performance tends to be obtained. The solid content of the paint composition refers to the total of components other than solvents contained in the paint composition.

[0068] (2) Thermoplastic resin (Y) The thermoplastic resin (Y) has a weight-average molecular weight (Mw) of 5,000 or more and is a resin containing a constituent unit (A). The constituent unit (A) is a constituent unit having at least one silicon atom-containing group selected from the group consisting of the group represented by formula (I), the group represented by formula (II), the group represented by formula (III), and the group represented by formula (IV). More specifically, the constituent unit (A) is a constituent 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 harsh conditions described above. From this 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 antifouling properties, particularly dynamic antifouling properties, 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 constituent units other than constituent unit (A). While not particularly limited, examples of such constituent units include: A constituent unit (B) having a triorganosilyloxycarbonyl group, The constituent unit (C) derived from monomer (c), which is a monofunctional (meth)acrylic acid ester represented by formula (c) described later, and A constituent unit (D) having a metal atom-containing group containing a divalent metal atom. And so on. The thermoplastic resin (Y) may contain one or more constituent units other than constituent unit (A). From the viewpoint of crack resistance and antifouling properties, particularly dynamic antifouling properties, the thermoplastic resin (Y) preferably further has one or more groups selected from the group consisting of metal atom-containing groups containing divalent metal atoms and triorganosilyloxycarbonyl groups, and more preferably further has metal atom-containing groups containing divalent metal atoms.

[0071] (2-1) Monomer (a) The silicon atom-containing group possessed by monomer (a) is at least one selected from the group consisting of the group represented by formula (I), the group represented by formula (II), the group represented by formula (III), and the group represented by formula (IV).

[0072] In equation (I), a and b each independently represent an integer between 2 and 5, m represents an integer between 0 and 50, and n represents an integer between 3 and 270.1 ~R 5 Each of these 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 equation (II), c and d each independently represent an integer between 2 and 5, and p represents an integer between 0 and 50. 6 , R 7 and R 8 Each of these is independently an alkyl group, R a or R b It represents. R a In this case, x represents an integer between 0 and 200. 23 ~R 27 These represent alkyl groups, either identical or different. R b In this case, y represents an integer between 1 and 200. 28 and R 29 These represent alkyl groups, either identical or different.

[0074] In equation (III), e, f, g, and h each independently represent an integer between 2 and 5, q and s each independently represent an integer between 0 and 50, and r represents an integer between 3 and 270. 9 ~R 12 Each of these 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 equation (IV), i, j, k, and l each independently represent an integer between 2 and 5, t and u each independently represent an integer between 0 and 50, and v and w each independently represent an integer between 0 and 70. 13 ~R 22 These represent alkyl groups, either identical or different.

[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, it may have two or more groups represented by formula (I), two or more groups represented by formula (II), two or more groups represented by formula (III), and / or two or more groups represented by formula (IV).

[0077] The monomer (a) is preferably at least one selected from the group consisting of monomer (a1) represented by formula (I'), monomer (a2) represented by formula (II'), monomer (a3) ​​represented by formula (III'), and monomer (a4) represented by formula (IV'). Monomer (a1) represented by formula (I'), monomer (a2) represented by formula (II'), monomer (a3) ​​represented by formula (III'), and 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 This expresses 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 represent hydrogen atoms or methyl groups. 6 ~R 8 This expresses the same meaning as above. [ka] [In formula (III'), R 33 and R 34Each of these independently represents a hydrogen atom or a methyl group, and e, f, g, h, q, r, s and R 9 ~R 12 This expresses the same meaning as above. [ka] [In formula (IV'), R 35 and R 36 Each of these independently represents a hydrogen atom or a methyl group, and the letters i, j, k, l, t, u, v, w and R represent the same thing. 13 ~R 22 This expresses the same meaning as above.

[0079] Polymerization of a monomer composition containing monomer (a) as described above yields a thermoplastic resin (Y) which is a (meth)acrylic resin containing a constituent unit (A) selected from the group consisting of monomer (a1), monomer (a2), monomer (a3), and monomer (a4). This thermoplastic resin (Y) has 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 constituent units (A) derived from the monomer (a).

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

[0081] Monomer (a1) is represented by formula (I'). By using monomer (a1) as 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 constituent units derived from two or more 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 viewpoints of water resistance of the coating film, adhesion to the substrate, etc., m is preferably 0 or more and 25 or less, more preferably 0 or more and 20 or less. m may be 3 or more or 5 or more, and may be 10 or less or 8 or less. From the viewpoints of antifouling performance of the coating film and solubility in general organic solvents, n is usually 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, still more preferably 45 or more and 160 or less. R 1 ~R 5 The substituents of the substituted phenyl group and substituted phenoxy group in are, for example, an alkyl group and a halogen atom. R 1 ~R 5 is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and particularly preferably a methyl group and an ethyl group.

[0083] Commercially available products may be used as the monomer (a1). Examples of commercially available products include "FM-0711" (mono-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 1,000), "FM-0721" (mono-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 5,000), "FM-0725" (mono-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 10,000) manufactured by JNC Corporation, Shin-Etsu Chemical Co., Ltd.'s "X-22-2404" (one-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 420), "X-22-174ASX" (one-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 900), "X-22-174BX" (one-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 2,300), "KF-2012" (one-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4,600), and "X-22-2426" (one-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 12,000) These are some examples.

[0084] Monomer (a2) is represented by formula (II'). By using monomer (a2) as 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 constituent units derived from two or more 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 and adhesion to the substrate, p is preferably 0 to 25, more preferably 0 to 20. p may be 3 or more or 5 or more, or 10 or less or 8 or less.

[0086] From the viewpoint of solubility in common organic solvents, x is usually between 0 and 200, preferably between 10 and 150, and more preferably between 20 and 125. From the viewpoint of solubility in general organic solvents, y is usually between 1 and 200, preferably between 10 and 150, and more preferably between 20 and 125. R 6 ~R 8 and R 23 ~R 29The alkyl group in [description] is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, and even more preferably methyl group and ethyl group. R 6 ~R 8 are all preferably alkyl groups.

[0087] Commercially available products may be used as the monomer (a2). Examples of commercially available products include "TM-0701T" manufactured by JNC Corporation (mono-terminal methacryloyloxyalkyl-modified organopolysiloxane, molecular weight: 423), etc.

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

[0089] In the formula (III') [the same applies to the formula (III)], e and h are each preferably 2 or 3. f and g are each preferably 2 or 3. From the viewpoints of water resistance of the coating film, adhesion to the substrate, etc., q and s are each preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, even more preferably 0 or more and 20 or less. q and s may each be 3 or more or 5 or more, and may also be 10 or less or 8 or less. From the viewpoints of antifouling performance of the coating film, solubility in general organic solvents, etc., r is usually 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, even more preferably 45 or more and 160 or less. R 9 ~R 12The substituents on the substituted phenyl group and substituted phenoxy group in this compound are, for example, alkyl groups and halogen atoms. R 9 ~R 12 The group is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, even more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, or tert-butyl group, and particularly preferably a methyl group or an ethyl group.

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

[0091] Monomer (a4) is represented by formula (IV'). By using monomer (a4) as 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 the polymer main chains). A commercially available product may be used as monomer (a4). The thermoplastic resin (Y) may contain constituent units derived from two or more monomers (a4).

[0092] In formula (IV') [and similarly for 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 and adhesion to the substrate, t and u are preferably 0 to 30, more preferably 0 to 25, and even more preferably 0 to 20, respectively. q and s may be 3 or more or 5 or more, or 10 or less or 8 or less, respectively. From the viewpoint of the antifouling performance of the coating film and solubility in general organic solvents, v and w are usually 0 to 70, preferably 5 to 60, and more preferably 10 to 50, respectively. R 13 ~R 22 The alkyl group in is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, or tert-butyl group, and even more preferably a methyl group or an ethyl group.

[0093] The molecular weight of 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, still particularly preferably 3,000 or more, most preferably 4,000 or more or 5,000 or more, and may also be 10,000 or more, from the viewpoint of improving the crack resistance and antifouling performance of the coating film under harsh environments. The molecular weight of monomer (a) is usually 25,000 or less, preferably 20,000 or less, more preferably 18,000 or less, still more preferably 15,000 or less, still still more preferably 12,000 or less. If the molecular weight of monomer (a) is too large, the coating film formed from the coating composition tends to be non-uniform in its components due to incompatibility between monomers in the monomer composition, which is a mixture of monomers used in the preparation of the silicon atom-containing resin, and incompatibility between polymers produced by the polymerization of the monomer composition. If the coating film is non-uniform in its composition, it may negatively affect the crack resistance and stain resistance of the coating film under harsh environmental conditions.

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

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

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

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

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

[0099] When the thermoplastic resin (Y) contains constituent units (B), the content of constituent units (B) 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 still more preferably 5% by mass or more and 25% by mass or less, and may also be 5% by mass or more and 20% by mass or less, from the viewpoint of crack resistance and antifouling performance of the coating film.

[0100] When the thermoplastic resin (Y) contains constituent units (B), the ratio of the content of constituent units (B) to the content of constituent units (A) is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 5 parts by mass or more and 90 parts by mass or less, and even more preferably 10 parts by mass or more and 80 parts by mass or less, with respect to 100 parts by mass of the content of constituent units (A), and may be 70 parts by mass or less, 60 parts by mass or less, 50 parts by mass or less, or 40 parts by mass or less.

[0101] (2-3) Monomers (d) In one preferred embodiment, the thermoplastic resin (Y) includes the above-described constituent unit (D). The constituent unit (D) may be a constituent unit derived from a monomer (d) having a metal atom-containing group containing a divalent metal atom. Preferably, the constituent unit (D) is a constituent unit having at least one metal atom-containing group selected from the group consisting of the group represented by formula (V) and the group represented by formula (VI). The thermoplastic resin (Y) may have both the group represented by formula (V) and the group represented by formula (VI). The above description applies to the constituent unit (D) and monomer (d). Preferably, monomer (d) is at least one selected from the group consisting of monomer (d1) represented by formula (V') and monomer (d2) represented by formula (VI'). The thermoplastic resin (Y) may include both a constituent unit derived from monomer (d1) and a constituent unit derived from monomer (d2). The same applies to formula (V) and formula (V). The divalent metal atom M in formula (VI') and formula (VI) (the same applies to formula (VI)) can be Mg, Zn, Cu, etc., and from the viewpoint of providing a paint composition that exhibits excellent crack resistance even under the above harsh environment, Zn or Cu is preferred, and Zn is more preferred.

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

[0103] When the thermoplastic resin (Y) contains constituent units (B) and (D), the total content of constituent units (B) and (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 still more preferably 5% by mass or more and 25% by mass or less, of the total constituent units contained in the thermoplastic resin (Y), from the viewpoint of crack resistance and antifouling performance of the coating film.

[0104] When the thermoplastic resin (Y) contains constituent units (D), the ratio of the content of constituent units (D) to the content of constituent units (A) is preferably 0.5 parts by mass or more and 70 parts by mass or less, more preferably 1 part by mass or more and 60 parts by mass or less, even more preferably 2 parts by mass or more and 55 parts by mass or less, and still more preferably 5 parts by mass or more and 55 parts by mass or less, with respect to 100 parts by mass of the content of constituent units (A), and may also 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 comprising a constituent unit (A) and one or more constituent units selected from the group consisting of a constituent unit (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Zn, a constituent unit (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Cu, and a constituent 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 harsh environment described above, the thermoplastic resin (Y) is preferably a (meth)acrylic resin comprising a constituent unit (A), a constituent unit (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Zn, and a constituent unit (B) derived from a monomer (b1) represented by formula (VII'), and more preferably a (meth)acrylic resin comprising a constituent unit (A), a constituent unit (D) derived from a monomer (d1) represented by formula (V') where M in formula (V') is divalent Zn.

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

[0107] (2-4) Monomer (c) The thermoplastic resin (Y) may further contain constituent units (C) derived from monomers (c). The above description applies to constituent units (C) and monomers (c). The presence of constituent units (C) in the thermoplastic resin (Y) is advantageous in improving the antifouling performance of the coating film. Furthermore, by including constituent units (C), the rate of coating film wear can be moderately increased. The thermoplastic resin (Y) may contain constituent units derived from two or more monomers (c).

[0108] When the thermoplastic resin (Y) contains constituent units (C), the content of constituent units (C) is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.5% by mass or more and 35% by mass or less, and even more preferably 1% by mass or more and 30% by mass or less, from the viewpoint of the antifouling performance of the coating film, of the total constituent units contained in the thermoplastic resin (Y), and may be 25% by mass or less, 20% by mass or less, 15% by mass or less, or 10% by mass or less.

[0109] When the thermoplastic resin (Y) contains constituent units (C), the ratio of the content of constituent units (C) to the content of constituent units (A) is, from the viewpoint of the antifouling performance of the coating film, preferably 0.5 parts by mass or more and 80 parts by mass or less, more preferably 1 part by mass or more and 70 parts by mass or less, even more preferably 1 part by mass or more and 60 parts by mass or less, and still more preferably 2 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the content of constituent units (A), and may also 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 constituent units (E) derived from monomer (e), which is a polyfunctional (meth)acrylic acid ester having two or more (meth)acryloyl groups. The above description applies to constituent units (E) and monomer (e). By further containing constituent units (E), the dynamic antifouling and / or crack resistance of the coating film can be further improved. The thermoplastic resin (Y) may contain two or more constituent units (E) derived from monomer (e).

[0111] When the thermoplastic resin (Y) contains constituent units (E), the content of constituent units (E) derived from monomers (e) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, even more preferably 1% by mass or more, and may be 2% by mass or more, 3% by mass or more, or 5% by mass or more, from the viewpoint of further improving crack resistance. The content of constituent units (E) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. If the content of constituent units (E) is too high, the thermoplastic resin (Y) tends to gel easily during preparation.

[0112] When the thermoplastic resin (Y) contains constituent units (E), the ratio of the content of constituent units (E) to the content of constituent units (A) is, from the viewpoint of crack resistance, preferably 1 to 50 parts by mass, more preferably 1 to 40 parts by mass, even more preferably 2 to 30 parts by mass, and still more preferably 2 to 20 parts by mass, per 100 parts by mass of the content of constituent units (A).

[0113] (2-6) Monomer (f) The thermoplastic resin (Y) may contain constituent units (F) derived from other monomers (f) not mentioned above. The above description applies to constituent units (F) and monomers (f). The thermoplastic resin (Y) may contain two or more types of constituent units (F).

[0114] When the thermoplastic resin (Y) contains constituent units (F), the content of constituent units (F) is usually 0.1% by mass or more and 85% by mass or less of the total constituent units contained in the thermoplastic resin (Y), 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 still more preferably 20% by mass or more and 70% by mass or less. By having a content of constituent units (F) of 0.1% by mass or more, it is possible to balance the various properties of the resulting paint composition and coating film. By having a content of constituent units (F) of 85% by mass or less, it is possible to form a coating film that exhibits good crack resistance and antifouling performance.

[0115] (2-7) Content of thermoplastic resin (Y) The content of thermoplastic resin (Y) in the paint composition is preferably 1% to 65% by mass, more preferably 2% to 60% by mass, even more preferably 4% to 55% by mass, even more preferably 10% to 55% by mass, particularly preferably 20% to 55% by mass, and particularly preferably 25% to 50% by mass, based on the solid content of the paint composition. When the content of thermoplastic resin (Y) is within the above range, excellent crack resistance tends to be obtained even under the harsh conditions described above, and furthermore, excellent antifouling performance tends to be obtained.

[0116] The content of thermoplastic resin (Y) in the paint 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 still 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 paint 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, still still 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 still 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, it tends to be easier to obtain excellent crack resistance even under the above harsh environment, and furthermore, it tends to be easier to obtain excellent antifouling performance.

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

[0118] From the viewpoint of crack resistance and antifouling performance, the thermoplastic resin (Y) preferably has, in addition to the constituent unit (A), a constituent unit derived from at least one monomer selected from monomer (b) and monomer (d). In cases where the thermoplastic resin (Y) has constituent units derived from a monomer (d), the metal atoms M contained in the monomer (d) are preferably Zn or Cu from the viewpoint of crack resistance and antifouling performance, and more preferably Zn from the viewpoint of crack resistance. Thermoplastic resins (Y) tend to have even more constituent units derived from monomers (c), which can further enhance their dynamic antifouling properties.

[0119] (3) Total content of thermoplastic resin (Z) and plasticizer The total content of thermoplastic resin (Z) and plasticizer in the paint 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 a total content of less than 1.0% by mass, a coating film exhibiting excellent crack resistance can be formed even under the harsh conditions described above. Thermoplastic resin (Z) refers to a thermoplastic resin with an Mw of less than 5,000.

[0120] Conventional antifouling paint compositions sometimes contained thermoplastic resins and / or plasticizers with relatively small molecular weights to improve the crack resistance of the paint film. However, paint films formed from such antifouling paint compositions tended not to exhibit sufficient crack resistance under the harsh conditions described above. This is presumed to be because, under the repeated expansion and contraction of the paint film in these harsh conditions, at least a portion of the thermoplastic resin and / or plasticizer leaches out of the paint film, causing a change in the properties or composition of the paint film.

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

[0122] Plasticizers are agents that can impart flexibility to coatings and are generally low molecular weight. Examples of plasticizers include phthalate esters 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, triaryl phosphate, and trichloroethyl phosphate; epoxy compounds such as epoxy soybean oil and epoxy octyl stearate; organotin compounds such as dioctyl staghorn laurylate and dibutyl staghorn laurylate; and trioctyl trimellitic acid and triacetylene.

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

[0124] (5) Other components that the paint composition may contain The paint composition may contain one or more other components besides those mentioned above. Examples of other components include additives such as antifouling agents, defoaming agents, anti-sagging agents, water binders, color separation inhibitors, settling inhibitors, paint film wear regulators, UV absorbers, surface modifiers, viscosity modifiers, leveling agents, and pigment dispersants, as well as thermoplastic resins other than thermoplastic resins (X) and (Y) having a weight-average molecular weight of 5,000 or more, pigments, and solvents. These additives, thermoplastic resins, pigments, and solvents may be used individually or in combination of two or more.

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

[0126] Examples of antifouling agents include: cuprous oxide; manganese ethylene bisdithiocarbamate; zinc dimethyldithiocarbamate; 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine; 2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyldichlorophenylurea; zinc ethylene bisdithiocarbamate; rhodane copper (cuprous thiocyanate); 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5,-dichloro-2-n-octyl Tyl-3(2H)isothiazolone; N-(fluorodichloromethylthio)phthalimide; N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide; pyrithione metal salts such as 2-pyridinethiol-1-oxide zinc salt (zinc pyrithione) or copper salt (copper pyrithione); tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine; 3-iodo-2-propylbutylcarb -mate; diiodomethyl p-trisulfone; phenyl(bispyridyl)bismuth dichloride; 2-(4-thiazolyl)-benzimidazole; triphenylborone pyridine salt; stearylamine-triphenylborone; laurylamine-triphenylborone; bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate; 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfenamide; 1,1-dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfenamide; Examples include [(n)sulfonyl]-1-fluoro-N-(4-methylphenyl)methanesulfenamide; 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] In particular, 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-carbonitride, and medetomidine.

[0128] In one embodiment, the paint composition contains one or more antifouling agents, which are organic compounds. In this embodiment, the antifouling agent may be an organic compound containing metal atoms or an organic compound not containing metal atoms. Preferably, the antifouling agent contains an organic compound not containing metal atoms. By using an organic antifouling agent, the amount of antifouling agent added can be reduced compared to when using an inorganic antifouling agent.

[0129] In the above embodiments, organic compounds that do not contain metal atoms may be able to provide a higher improvement in antifouling properties with a smaller amount compared to organic compounds that contain metal atoms, and are preferably organic compounds having heterocycles. Suitable examples of antifouling agents that are organic compounds having heterocycles are 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-3(2H)isothiazolon), 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile, and medetomidine.

[0130] If the paint composition contains an antifouling agent, the content of the antifouling agent in the paint composition is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass, but may be 0.5 parts by mass or more, 1 part by mass or more, or 5 parts by mass or more, based on 100 parts by mass of the total content of thermoplastic resin (X) and thermoplastic resin (Y). The content of the antifouling agent in the paint 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 still more preferably 50 parts by mass or less, based on 100 parts by mass of the total content of thermoplastic resin (X) and thermoplastic resin (Y). If the content of the antifouling agent is excessively high, it may conversely 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 dioxide, zircon 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; and coloring pigments such as chromium yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, and quinacridone. The paint composition may contain one or more pigments.

[0132] When the paint composition contains a pigment, the pigment content in the paint 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, based on 100 parts by mass of the total content of thermoplastic resin (X) and thermoplastic resin (Y). In the paint composition according to the present invention, when the paint composition 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 good 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 form 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 silicone-based antifoaming agents and non-silicone-based antifoaming agents. Silicone-based antifoaming agents are antifoaming agents that contain a surfactant polysiloxane or a modified thereof, while non-silicone-based antifoaming agents are antifoaming agents other than silicone-based antifoaming agents (antifoaming agents that do not contain polysiloxane or a modified thereof). Silicone-based antifoaming agents may also be fluorine-modified silicone-based antifoaming agents. A fluorine-modified silicone-based antifoaming agent is an antifoaming agent that contains a fluorine-modified polysiloxane. A paint composition may contain one or more types of antifoaming agents.

[0134] Examples of non-silicone defoaming agents include higher alcohol-based, higher alcohol derivative-based, fatty acid-based, fatty acid derivative-based, paraffin-based, (meth)acrylic polymer-based, and mineral oil-based agents. Examples of silicone-based defoaming agents include oil-type, compound-type, self-emulsifying, and emulsion-type agents.

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

[0136] From the viewpoint of improving defoaming properties, the content of the defoaming agent is 0.002 parts by mass or more and 0.60 parts by mass or less, more preferably 0.004 parts by mass or more and 0.55 parts by mass or less, 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, based on 100 parts by mass of the total content of thermoplastic resin (X) and thermoplastic resin (Y).

[0137] A sagging prevention agent is an agent that suppresses the occurrence of sagging of a paint composition that may occur between the time the paint composition is applied to the object to be coated and the completion of drying of the paint film. Examples of sagging prevention agents include amide-based sagging prevention agents; bentonite-based sagging prevention agents; polyethylene waxes such as oxidized polyethylene wax; hydrogenated castor oil wax; long-chain fatty acid ester polymers; polycarboxylic acids; silica fine particle-based sagging prevention agents; and mixtures of two or more of these. A paint composition may contain one or more sagging prevention agents.

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

[0139] Commercially available anti-sagging agents may be used. Examples of commercially available amide wax-based anti-sagging agents include "Talen 7200-20" from Kyoeisha Chemical Co., Ltd., "Disparon 6900-20X" and "Disparon RE-8000" from Kusumoto Chemical Co., Ltd., and "Monoral 3300" from HS CHEM Co., Ltd. Other commercially available anti-sagging agents include organic bentonite-based anti-sagging agents such as "Benton 38" from Elements Japan Co., Ltd. and "TIXOGEL" from BYK Co., Ltd.

[0140] From the viewpoint of improving anti-sagging 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, based on 100 parts by mass of the total content of thermoplastic resin (X) and 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 paint composition may contain one or more solvents.

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

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

[0144] The coating film can be formed by applying the above-mentioned coating composition to the surface of the object to be coated according to a conventional method, and then, if necessary, volatilizing and removing the solvent at room temperature or under heating. Examples of conventional methods for applying the coating composition include dipping, spraying, brushing, roller application, electrostatic coating, and electrodeposition coating. The thickness of the coating film is, for example, 50 μm to 500 μm, preferably 100 μm to 400 μm.

[0145] Examples of objects to be coated include underwater moving bodies and structures such as ships, various fishing nets and other fishing gear used for aquaculture, etc. Examples of underwater structures include port facilities, oil fences, water intake facilities for power plants, piping such as cooling water conduits, bridges, buoys, industrial water systems, and underwater bases. The object to be coated is preferably an underwater moving body.

[0146] The painted surface of the object to be painted may be pre-treated as necessary, and a composite coating may be formed by forming a coating film formed by the coating composition of the present invention on a primer coating film formed by another coating composition such as a rust-preventive coating composition (corrosion-preventive coating composition) formed on the object to be painted. The composite coating may have an intermediate coating film between the primer coating film formed by the rust-preventive coating composition, etc. and the coating film formed by the coating composition of the present invention.

[0147] As the paint composition for forming the intermediate coating, various paint compositions can be used, such as antifouling paint compositions, epoxy resin-based paint compositions, urethane resin-based paint compositions, (meth)acrylic resin-based paint compositions, chlorinated rubber-based paint compositions, alkyd resin-based paint compositions, silicone resin-based paint compositions, and fluororesin-based paint compositions. The antifouling paint composition for forming the intermediate coating may be the paint composition according to the present invention, or it may be any other antifouling paint composition.

[0148] The intermediate coating may be formed over the entire surface of the primer coating, or on a portion of the surface. The intermediate and primer coatings may be old coatings that have been used. In this case, the paint composition of the present invention and the coating formed therefrom may be used for repairing old coatings. [Examples]

[0149] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto.

[0150] <Example of resin manufacturing X1: Manufacturing of thermoplastic resin (X1)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 50.0 parts by mass of xylene as a solvent and maintaining the temperature at 105°C. A mixture of 25.0 parts by mass of n-BA, 58.3 parts by mass of EA, 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting 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-necked flask at a constant rate over 30 minutes, and the flask was kept warm for 1.0 hour after the end of the addition to obtain a resin composition containing a carboxyl group.

[0151] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing a thermoplastic resin (X1). The thermoplastic resin (X1) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) form, where Y is the structural part of naphthenic acid other than the carboxyl group.

[0152] <Example of resin manufacturing X2: Manufacturing of thermoplastic resin (X2)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 50.0 parts by mass of xylene as a solvent and maintaining the temperature at 105°C. A mixture of 40.0 parts by mass of n-BA, 43.3 parts by mass of EA, 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting 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-necked flask at a constant rate over 30 minutes, and the flask was kept warm for 1.0 hour after the end of the addition to obtain a resin composition containing a carboxyl group.

[0153] Next, 100 parts by mass of the above resin composition, 25.4 parts by mass of zinc(II) acetate, 12.1 parts by mass of hydrogenated rosin (Hyper CH), and 60.0 parts by mass of xylene were added to a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing a thermoplastic resin (X2). The thermoplastic resin (X2) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0154] <Example of resin manufacturing X3: Manufacturing of thermoplastic resin (X3)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 50.0 parts by mass of xylene as a solvent and maintaining the temperature at 105°C. A mixture of monomers (f) consisting of 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, 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 60 minutes after the completion of the addition. Subsequently, a mixture consisting of 30.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0155] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing thermoplastic resin (X3). The thermoplastic resin (X3) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) form, where Y is the structural part of naphthenic acid other than the carboxyl group.

[0156] <Example of resin manufacturing X4: Manufacturing of thermoplastic resin (X4)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 50.0 parts by mass of xylene as a solvent and maintaining the temperature at 105°C. A mixture of 15.0 parts by mass of t-BMA, 68.3 parts by mass of CHMA, 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting 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-necked flask at a constant rate over 30 minutes, and the flask was kept warm for 1.0 hour after the end of the addition to obtain a resin composition containing a carboxyl group.

[0157] Next, 100 parts by mass of the above resin composition, 25.4 parts by mass of zinc(II) acetate, 12.1 parts by mass of hydrogenated rosin (Hyper CH), and 60.0 parts by mass of xylene were added to a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing a thermoplastic resin (X4). The thermoplastic resin (X4) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

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

[0159] (2) Manufacturing of thermoplastic resin (X5) A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 15.0 parts by mass of PGM, 25.0 parts by mass of xylene, and 4.0 parts by mass of monomer (f) EA as solvents, and the temperature was raised while stirring and maintained at 100°C. A mixture containing 8.3 parts by mass of monomer (b) TIPSA, 21.7 parts by mass of the metal atom-containing polymerizable monomer mixture (M1) prepared in (1) above (d), 15.0 parts by mass of monomer (f) 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 chain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of azobisisobutyronitrile (AIBN), and 0.8 parts by mass of azobismethylbutyronitrile (AMBN) was pre-mixed and placed in a dropping funnel. This mixture was then added dropwise at a constant rate to a four-necked flask over 6 hours. Subsequently, 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 a further 1 hour and 30 minutes, 10.1 parts by mass of xylene were added to obtain a resin composition (X5) (solid content concentration: 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) (where M is Zn).

[0160] <Resin production example X6: Production of thermoplastic resin (X6)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 30.0 parts by mass of xylene as a solvent and maintaining the temperature at 95°C. A 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, 55.0 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 120 minutes after the completion of the addition. Subsequently, a mixture consisting of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate to a four-necked flask over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (X6) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (X6).

[0161] <Example of resin manufacturing X7: Manufacturing of thermoplastic resin (X7)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 30.0 parts by mass of xylene as a solvent and maintaining the temperature at 95°C. A mixture of monomers (f) consisting 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, 10.0 parts by mass of MMA, 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 120 minutes after the completion of the addition. Subsequently, a mixture consisting of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (X7) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (X7).

[0162] <Example of resin manufacturing X8: Manufacturing of thermoplastic resin (X8)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. A mixture of monomers (f) consisting 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, 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 pre-mixed and placed in a dropping funnel. This mixture was then added dropwise to the four-necked flask at a constant rate over 3 hours, and the flask was kept warm for 60 minutes after the completion of the addition. Subsequently, a mixture consisting of 30.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0163] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (X8). The thermoplastic resin (X8) contained in this resin composition is a resin having a carboxyl group, where the carboxyl group is -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0164] <Example of resin manufacturing X9: Manufacturing of thermoplastic resin (X9)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. A mixture of monomers (f) consisting 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, 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 mixture in a dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. The flask was then kept warm for 60 minutes after the completion of the addition. Subsequently, a mixture consisting of 30.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0165] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (X9). The thermoplastic resin (X9) contained in this resin composition is a resin having a carboxyl group, but the carboxyl group is -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0166] <Example of resin manufacturing X10: Manufacturing of thermoplastic resin (X10)> In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene as a solvent was added and maintained at 95°C. Thereto, a mixed solution prepared in advance by mixing 60.0 parts by mass of TIPSA as monomer (b), 10.0 parts by mass of t-BMA as monomer (f), 5.0 parts by mass of n-BMA, 10.0 parts by mass of n-BA, 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-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this was added dropwise to the four-necked flask at a constant rate over 3 hours, followed by keeping the temperature for 120 minutes after completion of the dropping. Thereafter, a mixed solution consisting of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butyl peroxy-2-ethylhexanoate was added dropwise to the four-necked flask at a constant rate over 30 minutes, and the temperature was kept for 1.0 hour after completion of the dropping to obtain a resin composition (X10) (solid content concentration: 50% by mass), which is a solution containing a thermoplastic resin (X10).

[0167] <Production Example of Resin X11: Production of Thermoplastic Resin (X11)> In a four-necked flask equipped with a thermometer, a cooling tube, a stirrer, a dropping funnel, a nitrogen inlet tube, and a temperature controller, 30.0 parts by mass of xylene as a solvent was added and maintained at 95°C. Thereto, a mixed solution prepared in advance by mixing 50.0 parts by mass of TIPSMA as monomer (b), 10.0 parts by mass of t-BMA as monomer (f), 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-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator was placed in the dropping funnel, and this was added dropwise to the four-necked flask at a constant rate over 3 hours, followed by keeping the temperature for 120 minutes after completion of the dropping. Thereafter, a mixed solution consisting of 50.0 parts by mass of xylene and 0.2 parts by mass of tert-butyl peroxy-2-ethylhexanoate was added dropwise to the four-necked flask at a constant rate over 30 minutes, and the temperature was kept for 1.0 hour after completion of the dropping to obtain a resin composition (X11) (solid content concentration: 50% by mass), which is a solution containing a thermoplastic resin (X11).

[0168] <Production Example Y1 of Resin: Production of Thermoplastic Resin (Y1)> Into a four-necked flask equipped with a thermometer, a condenser tube, 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, 40.0 parts by mass of FM-0711 as monomer (a), 20.4 parts by mass of MMA as monomer (f), 17.9 parts by mass of EA, 21.7 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 were premixed and put into the dropping funnel, and this was dropped into the four-necked flask at a constant rate over 3 hours and kept warm for 60 minutes after the completion of dropping. Thereafter, a mixed solution consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was dropped into the four-necked flask at a constant rate over 30 minutes and kept warm for 1.0 hour after the completion of dropping, whereby a resin composition containing a resin having a carboxyl group was obtained.

[0169] Next, into the same reaction vessel, 100 parts by mass of the above resin composition, 7.8 parts by mass of zinc acetate (II), 12.1 parts by mass of naphthenic acid (NA-165), and 60.0 parts by mass of xylene were added and the temperature was raised to the reflux temperature, and while removing the mixed solution of acetic acid, water, and solvent that distilled off, the same amount of xylene was replenished and the reaction was continued for 18 hours. The end point of the reaction was determined by quantifying the amount of acetic acid in the distilled-off solvent. After cooling the reaction solution, n-butanol and xylene were added to obtain a resin composition (Y1) (solid content concentration: 50% by mass), which is a solution containing the thermoplastic resin (Y1). The thermoplastic resin (Y1) contained in this resin composition is such that the carboxyl group of the resin having the above carboxyl group is converted to -COO-Zn 2+ (-OOC-Y). Y is the structural part other than the carboxyl group of naphthenic acid.

[0170] <Production Example Y2 of Resin: Production of Thermoplastic Resin (Y2)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. To this, 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 were added as monomer (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 were added as monomer (f), along with 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. This pre-mixed mixture was placed in a dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at an constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0171] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y2). The thermoplastic resin (Y2) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) form, where Y is the structural part of naphthenic acid other than the carboxyl group.

[0172] <Example of resin manufacturing Y3: Manufacturing of thermoplastic resin (Y3)> (1) Production of a polymerizable monomer mixture containing metal atoms (M1) In a four-necked flask equipped with a condenser, thermometer, dropping funnel, and stirrer, 85.4 parts by mass of PGM (propylene glycol methyl ether) and 40.7 parts by mass of zinc oxide were charged and heated to 75°C while stirring. Next, a mixture consisting of 43.1 parts by mass of MAA (methacrylic acid), 36.1 parts by mass of AA (acrylic acid), and 5.0 parts by mass of water was added dropwise at a constant rate over 3 hours from the dropping funnel. After stirring for a further 2 hours, 36.0 parts by mass of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture (M1) (solid content concentration: 44.8 parts by mass). This metal atom-containing polymerizable monomer mixture (M1) contains zinc (meth)acrylate, which belongs to monomer (d2) represented by the above formula (VI').

[0173] (2) Manufacturing of thermoplastic resin (Y3) A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was charged with 15.0 parts by mass of PGM, 25.0 parts by mass of xylene, and 4.0 parts by mass of monomer (f) EA as solvents, and the temperature was raised while stirring and maintained at 100°C. A mixture containing 40.0 parts by mass of monomer (a) FM-0711, 21.7 parts by mass of monomer (d) the metal atom-containing polymerizable monomer mixture (M1) produced in (1) above, 20.4 parts by mass of monomer (f) MMA and 13.9 parts by mass of EA, 10.0 parts by mass of xylene, 1.2 parts by mass of chain transfer agent (α-methylstyrene dimer), 2.5 parts by mass of azobisisobutyronitrile (AIBN), and 0.8 parts by mass of azobismethylbutyronitrile (AMBN) was pre-mixed and placed in a dropping funnel. This mixture was then added dropwise at a constant rate to a four-necked flask over 6 hours. Subsequently, 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 a further 1 hour and 30 minutes, 10.1 parts by mass of xylene were added to obtain a resin composition (Y3) (solid content concentration: 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) (where M is Zn).

[0174] <Example of resin manufacturing Y4: Manufacturing of thermoplastic resin (Y4)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. A mixture was prepared by first mixing 40.0 parts by mass of KF-2012 as monomer (a), 10.0 parts by mass of TIPSA as 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 monomer (c), 1.0 part by mass of NPG as 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, 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. This mixture was then placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at an constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0175] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y4). The thermoplastic resin (Y4) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) form, where Y is the structural part of naphthenic acid other than the carboxyl group.

[0176] <Example of resin manufacturing Y5: Manufacturing of thermoplastic resin (Y5)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 30.0 parts by mass of xylene as a solvent and maintained at 95°C. A mixture was prepared by first mixing 40.0 parts by mass of KF-2012 as monomer (a), 15.0 parts by mass of TIPSA as monomer (b), 5.0 parts by mass of CB-1 as monomer (c), 1.0 part by mass of NPG as monomer (e), 20.0 parts by mass of t-BMA, 8.0 parts by mass of n-BMA, 5.5 parts by mass of MMA, and 5.5 parts by mass of EA as monomer (f), 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 40.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (Y5) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y5).

[0177] <Example of resin manufacturing Y6: Manufacturing of thermoplastic resin (Y6)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 30.0 parts by mass of xylene as a solvent and maintained at 95°C. A mixture was prepared by first mixing 5.0 parts by mass of FM-0725 and 5.0 parts by mass of X-22-164C as monomer (a), 5.0 parts by mass of TIPSMA as monomer (b), 1.0 part by mass of M-40G as monomer (c), 1.0 part by mass of NPG as 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 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. This mixture was then placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 40.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (Y6) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y6).

[0178] <Example of resin manufacturing Y7: Manufacturing of thermoplastic resin (Y7)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 30.0 parts by mass of xylene as a solvent and maintained at 95°C. A mixture was prepared by first mixing 25.0 parts by mass of FM-0721 and 5.0 parts by mass of TM-0701T as monomer (a), 1.0 part by mass of TIPSA and 1.0 part by mass of TIPSMA as monomer (b), 5.0 parts by mass of NPG as monomer (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 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. This mixture was then placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 40.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (Y7) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y7).

[0179] <Example of resin manufacturing Y8: Manufacturing of thermoplastic resin (Y8)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. To this, a mixture was added containing 30.0 parts by mass of FM-0721 and 10.0 parts by mass of KF-2012 as monomer (a), 2.0 parts by mass of M-40G as monomer (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 6.3 parts by mass of MMA as monomer (f), 21.7 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at an constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0180] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 resin composition (Y8) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y8). The thermoplastic resin (Y8) contained in this resin composition is a resin having a carboxyl group, where the carboxyl group is -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0181] <Example of resin manufacturing Y9: Manufacturing of thermoplastic resin (Y9)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. In this mixture, 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 are used as monomer (a); 1.0 part by mass of M-230G and 1.0 part by mass of CB-1 are used as monomer (c); 1.0 part by mass of NPG is used as monomer (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 are used as monomer (f); 30.0 parts by mass of xylene is used as a solvent; and tert-butylperoxy-2-ethylhexanoate is used as a radical polymerization initiator. A pre-mixed mixture of 1.1 parts by mass was placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours. The mixture was then kept warm for 120 minutes after the addition of the mixture. Subsequently, a mixture consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate to the four-necked flask over 30 minutes. The mixture was then kept warm for 1.0 hour after the addition of the mixture to obtain a resin composition containing a carboxyl group.

[0182] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y9). The thermoplastic resin (Y9) contained in this resin composition is a resin having carboxyl groups, where the carboxyl groups are -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0183] <Example of resin manufacturing Y10: Manufacturing of thermoplastic resin (Y10)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. A mixture was prepared by first mixing 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 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at an constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0184] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, removing the distilled mixture of acetic acid, water, and solvent while replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y10). The thermoplastic resin (Y10) contained in this resin composition is a resin having carboxyl groups, where the carboxyl groups are -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0185] <Example of resin manufacturing Y11: Manufacturing of thermoplastic resin (Y11)> In a four-neck flask equipped with a thermometer, a cooling tube, 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 maintained at 105 °C. Thereto, 40.0 parts by mass of FM-0711 as monomer (a), 20.4 parts by mass of MMA as monomer (f), 17.9 parts by mass of EA, 21.7 parts by mass of AA, 40.0 parts by mass of xylene as a solvent, and 5.0 parts by mass of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator were premixed and placed in the dropping funnel. This was dropped into the four-neck flask at a constant rate over 3 hours, and after completion of the dropping, it was kept warm for 60 minutes. Then, a mixed solution consisting of 10.0 parts by mass of xylene and 1.0 parts by mass of tert-butyl peroxy-2-ethylhexanoate was dropped into the four-neck flask at a constant rate over 30 minutes, and after completion of the dropping, it was kept warm for 1.0 hour to obtain a resin composition containing a resin having a carboxyl group.

[0186] Next, into the same reaction vessel, 100 parts by mass of the above resin composition, 7.8 parts by mass of zinc acetate (II), 12.1 parts by mass of naphthenic acid (NA-165), and 60.0 parts by mass of xylene were added, and the temperature was raised to the reflux temperature. While removing the mixed solution of acetic acid, water, and solvent that distilled out, the reaction was continued for 18 hours while 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) (solid content concentration: 50% by mass), which is a solution containing a thermoplastic resin (Y11). The thermoplastic resin (Y11) contained in this resin composition is such that the carboxyl group of the resin having the above carboxyl group is converted to -COO-Zn 2+ (-OOC-Y). Y is the structural part other than the carboxyl group of naphthenic acid.

[0187] <Production Example of Resin Y12: Production of Thermoplastic Resin (Y12)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. To this, a mixture was added, which consisted of monomers (a) of FM-0721 (20.0 parts by mass), FM-0725 (10.0 parts by mass), and TM-0701T (5.0 parts by mass), monomers (f) of t-BMA (5.0 parts by mass), n-BMA (5.0 parts by mass), MMA (25.0 parts by mass), EA (15.0 parts by mass), and AA (15.0 parts by mass), along with 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0188] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y12). The thermoplastic resin (Y12) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) form, where Y is the structural part of naphthenic acid other than the carboxyl group.

[0189] <Example of resin manufacturing Y13: Manufacturing of thermoplastic resin (Y13)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. A mixture was prepared by first mixing 40.0 parts by mass of KF-2012 as monomer (a), 10.0 parts by mass of TIPSA as 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 monomer (c), 1.0 part by mass of NPG as 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. This mixture was then placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0190] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y13). The thermoplastic resin (Y13) contained in this resin composition has a carboxyl group, and the carboxyl group of the above resin is -COO-Zn 2+ This is the (-OOC-Y) form, where Y is the structural part of naphthenic acid other than the carboxyl group.

[0191] <Example of resin manufacturing Y14: Manufacturing of thermoplastic resin (Y14)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 30.0 parts by mass of xylene as a solvent and maintained at 95°C. A mixture was prepared by first mixing 40.0 parts by mass of KF-2012 as monomer (a), 15.0 parts by mass of TIPSA as monomer (b), 5.0 parts by mass of CB-1 as monomer (c), 1.0 part by mass of NPG as monomer (e), 20.0 parts by mass of t-BMA, 8.0 parts by mass of n-BMA, 5.5 parts by mass of MMA, and 5.5 parts by mass of EA as monomer (f), 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (Y14) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y14).

[0192] <Example of resin manufacturing Y15: Manufacturing of thermoplastic resin (Y15)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 30.0 parts by mass of xylene as a solvent and maintained at 95°C. A mixture was prepared by first mixing 5.0 parts by mass of FM-0725 and 5.0 parts by mass of X-22-164C as monomer (a), 5.0 parts by mass of TIPSMA as monomer (b), 1.0 part by mass of M-40G as monomer (c), 1.0 part by mass of NPG as 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 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. This mixture was then placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (Y15) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y15).

[0193] <Example of resin manufacturing Y16: Manufacturing of thermoplastic resin (Y16)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 30.0 parts by mass of xylene as a solvent and maintained at 95°C. A mixture was prepared by first mixing 25.0 parts by mass of FM-0721 and 5.0 parts by mass of TM-0701T as monomer (a), 1.0 part by mass of TIPSA and 1.0 part by mass of TIPSMA as monomer (b), 5.0 parts by mass of NPG as monomer (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 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours, and the flask was kept warm for 120 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition (Y16) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y16).

[0194] <Example of resin manufacturing Y17: Manufacturing of thermoplastic resin (Y17)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. To this, a mixture was added containing 30.0 parts by mass of FM-0721 and 10.0 parts by mass of KF-2012 as monomer (a), 2.0 parts by mass of M-40G as monomer (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 6.3 parts by mass of MMA as monomer (f), 21.7 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. This mixture was placed in a dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours, and the flask was kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0195] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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 content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y17). The thermoplastic resin (Y17) contained in this resin composition is a resin having a carboxyl group, and the carboxyl group is -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0196] <Example of resin manufacturing Y18: Manufacturing of thermoplastic resin (Y18)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was filled with 50.0 parts by mass of xylene as a solvent and maintained at 105°C. In this mixture, monomer (a) consists of 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; monomer (c) consists of 1.0 part by mass of M-230G and 1.0 part by mass of CB-1; monomer (e) consists of 1.0 part by mass of NPG; monomer (f) consists of 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; xylene as a solvent and tert-butylperoxy-2-ethylhexanoate as a radical polymerization initiator. A pre-mixed solution of 5.0 parts by mass was placed in a dropping funnel and added dropwise at a constant rate to a four-necked flask over 3 hours. The mixture was then kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise at a constant rate to the four-necked flask over 30 minutes. The mixture was kept warm for 1.0 hour after the end of the addition to obtain a resin composition containing a carboxyl group.

[0197] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, while removing the distilled mixture of acetic acid, water, and solvent, and replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y18). The thermoplastic resin (Y18) contained in this resin composition is a resin having a carboxyl group, and the carboxyl group is -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0198] <Example of resin manufacturing Y19: Manufacturing of thermoplastic resin (Y19)> A four-necked flask equipped with a thermometer, condenser, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller was prepared by adding 50.0 parts by mass of xylene as a solvent and maintaining the temperature 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 as monomer (f), and 5.0 parts by mass of AA, along with 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 a dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. The flask was then kept warm for 60 minutes after the end of the addition. Subsequently, a mixture consisting of 10.0 parts by mass of xylene and 1.0 part by mass of tert-butylperoxy-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate over 30 minutes, and the mixture was kept warm for 1.0 hour after the completion of the dropwise addition to obtain a resin composition containing a carboxyl group.

[0199] Next, 100 parts by mass of the above 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 a similar reaction vessel, and the temperature was raised to the reflux temperature. The reaction was continued for 18 hours, removing the distilled mixture of acetic acid, water, and solvent while replenishing with the same amount of xylene. The endpoint 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) (solid content concentration: 50% by mass), which is a solution containing thermoplastic resin (Y19). The thermoplastic resin (Y19) contained in this resin composition is a resin having carboxyl groups, where the carboxyl groups are -COO-Cu 2+ This is the (-OOC-Y) conversion. Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0200] Tables 1 to 6 show the monomers used in each resin production example and their amounts (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 and their amounts are those used in the production of the intermediate resin having a carboxyl group.

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

[0202] [i] Weight average molecular weight (Mw) The weight-average molecular weight (Mw) of the thermoplastic resins obtained in the above resin production example, thermoplastic resins 1-4 described later, and monomer (a) is the weight-average molecular weight on a polystyrene basis, measured by GPC. The measurement conditions were as follows. Equipment: Gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8220) Columns: TSKgelα-M (manufactured by Tosoh Corporation, 7.8mm x 30cm) and TSKguardcolumnα (manufactured by Tosoh Corporation, 6.0mm x 4cm) 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 monomers.

[0203] [ii] Solid content concentration The solid content concentration of the resin composition was calculated according to the following formula. Solid content concentration (mass%) = 100 × (total mass of raw materials used in the preparation of 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] The details of the abbreviations for the various monomers shown in Tables 1 to 6, as well as other components used in the resin production examples, are as follows.

[0211] [Monomer (a)] • FM-0711: Manufactured by JNC Corporation, a 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 A monomer in which the group is an n-butyl group, molecular weight: 1,000 • FM-0721: Manufactured by JNC Corporation, a 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 A monomer in which the group is an n-butyl group, molecular weight: 5,000 • FM-0725: Manufactured by JNC Corporation, a 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 A monomer in which the group is an n-butyl group, molecular weight: 10,000 • KF-2012: Manufactured by Shin-Etsu Chemical Co., Ltd., a 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 A monomer in which the group is an n-butyl group, molecular weight: 4,600 • TM-0701T: Manufactured by JNC Corporation, a methacryloyloxyalkyl-modified organopolysiloxane, in formula (II'), p=0, d=3, R 6 ~R 8 and R 32 A monomer in which the group 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 A silicon-containing polymerizable monomer in which the group is 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: Methoxypolyethylene glycol methacrylate (oxyethylene chain repeat count = 4), manufactured by Shin Nakamura Chemical Industry Co., Ltd. • M-90G: Methoxypolyethylene glycol methacrylate (oxyethylene chain repeat count = 9), manufactured by Shin Nakamura Chemical Industry Co., Ltd. • M-230G: Methoxypolyethylene glycol methacrylate (oxyethylene chain repeat count = 23), manufactured by Shin Nakamura Chemical Industry Co., Ltd. • CB-1: Methacryloyloxyethyl phthalate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. • HEMA: 2-hydroxyethyl methacrylate, manufactured by Mitsubishi Chemical Corporation

[0214] [monomer(e)] • NPG: Neopentyl glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry 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. • 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. • 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: Manufactured by Sakai Chemical Industry Co., Ltd. • Zinc(II) acetate: Manufactured by Nippon Chemical Industries, Ltd. • Copper(II) acetate: Manufactured by Nippon Chemical Industries, Ltd. NA-165: Naphthenic acid, acid value: 165 mg KOH / g, manufactured by Yamato Oil & Fat Industry Co., Ltd. • Hyper 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, Inc. • tert-butylperoxy-2-ethylhexanoate: radical polymerization initiator, manufactured by Kahka Akzo. 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 Corporation. • PGM: Propylene glycol methyl ether: Organic solvent, manufactured by Dow Chemical Company.

[0218] <Examples 1-37, Comparative Examples 1-19> (1) Preparation of paint composition Paint compositions 1-37 and H1-H19 were prepared by mixing and dispersing the ingredients shown in Tables 7-18 in the amounts indicated in the same tables using a disperser (2,000 rpm). The unit of the mixing amount is parts by mass. The mixing amount of each ingredient refers to the amount in its natural state (parts by mass), including volatile components such as solvents.

[0219] (2) Preparation of coating film Each of the paint compositions obtained in (1) above was spray-applied to an SPCC steel plate (150 mm × 70 mm × 3.2 mm) that had a rust-preventive coating film made of a rust-preventive paint composition (epoxy-based anticorrosive paint: NIPPON E-MARINE A / C, manufactured by Nippon Paint Marine Co., Ltd.) formed on it in advance, so that the dry film thickness was 300 μm. The plate was then left to dry in a room for two days and nights to obtain a test plate with a coating film.

[0220] The details of each ingredient shown in Tables 7 to 18 are as follows. • Thermoplastic resin 1: Chlorinated paraffin (Toyopalux A50, manufactured by Tosoh Corporation), solids content: 100% by mass, weight-average molecular weight: 750 ·Thermoplastic resin 2: Rosin (“WW Rosin” manufactured by Arakawa Chemical Industry Co., Ltd.), solid content concentration: 100% by mass, weight average molecular weight: 350 • Thermoplastic resin 3: Polyester polymer (Teslac 2450, manufactured by Resonaq Corporation), solids 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 Co., Ltd. • Antifouling agent 2: Zinc pyrithione, "Zinc Omazine" manufactured by Arch Chemical Co., Ltd. • Antifouling agent 3: Copper pyrithione, "Copper Omagine" manufactured by Arch Chemical Co., Ltd. • Antifouling agent 4: C9 211, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-3(2H)isothiazoline), manufactured by Rohm and Haas, "C9 211" • Antifouling agent 5: Econea, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitride, manufactured by Janssen PMP, "Econea" • Antifouling agent 6: Medetomidine, "Selektope" manufactured by I-TECH AB. Pigment 1: Titanium dioxide, manufactured by Ishihara Sangyo Co., Ltd., "Typake CR-50" Pigment 2: Iron oxide, Lanxess "Bayferox 130" Pigment 3: Zinc oxide, manufactured by Sakai Chemical Industry Co., Ltd. ("Zinc Oxide Type 2") • Anti-sagging agent: HS CHEM "Monoral 3300", non-volatile content: 20% by mass • Defoaming agent: BYK-066N manufactured by BYK Corporation, non-volatile content: 0.7% by mass • Solvent 1: Xylene, manufactured by JFE Chemical Co., Ltd. • Solvent 2: Methyl isobutyl ketone, manufactured by Mitsui Chemicals, Inc.

[0221] (Evaluation of antifouling paint compositions) [a] Crack resistance of the coating under harsh environmental conditions Adjusted seawater was prepared by adding sodium hydroxide to natural seawater collected from the Marine Evaluation Technology Center Research Institute of Nippon Paint Marine Co., Ltd. in Tamano City, Okayama Prefecture, to adjust the pH to 9 (normal seawater has a pH of approximately 8.2). 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 operations 1) to 4) were repeated 10 times. 1) Increase the temperature of the adjusted seawater from 20°C to 40°C over a period of 2 hours. 2) Maintain at 40°C for 4 hours 3) Reduce the temperature of the adjusted seawater from 40°C to 20°C over a period of 2 hours. 4) Maintain at 20°C for 4 hours

[0222] Next, the test plates were removed from the adjusted seawater and left to stand in a room at 25°C for one week. One cycle consisted of the above steps 1) to 4) followed by the one-week standing period in the room. A crack resistance test was conducted for a maximum of 15 cycles, and the condition of the coating on the test plates was observed. If cracks occurred in the coating during the test, the test was terminated at the point of cracking, and the number of cycles at that point was used as an indicator of crack resistance. The values ​​listed in Tables 7 to 18 represent the number of cycles at which cracks first occurred. A score of < 15 was used to indicate that no cracks occurred after 15 cycles. A score of 10 or higher is preferred.

[0223] [b] Antifouling properties of the coating (dynamic antifouling test after static immersion in seawater under harsh conditions) Adjusted seawater was prepared by adding sodium hydroxide to natural seawater collected from the Marine Evaluation Technology Center Research Institute of Nippon Paint Marine Co., Ltd. in Tamano City, Okayama Prefecture, to adjust the pH to 9 (normal seawater has a pH of approximately 8.2). 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 operations 1) to 4) were repeated 10 times. 1) Increase the temperature of the adjusted seawater from 20°C to 40°C over a period of 2 hours. 2) Maintain at 40°C for 4 hours 3) Reduce the temperature of the adjusted seawater from 40°C to 20°C over a period of 2 hours. 4) Maintain at 20°C for 4 hours

[0224] Next, the test plate was removed from the prepared seawater, attached to the side of a rotating cylinder, and rotated in natural seawater at approximately 10 knots per hour for 18 months. The attachment area of ​​marine organisms was then determined and evaluated according to the following criteria. The evaluation results at 18 months of testing are shown in Tables 7 to 18. An evaluation result of 3 or higher is preferable. 5: The surface area on which marine organisms attach is between 0% and less than 5%. 4: The surface area on which marine organisms attach is 5% or more but less than 10%. 3: The surface area on which marine organisms attach is between 10% and 15%. 2: The area on which marine organisms attach is between 15% and 30%. 1: The surface area on which 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 according to the present invention can form a coating film with excellent crack resistance even in harsh environments where the temperature of the seawater in which the coating film is immersed fluctuates drastically and where drying and wetting are repeated. The coating composition according to the present invention can form a coating film that exhibits excellent crack resistance and excellent antifouling performance even in the above-mentioned harsh environments. The coating composition according to the present invention can be suitably used as a coating composition applied to underwater moving objects such as ships or underwater structures, preferably as an antifouling coating composition.

Claims

1. A paint 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. It 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 Excluding the following constituent unit (A), The thermoplastic resin (Y) is The weight-average molecular weight is 5,000 or more. The constituent unit (A) is 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 paint composition in which the total content of a thermoplastic resin (Z) having a weight-average molecular weight of less than 5,000 and a plasticizer is less than 1.0% by mass in the paint composition. 【Chemistry 1】 [In formula (I), a and b each independently represent an integer between 2 and 5, m represents an integer between 0 and 50, and n represents an integer between 3 and 270. R １ ~R ５ Each of these 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 equation (II), c and d each independently represent an integer between 2 and 5, and p represents an integer between 0 and 50. R ６ , R ７ and R ８ Each of these is independently an alkyl group, R ａ or R ｂ It represents. R ａ teeth, 【Transformation 3】 (wherein, x represents any integer from 0 to 200. R ２３ ~R ２７ are the same or different and each represents an alkyl group.). R ｂ teeth, 【Chemistry 4】 (In the formula, y represents an integer between 1 and 200. R ２８ and R ２９ These represent alkyl groups, either identical or different. 【Transformation 5】 [In formula (III), e, f, g, and h each independently represent an integer between 2 and 5, q and s each independently represent an integer between 0 and 50, and r represents an integer between 3 and 270. R ９ ~R １２ Each of these 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 between 2 and 5, t and u each independently represent an integer between 0 and 50, and v and w each independently represent an integer between 0 and 70. R １３ ~R ２２ These represent alkyl groups, either identical or different.

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

5. The paint composition according to claim 1 or 2, wherein the thermoplastic resin (Y) further comprises 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 paint composition according to claim 1 or 2, wherein the pigment content is 20 parts by mass or more and 390 parts by mass or less based on the total content of thermoplastic resin (X) and thermoplastic resin (Y) per 100 parts by mass.

7. The paint composition according to claim 1 or 2, wherein the monomer (a) has a molecular weight of 25,000 or less.

8. The paint composition according to claim 1 or 2, further comprising an antifouling agent.

9. The paint 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-carbonitride, and medetomidine.

10. A coating film formed by the coating composition described in claim 1.

11. A composite coating film having a primer coating film formed by a rust-preventive coating composition and a coating film formed by the coating composition according to claim 1, which is laminated on the primer coating film.

12. A ship having the coating film described in claim 10 or the composite coating film described in claim 11.

13. An underwater structure having the coating film described in claim 10 or the composite coating film described in claim 11.

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