Antifouling coating composition and antifouling coating film

Abstract

Provided is an antifouling coating composition comprising a silicon atom-containing resin and a thermoplastic resin other than the silicon atom-containing resin, the silicon atom-containing resin comprising: a structural unit (A) having at least one silicon atom-containing group selected from the group consisting of a group represented by formula (I), a group represented by formula (II), a group represented by formula (III), and a group represented by formula (IV); the thermoplastic resin includes a thermoplastic resin having a weight-average molecular weight of 1000 or more; the content of the thermoplastic resin having a weight-average molecular weight of 1000 or more is 6.0 parts by mass or more and 11.0 parts by mass or less per 100 parts by mass of the silicon atom-containing resin.

Description

Technical Field

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

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

[0003] Existing technical documents Patent documents Patent Document 1: International Publication No. 2011 / 046086 Summary of the Invention The problem that the invention aims to solve The antifouling coating film formed by the antifouling coating composition is required to maintain excellent antifouling performance for a long period of time when immersed in water (seawater). In addition, the antifouling coating film is also required to have excellent crack resistance, for example, it should not easily crack even in repeated wet and dry environments.

[0004] The object of this invention is to provide an antifouling coating composition capable of forming an antifouling film with excellent antifouling properties and excellent crack resistance. Another object of this invention is to provide an antifouling film formed from the antifouling coating composition and a composite coating having the antifouling film, as well as ships and underwater structures having the antifouling film or the composite coating.

[0005] Methods for solving problems The present invention provides the following antifouling coating compositions, antifouling films, composite films, ships and underwater structures.

[0006] [1] An antifouling coating composition comprising a silicone-containing resin and a thermoplastic resin other than the silicone-containing resin, The silicon-containing resin comprises: a structural unit (A), the structural unit (A) having at least one silicon-containing group selected from the group represented by formula (I), the group represented by formula (II), the group represented by formula (III) and the group represented by formula (IV). The thermoplastic resin includes thermoplastic resins with a weight-average molecular weight of 1000 or more. Relative to 100 parts by weight of the silicon-containing atom resin, the content of the thermoplastic resin with a weight average molecular weight of 1000 or more is 6.0 parts by weight or more and 11.0 parts by weight or less. [Chemical Formula 1]

[0007] In equation (Ⅰ), a and b each independently represent any integer from 2 to 5, m represents any integer from 0 to 50, and n represents any integer from 3 to 270; R 1 ~R 5 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy. [Chemical Formula 2]

[0008] In equation (II), c and d each independently represent any integer from 2 to 5, and p represents any integer from 0 to 50; R 6 R 7 and R 8 Each independently represents an alkyl group, R. a Or R b ; R a yes [Chemical Formula 3]

[0009] In the formula, x represents any integer from 0 to 200; R 23 ~R 27 The same or different indicates an alkyl group; R b yes [Chemical Formula 4]

[0010] In the formula, y represents any integer from 1 to 200; R 28 and R 29 The same or different indicates an alkyl group; [Chemical Formula 5]

[0011] In equation (Ⅲ), e, f, g, and h each independently represent any integer from 2 to 5, q and s each independently represent any integer from 0 to 50, and r represents any integer from 3 to 270; R 9 ~R 12 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy. [Chemical Formula 6]

[0012] In equation (Ⅳ), i, j, k, and l each independently represent any integer from 2 to 5, t and u each independently represent any integer from 0 to 50, and v and w each independently represent any integer from 0 to 70; R 13 ~R 22 Same or different indicates alkyl group.

[0013] [2] According to the antifouling coating composition of [1], the silicon-containing resin further has a structural unit (B) having a triorganosilyloxycarbonyl group.

[0014] [3] According to the antifouling coating composition of [1] or [2], the silicon-containing resin further has a structural unit (C) derived from a monomer (c), which is a monofunctional (meth)acrylate represented by the following formula (c); CH2=C(R A (COOR) B (c) In equation (c), R A Represents a hydrogen atom or a methyl group; R B It indicates that it contains one or more monovalent groups selected from hydroxyl, carboxyl and oxoalkylene chains.

[0015] [4] The antifouling coating composition according to any one of [1] to [3] further comprises a structural unit (D), the structural unit (D) having at least one metal atom-containing group selected from the groups represented by the following formula (V) and the groups represented by the following formula (VI); [Chemical Formula 7]

[0016] In formula (V), M represents a divalent metal atom, and R 30 Indicates an organic acid residue or an alcohol residue; [Chemical Formula 8]

[0017] In equation (VI), M represents a divalent metal atom.

[0018] [5] In any one of [1] to [4], the content of the structural unit (A) in the total number of structural units contained in the silicon-containing resin is 20% by mass or more.

[0019] [6] The antifouling coating composition according to any one of [1] to [5] is free of antifouling agent.

[0020] [7] The antifouling coating composition according to any one of [1] to [5] further comprises an antifouling agent.

[0021] [8] According to the antifouling coating composition of [7], the antifouling agent is selected from at least one of cuprous oxide, pyridinethione metal salt, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxynitrile and metopridine.

[0022] [9] An antifouling coating, formed from any one of the antifouling coating compositions described in [1] to [8].

[0023]

[10] A composite coating film having: a primer film formed of an anti-rust coating composition; and an anti-fouling coating film formed of any one of [1] to [8] laminated on the primer film.

[0024]

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

[10] .

[0025]

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

[10] .

[0026] Invention Effects An antifouling coating composition can be provided, which can form an antifouling film with excellent antifouling properties and excellent crack resistance. Furthermore, an antifouling film formed from the antifouling coating composition and a composite film having the antifouling film can be provided, as well as ships and underwater structures having the antifouling film or the composite film. Attached Figure Description

[0027] Figure 1 This is a schematic top view illustrating the evaluation method for the antifouling properties of coatings.

[0028] Figure 2 This is a schematic cross-sectional diagram illustrating the evaluation method for the antifouling properties of coatings. Detailed Implementation

[0029] <Antifouling Coating Composition> The antifouling coating composition of the present invention (hereinafter also referred to as the "coating composition") comprises a specific silicone-containing resin described later and a thermoplastic resin other than the silicone-containing resin. The thermoplastic resin comprises a thermoplastic resin with a weight-average molecular weight of 1000 or more, and the content of the thermoplastic resin with a weight-average molecular weight of 1000 or more is 6.0 parts by weight or more and 11.0 parts by weight or less relative to 100 parts by weight of the silicone-containing resin.

[0030] According to the coating composition of the present invention, an antifouling coating film (hereinafter also simply referred to as "coating film") can be formed that exhibits excellent antifouling performance over a long period when immersed in water (seawater). When the coating film of the present invention is formed on the surface of a moving body in water, such as a ship, the coating film can maintain excellent antifouling performance even during the movement of the moving body in seawater. Conventional antifouling coating films tend to show a decline in antifouling performance in the later stages of the movement of the moving body in seawater, while the coating film of the present invention can maintain excellent antifouling performance even in the later stages.

[0031] Furthermore, the coating composition according to the present invention can form a coating film that exhibits excellent crack resistance over a long period when immersed in water (seawater). Conventional antifouling coatings tend to show a decrease in crack resistance in the later stages of prolonged immersion of moving objects in seawater. This decrease in crack resistance exacerbates the decline in antifouling performance. The coating film of the present invention maintains excellent crack resistance even in this later stage. Moreover, the coating film of the present invention maintains excellent crack resistance even after being immersed in seawater for a certain period of time, and then subjected to repeated alternations of exposure to seawater immersion and non-immersion.

[0032] The coating composition of the present invention is suitable for use as an antifouling coating composition for waterborne moving bodies or underwater structures such as ships, and is particularly suitable as an antifouling coating composition for waterborne moving bodies such as ships.

[0033] The following provides a detailed description of the components contained in or that may be contained in the coating composition.

[0034] (1) Silicon-containing resin The coating composition contains a silicon-containing resin comprising a structural unit (A). The structural unit (A) is a structural unit having at least one silicon-containing group selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV). The structural unit (A) may be a structural unit derived from a monomer (a) having at least one silicon-containing group selected from the above groups.

[0035] Silicon-containing resins may contain structural units other than structural unit (A). Examples of such structural units include: The structural unit (B) has three organosilasiloxycarbonyl groups; Derived from the structural unit (C) of the monofunctional (meth)acrylate monomer (c) represented by formula (c); and, It has at least one structural unit (D) containing a metal atom group selected from groups represented by formula (V) and groups represented by formula (VI).

[0036] In this specification, "(meth)acryloyl" means at least one of methacryloyl and acryloyl, "(meth)acrylic acid" means at least one of methacrylic acid and acrylic acid, and "(meth)acrylate" means at least one of methacrylate and acrylate.

[0037] (1-1) Silicon-containing groups The silicon-containing group is selected from at least one of the groups represented by formula (I), formula (II), formula (III), and formula (IV).

[0038] In equation (Ⅰ), a and b each independently represent any integer from 2 to 5, m represents any integer from 0 to 50, and n represents any integer from 3 to 270. R 1 ~R 5 Each can be independently represented as alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy.

[0039] In equation (II), c and d each independently represent any integer from 2 to 5, and p represents any integer from 0 to 50. R 6 R 7 and R 8 Each independently represents an alkyl group, R. a Or R b ; In R a In R, x represents any integer from 0 to 200. 23 ~R 27 Same or different indicates alkyl group.

[0040] In R b In R, y represents any integer from 1 to 200. 28 and R 29 Same or different indicates alkyl group.

[0041] In equation (Ⅲ), e, f, g, and h each independently represent any integer from 2 to 5, q and s each independently represent any integer from 0 to 50, and r represents any integer from 3 to 270. 9 ~R 12 Each can be independently represented as alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy.

[0042] In equation (Ⅳ), i, j, k, and l each independently represent any integer from 2 to 5, t and u each independently represent any integer from 0 to 50, and v and w each independently represent any integer from 0 to 70. R 13 ~R 22 Same or different indicates alkyl group.

[0043] Silicon-containing resins may have two or more silicon-containing groups selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV). In this case, it may also 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).

[0044] (1-2) Monomer (a) The structural unit (A) may be a structural unit derived from the monomer (a), which has at least one silicon-containing group selected from the group represented by formula (I), the group represented by formula (II), the group represented by formula (III), and the group represented by formula (IV).

[0045] Monomer (a) is preferably selected from at least one 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 each silicon-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).

[0046] [Chemical Formula 9]

[0047] In equation (Ⅰ'), R 31 Represents hydrogen atoms or methyl groups, a, b, m, n, and R. 1 ~R 5 It means the same as above; [Chemical Formula 10]

[0048] In formula (Ⅱ'), R 32 Represents hydrogen atoms or methyl groups, c, d, p, and R. 6 ~R 8 It means the same as above; [Chemical Formula 11]

[0049] In formula (Ⅲ'), R 33 and R 34 Each of the following independently represents a hydrogen atom or a methyl group: e, f, g, h, q, r, s, and R. 9 ~R 12 It means the same as above; [Chemical Formula 12]

[0050] In equation (Ⅳ'), R 35 and R 36 Each of these independently represents a hydrogen atom or a methyl group, i, j, k, l, t, u, v, w, and R. 13 ~R 22 It means the same as above.

[0051] By polymerizing a monomer composition comprising the aforementioned monomer (a), a silicon-containing resin comprising a structural unit (A) derived from monomer (a) can be obtained as a (meth)acrylic resin, wherein the monomer (a) is selected from monomer (a1), monomer (a2), monomer (a3), and monomer (a4). The silicon-containing resin has at least one silicon-containing group selected from the groups represented by formula (I), formula (II), formula (III), and formula (IV).

[0052] Silicon-containing resins may contain two or more structural units (A) derived from monomer (a).

[0053] Monomer (a) can be a combination of two or more monomers belonging to monomer (a). These two or more monomers can have different molecular weights.

[0054] The monomer (a1) is represented by formula (Ⅰ'). By using monomer (a1) as monomer (a), a silicon-containing resin that has a silicon-containing group represented by formula (Ⅰ) in the side chain can be obtained.

[0055] Silicon-containing resins can contain structural units derived from two or more monomers (a1).

[0056] In formula (Ⅰ') [and formula (Ⅰ) are the same.], 'a' is preferably 2 or 3.

[0057] b is preferably 2 or 3.

[0058] From the viewpoint of the coating's water resistance and adhesion to the substrate, m is preferably 0 or more and 25 or less, more preferably 0 or more and 20 or less. m can be 3 or more or 5 or more, or 10 or less or 8 or less.

[0059] From the viewpoint of the antifouling performance of the coating and its solubility in common organic solvents, n is generally 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, and even more preferably 45 or more and 160 or less.

[0060] R 1 ~R 5The substituted phenyl and substituted phenoxy groups in the form of substituents are, for example, alkyl or halogen atoms.

[0061] R 1 ~R 5 Preferably, it is an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., and particularly preferably methyl or ethyl.

[0062] Commercially available products can also be used as monomers (a1). Examples of commercially available products include: JNC manufactures "FM-0711" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 1000), "FM-0721" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 5000), and "FM-0725" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 10000). Shin-Etsu Chemical Industry Co., Ltd. produces products such as "X-22-2404" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 420), "X-22-174ASX" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 900), "X-22-174BX" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 2300), "KF-2012" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4600), and "X-22-2426" (single-terminal methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 12000).

[0063] Monomer (a2) is represented by formula (Ⅱ'). By using monomer (a2) as monomer (a), a silicon-containing resin that has a silicon-containing group represented by formula (Ⅱ) in the side chain can be obtained.

[0064] Silicon-containing resins can contain structural units derived from two or more monomers (a2).

[0065] In formula (Ⅱ') [and formula (Ⅱ) are the same.], c is preferably 2 or 3.

[0066] d is preferably 2 or 3.

[0067] From the viewpoint of the coating's water resistance and adhesion to the substrate, p is preferably 0 or higher and 25 or lower, more preferably 0 or higher and 20 or lower. p can be 3 or higher or 5 or higher, or 10 or lower or 8 or lower.

[0068] From the viewpoint of solubility in common organic solvents, x is generally 0 or more and 200 or less, preferably 10 or more and 150 or less, and more preferably 20 or more and 125 or less.

[0069] From the viewpoint of solubility in common organic solvents, y is generally 1 or more and 200 or less, preferably 10 or more and 150 or less, and more preferably 20 or more and 125 or less.

[0070] R 6 ~R 8 and R 23 ~R 29 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., and even more preferably methyl or ethyl.

[0071] R 6 ~R 8 All are preferably alkyl groups.

[0072] Commercially available products can also be used as monomers (a2). Examples of commercially available products include JNC's "TM-0701T" (single-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 423), etc.

[0073] Monomer (a3) ​​is represented by formula (Ⅲ'). By using monomer (a3) ​​as monomer (a), a silicon-containing resin of (meth)acrylic acid resin having silicon-containing atomic groups represented by formula (Ⅲ) (the silicon-containing atomic groups are crosslinking groups that crosslink the polymer backbone) can be obtained.

[0074] Silicon-containing resins can contain structural units derived from two or more monomers (a3).

[0075] In equation (Ⅲ') [and equation (Ⅲ) are the same.], e and h are preferably 2 or 3 respectively.

[0076] f and g are preferably 2 or 3 respectively.

[0077] From the viewpoint of the coating's water resistance and adhesion to the substrate, q and s are preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, and even more preferably 0 or more and 20 or less. q and s can each be 3 or more or 5 or more, or 10 or less or 8 or less.

[0078] From the viewpoint of the antifouling performance of the coating film and its solubility in common organic solvents, r is generally 3 or more and 270 or less, preferably 35 or more and 245 or less, more preferably 45 or more and 205 or less, and even more preferably 45 or more and 160 or less.

[0079] R 9 ~R 12 The substituted phenyl and substituted phenoxy groups in the form of substituents are, for example, alkyl or halogen atoms.

[0080] R 9 ~R 12 Preferably, it is an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., and particularly preferably methyl or ethyl.

[0081] Commercially available products can also be used as monomers (a3). Examples of commercially available products include: JNC manufactures "FM-7711" (diterminated methacryloxyalkyl modified organopolysiloxane, molecular weight: 1000); "FM-7721" (diterminated methacryloxyalkyl modified organopolysiloxane, molecular weight: 5000); and "FM-7725" (diterminated methacryloxyalkyl modified organopolysiloxane, molecular weight: 10000). Shin-Etsu Chemical Industry Co., Ltd. produces the following products: "X-22-164" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 380), "X-22-164AS" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 900), "X-22-164A" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 1720), "X-22-164B" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 3200), "X-22-2445" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 3200), "X-22-164C" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 4800), and "X-22-164E" (two-terminated methacryloyloxyalkyl modified organopolysiloxane, molecular weight: 7800).

[0082] Monomer (a4) is represented by formula (Ⅳ'). By using monomer (a4) as monomer (a), a silicone-containing resin of (meth)acrylic acid resin having a silicon-containing group (which is a crosslinking group that crosslinks the polymer backbone) represented by formula (Ⅳ) can be obtained. Commercially available products can also be used as monomer (a4).

[0083] Silicon-containing resins can contain structural units derived from two or more monomers (a4).

[0084] In formula (Ⅳ') [and formula (Ⅳ) are the same.], i and l are preferably 2 or 3 respectively.

[0085] j and k are preferably 2 or 3 respectively.

[0086] From the viewpoint of the coating's water resistance and adhesion to the substrate, t and u are each preferably 0 or more and 30 or less, more preferably 0 or more and 25 or less, and even more preferably 0 or more and 20 or less. q and s can each be 3 or more or 5 or more, or 10 or less or 8 or less.

[0087] From the viewpoint of the antifouling performance of the coating and its solubility in common organic solvents, v and w are generally 0 or more and 70 or less, preferably 5 or more and 60 or less, and more preferably 10 or more and 50 or less.

[0088] R 13 ~R 22 The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc., and even more preferably methyl or ethyl.

[0089] From the viewpoint of improving the antifouling performance of the obtained coating film, the molecular weight of monomer (a) is preferably 400 or more, more preferably 500 or more, further preferably 1000 or more, even more preferably 2000 or more, and particularly preferably 2500 or more; additionally, particularly preferably 3000 or more, most preferably 4000 or more or 5000 or more, and may also be 10000 or more. The molecular weight of monomer (a) is usually 20000 or less, preferably 18000 or less, more preferably 15000 or less, and further preferably 12000 or less. When the molecular weight of monomer (a) is too large, due to the immiscibility of the monomers in the monomer composition, which is a mixture of monomers used in the preparation of silicone atom resin, or the immiscibility of the polymers generated by the polymerization of the monomer composition, the composition of the coating film formed by the coating composition is prone to become uneven.

[0090] The molecular weight of monomer (a) can also be a number-average molecular weight. The number-average molecular weight of monomer (a) is the number-average molecular weight converted from polystyrene determined by gel permeation chromatography (GPC).

[0091] From the viewpoint of improving the antifouling performance of the coating film, the content of structural unit (A) in all structural units contained in the silicone atomizing resin is preferably 20% by mass or more, more preferably 21% by mass or more, even more preferably 25% by mass or more, and may also be 30% by mass or more, 35% by mass or more, 40% by mass or more, or 50% by mass or more. By making the content of structural unit (A) 20% by mass or more, a coating composition exhibiting sufficient antifouling performance can be obtained even without additional antifouling agents. Furthermore, from the viewpoint of coating film properties and the uniformity of the coating film, the content of structural unit (A) in all structural units contained in the silicone atomizing resin 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.

[0092] (1-3) Monomer (b) The silicon-containing resin may further contain a structural unit (B) having a triorganosilyloxycarbonyl group. The structural unit (B) may be derived from a monomer (b) having a triorganosilyloxycarbonyl group. By further incorporating the structural unit (B) into the silicon-containing resin, the antifouling properties of the coating film can be further improved.

[0093] As a triorganosylsiloxycarbonyl group, groups represented by formula (VII) can be listed.

[0094] [Chemical Formula 13]

[0095] In equation (Ⅶ), R 40 R 41 and R 42 Same or different indicates hydrocarbon residues with 1 to 20 carbon atoms.

[0096] The monomer (b) is preferably the monomer (b1) represented by formula (Ⅶ').

[0097] [Chemical Formula 14]

[0098] In equation (Ⅶ'), R 43 R represents a hydrogen atom or a methyl group. 40 R 41 and R 42 Same or different indicates hydrocarbon groups with 1 to 20 carbon atoms.

[0099] By polymerizing a monomer composition containing monomer (b1), a silicon-containing resin, which is a (meth)acrylic resin containing a structural unit (B) derived from monomer (b1), can be obtained. This silicon-containing resin has the structure -C(=O)-O-SiR. 40 R41 R 42 It is a triorganosylsilyloxycarbonyl group.

[0100] Silicon-containing resins can contain two or more structural units (B). For example, silicon-containing resins can contain two or more structural units (B) with different triorganosilyloxycarbonyl groups.

[0101] The same applies to equation (VII'). R in equation (VII) 40 R 41 and R 42 "Same or different" refers to hydrocarbon residues (monovalent hydrocarbon groups) with 1 to 20 carbon atoms. Examples of hydrocarbon residues with 1 to 20 carbon atoms include: straight-chain or branched alkyl groups with 20 or fewer carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl; cyclic alkyl groups that may have substituents, such as cyclohexyl and substituted cyclohexyl; and aryl groups that may have substituents, such as aryl and substituted aryl.

[0102] Examples of cyclic alkyl groups with substituents include cyclic alkyl groups substituted with halogens, alkyl groups with a maximum of about 18 carbon atoms, acyl groups, nitro groups, or amino groups. Examples of aryl groups with substituents include aryl groups substituted with halogens, alkyl groups with a maximum of about 18 carbon atoms, acyl groups, nitro groups, or amino groups.

[0103] Among these, R is preferred due to its tendency to maintain the antifouling properties of the coating film stably over a long period of time. 40 R 41 and R 42 One or more of them are isopropyl, preferably R. 40 R 41 and R 42 All are isopropyl.

[0104] When the silicone-containing resin contains structural unit (B), from the viewpoint of the antifouling performance of the coating, the content of structural unit (B) among all the structural units contained in the silicone-containing resin is preferably 2% by mass or more and 50% by mass or less, more preferably 3% by mass or more and 40% by mass or less, even more preferably 5% by mass or more and 35% by mass or less, and even more preferably 5% by mass or more and 25% by mass or less.

[0105] When the silicon-containing resin contains structural unit (B), the ratio of the content of structural unit (B) to the content of structural unit (A) relative to 100 parts by mass 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, even more preferably 10 parts by mass or more and 80 parts by mass or less, and may also 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.

[0106] (1-4) Monomer (c) The silicon-containing resin can further contain structural units (C) derived from monomer (c). Monomer (c) is a monofunctional (meth)acrylate represented by formula (c). By further incorporating structural units (C) into the silicon-containing resin, the antifouling properties of the coating film can be further improved. In addition, by containing structural units (C), the coating film consumption rate can be moderately increased.

[0107] CH2=C(R A (COOR) B (c) In equation (c), R A Represents a hydrogen atom or a methyl group. R B This indicates the presence of one or more monovalent groups selected from hydroxyl, carboxyl, and alkylene oxide chains. Silicon-containing resins may contain structural units derived from two or more monomers (c). Furthermore, monomer (c) may also be a monomer having two or more groups selected from hydroxyl, carboxyl, and alkylene oxide chains.

[0108] From the perspective of improving the antifouling performance of the coating, the R of monomer (c) B Preferably, it contains at least an oxoalkylene chain. The alkylene chain may be straight-chain or branched, and the number of carbon atoms in the alkylene chain is, for example, 1 or more and 24 or less, preferably 1 or more and 13 or less, more preferably 1 or more and 6 or less, and even more preferably 2 or 3. Examples of such alkylene chains include -CH2-, -(CH2)2-, -(CH2)3-, -CH(CH3)CH2-, and -CH2CH(CH3)-.

[0109] Examples of monomers (c) include: alkyl methacrylates containing hydroxyl groups, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl methacrylate, and 4-hydroxybutyl methacrylate; alkyl methacrylates containing carboxyl groups, such as methoxyethyl methacrylate; alkoxyalkyl methacrylates containing 1 to 20 carbon atoms in the ester portion; and methoxypolyethylene glycol [-OC2H4-]. The repeating number is, for example, 1 to 50, preferably 1 to 24, more preferably 2 to 14, and even more preferably 2 to 9; (meth)acrylates whose ester portion contains a polyalkylene glycol chain, such as (meth)acrylate methoxy polypropylene glycol [-OC3H6-] whose repeating number is, for example, 1 to 50, preferably 1 to 24, more preferably 2 to 14, and even more preferably 2 to 9; (meth)acrylates whose ester portion contains a polyalkylene glycol chain and a carboxyl group, such as (meth)acrylate ethyl succinic acid, (meth)acrylate ethyl phthalic acid, (meth)acrylate ethyl hexahydrophthalic acid, (meth)acrylate propyl phthalic acid, (meth)acrylate propyl hexahydrophthalic acid, etc.

[0110] In the above, monomer (c) is preferably an alkoxyalkyl ester of (meth)acrylate with 1 or more and 20 or less carbon atoms in the ester portion, a (meth)acrylate with a polyalkylene glycol chain in the ester portion, and / or a (meth)acrylate with a polyalkylene glycol chain and a carboxyl group in the ester portion.

[0111] When the silicone-containing resin contains structural units (C), from the viewpoint of the antifouling performance of the coating, the content of structural units (C) in all the structural units contained in the silicone-containing resin 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, even more preferably 1% by mass or more and 30% by mass or less, and may also be 25% by mass or less, 20% by mass or less, 15% by mass or less or 10% by mass or less.

[0112] When the silicon-containing resin contains structural unit (C), the ratio of the content of structural unit (C) to the content of structural unit (A) is preferably 0.5 parts by mass or more and 80 parts by mass or less, more preferably 1 part by mass or more and 70 parts by mass or less, even more preferably 1 part by mass or more and 60 parts by mass or less, even more preferably 2 parts by mass or more and 50 parts by mass or less, 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.

[0113] (1-5) Monomer (d) The silicon-containing resin may also have a structural unit (D) having at least one metal-containing group selected from the groups represented by formula (V) and formula (VI). The structural unit (D) may be derived from a monomer (d) having at least one metal-containing group selected from the above groups. By further incorporating the structural unit (D) into the silicon-containing resin, the antifouling properties of the coating film can be further improved.

[0114] Silicon-containing resins can also have both groups represented by formula (V) and groups represented by formula (VI).

[0115] The monomer (d) is preferably selected from at least one of the monomer (d1) represented by formula (V') and the monomer (d2) represented by formula (VI').

[0116] [Chemical Formula 15]

[0117] In equation (V'), R 37 Indicates a hydrogen atom or a methyl group, M and R 30 It means the same as above.

[0118] [Chemical Formula 16]

[0119] In equation (VI'), R 38 and R 39 Each can be used independently to represent a hydrogen atom or a methyl group, with M representing the same meaning as above.

[0120] By polymerizing a monomer composition containing the aforementioned monomer (d), a silicon-containing resin comprising a structural unit (D) derived from monomer (d) can be obtained as a (meth)acrylic resin, wherein the monomer (d) is selected from monomer (d1) and monomer (d2). The silicon-containing resin has at least one metal-containing group selected from groups represented by formula (V) and groups represented by formula (VI).

[0121] Silicon-containing resins can contain more than two structural units (D).

[0122] The divalent metal atom M in formula (V') [and formula (V) are the same.] and formula (VI') [and formula (VI) are the same.] can be Mg, Zn, Cu, etc., with Zn or Cu being preferred.

[0123] In equation (V') [and equation (V) as well, R...] 30 Organic acid residues are preferred.

[0124] Monomer (d1) is represented by formula (V'). By using monomer (d1) as monomer (d), a silicone-containing resin that further has a metal-containing group represented by formula (V) can be obtained.

[0125] As R 30 Organic acids that form organic acid residues include, for example: acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, decanoic acid, tert-carbonic acid, isostearic acid, palmitic acid, cresolic acid, oleic acid, transoleic acid, linoleic acid, linolenic acid, stearic acid, ricinoleic acid, transricinoleic acid, brassinolic acid, erucic acid, α-naphthoic acid, β-naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline carboxylic acid, nitrobenzoic acid, nitronaphthoic acid, pyruvic acid, and other monoprotic organic acids.

[0126] Among these, if the organic acid residue is a fatty acid residue, it tends to maintain a coating film without cracking or peeling for a long time, and is therefore preferred. In particular, zinc oleate (meth)acrylate or zinc tert-carbonate (meth)acrylate, which have high plasticizing properties, are preferred as monomers (d1).

[0127] In addition, other preferred organic acids include monocyclic organic acids other than aromatic organic acids. Examples of monocyclic organic acids include, for example, cycloalkyl organic acids such as cycloalkane acids, resin acids such as tricyclic resin acids, and their salts.

[0128] Examples of tricyclic resin acids include monocarboxylic acids having a diterpenoid hydrocarbon skeleton. Examples of monocarboxylic acids having a diterpenoid hydrocarbon skeleton include compounds having apigenine, pirarin, isopirarin, or semagenine skeletons. More specifically, examples include abietic acid, neoabietic acid, dehydroabietic acid, hydrogenated abietic acid, longleaf abietic acid, pirarinic acid, isopirarinic acid, levorotatory abietic acid, dextrorotatory abietic acid, sedar abietic acid, and their salts. From the viewpoint of antifouling properties of the coating, abietic acid, hydrogenated abietic acid, and their salts are preferred.

[0129] As monocyclic organic acids, rosin and resin acids from pine trees can also be used. Examples of such organic acids include rosin derivatives, hydrogenated rosin derivatives, disproportionated rosin derivatives, and naphthenic acids. Rosin derivatives refer to resin rosin, wood rosin, and topaz rosin. Considering their low cost, easy availability, excellent operability, and ease of improving antifouling properties, rosin derivatives, hydrogenated rosin derivatives, and disproportionated rosin derivatives are preferred.

[0130] The acid value of the monocyclic organic acid is preferably 100 mg KOH / g or more and 220 mg KOH / g or less, more preferably 120 mg KOH / g or more and 190 mg KOH / g or less, and even more preferably 140 mg KOH / g or more and 185 mg KOH / g or less.

[0131] As a form of R 30 Monocyclic organic acids, when used, tend to maintain the good antifouling properties of the coating for a longer period of time.

[0132] The organic acid residues in the monomer (d1) can be formed from one organic acid or from two or more organic acids.

[0133] As having organic acid residues as R 30 Methods for producing monomer (d1) include, for example, reacting an inorganic metal compound, a carboxyl-containing free radical polymerizable monomer (such as (meth)acrylic acid), and a non-polymerizable organic acid (the organic acid constituting the organic acid residues mentioned above) in an organic solvent containing an alcohol compound.

[0134] The structural unit (D) derived from the monomer (d1) can also be formed by reacting a resin obtained by polymerizing a monomer composition containing a carboxyl-containing free radical polymerizable monomer (such as (meth)acrylic acid) with a metal compound and a non-polymerizable organic acid (the organic acid constituting the organic acid residues mentioned above).

[0135] Monomer (d2) is represented by formula (VI'). By using monomer (d2) as monomer (d), a silicone-containing resin of (meth)acrylic acid resin further having a metal-containing group (which is a crosslinking group that crosslinks the polymer backbone) represented by formula (VI) can be obtained.

[0136] Examples of monomers (d2) include: magnesium acrylate [(CH2=CHCOO)2Mg], magnesium methacrylate [(CH2=C(CH3)COO)2Mg], zinc acrylate [(CH2=CHCOO)2Zn], zinc methacrylate [(CH2=C(CH3)COO)2Zn], copper acrylate [(CH2=CHCOO)2Cu], and copper methacrylate [(CH2=C(CH3)COO)2Cu], etc. One or more of these can be selected as needed.

[0137] Methods for producing monomer (d2) include, for example, reacting a polymerizable unsaturated organic acid (such as (meth)acrylic acid) and a metal compound with water in an organic solvent containing an alcohol compound. In this case, preferably, the water content in the reactants is adjusted to 0.01% by mass or more and 30% by mass or less.

[0138] Silicon-containing atomized resins can contain both structural units derived from monomers (d1) and structural units derived from monomers (d2).

[0139] When the silicone-containing resin contains structural unit (D), from the viewpoint of the antifouling performance of the coating, the content of structural unit (D) in all structural units contained in the silicone-containing resin 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.

[0140] When the silicon-containing resin contains structural unit (D), the ratio of the content of structural unit (D) to the content of structural unit (A) is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, even more preferably 2 parts by mass or more and 35 parts by mass or less, even more preferably 5 parts by mass or more and 30 parts by mass or less, and may also be 25 parts by mass or less, 20 parts by mass or less, or 15 parts by mass or less.

[0141] (1-6) Monomer (e) The silicon-containing resin can further have structural units (E) derived from monomer (e), which is a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups. By further having structural units (E) in the silicon-containing resin, the dynamic antifouling and / or crack resistance of the coating film can be further improved.

[0142] Silicon-containing resins can contain two or more structural units (E) derived from monomers (e).

[0143] As monomers (b), examples include: difunctional (meth)acrylates having two (meth)acryloyloxy groups in the molecule, and trifunctional (meth)acrylates having three or more (meth)acryloyloxy groups in the molecule.

[0144] Examples of difunctional (meth)acrylates include compounds represented by formula (e-1).

[0145] [Chemical Formula 17]

[0146] In the formula, R C Each can independently represent a hydrogen atom or a methyl group. R D This indicates a divalent hydrocarbon group that can have substituents, wherein at least one -CH2- group can be replaced by -O- or -C(=O)-.

[0147] R C Methyl is preferred.

[0148] As R D There are no particular restrictions, and examples include: alkylene groups, poly(oxyalkylene) groups, etc. The number of carbon atoms in an alkylene group can be, for example, 1 or more and 20 or less, 2 or more and 12 or less, or 3 or more and 10 or less. Alkylene groups can be linear, branched, or cyclic.

[0149] The poly(oxoalkylene) group can be represented by -(oxoalkylene). x - indicates. x indicates the number of repetitions of the oxoalkylene group, which can be, for example, 1 or more and 50 or less, 1 or more and 23 or less, 2 or more and 23 or less, 2 or more and 20 or less, 2 or more and 12 or less, or 2 or more and 10 or less. The number of carbon atoms in the oxoalkylene group can be, for example, 2 or more and 6 or less, 2 or more and 4 or less, or 2 or more and 3 or less.

[0150] Specifically, difunctional (meth)acrylates include: ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentanediol dimethacrylate, 3-methyl-1,5-pentanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentanediol dimethacrylate, 1,8-octanediol dimethacrylate, and 1,9-nonanediol dimethacrylate. 1,10-Decanediol di(meth)acrylate, tricyclodecanediethanol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate (the number of repeating alkyl oxide is, for example, 4 or more and 23 or less), propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate (the number of repeating alkyl oxide is, for example, 4 or more and 23 or less).

[0151] Examples of trifunctional or higher (meth)acrylates include: glycerol trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, tripentaerythritol octamethacrylate, tripentaerythritol heptamethacrylate, tetrapentaerythritol decamethacrylate, tetrapentaerythritol nonamethacrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol-modified pentaerythritol tetramethacrylate, and ethylene glycol-modified... Trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, ethylene glycol modified pentaerythritol hexa(meth)acrylate, ethoxylated pentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified pentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified pentaerythritol hexa(meth)acrylate, pentaerythritol triacrylate succinate monoester, pentaerythritol pentaacrylate succinate monoester, pentaerythritol triacrylate maleate monoester, pentaerythritol pentaacrylate maleate monoester, etc.

[0152] (Meth)acrylates with trifunctionality or higher are preferably 3 to 6 functionalities, and more preferably 3 or 4 functionalities.

[0153] When a silicon-containing resin contains structural units (E), from the viewpoint of further improving crack resistance, the content of structural units (E) derived from monomers (e) in all structural units contained in the silicon-containing resin 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 also be 2% by mass or more, 3% by mass or more, 5% by mass or more, or 10% by mass or more. The content of structural units (E) is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, and particularly preferably 10% by mass or less. If the content of structural units (E) is too high, the resin tends to gel easily during the preparation of the silicon-containing resin.

[0154] When the silicon-containing resin contains structural unit (E), the ratio of the content of structural unit (E) to the content of structural unit (A) is preferably 1 part or more and 50 parts or less, more preferably 1 part or more and 40 parts or less, and even more preferably 2 parts or more and 30 parts or less, relative to 100 parts by mass of structural unit (A).

[0155] (1-7) Other monomers Silicon-containing resins may also contain structural units (F) derived from other monomers (f) besides those mentioned above. Silicon-containing resins may contain more than two types of structural units (F).

[0156] As for other monomers (f), there are no particular limitations as long as they are unsaturated monomers capable of copolymerizing with monomers (a) to (e). Examples include: Methyl (meth)acrylate, ethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-(2-ethylhexyloxy)ethyl methacrylate, 1-methyl-2-methoxyethyl methacrylate, 3-methoxybutyl (meth)acrylate, 3-methyl-3-methoxybutyl (meth)acrylate, m-methoxyphenyl (meth)acrylate, p-methoxyphenyl (meth)acrylate, o-methoxyphenyl ethyl (meth)acrylate, m-methoxyphenyl (meth)acrylate ethyl methacrylate, p-methoxyphenyl ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, glycidyl methacrylate, etc., and (meth)acrylate monomers that do not belong to monomers (c) and (e); Vinyl monomers containing primary or secondary amino groups, such as (meth)acrylate, (meth)acrylamide, etc. Vinyl monomers containing tertiary amino groups, such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl methacrylate, dibutylaminoethyl methacrylate, 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, and other vinyl monomers.

[0157] Silicon-containing resins preferably contain methyl methacrylate.

[0158] When a silicone-containing resin contains structural units (F), the content of structural units (F) in all structural units contained in the silicone-containing resin is typically 0.1% by mass or more and 85% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably 5% by mass or more and 75% by mass or less, further preferably 10% by mass or more and 70% by mass or less, and even more preferably 20% by mass or more and 70% by mass or less. By making the content of structural units (F) 0.1% by mass or more, the balance of various properties of the obtained coating composition and coating film can be adjusted. By making the content of structural units (F) 85% by mass or less, a coating film exhibiting sufficient antifouling performance can be formed even without additional antifouling agents.

[0159] (1-8) Molecular weight of silicone-containing resins The number-average molecular weight of the silicone-containing resin is typically 2,000 or more and 100,000 or less, preferably 3,000 or more and 50,000 or less, and more preferably 5,000 or more and 30,000 or less. When the number-average molecular weight of the silicone-containing resin is 2,000 or more, the coating film formed by the coating composition tends to exhibit antifouling properties. When the number-average molecular weight of the silicone-containing resin is 100,000 or less, the silicone-containing resin tends to be easily and uniformly dispersed in the coating composition. The number-average molecular weight of the silicone-containing resin is the number-average molecular weight converted from polystyrene by gel permeation chromatography (GPC).

[0160] (1-9) Manufacturing method of silicone-containing resin There are no particular limitations on the manufacturing method of silicone-containing resins. For example, they can be manufactured by reacting a monomer composition containing the above-mentioned monomers at a reaction temperature of 60–180°C for 5–14 hours in the presence of a free radical initiator. The polymerization conditions can be adjusted appropriately.

[0161] Examples of free radical initiators include: 2,2-azobisisobutyronitrile, 2,2-azobis(2,4-dimethylpentanonitrile), 2,2-azobis(2-methylbutyronitrile), benzoyl peroxide, cumene hydroperoxide, lauroyl peroxide, di-tert-butyl peroxide, and tert-butyl peroxide-2-ethylhexanoate.

[0162] Examples of polymerization methods include solution polymerization, emulsion polymerization, and suspension polymerization carried out in organic solvents. From the viewpoint of manufacturing efficiency of silicone-containing resins, solution polymerization is preferred. Examples of common organic solvents include toluene, xylene, methyl isobutyl ketone, and n-butyl acetate.

[0163] (1-10) Content of silicon-containing resin The content of silicone-containing resin in the coating composition is preferably 25% by mass or more and 99% by mass or less, more preferably 30% by mass or more and 98% by mass or less, even more preferably 35% by mass or more and 97% by mass or less, and may also be 90% by mass or less, 80% by mass or less, or 70% by mass or less. When the content of silicone-containing resin is less than 25% by mass, there is a tendency for decreased antifouling properties and reduced adhesion of the coating film to the substrate. The solid content in the coating composition refers to the total amount of components other than solvents contained in the coating composition.

[0164] (1-11) Implementation methods of silicone-containing resins The following examples illustrate preferred embodiments of silicone-containing resins.

[0165] (i) A silicon-containing resin having structural units derived from monomer (a) and monomer (b).

[0166] (ii) Silicon-containing resins having structural units derived from monomers (a) and (c).

[0167] (iii) Silicon-containing resins having structural units derived from monomers (a) and (e).

[0168] (iv) A silicon-containing resin having structural units derived from monomer (a), monomer (b) and monomer (e).

[0169] (v) Silicon-containing resins having structural units derived from monomers (a) and (d).

[0170] (vi) A silicon-containing resin having structural units derived from monomer (a), monomer (b) and monomer (d).

[0171] (vii) In any of (i), (iii) to (vii) above, there is also a silicon-containing atom resin with structural units derived from monomer (c).

[0172] From the viewpoint of dynamic antifouling and crack resistance, the silicon-containing atom resin preferably has a structural unit derived from at least one monomer selected from monomer (b) and monomer (d), and more preferably has a structural unit derived from monomer (b).

[0173] From the viewpoint of dynamic antifouling and crack resistance, the silicon-containing atom resin preferably has structural units derived from monomer (e), and more preferably has structural units derived from monomer (b) and monomer (e).

[0174] In the case where the silicon-containing resin has a structural unit derived from the monomer (d), from the viewpoint of dynamic antifouling and crack resistance, the metal atom M contained in the monomer (d) is preferably Zn or Cu; from the viewpoint of crack resistance, Zn is more preferred.

[0175] By further endowing the silicon-containing atom resin with structural units derived from monomer (c), it tends to further improve dynamic antifouling properties.

[0176] (2) Thermoplastic resin The coating composition comprises a thermoplastic resin other than a silicone-containing resin, wherein the thermoplastic resin comprises a thermoplastic resin with a weight average molecular weight of 1000 or more. Hereinafter, thermoplastic resins with a weight average molecular weight of 1000 or more are also referred to as "high molecular weight thermoplastic resins". The content of high molecular weight thermoplastic resin in the coating composition is 6.0 parts by weight or more and 11.0 parts by weight or less, relative to 100 parts by weight of silicone-containing resin.

[0177] The coating composition may contain two or more high molecular weight thermoplastic resins.

[0178] The coating composition according to the present invention contains, in addition to a silicon-containing resin, a specified amount of a high molecular weight thermoplastic resin, which enables the coating film formed therefrom to achieve both excellent antifouling properties (dynamic antifouling) and excellent crack resistance at a significantly high level.

[0179] From the viewpoint of improving the crack resistance of the coating film, or further improving dynamic antifouling properties, the weight-average molecular weight of the high molecular weight thermoplastic resin is preferably 2000 or more, more preferably 2500 or more, further preferably 3000 or more, and even more preferably 4000 or more. From the viewpoint of improving dynamic antifouling and / or crack resistance, the weight-average molecular weight of the high molecular weight thermoplastic resin is preferably 200,000 or less, more preferably 150,000 or less, further preferably 100,000 or less, even more preferably 50,000 or less, particularly preferably 25,000 or less, even more particularly preferably 10,000 or less, especially preferably 9,000 or less, and most preferably 6,000 or less or 5,000 or less. The weight-average molecular weight of the thermoplastic resin is the weight-average molecular weight converted from polystyrene as determined by gel permeation chromatography (GPC).

[0180] Examples of high molecular weight thermoplastic resins include: chlorinated rubber, chlorinated polyethylene, chlorinated polypropylene and other chlorinated polyolefins; polyvinyl ether; polyacrylic sebacate; partially hydrogenated terphenyl; polyvinyl acetate; (meth)acrylic resin; polyether polyol; alkyd resin; polyester resin; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer, vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, vinyl chloride-ethyl vinyl ether copolymer and other vinyl chloride resins; silicone oil; greases and their refined products, etc.

[0181] Examples of the aforementioned (meth)acrylic resins include, for example, homopolymers or copolymers formed from monomers selected from (meth)acrylic ester monomers exemplified above as other monomers (f), and more specifically, examples include, for example, poly(meth)acrylic alkyl ester copolymers such as (meth)acrylic methyl ester copolymers, (meth)acrylic ethyl ester copolymers, (meth)acrylic propyl ester copolymers, (meth)acrylic butyl ester copolymers, and (meth)acrylic cyclohexyl ester copolymers.

[0182] The aforementioned (meth)acrylic resin may also contain at least one structural unit selected from the above structural units (B), (C), and (D).

[0183] From the viewpoint of achieving both excellent antifouling performance and excellent crack resistance at a significantly high level, the high molecular weight thermoplastic resin is preferably selected from polyvinyl ether, vinyl chloride-isobutyl vinyl ether copolymer, poly(meth)acrylate alkyl ester, and (meth)acrylate resin containing structural unit (D).

[0184] From the viewpoint of balancing dynamic stain resistance and crack resistance, the content of high molecular weight thermoplastic resin is 6.0 parts by mass or more and 11.0 parts by mass or less, preferably 6.5 parts by mass or more and 10.5 parts by mass or less, and more preferably 7.0 parts by mass or more and 10.0 parts by mass or less, relative to 100 parts by mass of silicone atomized resin.

[0185] The coating composition may contain a thermoplastic resin with a weight average molecular weight of less than 1000. By also containing such a thermoplastic resin, the antifouling properties and / or crack resistance of the coating film can be adjusted. Examples of thermoplastic resins with a weight average molecular weight of less than 1000 include: chlorinated paraffin; rosin, hydrogenated rosin, naphthenic acids, fatty acids and their divalent metal salts, etc. Furthermore, examples of thermoplastic resins with a weight average molecular weight of less than 1000, which are listed as examples of high molecular weight thermoplastic resins, can also be included.

[0186] The content of thermoplastic resin with a weight average molecular weight of less than 1000 is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, can be 15 parts by mass or less, further preferably 10 parts by mass or less, and can be more than 1 part by mass or more than 2 parts by mass, relative to 100 parts by mass of silicone atom resin.

[0187] (3) Other ingredients that may be contained in the coating composition The coating composition may contain one or more components other than silicone-containing resins and thermoplastic resins. Examples of such components include: defoamers, anti-sagging agents, plasticizers, antifouling agents, water binders, anti-color separation agents, anti-settling agents, film consumption regulators, UV absorbers, surface conditioners, viscosity modifiers, leveling agents, pigment dispersants, etc., as well as pigments and solvents. These additives, pigments, and solvents may be used individually or in combination of two or more.

[0188] Defoamers are agents that inhibit bubble formation by making the surface of an impending bubble uneven, or that destroy the surface of an already formed bubble by locally thinning its surface. Examples of defoamers include silicone-based defoamers and non-silicone-based defoamers. Silicone-based defoamers contain surface-active polysiloxanes or their modified forms, while non-silicone-based defoamers are defoamers other than silicone-based defoamers (defoamers that do not contain polysiloxanes or their modified forms). Silicone-based defoamers can be fluorinated silicone-based defoamers. Fluorinated silicone-based defoamers are defoamers containing fluorinated polysiloxanes.

[0189] Examples of non-silicone defoamers include: higher alcohols, higher alcohol derivatives, fatty acids, fatty acid derivatives, paraffin waxes, (meth)acrylic acid polymers, and mineral oils. Examples of silicone defoamers include: oil-based, compound-based, self-emulsifying, and emulsion-based types.

[0190] Commercially available products can be used as defoamers. Examples of commercially available non-silicone defoamers include: mineral oil defoamers such as "BYK-030" manufactured by BYK Corporation; polymer defoamers such as "DISPARON OX68" manufactured by Kusunoki Chemical Co., Ltd. and "BYK-1790" manufactured by BYK Corporation. Examples of commercially available silicone defoamers other than fluorinated silicone defoamers include: silicone oil defoamers such as "KF-96" manufactured by Shin-Etsu Chemical Co., Ltd. and "BYK-081" manufactured by BYK Corporation. Examples of commercially available fluorinated silicone defoamers include: fluorosilicone oil defoamers such as "BYK-063", "BYK-065", "BYK-066N" manufactured by BYK Corporation and "FA-630" manufactured by Shin-Etsu Chemical Co., Ltd.

[0191] From the viewpoint of improving defoaming properties, the content of defoamer relative to 100 parts by weight of silicone atomized resin is 0.002 parts by weight or more and 0.60 parts by weight or less, more preferably 0.004 parts by weight or more and 0.55 parts by weight or less, even more preferably 0.01 parts by weight or more and 0.40 parts by weight or less, and even more preferably 0.01 parts by weight or more and 0.20 parts by weight or less.

[0192] Anti-sagging agents are agents that inhibit sagging of the coating composition that may occur between the application of the coating composition to the substrate and the completion of the drying of the coating film. Examples of anti-sagging agents include: amide-based anti-sagging agents; bentonite-based anti-sagging agents; polyethylene waxes such as oxidized polyethylene wax; hydrogenated castor oil wax; long-chain fatty acid ester polymers; polycarboxylic acids; silica microparticle-based anti-sagging agents; and mixtures of two or more thereof.

[0193] Examples of amide-based anti-sagging agents include fatty acid amide waxes and polyamide waxes. Examples of fatty acid amide waxes include stearamide wax and oleamide wax.

[0194] Commercially available products can be used as anti-sagging agents. Examples of commercially available anti-sagging agents based on amide waxes include: TALEN7200-20 manufactured by Kyoei Chemical Co., Ltd., DISPARON 6900-20X and DISPARON RE-8000 manufactured by Kusunoki Chemical Co., Ltd., and MONORAL3300 manufactured by HS CHEM Co., Ltd. Other commercially available anti-sagging agents include: BENTON 38 manufactured by ELEMENTIS JAPAN Co., Ltd., and TIXOGEL manufactured by BYK Co., Ltd., which are organobentonite-based anti-sagging agents.

[0195] From the viewpoint of improving anti-sagging properties, the content of anti-sagging agent is 0.1 parts by mass or more and 6.0 parts by mass or less, more preferably 0.2 parts by mass or more and 5.0 parts by mass or less, and even more preferably 0.25 parts by mass or more and 4.0 parts by mass or less, relative to 100 parts by mass of silicone atomized resin.

[0196] The coating composition may contain plasticizers. By further containing plasticizers, the antifouling properties and / or crack resistance of the coating film can be adjusted. Examples of plasticizers include: phthalate esters such as dioctyl phthalate (DOP), dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate (DIDP); aliphatic diester esters such as isobutyl adipate and dibutyl sebacate; diol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl esters; phosphate esters such as tricresyl phosphate, triaryl phosphate, and trichloroethyl phosphate; epoxy compounds such as epoxidized soybean oil and octyl epoxidized stearate; organotin compounds such as dioctyltin laurate and dibutyltin laurate; and trioctyl trimellitate and triacetylene.

[0197] The content of plasticizer is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, less than 15 parts by mass, more preferably 10 parts by mass or less, and may be more than 1 part by mass or more than 2 parts by mass relative to 100 parts by mass of silicone atom resin.

[0198] The coating film formed by the coating composition of the present invention exhibits good antifouling performance due to the antifouling effect of the silicone-containing resin, therefore it is not necessary to contain an antifouling agent in addition to the silicone-containing resin. However, to further improve the antifouling performance or to further improve the long-term durability of the antifouling performance, an antifouling agent may be included in the coating composition as needed. Known antifouling agents can be used, such as inorganic compounds, metal-containing organic compounds, and metal-free organic compounds.

[0199] Examples of antifouling agents include: zinc oxide; cuprous oxide; manganese ethylene didithiocarbamate; zinc dimethyl dithiocarbamate; 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine; 2,4,5,6-tetrachloroisophthalonitrile; N,N-dimethyldichlorophenylurea; zinc ethylene didithiocarbamate; copper rhodane (cuprous thiocyanate); 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5- Dichloro-2-n-octyl-3(2H)isothiazolidinone; N-(fluorodichloromethylthio)phthalimide; N,N'-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfonamide; pyridinethione metal salts such as zinc salt (zinc pyridinethione zinc) or copper salt (copper pyridinethione copper); tetramethylthiuram disulfide; 2,4,6-trichlorophenylmaleimide; 2,3,5,6-tetrachloro-4-(methylsulfonyl) Pyridine; 3-Iodo-2-propylbutylcarbamate; Diiodomethyl-p-trisulfone; Phenyl(bispyridyl)bismuth dichloride; 2-(4-thiazolyl)-benzimidazole; Triphenylborone pyridine salt; Stearamine triphenylborone; Laurylamine triphenylborone; Dimethyl dithiocarbamoyl zinc ethylene bis(dithiocarbamate); 1,1-Dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide; 1,1-Dichloro-N-[(dimethylamino)sulfonyl]-1-fluoro-N-phenylmethanesulfonamide [Acyl]-1-fluoro-N-(4-methylphenyl)methanesulfonamide; N'-(3,4-dichlorophenyl)-N,N'-dimethylurea; N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine; 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxylonitrile; 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazolium (generic name: metomididine).

[0200] Preferably, the antifouling agent is selected from at least one of the following: cuprous oxide, pyridinethione metal salt, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxynitrile, and metopridine.

[0201] When the coating composition contains an antifouling agent, the content of the antifouling agent in the coating composition is preferably 0.1 parts by weight or more, more preferably 0.2 parts by weight, and may also be 0.5 parts by weight or more, 1 part by weight or more, or 5 parts by weight or more, relative to 100 parts by weight of the silicone-containing resin. The content of the antifouling agent in the coating composition is preferably 150 parts by weight or less, more preferably 120 parts by weight or less, and even more preferably 100 parts by weight or less, and may also be 80 parts by weight or less, 60 parts by weight or less, 50 parts by weight or less, 40 parts by weight or less, 30 parts by weight or less, 20 parts by weight or less, or 10 parts by weight or less. By keeping the content of the antifouling agent within the above ranges, the antifouling performance can be further improved without affecting the various properties of the resulting coating film, and the long-term durability of the antifouling performance can be further improved.

[0202] As pigments, examples include: extender pigments such as: precipitating barium, talc, clay, chalk, white silica, alumina white, bentonite, calcium carbonate, magnesium carbonate, silicic acid, silicates, alumina hydrate, calcium sulfate, etc.; coloring pigments such as: titanium oxide, zirconium oxide, alkaline lead sulfate, tin oxide, carbon black, white lead, graphite, zinc sulfide, zinc oxide, chromium oxide, nickel titanium yellow, chromium titanium yellow, iron oxide yellow, iron oxide red (red lead), iron oxide black, azo red / yellow pigments, chrome yellow, phthalocyanine green, phthalocyanine blue, ultramarine blue, quinacridone, etc.

[0203] Examples of solvents include: hydrocarbons such as toluene, xylene, ethylbenzene, cyclopentane, octane, heptane, cyclohexane, and petroleum solvents; ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and butyl cellosolve; esters such as butyl acetate, propyl acetate, benzyl acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate; ketones such as ethyl isobutyl ketone and methyl isobutyl ketone; and alcohols such as n-butanol and propanol.

[0204] (4) Preparation of coating composition The coating composition can be prepared, for example, by adding a high molecular weight thermoplastic resin and other components as needed to a silicone atom resin or a resin composition containing the same (e.g., a solution or dispersion containing a silicone atom resin), and mixing it using a mixer such as a ball mill, pebble ball mill, roller mill, sand mill, or high-speed disperser.

[0205] Preferably, the coating composition has low VOC. VOC is an abbreviation for Volatile Organic Compound, which refers to the value (unit: g / L) calculated by actually measuring the non-volatile components (solid content, unit: mass%) and the specific gravity of the coating composition (unit: g / cm³) and substituting them into the following formula. Generally speaking, high VOC means a decrease in the non-volatile components in the coating composition, and low VOC means an increase in the non-volatile components.

[0206] VOC = 1000 × specific gravity of the coating composition × (1 - non-volatile components of the coating composition / 100) The VOC content of the coating composition is, for example, 570 or less or 550 or less, preferably 500 or less.

[0207] <Antifouling coatings and composite coatings> The antifouling coating of the present invention (hereinafter also simply referred to as "coating") is a coating formed from the above-described antifouling coating composition of the present invention. The coating is an antifouling coating with antifouling properties. According to this coating, since it is formed from the antifouling coating composition of the present invention, it is possible to achieve both excellent antifouling performance and excellent crack resistance at a significantly high level.

[0208] The coating film can be formed by applying the above-mentioned coating composition to the surface of the object using conventional methods, and then evaporating and removing the solvent at room temperature or under heating as needed. Examples of coating methods for the coating composition include, for instance, dip coating, spray coating, brush coating, roller coating, electrostatic coating, electrodeposition coating, and other conventionally known methods. The thickness of the coating film is, for example, 50 μm or more and 500 μm or less, preferably 100 μm or more and 400 μm or less.

[0209] Examples of objects to be coated include ships and other moving bodies in the water, as well as underwater structures. Examples of underwater structures include: various fishing nets and other fishing gear such as aquaculture nets; port facilities; oil booms; water intake equipment for power plants; piping for cooling; bridges; buoys; industrial water facilities; and seabed bases. Moving bodies in the water are preferred as the object to be coated; examples of moving bodies in the water include: ships, fishing nets, and fishing gear.

[0210] The coating surface of the object to be coated can be pretreated as needed. In addition, a coating film formed by the coating composition of the present invention can be formed on a primer film formed by other coating compositions such as rust-preventive coating composition (corrosion-preventive coating composition) formed on the object to be coated, thereby forming a composite coating film.

[0211] According to the coating composition of the present invention, since the silicon-containing resin acting as a carrier itself exhibits good antifouling properties, the additional antifouling agent can be omitted or its mixing amount can be reduced. Therefore, the coating composition according to the present invention can form a clear (highly transparent) antifouling coating film.

[0212] For example, in a composite coating having a primer film formed from a rust-preventive coating composition and the like, and the coating film of the present invention formed on the primer film, by using the coating film of the present invention as a clear antifouling coating and using rust-preventive coating compositions of various shades, it is possible to provide a coated object such as a ship that has antifouling properties and a composite coating surface with a shade not previously seen. Furthermore, by forming an intermediate coating film formed from a paint of various shades between the primer film formed from a rust-preventive coating composition and the like, and the clear antifouling coating film, it is also possible to provide a coated object with a shade not previously seen.

[0213] As the coating composition for forming the intermediate coating film, various coating compositions can be used, such as antifouling coating compositions, epoxy resin coating compositions, polyurethane resin coating compositions, (meth)acrylic resin coating compositions, chlorinated rubber coating compositions, alkyd resin coating compositions, silicone resin coating compositions, fluoropolymer coating compositions, and so on. The antifouling coating composition for forming the intermediate coating film can be the coating composition of the present invention, or it can be other antifouling coating compositions, such as conventional antifouling coating compositions containing a larger amount of antifouling agent.

[0214] The intermediate coating film can be formed over the entire surface of the primer film or on a portion of the primer film. Both the intermediate coating film and the primer film can be existing coatings in use. In this case, the coating composition of the present invention and the film formed therefrom can be used to repair existing coatings.

[0215] Example The present invention will be described in more detail below with examples and comparative examples, but the present invention is not limited thereto.

[0216] <Example 1 of resin manufacturing: Manufacturing of silicone-containing resin (S1)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as solvents were added, and the temperature was maintained at 100°C. Meanwhile, a mixture of 40.0 parts by mass of FM-0721 (monomer (a)), 14.2 parts by mass of TIPSMA (monomer (b)), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, and 20.0 parts by mass of EA (monomer (f)), and 2.0 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator was pre-mixed. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 24.0 parts by mass of xylene, 24 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours to obtain a resin composition (solution) containing a silicon-containing resin (S1).

[0217] <Resin Manufacturing Example 2: Manufacturing of Silicon-Containing Resin (S2)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as solvents were added, and the temperature was maintained at 100°C. Meanwhile, a mixture of 40.0 parts by mass of FM-0721 as monomer (a), 10.0 parts by mass of EHMA, 30.0 parts by mass of MMA, and 20.0 parts by mass of EA as monomers (f), and 2.0 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 15.0 parts by mass of xylene, 15.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S2).

[0218] <Resin Manufacturing Example 3: Manufacturing of Silicon-Containing Resin (S3)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as solvents were added, and the temperature was maintained at 100°C. Pre-mixed monomers included 40.0 parts by mass of FM-0721 (a), 14.2 parts by mass of TIPSMA (b), 5.0 parts by mass of CB-1 (c), 10.0 parts by mass of EHMA, 10.8 parts by mass of MMA, and 20.0 parts by mass of EA (f), and 2.0 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 18.0 parts by mass of xylene, 18.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S3).

[0219] <Example 4 of resin manufacturing: Manufacturing of silicone-containing resin (S4)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as solvents were added, and the temperature was maintained at 100°C. Meanwhile, a mixture of 40.0 parts by mass of FM-0721 (monomer (a)), 14.2 parts by mass of TIPSA (monomer (b)), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, and 20.0 parts by mass of EA (monomer (f)), and 2.0 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator was pre-mixed. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 4.0 parts by mass of xylene, 4.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S4).

[0220] <Resin Manufacturing Example 5: Manufacturing of Silicon-Containing Resin (S5)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as solvents were added, and the temperature was maintained at 100°C. Pre-mixed monomers included 40.0 parts by mass of FM-0721 (a), 14.2 parts by mass of TIPSA (b), 1.0 part by mass of NPG (e), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, and 19.0 parts by mass of EA (f), and 2.0 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 4.0 parts by mass of xylene, 4.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S5).

[0221] <Resin Manufacturing Example 6: Manufacturing of Silicon-Containing Resin (S6)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 80.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The following monomers were pre-mixed: 40.0 parts by mass of KF-2012 (monomer (a)), 15.0 parts by mass of TISPA (monomer (b)), 5.0 parts by mass of CB-1 (monomer (c)), 1.0 part by mass of NPG (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 (monomers (f)), and 1.1 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 60 minutes. Then, a mixture consisting of 20.0 parts by mass of xylene and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S6).

[0222] <Resin Manufacturing Example 7: Manufacturing of Silicon-Containing Resin (S7)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The mixture consisted of 21.0 parts by mass of FM-0721 (monomer a), 4.0 parts by mass of M-40G and 1.0 parts by mass of HEMA (monomer c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 5.0 parts by mass of EHMA and 39.0 parts by mass of MMA (monomer f), 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 80 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S7).

[0223] <Example 8 of resin manufacturing: Manufacturing of silicone-containing resin (S8)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The mixture consisted of 21.0 parts by mass of FM-0711 (monomer a), 4.0 parts by mass of M-40G and 1.0 parts by mass of HEMA (monomer c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 5.0 parts by mass of EHMA and 39.0 parts by mass of MMA (monomer f), 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 80 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S8).

[0224] <Example 9 of Resin Manufacturing: Manufacturing of Silicon-Containing Resin (S9)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The mixture consisted of 21.0 parts by mass of TM-0701T as monomer (a), 4.0 parts by mass of M-40G and 1.0 parts by mass of HEMA as monomer (c), 20.0 parts by mass of t-BMA, 10.0 parts by mass of n-BMA, 5.0 parts by mass of EHMA and 39.0 parts by mass of MMA as monomer (f), 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 80 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a silicon-containing resin (S9).

[0225] <Resin Manufacturing Example 10: Manufacturing of Silicon-Containing Atom Resin (S10)> (1) Preparation of a polymerizable monomer mixture (M1) containing metal atoms: Monomer (d) In a four-necked flask equipped with a cooler, 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 added, and the mixture was heated to 75°C while stirring. Then, 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 over 3 hours at a constant rate. After stirring for another 2 hours, 36.0 parts by mass of PGM was added, yielding a transparent polymerizable monomer mixture (M1) containing metal atoms (solid content concentration: 44.8 parts by mass). This polymerizable monomer mixture (M1) contains zinc (meth)acrylate belonging to the monomer (d2) represented by formula (VI') above.

[0226] (2) Manufacturing of silicon-containing atom resin (S10) In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 15.0 parts by mass of PGM as solvent, 65.0 parts by mass of xylene, and 4.0 parts by mass of EA as monomer (f) were added, and the mixture was heated to 100°C while stirring. The mixture was pre-mixed with 40.0 parts by mass of FM-0711 as monomer (a), 21.7 parts by mass of the metal-atom polymerizable monomer mixture (M1) prepared in (1) above as monomer (d), 20.4 parts by mass of MMA and 13.9 parts by mass of EA as monomer (f), 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). This mixture was added to the dropping funnel and added dropwise to the four-necked flask at a constant rate for 6 hours. Then, 0.5 parts by weight of tert-butyl peroxyoctanoate and 10.0 parts by weight of xylene were added dropwise over 30 minutes. After stirring for 1 hour and 30 minutes, 10.1 parts by weight of xylene were added to obtain a resin composition (solution) containing silicon atoms (S10).

[0227] <Resin Manufacturing Example 11: Manufacturing of Silicon-Containing Atom Resin (S11)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The mixture consisted of 30.0 parts by mass of FM-0725 as monomer (a), 6.0 parts by mass of t-BMA, 10.0 parts by mass of EHMA, 30.0 parts by mass of MMA, 10.0 parts by mass of EA, 14.0 parts by mass of AA, 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.0 hour, thereby obtaining a resin composition (solution) containing a resin having a carboxyl group.

[0228] Next, in the same reaction vessel, 100 parts by weight of the above resin composition, 18.6 parts by weight of zinc acetate (II), 33.2 parts by weight of naphthenic acid (NA-165), and 60.0 parts by weight of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction was continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, n-butanol and xylene were added to make the solid content concentration of the resin composition 50.2% by weight, resulting in a resin composition (solution) containing resin (S11). Resin (S11) is formed when the carboxyl groups of the above-mentioned carboxyl-containing resin are converted to -COO-Zn. 2+ ( - It is obtained by OOC-Y. Y is the structural part of the cycloalkanoic acid other than the carboxyl group.

[0229] <Resin Manufacturing Example 12: Manufacturing of Silicon-Containing Atom Resin (S12)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 35.0 parts by mass of xylene and 35.0 parts by mass of n-butanol as solvents were added, and the temperature was maintained at 100°C. Meanwhile, a mixture of 40.0 parts by mass of FM-0711 as monomer (a), 10.0 parts by mass of EHMA, 15.8 parts by mass of MMA, 20.0 parts by mass of EA, 14.2 parts by mass of AA as monomer (f), and 2.0 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator was pre-mixed. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 25.0 parts by mass of xylene, 25.0 parts by mass of n-butanol, and 0.2 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a resin with carboxyl groups.

[0230] Next, in the same reaction vessel, 100 parts by mass of the above resin composition, 19.6 parts by mass of copper acetate (II), 27.5 parts by mass of naphthenic acid (NA-200), and 60.0 parts by mass of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction was continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, xylene was added to make the solid content concentration of the resin composition 46.4% by mass, resulting in a resin composition (solution) containing resin (S12). Resin (S12) is formed when the carboxyl groups of the above-mentioned carboxyl-containing resin are converted to -COO-Cu. 2+ (- It is obtained by OOC-Y. Y is the structural part of the cycloalkanoic acid other than the carboxyl group.

[0231] <Resin Manufacturing Example 13: Manufacturing of Silicon-Containing Atom Resin (S13)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The following were pre-mixed: 35.0 parts by mass of FM-0721 as monomer (a), 19.0 parts by mass of TIPSA as monomer (b), 1.0 part by mass of M-230G as monomer (c), 10.0 parts by mass of n-BA and 26.0 parts by mass of MMA, 9.0 parts by mass of AA, 10 parts by mass of xylene, and 1.5 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a resin with a carboxyl group.

[0232] Next, in the same reaction vessel, 100 parts by weight of the above resin composition, 13.1 parts by weight of copper acetate (II), 22.1 parts by weight of hydrogenated rosin (HYPALE CH), and 60.0 parts by weight of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction was continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, xylene was added to make the solid content concentration of the resin composition 50.5% by weight, resulting in a resin composition (solution) containing resin (S13). Resin (S13) is formed when the carboxyl groups of the above-mentioned carboxyl-containing resin are converted to -COO-Cu. 2+ ( - It is obtained by (OOC-Y). Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0233] <Resin Manufacturing Example 14: Manufacturing of Silicon-Containing Atom Resin (S14)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. The following were pre-mixed: 35.0 parts by mass of FM-0721 as monomer (a), 19.0 parts by mass of TIPSA as monomer (b), 1.0 part by mass of M-230G as monomer (c), 10.0 parts by mass of n-BA and 26.0 parts by mass of MMA, 9.0 parts by mass of AA, 10 parts by mass of xylene, and 1.5 parts by mass of tert-butylperoxide-2-ethylhexanoate as a free radical polymerization initiator. This mixture was added to the dropping funnel and added dropwise at a constant rate to the four-necked flask over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butylperoxide-2-ethylhexanoate was added dropwise to a four-necked flask at a constant rate for 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1.5 hours, thereby obtaining a resin composition (solution) containing a resin with a carboxyl group.

[0234] Next, in the same reaction vessel, 100 parts by weight of the above resin composition, 13.1 parts by weight of zinc acetate (II), 22.1 parts by weight of hydrogenated rosin (HYPALE CH), and 60.0 parts by weight of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction was continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, n-butanol and xylene were added to make the solid content concentration of the resin composition 50.7% by weight, yielding a resin composition (solution) containing resin (S14). Resin (S14) is formed by converting the carboxyl groups of the above-mentioned carboxyl-containing resin to -COO-Zn. 2+ ( - It is obtained by (OOC-Y). Y is the structural part of hydrogenated rosin other than the carboxyl group.

[0235] <Resin Manufacturing Example 15: Manufacturing of Silicon-Containing Atom Resin (S15)> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube and temperature controller, add 70.0 parts by mass of xylene and 30.0 parts by mass of n-butanol as solvents, and maintain the temperature at 105°C. The mixture was premixed with 10.0 parts by mass of FM-0711, 10.0 parts by mass of FM-0721 and 10.0 parts by mass of X-22-164C as monomers (a), 30.0 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, 8.6 parts by mass of MMA, 10.0 parts by mass of EA and 6.4 parts by mass of AA as monomers (f), and 2.0 parts by mass of azobisisobutyronitrile as a free radical polymerization initiator. The mixture was added to a dropping funnel and added dropwise at a constant rate to a four-necked flask for 3 hours. After the addition was completed, the mixture was kept warm for 60 minutes to obtain a resin composition (solution) containing a resin with carboxyl groups.

[0236] Next, in the same reaction vessel, 100 parts by weight of the above resin composition, 9.3 parts by weight of copper acetate (II), 27.5 parts by weight of naphthenic acid (NA-200), and 60.0 parts by weight of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction was continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, xylene was added to make the solid content concentration of the resin composition 51.8% by weight, resulting in a resin composition (solution) containing resin (S15). Resin (S15) is obtained by converting the carboxyl groups of the above-mentioned carboxyl-containing resin to -COO-Cu. 2+ ( - It is obtained by OOC-Y. Y is the structural part of the cycloalkanoic acid other than the carboxyl group.

[0237] Tables 1 and 2 show the monomers used in each resin manufacturing example and their amounts (parts by mass). For resin manufacturing examples 11 to 15, the monomers used to manufacture resins having carboxyl groups and their amounts are shown.

[0238] The number-average molecular weight (Mn) of the obtained resins (S1) to (S15) and the solid content concentration of the obtained resin compositions were determined. The results are shown in Tables 1 and 2. The determination methods are described below. In Table 2, the number-average molecular weight (Mn) described in resin manufacturing examples 11 to 15 is for resins containing carboxyl groups (in the process of converting carboxyl groups to -COO-Me). 2+ ( - Mn was determined from the resin prior to the reaction of OOC-Y. Me was either Cu or Zn.

[0239] [i] Number-average molecular weight (Mn) The number-average molecular weights (Mn) of the obtained resin and monomer (a) are converted from the number-average molecular weights of polystyrene determined by GPC. The determination conditions are as follows.

[0240] Device: Tosoh Corporation "HLC-8220GPC" Chromatographic column: TSKgel SuperHZM-M × 2 columns Eluent: Tetrahydrofuran Measurement temperature: 35℃ Detector: RI [ii] Solid content concentration The solid content concentration of the resin composition is calculated using the following formula.

[0241] Solid content concentration (mass %) = 100 × (total mass of raw materials used in the preparation of the resin composition excluding solvent) / (mass of the obtained resin composition) [Table 1]

[0242] [Table 2]

[0243] The abbreviations of the various monomers shown in Tables 1 and 2, and other components used in the resin manufacturing examples, are detailed below.

[0244] [Single(a)] FM-0711: Manufactured by JNC Corporation, a single-terminated methacryloxyalkyl-modified organopolysiloxane, in formula (I'), m=0, b=3, n=10, R 1 ~R 4 and R 31 Methyl, R 5 It is a monomer of n-butyl, with a molecular weight of 1000. FM-0721: Manufactured by JNC Corporation, a single-terminated methacryloxyalkyl-modified organopolysiloxane, in formula (I'), m=0, b=3, n=65, R 1 ~R 4 and R 31 Methyl, R 5 It is a monomer of n-butyl, with a molecular weight of 5000. FM-0725: Manufactured by JNC Corporation, a single-terminated methacryloxyalkyl-modified organopolysiloxane, in formula (I'), m=0, b=3, n=132, R 1 ~R 4 and R 31 Methyl, R 5It is a monomer of n-butyl, with a molecular weight of 10,000. KF-2012: Manufactured by Shin-Etsu Chemical Industry Co., Ltd., a single-terminated methacryloyloxyalkyl-modified organopolysiloxane, in formula (I'), m=0, R 1 ~R 5 and R 31 It is a monomer of methyl group, with a molecular weight of 4600. TM-0701T: Manufactured by JNC Corporation, a single-terminated methacryloxyalkyl-modified organopolysiloxane, in formula (II'), p=0, d=3, R 6 ~R 8 and R 32 It is a monomer of methyl group, with a molecular weight of 423. X-22-164C: Manufactured by Shin-Etsu Chemical Industry Co., Ltd. In the above general formula (Ⅲ'), q and s = 0, f and g = 3, R... 9 ~R 12 R 33 and R 34 It is a silicon-containing polymerizable monomer of methyl, with a molecular weight of 10,000. [Single(b)] TIPSA: Triisopropylsilyl acrylate, manufactured by Shin-Etsu Chemical Industry Co., Ltd. TIPSMA: Triisopropylsilyl methacrylate, manufactured by Shin-Etsu Chemical Industry Co., Ltd. [Single(c)] M-40G: Methoxylated polyethylene glycol methacrylate (repeating number of oxyethylene chains = 4), manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-90G: Methoxylated polyethylene glycol methacrylate (repeating number of oxyethylene chains = 9), manufactured by Shin-Nakamura Chemical Industry Co., Ltd. M-230G: Methoxylated polyethylene glycol methacrylate (repetition number of oxyethylene chains = 23), manufactured by Shin-Nakamura Chemical Industry Co., Ltd. CB-1: Methacryloxyethyl phthalic acid, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. HEMA: 2-Hydroxyethyl methacrylate, manufactured by Mitsubishi Chemical Corporation. [Single(e)] NPG: Neopentyl glycol dimethacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd. [Single (f)] t-BMA: tert-butyl methacrylate, manufactured by Mitsubishi Chemical Corporation n-BMA: n-Butyl methacrylate, manufactured by Mitsubishi Gas Chemical Company. n-BA: n-Butyl acrylate, manufactured by Dong-A Synthetic Co., Ltd. EHMA: 2-Ethylhexyl methacrylate, manufactured by Mitsubishi Chemical Corporation. MMA: Methyl methacrylate, manufactured by Mitsubishi Gas Chemical Company. EA: Ethyl acrylate, manufactured by Dong-A Synthetic Co., Ltd. [Other monomers] AA: Acrylic acid, manufactured by Osaka Organic Chemical Industry Co., Ltd. MAA: Methacrylic acid, manufactured by Kuraray Co., Ltd. [Other ingredients] Zinc oxide: manufactured by Sakai Chemical Industry Co., Ltd. Zinc acetate (II): Manufactured by Nippon Chemical Industries Co., Ltd. Copper acetate (II): manufactured by Nippon Chemical Industries, Ltd. NA-165: Naphthenic acid, acid value: 165 mg KOH / g, manufactured by Daiwa Oil & Fat Co., Ltd. NA-200: Naphthenic acid, acid value: 200 mg KOH / g, manufactured by Daiwa Oil & Fat Co., Ltd. HYPALE CH: Hydrogenated rosin, acid value: 160 mg KOH / g, manufactured by Arakawa Chemical Industry Co., Ltd. Chain transfer agent; α-Methylstyrene dimer, manufactured by Mitsui Chemicals Co., Ltd. Free radical polymerization initiators; tert-butylperoxide-2-ethylhexanoate, manufactured by Akzo Chemical Co., Ltd. AIBN: Azobisisobutyronitrile, manufactured by Otsuka Chemical Co., Ltd. AMBN: Azodimethylbutyronitrile, manufactured by Otsuka Chemical Co., Ltd. Organic solvents; Xylene: Manufactured by JFE Chemical Company n-Butanol: Manufactured by JNC PGM: Propylene Glycol Methyl Ether: Manufactured by Dow Chemical Company <Example 1> (1) Preparation of antifouling coating composition 1 The above-prepared silicone resin (S1) 83.20 parts by mass, (meth)acrylic resin containing structural unit (D) as thermoplastic resin 6 6.74 parts by mass, titanium dioxide CR-50 as pigment 1 0.30 parts by mass, Bayferox 130 as pigment 2 3.40 parts by mass, and xylene as solvent 1 6.36 parts by mass were mixed and dispersed using a disperser (2000 rpm) to prepare antifouling coating composition 1. It should be noted that the mixing amount refers to the actual amount (parts by mass) including volatile components such as solvents. The VOC values ​​of antifouling coating composition 1 are shown in Table 3.

[0245] (2) Coating preparation The antifouling coating composition 1 was sprayed onto an SPCC steel plate (150mm×70mm×3.2mm) that had a rust-preventive coating film formed on it, which was composed of an anti-rust coating composition (epoxy anti-corrosion coating: NIPPON E-MARINE A / C, manufactured by Japan Marine Coatings Co., Ltd.). The dried film thickness was 300μm. The plate was then placed indoors for 2 days and nights to dry, resulting in a test plate with an antifouling coating film.

[0246] <Examples 2-32, Comparative Examples 1-6> Except for changing the types and amounts of each compounding component as described in Tables 3 to 8, antifouling coating compositions 2 to 32 and comparative antifouling coating compositions 1 to 6 were prepared in the same manner as in Example 1. Furthermore, except that antifouling coating compositions 2 to 32 and comparative antifouling coating compositions 1 to 6 were used respectively, test panels with antifouling coatings were obtained in the same manner as in Example 1. The VOC values ​​of antifouling coating compositions 2 to 32 and comparative antifouling coating compositions 1 to 6 are shown in Tables 3 to 8.

[0247] The details of each compound component shown in Tables 3 to 8 are as follows.

[0248] Thermoplastic Resin 1: Chlorinated paraffin, Tosoh Corporation's "Toyoparax A50", solids content concentration: 100% by mass, weight average molecular weight: 750 Thermoplastic resin 2: Rosin, "WW Rosin" manufactured by Arakawa Chemical Industry Co., Ltd., solid content concentration: 100% by mass, weight average molecular weight: 350 Thermoplastic resin 3: Polyvinyl ethyl ether, BASF "Lutonal A25", solids content concentration: 95% by mass, weight average molecular weight: 4500 Thermoplastic resin 4: Vinyl chloride-isobutyl vinyl ether copolymer, BASF Japan "Laroflex MP25", solids content concentration: 100% by mass, weight average molecular weight: 28000 Thermoplastic resin 5: Acrylic resin, BASF "DIANAL BR-106", solids concentration: 100% by mass, weight average molecular weight: 55,000 Thermoplastic resin 6: A (meth)acrylic resin containing structural unit (D) manufactured by the method described later, with a solids content concentration of 46.0% by mass and a weight-average molecular weight of 8000. Antifouling agent 1: Cuprous oxide, manufactured by Furukawa Chemical Co., Ltd. Antifouling agent 2: Zinc pyrithione, manufactured by Azithropoietin, "Zinc Omadine". Antifouling agent 3: Copper Omadine (manufactured by Archie Chemicals) Antifouling agent 4: Sea-Nine 211, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (4,5-dichloro-2-n-octyl-3(2H)isothiazolinone), manufactured by Rohm and Haas, "Sea-Nine 211". Antifouling agent 5: Irgarol, N'-tert-butyl-N-cyclopropyl-6-(methylthio)-1,3,5-triazine-2,4-diamine, manufactured by Ciba Specialty Chemicals, "Irgarol 1051" Antifouling agent 6: ECONEA, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxylonitrile, manufactured by Janssen PMP. Antifouling agent 7: Metopidine, manufactured by I-TECH AB as "Selektope" Pigment 1: Titanium oxide, "Tipaque CR-50" manufactured by Ishihara Sangyo Co., Ltd. Pigment 2: Iron oxide, Lanxess "Bayferox 130" <Example 1 of the manufacture of thermoplastic resins: Manufacture of thermoplastic resin 6> In a four-necked flask equipped with a thermometer, cooling tube, stirrer, dropping funnel, nitrogen inlet tube, and temperature controller, 50.0 parts by mass of xylene as a solvent were added, and the temperature was maintained at 95°C. A mixture of 58.3 parts by mass of EA, 25.0 parts by mass of CHA (cyclohexyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.), 16.7 parts by mass of AA, 10.0 parts by mass of xylene, and 1.2 parts by mass of tert-butyl peroxide-2-ethylhexanoate as a free radical polymerization initiator was pre-mixed and added to the dropping funnel at a constant rate over 3 hours. After the addition was completed, the mixture was kept at the temperature for 30 minutes. Then, a mixture consisting of 40.0 parts by mass of xylene and 0.3 parts by mass of tert-butyl peroxide-2-ethylhexanoate was added dropwise to the four-necked flask at a constant rate over 30 minutes. After the addition was completed, the mixture was kept at the temperature for 1 hour, thereby obtaining a resin composition (solution) containing a resin with carboxyl groups.

[0249] Next, in the same reaction vessel, 100.0 parts by weight of the above resin composition, 18.6 parts by weight of zinc acetate (II), 33.2 parts by weight of naphthenic acid (NA-165), and 60.0 parts by weight of xylene were added. The mixture was heated to reflux temperature, and while removing the distilled mixture of acetic acid, water, and solvent, an equal amount of xylene was added, and the reaction was continued for 18 hours. The endpoint of the reaction was determined by quantitatively measuring the amount of acetic acid in the distilled solvent. After cooling the reaction solution, the same mass of n-butanol and xylene were added to make the solid content concentration of the resin composition 46.0% by weight, resulting in a resin composition (solution) containing thermoplastic resin 6.

[0250] The weight-average molecular weight (Mw) of thermoplastic resins 1 to 6 is the weight-average molecular weight converted from polystyrene obtained by GPC, and the determination conditions are as follows.

[0251] Device: Tosoh Corporation "HLC-8220GPC" Chromatographic column: TSKgel SuperHZM-M × 2 columns Eluent: Tetrahydrofuran Measurement temperature: 35℃ Detector: RI (Evaluation of antifouling coating compositions) [a] Antifouling performance of the coating (dynamic antifouling test) Prepare Figure 1 and Figure 2The water channel 10 shown is made of metal. The water channel 10 has a groove with a width of 450 mm and a depth of 200 mm. As shown, the test plate 20 obtained in the embodiment and comparative example is placed on the bottom surface of the groove with the antifouling coating side facing up.

[0252] The waterway 10, on which the test panel 20 is installed, is placed in a sunlit indoor area within the Marine Evaluation Technology Center of Japan Marine Coatings Co., Ltd. in Tamano City, Okayama Prefecture, Japan. At this time, to maximize the duration of sunlight exposure to the test panel 20, the waterway 10 is configured along a north-south direction. Figure 1 Natural seawater continuously pumped from the Seto Inland Sea flows continuously into waterway 10. The natural seawater flows from north to south. The water level of the natural seawater flowing through waterway 10 varies in a 12-hour cycle between 40mm and 200mm to simulate natural tides. The flow velocity of the natural seawater flowing through waterway 10 is adjusted according to the water level, set from approximately 30cm / s (at the lowest water level) to approximately 10cm / s (at the highest water level).

[0253] The experiment of continuously flowing natural seawater into waterway 10 was conducted for 12 months. The attachment area of ​​marine organisms was determined, and the results were evaluated according to the following criteria. Tables 3 to 8 show the evaluation results at 6 months and 12 months. An evaluation result of 3 or higher is preferred.

[0254] 5: The surface area covered by marine organisms is between 0% and 5%. 4: The surface area covered by marine organisms is more than 5% but less than 10%. 3: The surface area covered by marine organisms is more than 10% but less than 15%. 2: The surface area covered by marine organisms is more than 15% but less than 30%. 1: The attachment area of ​​marine organisms is over 30%. [b] Crack resistance of the coating (crack resistance test under repeated wet and dry conditions after static impregnation) Natural seawater collected from the Marine Evaluation Technology Center Research Institute of Nippon Marine Coatings Co., Ltd. in Tamano City, Okayama Prefecture, Japan, was prepared by adding sodium hydroxide to adjust the pH value to 9 (the pH value of ordinary seawater is about 8.2). The test panels obtained in the examples and comparative examples were then immersed in the adjusted seawater at 30°C for one month. During this one-month immersion period, the adjusted seawater was replaced every few days.

[0255] After being soaked for one month, the test panel 20 was immersed in natural seawater at 40°C for one week, followed by one week of indoor drying. This constituted one cycle, and a maximum of 20 cycles of alternating wet and dry testing were conducted, observing the state of the coating on the test panel. If cracking occurred in the coating midway, the test was terminated at the point of cracking, and the number of cycles at that point was used as the index of crack resistance. The values ​​recorded in the table represent the number of cycles at which cracking first occurred. It should be noted that test panels that did not crack even after 20 cycles were marked as 20 <. The preferred evaluation result is 15 or higher.

[0256] In Examples 1 to 32, excellent antifouling performance and excellent crack resistance can be achieved at a significantly high level.

[0257] Comparative Examples 1 to 4 are examples where the content of thermoplastic resin exceeds the specified range, and a coating that simultaneously satisfies both antifouling and crack resistance was not obtained.

[0258] Comparative Examples 5 and 6 are examples that only contain thermoplastic resins with a weight average molecular weight of less than 1000, and failed to obtain coatings that simultaneously satisfy both antifouling and crack resistance.

[0259] [Table 3]

[0260] [Table 4]

[0261] [Table 5]

[0262] [Table 6]

[0263] [Table 7]

[0264] [Table 8]

[0265] Industrial availability The antifouling coating composition according to the present invention can form a coating film that achieves a remarkably high level of both excellent antifouling performance (especially dynamic antifouling) and excellent crack resistance. The antifouling coating composition of the present invention is preferably used as an antifouling coating composition suitable for underwater moving bodies such as ships, or underwater structures.

[0266] Symbol Explanation 10: Waterway; 20: Test board; 25: Second adhesive layer; 30: Direction of natural seawater flow.

Claims

1. An antifouling coating composition comprising a silicone-containing resin and a thermoplastic resin other than the silicone-containing resin, The silicon-containing resin comprises: a structural unit (A), the structural unit (A) having at least one silicon-containing group selected from the group represented by formula (I), the group represented by formula (II), the group represented by formula (III) and the group represented by formula (IV). The thermoplastic resin includes thermoplastic resins with a weight-average molecular weight of 1000 or more. Relative to 100 parts by weight of the silicon-containing atom resin, the content of the thermoplastic resin with a weight average molecular weight of 1000 or more is 6.0 parts by weight or more and 11.0 parts by weight or less. [Chemical Formula 1] In equation (Ⅰ), a and b each independently represent any integer from 2 to 5, m represents any integer from 0 to 50, and n represents any integer from 3 to 270; R 1 ~R 5 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy. [Chemical Formula 2] In equation (II), c and d each independently represent any integer from 2 to 5, and p represents any integer from 0 to 50; R 6 R 7 and R 8 Each independently represents an alkyl group, R. a Or R b ; R a yes [Chemical Formula 3] In the formula, x represents any integer from 0 to 200; R 23 ~R 27 The same or different indicates an alkyl group; R b yes [Chemical Formula 4] In the formula, y represents any integer from 1 to 200; R 28 and R 29 The same or different indicates an alkyl group; [Chemical Formula 5] In equation (Ⅲ), e, f, g, and h each independently represent any integer from 2 to 5, q and s each independently represent any integer from 0 to 50, and r represents any integer from 3 to 270; R 9 ~R 12 Each can independently represent alkyl, alkoxy, phenyl, substituted phenyl, phenoxy, or substituted phenoxy. [Chemical Formula 6] In equation (Ⅳ), i, j, k, and l each independently represent any integer from 2 to 5; t and u each independently represent any integer from 0 to 50; and v and w each independently represent any integer from 0 to 70. 13 ~R 22 Same or different indicates alkyl group.

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

3. The antifouling coating composition according to claim 1 or 2, wherein the silicon-containing resin further comprises a structural unit (C) derived from a monomer (c), the monomer (c) being a monofunctional (meth)acrylate represented by the following formula (c); CH2=C(R A )(COOR B ) (c) In equation (c), R A Represents a hydrogen atom or a methyl group; R B It indicates that it contains one or more monovalent groups selected from hydroxyl, carboxyl and oxoalkylene chains.

4. The antifouling coating composition according to claim 1 or 2, wherein the silicon-containing resin further comprises a structural unit (D), the structural unit (D) having at least one metal-containing group selected from the groups represented by formula (V) and the groups represented by formula (VI); [Chemical Formula 7] In formula (V), M represents a divalent metal atom, and R 30 Indicates an organic acid residue or an alcohol residue; [Chemical Formula 8] In equation (VI), M represents a divalent metal atom.

5. The antifouling coating composition according to claim 1 or 2, wherein the content of structural unit (A) in all structural units contained in the silicon-containing atom resin is 20% by mass or more.

6. The antifouling coating composition according to claim 1 or 2, wherein the antifouling agent is not contained.

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

8. The antifouling coating composition according to claim 7, wherein the antifouling agent is selected from at least one of: cuprous oxide, pyridinethione metal salt, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine, 4-bromo-2-(4-chlorophenyl)-5-(trifluoromethyl)-1H-pyrrole-3-carboxylonitrile and metopridine.

9. An antifouling coating film formed from the antifouling coating composition of claim 1.

10. A composite coating having: a primer coating formed of a rust-preventive coating composition; and an antifouling coating formed of the antifouling coating composition of claim 1, laminated on the primer coating.

11. A ship having the antifouling coating of claim 9 or the composite coating of claim 10.

12. An underwater structure having the antifouling coating of claim 9 or the composite coating of claim 10.

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