JP2018062640A - (meth)acrylic copolymer, resin composition, antifouling coating composition, and method for producing (meth)acrylic copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifouling coating composition capable of forming a coating film excellent in antifouling properties and water resistance, a (meth)acrylic copolymer and a resin composition suitable for obtaining the antifouling coating composition, and a method for producing the (meth)acrylic copolymer.SOLUTION: The (meth)acrylic copolymer according to a first embodiment of the present invention has at least one of structures (I) represented by formula (1), formula (2), and formula (3) and a polysiloxane group. In the formulae, X represents -O-, -S-, or -NR-; Rrepresents a hydrogen atom or an alkyl group; Rand Reach represent a hydrogen atom or a C1-10 alkyl group; Rand Reach represent a C1-20 alkyl group, a cycloalkyl group, or an aryl group; and Rand Reach represent a C1-10 alkylene group.SELECTED DRAWING: None

Description

  The present invention relates to a (meth) acrylic copolymer, a resin composition, an antifouling coating composition, and a method for producing a (meth) acrylic copolymer.

It has been known that antifouling paints are applied to offshore structures and ships for the purpose of preventing adhesion of marine organisms that cause corrosion of a portion in contact with seawater and a decrease in navigation speed.
Self-polishing antifouling paints are known as antifouling paints. The coating film obtained from the self-polishing antifouling paint has a coating surface that gradually dissolves in seawater and is renewed (self-polishing). Demonstrate the soiling effect.
As a self-polishing antifouling paint, for example, a combination of a vinyl polymer having a hemiacetal ester group and / or a hemiketal ester group in the side chain and an antifouling agent (Patent Document 1), a silicon-containing group and 2 The thing (patent documents 2-3) using the (meth) acrylic-type copolymer which has a valent metal atom is proposed. The polymer used for these antifouling paints has hydrolyzability, and the coating film containing the polymer exhibits self-polishing properties.

JP-A-4-103671 International Publication No. 2004/081121 International Publication No. 2011/046086

The antifouling coating film using the vinyl polymer described in Patent Document 1 has insufficient antifouling properties.
The antifouling coating film using the (meth) acrylic copolymer described in Patent Documents 2 to 3 is also not sufficiently antifouling. There is also a problem of low water resistance.

  An object of the present invention is to provide an antifouling coating composition capable of forming a coating film excellent in antifouling property and water resistance, and a (meth) acrylic copolymer and a resin composition suitable for obtaining the antifouling coating composition And a method for producing the (meth) acrylic copolymer.

（式中、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ^１４−を示し、Ｒ^１４は水素原子又はアルキル基を示し、Ｒ^１及びＲ^２はそれぞれ、水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^３及びＲ^５はそれぞれ、炭素数１〜２０のアルキル基、シクロアルキル基又はアリール基を示し、Ｒ^４及びＲ^６はそれぞれ、炭素数１〜１０のアルキレン基を示す。）
〔２〕下記単量体（ｍ１）に由来の構成単位と、下記単量体（ｍ２）に由来の構成単位とを有する、〔１〕に記載の（メタ）アクリル系共重合体。
単量体（ｍ１）：前記構造（Ｉ）の少なくとも１種とエチレン性不飽和結合とを有する単量体。
単量体（ｍ２）：前記ポリシロキサン基とエチレン性不飽和結合とを有する単量体。
〔３〕〔１〕又は〔２〕に記載の（メタ）アクリル系共重合体を含む樹脂組成物。
〔４〕４０℃３０日間貯蔵後における前記（メタ）アクリル系共重合体中の前記構造（Ｉ）の分解率が２０％以下である、〔３〕に記載の樹脂組成物。
〔５〕酸と反応する化合物、塩基性化合物、酸性化合物及び脱水剤からなる群から選ばれる少なくとも１種をさらに含む、〔３〕又は〔４〕に記載の樹脂組成物。
〔６〕前記酸と反応する化合物が、下記式（３１）で表される化合物、下記式（３２）で表される化合物、及び下記式（３３）で表される化合物からなる群から選ばれる少なくとも１種の化合物（Ｂ）である、〔５〕に記載の樹脂組成物。

（式中、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ^１４−を示し、Ｒ^１４は水素原子又はアルキル基を示し、Ｒ^７は、水素原子又は炭素数１〜９のアルキル基を示し、Ｒ^８は、水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^９及びＲ^１１はそれぞれ、炭素数１〜２０のアルキル基、シクロアルキル基又はアリール基を示し、Ｒ^１０は、単結合、又は炭素数１〜９のアルキレン基を示し、Ｒ^１２は、炭素数１〜９のアルキレン基を示す。）
〔７〕シリコーンオイルをさらに含む、〔３〕〜〔６〕のいずれかに記載の樹脂組成物。
〔８〕〔３〕〜〔７〕のいずれかに記載の樹脂組成物を含む、防汚塗料組成物。
〔９〕防汚剤をさらに含む、〔８〕に記載の防汚塗料組成物。
〔１０〕前記防汚剤が、亜酸化銅、ピリジントリフェニルボラン、４，５−ジクロロ−２−ｎ−オクチル−４−イソチアゾリン−３−オン、４−ブロモ−２−（４−クロロフェニル）−５−（トリフルオロメチル）−１Ｈ−ピロール−３−カルボニトリル及びメデトミジンからなる群から選ばれる少なくとも１種を含む、〔９〕に記載の防汚塗料組成物。
〔１１〕前記（メタ）アクリル系共重合体以外の熱可塑性樹脂をさらに含む、〔８〕〜〔１０〕のいずれかに記載の防汚塗料組成物。
〔１２〕下記単量体（ｍ１）と、下記単量体（ｍ２）とを含む単量体混合物を重合して（メタ）アクリル系共重合体を得る、（メタ）アクリル系共重合体の製造方法。
単量体（ｍ１）：下記式（１）、下記式（２）又は下記式（３）で表される構造（Ｉ）の少なくとも１種とエチレン性不飽和結合とを有する単量体。
単量体（ｍ２）：ポリシロキサン基とエチレン性不飽和結合とを有する単量体。

（式中、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ^１４−を示し、Ｒ^１４は水素原子又はアルキル基を示し、Ｒ^１及びＲ^２はそれぞれ、水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^３及びＲ^５はそれぞれ、炭素数１〜２０のアルキル基、シクロアルキル基又はアリール基を示し、Ｒ^４及びＲ^６はそれぞれ、炭素数１〜１０のアルキレン基を示す。） The present invention has the following aspects.
[1] A (meth) acrylic copolymer having at least one structure (I) represented by the following formula (1), the following formula (2) or the following formula (3) and a polysiloxane group.

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, and R ¹ and R ² represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively. R ³ and R ⁵ each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R ⁴ and R ⁶ each represents an alkylene group having 1 to 10 carbon atoms.)
[2] The (meth) acrylic copolymer according to [1], having a structural unit derived from the following monomer (m1) and a structural unit derived from the following monomer (m2).
Monomer (m1): A monomer having at least one of the structures (I) and an ethylenically unsaturated bond.
Monomer (m2): A monomer having the polysiloxane group and an ethylenically unsaturated bond.
[3] A resin composition comprising the (meth) acrylic copolymer according to [1] or [2].
[4] The resin composition according to [3], wherein the decomposition rate of the structure (I) in the (meth) acrylic copolymer after storage at 40 ° C. for 30 days is 20% or less.
[5] The resin composition according to [3] or [4], further comprising at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent.
[6] The compound that reacts with the acid is selected from the group consisting of a compound represented by the following formula (31), a compound represented by the following formula (32), and a compound represented by the following formula (33). [5] The resin composition according to [5], which is at least one compound (B).

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁹ and R ¹¹ each represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms, and R ¹⁰ represents a single bond Or an alkylene group having 1 to 9 carbon atoms, and R ¹² represents an alkylene group having 1 to 9 carbon atoms.)
[7] The resin composition according to any one of [3] to [6], further including silicone oil.
[8] An antifouling paint composition comprising the resin composition according to any one of [3] to [7].
[9] The antifouling paint composition according to [8], further comprising an antifouling agent.
[10] The antifouling agent is cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl)- The antifouling paint composition according to [9], comprising at least one selected from the group consisting of 5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile and medetomidine.
[11] The antifouling coating composition according to any one of [8] to [10], further comprising a thermoplastic resin other than the (meth) acrylic copolymer.
[12] A (meth) acrylic copolymer obtained by polymerizing a monomer mixture containing the following monomer (m1) and the following monomer (m2). Production method.
Monomer (m1): A monomer having at least one structure (I) represented by the following formula (1), the following formula (2) or the following formula (3) and an ethylenically unsaturated bond.
Monomer (m2): A monomer having a polysiloxane group and an ethylenically unsaturated bond.

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, and R ¹ and R ² represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively. R ³ and R ⁵ each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R ⁴ and R ⁶ each represents an alkylene group having 1 to 10 carbon atoms.)

  According to the present invention, an antifouling coating composition capable of forming a coating film excellent in antifouling properties and water resistance, a (meth) acrylic copolymer and a resin composition suitable for obtaining the antifouling coating composition And a method for producing the (meth) acrylic copolymer.

The following definitions of terms apply throughout this specification and the claims.
The “(meth) acrylic copolymer” means a copolymer in which at least a part of the structural unit is a structural unit derived from a (meth) acrylic monomer. The (meth) acrylic copolymer may further have a structural unit derived from a monomer other than the (meth) acrylic monomer (for example, a vinyl monomer such as styrene).
“Structural unit” means a structural unit derived from a monomer formed by polymerizing a monomer, or a structural unit in which a part of the structural unit is converted into another structure by treating a polymer. Means.
“Monomer” means a polymerizable compound (polymerizable monomer).
“(Meth) acrylic monomer” means a monomer having a (meth) acryloyl group.
“(Meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group. “(Meth) acrylate” is a general term for acrylate and methacrylate. “(Meth) acrylic acid” is a general term for acrylic acid and methacrylic acid. “(Meth) acrylonitrile” is a general term for acrylonitrile and methacrylonitrile. “(Meth) acrylamide” is a general term for acrylamide and methacrylamide.
“Volatile organic compound (VOC)” means an organic compound (volatile organic compound) that easily volatilizes at normal temperature and pressure. In addition, normal temperature normal pressure means 10 to 30 degreeC and 1000 Pa to 1050 Pa.

[(Meth) acrylic copolymer]
A first aspect of the present invention is a (meth) acryl having at least one structure (I) represented by the following formula (1), the following formula (2) or the following formula (3) and a polysiloxane group. A copolymer (hereinafter also referred to as “copolymer (A)”).

（式中、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ^１４−を示し、Ｒ^１４は水素原子又はアルキル基を示し、Ｒ^１及びＲ^２はそれぞれ、水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^３及びＲ^５はそれぞれ、炭素数１〜２０のアルキル基、シクロアルキル基又はアリール基を示し、Ｒ^４及びＲ^６はそれぞれ、炭素数１〜１０のアルキレン基を示す。）

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, and R ¹ and R ² represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively. R ³ and R ⁵ each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R ⁴ and R ⁶ each represents an alkylene group having 1 to 10 carbon atoms.)

The structure (I) and polysiloxane group possessed by the copolymer (A) may each be one kind or two or more kinds.
Each of the structure (I) and the polysiloxane group may be contained in the constituent unit of the copolymer (A), may be contained at the end of the main chain, or may be contained in both of them. In terms of antifouling properties, it is preferably contained in at least a structural unit.
When the structure (I) and the polysiloxane group are each contained in a structural unit, the structure (I) and the polysiloxane group are preferably contained in different structural units.

As the copolymer (A), a structural unit derived from the monomer (m1) having the structure (I) and an ethylenically unsaturated bond (polymerizable carbon-carbon double bond) (hereinafter referred to as “structural unit (u1)”). And a structural unit derived from the monomer (m2) having a polysiloxane group and an ethylenically unsaturated bond (hereinafter also referred to as “structural unit (u2)”). Is preferred.
Each of the structural unit (u1) and the structural unit (u2) of the copolymer (A) may be one kind or two or more kinds.
In addition to the structural unit (u1) and the structural unit (u2), the copolymer (A) includes other structural units other than the structural unit (u1) and the structural unit (u2) (hereinafter referred to as “structural unit (u3)”). May also be included.

At least a part of the structural units of the copolymer (A) is a structural unit derived from a (meth) acrylic monomer. 20-100 mass% is preferable, and, as for the ratio of the structural unit derived from the (meth) acrylic-type monomer with respect to the sum total (100 mass%) of all the structural units in a copolymer (A), 40-100 mass% is more. preferable.
When the copolymer (A) has the structural unit (u1) and the structural unit (u2), one of the structural unit (u1) and the structural unit (u2) is derived from the (meth) acrylic monomer These structural units may be included, and both may include a structural unit derived from a (meth) acrylic monomer.
When the copolymer (A) has the structural unit (u1), the structural unit (u2), and the structural unit (u3), any one of the structural unit (u1), the structural unit (u2), and the structural unit (u3) 1 type may contain the structural unit derived from a (meth) acrylic-type monomer, and 2 or 3 types may contain the structural unit derived from a (meth) acrylic-type monomer.

(Structure (I))
The structure (I) is represented by the formula (1), the formula (2), or the formula (3). In each formula, of the single lines extending from the carbon atom of the carbonyl group, the line not bonded to the oxygen atom represents a bond.
In the formulas (1) to (3), X may be any of —O— (etheric oxygen atom), —S— (sulfide sulfur atom), and —NR ¹⁴ —, and is preferably —O—. .

In formula (1), examples of the alkyl group having 1 to 10 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, 2- An ethylhexyl group etc. are mentioned.
1-4 are preferable, as for carbon number of the alkyl group in R < ¹ > and R < ² >, 1-3 are more preferable, and 1 or 2 is more preferable.

As a preferable combination of R ¹ and R ^2, a combination of a hydrogen atom and a methyl group, a combination of a methyl group and a methyl group, a hydrogen atom and an alkyl group having 2 to 10 carbon atoms (hereinafter also referred to as “long-chain alkyl group”) .), A combination of a methyl group and a long chain alkyl group, a combination of a hydrogen atom and a hydrogen atom, a combination of a long chain alkyl group and a long chain alkyl group, and the like. Among these, a combination of a hydrogen atom and a methyl group is preferable in terms of hydrolyzability.

As a C1-C20 alkyl group in R < ³ >, the alkyl group, decyl group, dodecyl group, tetradecyl group, etc. which were mentioned as a C1-C10 alkyl group mentioned above are mentioned, for example. The number of carbon atoms in the alkyl group for R ^3, 1-10 are preferred.
The cycloalkyl group is preferably a cycloalkyl group having 4 to 8 carbon atoms, and examples thereof include a cyclohexyl group and a cyclopentyl group.
As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group.
As R < ³ >, a C1-C10 alkyl group and a cycloalkyl group are preferable.

The alkyl group, cycloalkyl group or aryl group may be substituted with a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxy group, an alkanoyloxy group, an aralkyl group and an acetoxy group. When substituted by a substituent, the number of substituents may be one or two or more.
Examples of the cycloalkyl group and aryl group as substituents are the same as those described above. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkanoyloxy group include an ethanoyloxy group. Examples of the aralkyl group include a benzyl group.

In formula (2), examples of the alkylene group having 1 to 10 carbon atoms in R ⁴ include a methylene group, an ethylene group, a propylene group, a butylene group, and a hexylene group.
The number of carbon atoms in the alkylene group for R ⁴ is 2-7 preferably 3-4 and more preferably.
The alkylene group may be substituted with a substituent selected from the group consisting of a cycloalkyl group, an aryl group, an alkoxyl group, an alkanoyloxy group, an aralkyl group, and an acetoxy group. When substituted by a substituent, the number of substituents may be one or two or more. Specific examples of the substituent that may be substituted on the alkylene group include the same substituents as those described for R ³ .

In formula (3), R ⁵ is the same as R ³ in formula (1), and the preferred embodiment is also the same.
R ⁶ is the same as R ⁴ in formula (2), and the preferred embodiment is also the same.

(Polysiloxane group)
The polysiloxane group is a group having a Si—O—Si bond. Examples of the polysiloxane group include a divalent polysiloxane group represented by the following formula (i) or (ii), a monovalent polysiloxane group represented by the following formula (iii) or (iv), and organopolysiloxane. Examples thereof include trivalent or higher polysiloxane groups in which three or more organic groups bonded to silicon atoms constituting the skeleton are removed from siloxane.
-(SiR ^1b R ^1c -O) _n -SiR ^1d R ^1e- (i)
_{^{-Si ((OSiR 2b R 2c)}} r -OSiR 2d R 2e R 2f) 2 -OSi ((OSiR 2g R 2h) s -OSiR 2i R 2j R 2k) 2 - ··· (ii)
_{^{- (SiR 3b R 3c -O)}} x -SiR 3d R 3e R 3f ··· (iii)
-Si (OSiR ^4b R ^4c R ^4d ) ₃ (iv)

In formula (i), n represents 3 to 80, and R ^{1b to} R ^1e each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.
In formula (ii), r and s each represent 0 to 20, and R ^{2b to} R ^2k each represents an alkyl group.
In formula (iii), x represents ^{3 to} 80, and R ^{3b to} R ^3f each represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.
In the formula (iv), R ^{4b to} R ^4d are each an alkyl group, — (OSiR ⁵¹ R ⁵² ) _y —OSiR ⁵³ R ⁵⁴ R ⁵⁵ (where y is an integer of 0 to 20, and R ^{51 to} R ⁵⁵ are alkyls) . showing a group), or _{^{-R 56 - (OC 2 H 4}} ) y '-OR 57 ( where, y' is an integer of 1 to ^{20, R 56} represents an alkylene ^{group, R 57} is an alkyl group). Indicates.

In said formula (i), n is an average degree of polymerization of a polysiloxane structure. If n is not less than the lower limit of the above range, even if the antifouling coating composition containing the copolymer (A) does not contain an antifouling agent, the antifouling effect tends to develop in the coating film, If it is below the upper limit of the above range, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is good. . n is preferably from 5 to 50, and more preferably from 8 to 40.
As for carbon number of the alkyl group and alkoxy group in R ^{< 1b} > -R < ^1e >, 1-18 are respectively preferable. Examples of the substituent in the substituted phenyl group and the substituted phenoxy group include an alkyl group and an alkoxy group.
R ^{1b to} R ^1e are each preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In the above formula (ii), r and s are the average degree of polymerization of the polysiloxane structure. If r and s are each less than or equal to the upper limit, the monomer having a polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is high. It is good. r and s are each preferably 10 or less, and more preferably 5 or less.
As an alkyl group in R ^{< 2b} > -R < ^2k >, a C1-C18 alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned. Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

In the above formula (iii), x is the average degree of polymerization of the polysiloxane structure. If x is not less than the lower limit of the above range, even if the antifouling coating composition containing the copolymer (A) does not contain an antifouling agent, the antifouling effect tends to be exhibited in the coating film, If it is below the upper limit of the above range, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is good. . x is preferably from 5 to 50, and more preferably from 8 to 40.
As for carbon number of the alkyl group and alkoxy group in R ^{< 3b} > -R <^3f> , 1-18 are respectively preferable. Examples of the substituent in the substituted phenyl group and the substituted phenoxy group include an alkyl group and an alkoxy group.
R ^{3b to} R ^3f are each preferably an alkyl group having 1 to 18 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

In said formula (iv), as an alkyl group in R ^{< 4b} > -R < ^4d >, a C1-C18 alkyl group is preferable, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned. . Among these, a methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.
y is the average degree of polymerization of the polysiloxane structure, and y ′ is the average degree of polymerization of the polyether structure. If y and y ′ are not more than the above upper limit values, the monomer having the polysiloxane group is compatible with the monomer (m1) and the like, and the solvent solubility of the resulting copolymer (A) is high. It is good. y and y ′ are each preferably 10 or less, and more preferably 5 or less.
The alkyl group in ^{R 51} ~R ^55, R ^57, include the same alkyl group for R 4b ^{to R 4d,} preferable embodiments thereof are also the same. In R ⁵⁶ , the alkylene group preferably has 1 to 18 carbon atoms.

(Structural unit (u1))
The structural unit (u1) has a structure in which the ethylenically unsaturated bond of the monomer (m1) is cleaved to form a single bond.
The monomer (m1) is preferably a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint of lowering the viscosity when the copolymer (A) is dissolved in a solvent.
Examples of the monomer (m1) include a compound represented by the following formula (11), a compound represented by the following formula (12), a compound represented by the following formula (13), and the like.

（式中、Ｚは、ＣＨ_２＝ＣＨ−ＣＯＯ−、ＣＨ_２＝Ｃ（ＣＨ_３）−ＣＯＯ−、ＣＨＲ^Ｘ＝ＣＨ−ＣＯＯ−、ＣＨ_２＝Ｃ（ＣＨ_２Ｒ^Ｘ）−ＣＯＯ−又はＣＨ_２＝ＣＲ^Ｘ−ＣＨ_２ＣＯＯ−を示し、Ｒ^Ｘは、前記構造（Ｉ）又はアルキルエステル基を示し、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ^１４−を示し、Ｒ^１４は水素原子又はアルキル基を示し、Ｒ^１〜Ｒ^６は前記と同義である。）

(In the formula, Z is CH ₂ ═CH—COO—, CH ₂ ═C (CH ₃ ) —COO—, CHR ^X = CH—COO—, CH ₂ ═C (CH ₂ R ^X ) —COO— or CH ₂ = CR ^X —CH ₂ COO—, R ^X represents the structure (I) or an alkyl ester group, X represents —O—, —S— or —NR ¹⁴ —, and R ¹⁴ represents a hydrogen atom. Or an alkyl group is shown, and R ^{1 to} R ⁶ are as defined above.)

In Z, CH ₂ ═CH—COO— is an acryloyloxy group, and CH ₂ ═C (CH ₃ ) —COO— is a methacryloyloxy group.
CH (CH ₃ ) ═CH—COO— is a crotonoyloxy group (ethylenically unsaturated bond is trans-type) or an isocrotonoyloxy group (ethylenically unsaturated bond is cis-type).
CHR ^X = CH-COO- is a maleoyloxy group (ethylenically unsaturated bond is cis type) or a fumaroyloxy group (ethylenically unsaturated bond is trans), wherein the carboxy group is substituted with the structure (I) or an alkyl ester group. Type).
Structure in R ^X (I) is as defined above. R ^X preferably has the same structure as the group to which Z is bonded. For example, in the case of the compound represented by formula (11), R ^X is preferably a group represented by —CR ¹ R ² —OR ³ .
The alkyl ester group in R ^X is represented by —COOR ^X1 . R ^X1 represents an alkyl group. As the alkyl group for R ^X1 , an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is particularly preferable.
^{_{CH 2 = C (CH 2 R}} X) -COO- or _CH 2 ⁼ CR _X -CH 2 COO- is a itaconoyloxy alkanoyloxy group carboxy group is substituted on the structure (I) or an alkyl ester group. R ^X is the same as described above.
Z is preferably CH ₂ ═CH—COO— or CH (CH ₃ ) ═CH—COO—.

  Examples of the monomer (m1) include those shown below.

(Structural unit (u2))
The structural unit (u2) has a structure in which the ethylenically unsaturated bond of the monomer (m2) is cleaved to form a single bond.
The number of polysiloxane groups and ethylenically unsaturated bonds that the monomer (m2) has in the molecule is not particularly limited, and may be one or two or more.
As the monomer (m2), a monomer having a divalent polysiloxane group and an ethylenically unsaturated bond-containing group bonded to both ends thereof (hereinafter referred to as “both terminal polysiloxane” is used as the monomer (m2). A monomer having a monovalent polysiloxane group and an ethylenically unsaturated bond-containing group bonded to one end thereof (hereinafter also referred to as “one-end polysiloxane macromonomer”) is preferable. . Any one of these may be used alone or in combination.
Examples of the both-end polysiloxane macromonomer include monomers represented by the following formula (m2-1) or (m2-2).
As a single terminal polysiloxane macromonomer, the monomer represented, for example by a following formula (m2-3) or (m2-4) is mentioned.
Therefore, the monomer (m2) is represented by the monomer represented by the following formula (m2-1), the monomer represented by the formula (m2-2), and the formula (m2-3). At least one selected from the group consisting of a monomer and a monomer represented by the formula (m2-4) is preferable.

^{_{CH 2 = CR 1a -CO-O-}} (C k H 2k -O) l -C m H 2m - (SiR 1b R 1c -O) n -SiR 1d R 1e -C о H 2о - (O-C p ^{_{H 2p) q -O-CO-}} CR 1f = CH 2 ··· (m2-1)
^{_{CH 2 = CR 2a -CO-O-}} (C k 'H 2k' -O) l '-C m' H 2m '-Si ((OSiR 2b R 2c) r -OSiR 2d R 2e R 2f) 2 -OSi _{^{((OSiR 2g R 2h) s}} -OSiR 2i R 2j R 2k) 2 -C о 'H 2о' - (O-C p 'H 2p') q '-O-CO-CR 2l = CH 2 ··· (M2-2)
^{_{CH 2 = CR 3a -CO-O-}} (C u H 2u -O) v -C w H 2w - (SiR 3b R 3c -O) x -SiR 3d R 3e R 3f ··· (m2-3)
^{_{CH 2 = CR 4a -CO-O-}} (C u 'H 2u' -O) v '-C w' H 2w '-Si (OSiR 4b R 4c R 4d) 3 ··· (m2-4)

In formula (m2-1), R ^1a and R ^1f are each a hydrogen atom or a methyl group, k and p are each an integer of 2 to 5, l and q are each 0 to 50, m and o are each 2 to 5 An integer, n is 3 to 80, and R ^{1b to} R ^1e are each an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group.
Wherein ^(m2-2), respectively ^{R 2a} and ^{R 2l} is a hydrogen atom or a methyl group, k 'and p' is 2-5 each an integer, l 'and q' respectively 0 to 50, m 'and o' Are each an integer of 2 to 5, r and s are each 0 to 20, and R ^{2b to} R ^2k are each an alkyl group.
In formula (m2-3), R ^3a is a hydrogen atom or a methyl group, u is an integer of 2 to 5, v is 0 to 50, w is an integer of 2 to 5, x is ^{3 to} 80, R ^{3b to} R ^3f Represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group or a substituted phenoxy group, respectively.
In formula (m2-4), R ^4a is a hydrogen atom or a methyl group, u ′ is an integer of 2 to 5, v ′ is 0 to 50, w ′ is an integer of 2 to 5, and R ^{4b to} R ^4d are alkyls, respectively. _{^{group, - (OSiR 51 R 52)}} y -OSiR 53 R 54 R 55 ( where, y is an integer of 0 to ^20, R 51 ^{to R 55} represents an alkyl group.), or ^R 56 - _(OC 2 H _{4) y '-OR} ⁵⁷ (where, y' denotes the integer of 1 to ^20, each ^{R 56} and ^{R 57} alkyl group.) shows a.

In formula (m2-1), l and q are the average degree of polymerization of the polyether structure. If l and q are 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. l and q may be 0, but are preferably larger than 0 because recoatability with the old coating film tends to be good. l and q are preferably 3 to 25, and more preferably 5 to 20.
k and p are integers of 2 to 5, and 2 or 3 is preferable from the viewpoint of inexpensiveness. It is also possible to use those having k and p of 2 and 3.
m and o are integers of 2 to 5, and 2 or 3 is preferable.
n and ^R 1b ^{to R 1e} is similar to n and ^R 1b ^{to R 1e} of each of the formula (i), preferable embodiments thereof are also the same.
Note that R ^{1a to} R ^1f , k, l, m, n, o, p, and q are independent of each other, and may be different when the same symbol exists in or between molecules.

Specific examples of the monomer represented by the formula (m2-1) include, for example, FM-7711, FM-7721, FM-7725 (trade name, manufactured by Chisso Corporation) where l and q are 0. ), F2-311-02 (trade name) manufactured by Toray Dow Corning. Examples of those in which l and q are larger than 0 include F2-354-04 (trade name) manufactured by Toray Dow Corning.
As the monomer represented by the formula (m2-1), one type may be used alone, or a plurality of types may be used in combination.

In the formula (m2-2), l ′ and q ′ are the average degree of polymerization of the polyether structure. If l ′ and q ′ are 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. l ′ and q ′ may be 0, but are preferably larger than 0 because recoatability with the old coating film tends to be good. l ′ and q ′ are preferably 3 to 25, and more preferably 5 to 20.
k ′ and p ′ are integers of 2 to 5, and 2 or 3 is preferable from the viewpoint of inexpensiveness. It is also possible to use a combination of k ′ and p ′ of 2 and 3.
m ′ and o ′ are integers of 2 to 5, and 2 or 3 is preferable.
r, s and ^R 2b ^{to R 2k} is the same as each r in formula (ii), s and ^R 2b ^{to R 2k,} preferable embodiments thereof are also the same.
R ^{2a to} R ²¹ , k ′, l ′, m ′, n ′, o ′, p ′, q ′, r, and s are each independent, and the same code exists in or between molecules. If so, they may be different.

Specific examples of the monomer represented by the formula (m2-2) include, for example, F2-212-01 (trade name) manufactured by Toray Dow Corning Co., Ltd., assuming that l ′ and q ′ are 0. It is done. Examples of those in which l ′ and q ′ are greater than 0 include F2-212-04 (trade name) manufactured by Toray Dow Corning.
The monomer represented by the formula (m2-2) may be used alone or in combination of two or more.

In formula (m2-3), v is the average degree of polymerization of the polyether structure. If v is 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. v may be 0, but it is preferably larger than 0 because recoatability with the old coating film tends to be good. v is preferably from 3 to 25, more preferably from 5 to 20.
u is an integer of 2 to 5, and 2 or 3 is preferable from the viewpoint of low cost. It is also possible to use a combination of u 2 and 3.
w is an integer of 2 to 5, and 2 or 3 is preferable.
x and ^R 3b ^{to R 3f} are the same as x and ^R 3b ^{to R 3f} of each of the formula (iii), a preferable embodiment thereof is also the same.
In addition, R < ^3a > -R <^3f> , u, v, w, and x are respectively independent, and when the same code | symbol exists in a molecule | numerator or between molecules, they may differ.

Specific examples of the monomer represented by the formula (m2-3) include, for example, FM-0711, FM-0721, FM-0725 (trade name) manufactured by Chisso Corporation, where v is 0. X-24-8201, X-22-174DX, X-22-2426 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. and the like can be mentioned. Examples of v larger than 0 include Toray Dow Corning F2-254-04, F2-254-14 (trade name), and the like.
The monomer represented by the formula (m2-3) may be used alone or in combination of two or more.

In formula (m2-4), v ′ is the average degree of polymerization of the polyether structure. If v 'is 50 or less, the water resistance of the coating film tends to be good. In particular, it is preferably 30 or less because of excellent recoatability with the old coating film. v ′ may be 0, but is preferably larger than 0 because recoatability with the old coating film tends to be good. v ′ is preferably from 3 to 25, and more preferably from 5 to 20.
u ′ is an integer of 2 to 5, and 2 or 3 is preferable from the viewpoint of low cost. It is possible to use a combination of u ′ of 2 and 3.
w ′ is an integer of 2 to 5, and 2 or 3 is preferable.
R ^4b to R ^4d are each same as ^R 4b ^{to R 4d} in the formula (iv), preferable embodiments thereof are also the same.
Note that R ^{4a to} R ^4d , u ′, v ′, w ′, y, and y ′ are each independent, and they may be different when the same symbol exists in or between molecules.

Specific examples of the monomer represented by the formula (m2-4) include, for example, those having v ′ of 0, TM-0701 (trade name) manufactured by Chisso Corporation, and X-22-2 manufactured by Shin-Etsu Chemical Co., Ltd. 2404 (trade name), F2-250-01 manufactured by Toray Dow Corning, F2-302-01 (above, trade name), and the like. Examples of v 'greater than 0 include F2-302-04 (trade name) manufactured by Toray Dow Corning.
As the monomer represented by the formula (m2-4), one type may be used alone, or a plurality of types may be used in combination.

The structural unit (u2) is preferably composed of only a structural unit derived from a single-terminal polysiloxane macromonomer in terms of crack resistance and adhesion to a substrate.
The structural unit (u2) preferably includes a structural unit derived from a polysiloxane macromonomer at both ends and a structural unit derived from a polysiloxane macromonomer at one end in terms of recoatability.

  When the structural unit (u2) includes a structural unit derived from a polysiloxane macromonomer at both ends and a structural unit derived from a polysiloxane macromonomer at one end, the ratio of the structural units derived from the polysiloxane macromonomer at both ends / single terminal The structural unit derived from polysiloxane macromonomer = 1/99 to 80/20 (molar ratio) is preferable, and 3/97 to 60/40 is more preferable. If the ratio of the structural unit derived from the polysiloxane macromonomer at both ends is 80/20 or less, a coating film excellent in crack resistance and adhesion to the substrate tends to be obtained. If the ratio of the structural units derived from the polysiloxane macromonomer at both ends is 1/99 or more, the long-term antifouling property and recoatability of the formed coating film tend to be better.

(Structural unit (u3))
The structural unit (u3) is a structural unit other than the structural unit (u1) and the structural unit (u2). That is, the structural unit does not contain the structure (I) and the polysiloxane group.
As the structural unit (u3), structural units derived from the monomer (m3) having an ethylenically unsaturated bond and not containing the structure (I) and the polysiloxane group can be mentioned. Such a structural unit has a structure in which the ethylenically unsaturated bond of the monomer (m3) is cleaved to form a single bond.

Examples of the monomer (m3) include the following.
Substituted or unsubstituted alkyl (meth) acrylate [e.g., methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i -Butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 1-methyl-2-methoxyethyl ( Meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate], substituted or unsubstituted aralkyl (meth) acrylate [eg benzyl (meth) acrylate, m-methoxyphenyl ethyl( ) Acrylate, p-methoxyphenylethyl (meth) acrylate], substituted or unsubstituted aryl (meth) acrylate [eg, phenyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) Acrylate, o-methoxyphenylethyl (meth) acrylate], alicyclic (meth) acrylate [eg, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate], trifluoroethyl (meth) acrylate, perfluorooctyl (meth) Hydrophobic group-containing (meth) acrylic acid ester monomers such as acrylate and perfluorocyclohexyl (meth) acrylate;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, butoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate , Oxyethylene group-containing (meth) acrylic acid ester monomers such as phenoxyethyl (meth) acrylate and 2- (2-ethylhexaoxy) ethyl (meth) acrylate;
Hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and glycerol (meth) acrylate;
Single-terminal alkoxyallylated polyether such as methoxypolyethylene glycol allyl ether, methoxypolypropylene glycol allyl ether, butoxypolyethylene glycol allyl ether, butoxypolypropylene glycol allyl ether, methoxypolyethylene glycol-polypropylene glycol allyl ether, butoxypolyethylene glycol-polypropylene glycol allyl ether Mer;
Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, 3,4-epoxybutyl (meth) acrylate;
Primary or secondary amino group-containing vinyl monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide;
Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl Tertiary amino group-containing vinyl monomers such as (meth) acrylamide;
Heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole;
Trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, tri-n-propylsilyl (meth) acrylate, tri-n-butylsilyl (meth) acrylate, tri-n-amylsilyl (meth) acrylate, tri-n-hexylsilyl (Meth) acrylate, tri-n-octylsilyl (meth) acrylate, tri-n-dodecylsilyl (meth) acrylate, triphenylsilyl (meth) acrylate, tri-p-methylphenylsilyl (meth) acrylate, tribenzylsilyl (Meth) acrylate, triisopropylsilyl (meth) acrylate, triisobutylsilyl (meth) acrylate, tri-s-butylsilyl (meth) acrylate, tri-2-methylisopropylsilyl (meth) acrylate, Li-t-butylsilyl (meth) acrylate, ethyldimethylsilyl (meth) acrylate, n-butyldimethylsilyl (meth) acrylate, diisopropyl-n-butylsilyl (meth) acrylate, n-octyldi-n-butylsilyl (meth) acrylate, Diisopropylstearylsilyl (meth) acrylate, dicyclohexylphenylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, lauryldiphenylsilyl (meth) acrylate, triisopropylsilylmethyl malate, triisopropylsilylamyl malate, tri- n-butylsilyl-n-butylmalate, t-butyldiphenylsilylmethylmalate, t-butyldiphenylsilyl-n-butylmalate, triisopropylsilane Contains organosilyl groups such as rumethyl fumarate, triisopropylsilyl amyl fumarate, tri-n-butylsilyl-n-butyl fumarate, t-butyldiphenylsilylmethyl fumarate, t-butyldiphenylsilyl-n-butyl fumarate Vinyl monomer;
Acid anhydride group-containing vinyl monomers such as maleic anhydride and itaconic anhydride;
Methacrylic acid, acrylic acid, crotonic acid, vinyl benzoic acid, fumaric acid, itaconic acid, maleic acid, citraconic acid, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monomethyl itaconate, monoethyl itaconate, Monobutyl itaconate, monooctyl itaconate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monooctyl fumarate, monoethyl citraconic acid, monohydroxyethyl tetrahydrophthalate (meth) acrylate, monohydroxypropyl tetrahydrophthalate (meth) Acrylate, monohydroxybutyl (meth) acrylate tetrahydrophthalate, monohydroxyethyl phthalate (meth) acrylate, monohydroxypropyl phthalate (meth) acrylate Carboxyl group-containing ethylenic unsaturation such as relate, monohydroxyethyl (meth) acrylate succinate, monohydroxypropyl (meth) acrylate succinate, monohydroxyethyl (meth) acrylate maleate, monohydroxypropyl maleate (meth) acrylate Monomer;
Unsaturated dicarboxylic acid diester monomers such as dimethyl malate, dibutyl malate, dimethyl fumarate, dibutyl fumarate, dibutyl itaconate, diperfluorocyclohexyl fumarate;
Cyano group-containing vinyl monomers such as acrylonitrile and methacrylonitrile;
Vinyl ether monomers such as alkyl vinyl ethers [eg, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, 2-ethylhexyl vinyl ether, etc.], cycloalkyl vinyl ethers [eg, cyclohexyl vinyl ether, etc.];
Vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene;
Halogenated olefins such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and chlorotrifluoroethylene;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl methacrylate, triallyl cyanurate, diallyl maleate, polypropylene glycol diallyl ether, etc. Polyfunctional monomers;
Macromonomer; etc.
These can be used by appropriately selecting one or two or more as necessary.

Examples of the macromonomer include compounds having two or more structural units derived from monomers having an ethylenically unsaturated bond-containing group and having an ethylenically unsaturated bond-containing group. Two or more structural units of the macromonomer may be the same or different.
Examples of the ethylenically unsaturated bond-containing group include CH ₂ ═C (COOR) —CH ₂ —, (meth) acryloyl group, 2- (hydroxymethyl) acryloyl group, vinyl group and the like. Here, R represents a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted alicyclic group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted group. The heterocyclic group which has is shown. Examples of the substituent include an alkyl group (except when R is an alkyl group having a substituent), an aryl group, -COOR ⁶¹ , a cyano group, -OR ⁶² , -NR ⁶³ R ⁶⁴ , -CONR ^65. Examples thereof include at least one selected from the group consisting of R ⁶⁶ , a halogen atom, an allyl group, an epoxy group, a siloxy group, and a group exhibiting hydrophilicity or ionicity. Here, R < ⁶¹ > -R < ⁶⁶ > shows a hydrogen atom, an alkyl group, an alicyclic group, or an aryl group each independently.
As the monomer having an ethylenically unsaturated bond-containing group, for example, various monomers mentioned above as examples of the monomer (m3) can be used (excluding the macromonomer).
Specific examples of the macromonomer include monomers disclosed in International Publication No. 2013/108880.

  The monomer (m3) is a monofunctional monomer having one ethylenically unsaturated bond from the viewpoint that when the copolymer (A) is dissolved in a solvent, it is easy to have a low viscosity even at a high solid content. Preferably, the ethylenically unsaturated bond is particularly preferably derived from an acryloyl group. That is, the monomer (m3) is particularly preferably a monofunctional monomer having one acryloyl group.

The structural unit (u3) has a hydrophobic group-containing (meta) property in that the flexibility or / and crack / peeling resistance of the coating film to be formed and the long-term self-polishing property can be improved in a good balance. ) It is preferable to include a structural unit derived from an acrylate monomer.
As the hydrophobic group-containing (meth) acrylic acid ester monomer, alkyl (meth) acrylate is preferable.

The structural unit (u3) preferably includes a structural unit derived from an oxyethylene group-containing (meth) acrylic acid ester monomer in terms of solubility and crack resistance of the coating film to be formed.
As the oxyethylene group-containing (meth) acrylic acid ester monomer, a compound represented by the following formula (3-1) is preferable.
^{_{Z 1 - (CH 2 CH 2}} O) n R 21 (3-1)
(In the formula, Z ¹ represents an acryloyloxy group or a methacryloyloxy group, R ²¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group, and n represents an integer of 1 to 15)

In Formula (3-1), when Z ¹ is an acryloyloxy group or a methacryloyloxy group, the hydrolysis rate tends to be faster in the case of acryloyloxy group, and is arbitrarily selected according to the dissolution rate. can do.
Examples of the alkyl group having 1 to 10 carbon atoms and the aryl group in R ²¹ are the same as those described above for R ¹ and R ³ .
n is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably an integer of 1 to 3, and particularly preferably 1 or 2, from the viewpoint of water resistance and crack resistance.

(Content of each structural unit)
1-80 mass% is preferable with respect to the sum total (100 mass%) of all the structural units, and, as for content of the structural unit (u1) in a copolymer (A), 10-70 mass% is more preferable, and 20-60. More preferred is mass%. If content of a structural unit (u1) is more than the lower limit of the said range, the self-polishing property of the coating film formed will be more excellent. If the content of the structural unit (u1) is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. It will be a thing.

  The content of the structural unit (u2) in the copolymer (A) is preferably from 1 to 80 mass%, more preferably from 5 to 70 mass%, more preferably from 10 to 60, based on the total (100 mass%) of all the structural units. More preferred is mass%. If content of a structural unit (u2) is more than the lower limit of the said range, the antifouling property of the coating film formed will be more excellent. If content of a structural unit (u2) is below the upper limit of the said range, crack resistance will be more excellent.

  In the copolymer (A), the content of the structural unit derived from the polysiloxane macromonomer at both terminals is preferably 30% by mass or less, more preferably 25% by mass or less, based on the total of all the structural units (100% by mass). 20 mass% or less is more preferable. If the content of the structural unit derived from the polysiloxane macromonomer at both ends is not more than the above upper limit value, the copolymer tends to be obtained without proceeding to gelation by crosslinking during the production of the copolymer (A). Moreover, it exists in the tendency for the viscosity of the solution of a copolymer (A) to become low.

  The content of the structural unit (u3) is preferably 0 to 98% by weight, more preferably 5 to 85% by weight, and still more preferably 10 to 70% by weight with respect to the total of all the structural units (100% by weight).

  When the copolymer (A) has a structural unit derived from an oxyethylene group-containing (meth) acrylic acid ester monomer, the content of the structural unit is 1 to 80% by mass relative to the total of all the structural units. Is preferable, 5-60 mass% is more preferable, and 20-50 mass% is more preferable. When the content of the structural unit is not less than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.

  The copolymer (A) has a structural unit derived from a monomer (m3) other than the oxyethylene group-containing (meth) acrylate monomer, such as a hydrophobic group-containing (meth) acrylate monomer. In this case, the content of the structural unit is preferably 1 to 90% by mass and more preferably 10 to 80% by mass with respect to the total of all the structural units. When the content of this structural unit is within the above range, the flexibility and crack resistance / peeling resistance of the coating film to be formed become higher, and the antifouling effect becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.

The total of the structural unit (u1), the structural unit (u2), and the structural unit (u3) is 100% by mass.
Content (mass%) of each structural unit in a copolymer can be measured by well-known methods, such as a gas chromatography, a high performance liquid chromatography, and a nuclear magnetic resonance spectrum method.

The copolymer (A) is preferably a copolymer obtained by polymerizing a monomer mixture containing the monomer (m1) and the monomer (m2). In such a copolymer, a monomer mixture containing a monomer (m0) having an ethylenically unsaturated bond and a carboxy group and a monomer (m2) is polymerized to obtain a copolymer having a carboxy group. Compared with the copolymer obtained by obtaining the polymer (A0) and converting the carboxy group of the copolymer (A0) into the structure (I), the water resistance is more excellent.
The monomer mixture is preferably composed of 1 to 80% by mass of monomer (m1), 1 to 80% by mass of monomer (m2), and 0 to 98% by mass of monomer (m3). . The content of each monomer is a ratio with respect to the total amount of the monomer mixture. The range of the more preferable content of each monomer is the same as the range of the preferable content of the structural unit derived from each monomer.

The weight average molecular weight (Mw) of the copolymer (A) is preferably from 2,000 to 100,000, more preferably from 3,000 to 80,000, and even more preferably from 5,000 to 60,000.
If the weight average molecular weight of the copolymer (A) is less than or equal to the upper limit of the above range, the viscosity of the solution obtained by dissolving the copolymer (A) in a solvent will be lower, and the anti-fouling coating composition will have a low high solid content. Viscosity is easy to obtain. Moreover, the antifouling property of the coating film formed is excellent. If a weight average molecular weight is more than the lower limit of the said range, the hardness and durability of the coating film formed will be more excellent.

The number average molecular weight (Mn) of the copolymer (A) is preferably from 1,000 to 50,000, more preferably from 2,000 to 40,000.
The polydispersity (Mw / Mn) of the copolymer (A) is preferably 1.5 to 5.0, and more preferably 2.2 to 3.0.
The weight average molecular weight and the number average molecular weight of the copolymer (A) are each measured by gel filtration chromatography (GPC) using polystyrene as a reference resin.

(Production method of copolymer (A))
Examples of the method for producing the copolymer (A) include the following production methods (α) and (β).
Production method (α): A method of polymerizing a monomer mixture containing the monomer (m1) and the monomer (m2).
Production method (β): a monomer mixture containing a monomer (m0) having an ethylenically unsaturated bond and a carboxy group and a monomer (m2), and a copolymer having a carboxy group ( A0) is obtained, and the carboxy group of the copolymer (A0) is converted to the structure (I).

"Manufacturing method (α)"
Monomer mixture:
The monomer mixture used in the production method (α) includes at least the monomer (m1) and the monomer (m2), and may further include the monomer (m3).

  As for content of the monomer (m1) in a monomer mixture, 1-80 mass% is preferable with respect to the total mass (100 mass%) of all the monomers. That is, the copolymer (A) is obtained by polymerizing a monomer mixture containing 1 to 80% by mass (charge amount) of the monomer (m1) with respect to the total mass of all monomers. Preferably there is. As for content of a monomer (m1), 10-70 mass% is more preferable, and 20-60 mass% is further more preferable. If content of a monomer (m1) is more than the lower limit of the said range, the self-polishing property of the coating film formed will be more excellent. If the content of the monomer (m1) is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. It will be.

  The content of the monomer (m2) in the monomer mixture is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, and 10 to 60% by mass with respect to the total mass of all monomers. Further preferred. If content of a monomer (m2) is more than the lower limit of the said range, the antifouling property of the coating film formed will be more excellent. If content of a monomer (m2) is below the upper limit of the said range, crack resistance will be more excellent.

  The content of the both-end polysiloxane macromonomer in the monomer mixture is preferably 30% by mass or less, more preferably 25% by mass or less, and still more preferably 20% by mass or less based on the total mass of all monomers. If the content of the both-end polysiloxane macromonomer is not more than the above upper limit value, a copolymer tends to be obtained without proceeding to gelation by crosslinking during polymerization of the monomer mixture. Moreover, it exists in the tendency for the viscosity of the solution of the obtained copolymer (A) to become low.

  The content of the monomer (m3) in the monomer mixture is preferably 0 to 98% by mass, more preferably 5 to 85% by mass, and 10 to 70% by mass with respect to the total mass of all monomers. Further preferred.

  When the monomer mixture contains an oxyethylene group-containing (meth) acrylic acid ester monomer, the content of this monomer is preferably 1 to 80% by mass relative to the total mass of all monomers, 5-60 mass% is more preferable, and 20-50 mass% is further more preferable. If the content of this monomer is not less than the lower limit of the above range, the hydrophilicity of the formed coating film becomes higher and the self-polishing property becomes more excellent. If the content of this structural unit is less than or equal to the upper limit of the above range, the formed coating film has moderate hydrolyzability, maintains self-polishing properties over a long period of time, and has a better antifouling effect. Become.

When the monomer mixture contains a monomer (m3) other than the oxyethylene group-containing (meth) acrylate monomer, such as a hydrophobic group-containing (meth) acrylate monomer, this monomer The content of is preferably 1 to 90% by mass and more preferably 10 to 80% by mass with respect to the total mass of all monomers.
The total of the monomer (m1), the monomer (m2), and the monomer (m3) (including the case where the monomer (m3) is not included) is 100% by mass.

The monomer (m1), the monomer (m2), and the monomer (m3) can each be purchased as a commercial product, or can be appropriately synthesized using a known method.
The monomer (m1) can be synthesized by converting the carboxy group of the monomer (m0) having an ethylenically unsaturated bond and a carboxy group into the structure (I).
Examples of the monomer (m0) include (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, monomethyl maleate, monomethyl fumarate, and the like.

  Examples of the method for converting the carboxy group of the monomer (m0) into the structure (I) include, for example, the monomer (m0), a compound represented by the following formula (31), and the following formula (32). Examples include a method of reacting (addition reaction) a compound and at least one compound (B) selected from the group consisting of the compound represented by the following formula (33). You may use a compound (B) individually or in combination of 2 or more types.

（式中、Ｘは−Ｏ−、−Ｓ−又は−ＮＲ^１４−を示し、Ｒ^１４は水素原子又はアルキル基を示し、Ｒ^７は、水素原子又は炭素数１〜９のアルキル基を示し、Ｒ^８は、水素原子又は炭素数１〜１０のアルキル基を示し、Ｒ^９及びＲ^１１はそれぞれ、炭素数１〜２０のアルキル基、シクロアルキル基又はアリール基を示し、Ｒ^１０は、単結合、又は炭素数１〜９のアルキレン基を示し、Ｒ^１２は、炭素数１〜９のアルキレン基を示す。）

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁹ and R ¹¹ each represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms, and R ¹⁰ represents a single bond Or an alkylene group having 1 to 9 carbon atoms, and R ¹² represents an alkylene group having 1 to 9 carbon atoms.)

When the compound represented by the formula (31) is used as the compound (B), as the monomer (m1), R ¹ in the formula (11) is CH ₂ R ⁷ , R ² is R ⁸ , and R ³ is A compound of R ⁹ is obtained.
In formula (31), the alkyl group having 1 to 9 carbon atoms in R ⁷ is the same as the alkyl group having 1 to 10 carbon atoms in R ¹ except that the number of carbon atoms is 9 or less.
R ⁸ and R ⁹ are the same as R ² and R ³ in the formula (11), respectively.

Examples of the compound represented by the formula (31) include 1-alkenylalkyl ether in which X in the formula (31) is —O—, and 1-alkenylalkyl in which X in the formula (31) is —S—. Examples thereof include sulfide and 1-alkenyldialkylamine in which X in formula (31) is —NR ¹⁴ —. Examples of 1-alkenyl alkyl ethers include vinyl ethers such as alkyl vinyl ethers (eg, ethyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether), and cycloalkyl vinyl ethers (eg, cyclohexyl vinyl ether). 1-propenyl ethers such as ethyl-1-propenyl ether; 1-butenyl ethers such as ethyl-1-butenyl ether; and the like. Examples of 1-alkenylalkyl sulfide include 1- (ethenylthio) ethane, 1- (ethenylthio) propane, 1- (ethenylthio) butane, 2- (ethenylthio) butane, 1- (ethenylthio) -2-methylpropane, 1 1-alkenyl alkyl sulfides such as-(propylthio) -1-propene and 2- (propylthio) -1-propene; Examples of 1-alkenyldialkylamine include 1-alkenyldialkylamines such as N, N-dimethylethenamine, N-methyl-N-ethylethenamine, N, N-diethylethenamine, and N-vinylpyrrolidine. .
Among these, 1-alkenyl alkyl ether is preferable, and vinyl ethers and 1-propenyl ethers are more preferable.

When the compound represented by the formula (32) is used as the compound (B), a compound in which R ⁴ in the formula (12) is CH ₂ —R ¹⁰ is obtained as the monomer (m1).
In formula (32), the alkylene group having 1 to 9 carbon atoms in R ¹⁰ is the same as R ⁴ except that the number of carbon atoms is 9 or less.

Examples of the compound represented by the formula (32) include dihydrofurans such as 2,3-dihydrofuran and 5-methyl-2,3-dihydrofuran; 3,4-dihydro-2H-pyran, 5,6 Dihydropyrans such as dihydro-4-methoxy-2H-pyran; dihydrothiophenes such as 2,3-dihydrothiophene; dihydrothiopyrans such as 3,4-dihydro-2H-thiopyran; 2,3-dihydro- Dihydropyrroles such as 1-methylpyrrole; tetrahydropyridines such as 1,2,3,4-tetrahydro-1-methylpyridine; and the like.
Of these, dihydrofurans and dihydropyrans are preferable, and dihydropyrans are more preferable.

When a compound represented by the formula (33) is used as the compound (B), a compound in which R ⁵ in the formula (13) is R ¹¹ and R ⁶ is CH ₂ -R ¹² as the monomer (m1). Is obtained.
In formula (33), R ¹¹ is the same as R ⁵ . R ¹² is the same as R ⁶ except that the number of carbon atoms is 9 or less.

Examples of the compound represented by the formula (33) include 1-methoxy-1-cyclopentene, 1-methoxy-1-cyclohexene, 1-methoxy-1-cycloheptene, 1-ethoxy-1-cyclopentene, 1-ethoxy- 1-alkoxy-1-cycloalkylenes such as 1-cyclohexene, 1-butoxy-1-cyclopentene, 1-butoxy-1-cyclohexene; 1-alkoxy having substituents such as 1-ethoxy-3-methyl-1-cyclohexene -1-cycloalkylenes; 1- (alkylthio) -1-cycloalkylenes such as 1- (methylthio) -1-cyclopentene and 1- (methylthio) -1-cyclohexene; 1- (1-pyrrolidinyl) -1- 1- (1-pyrrolidinyl) such as cyclopentene, 1- (1-pyrrolidinyl) -1-cyclohexene 1-cycloalkylene ethers; and the like.
Compound (B) can be purchased commercially or synthesized as appropriate.

The reaction between the monomer (m0) and the compound (B) proceeds under relatively mild conditions. For example, the desired product can be obtained by reacting in the presence or absence of an acidic catalyst such as hydrochloric acid, sulfuric acid, phosphoric acid or the like at a reaction temperature of 40 to 100 ° C. for 5 to 10 hours.
After completion of the reaction, the objective monomer can be recovered by distillation under reduced pressure under predetermined conditions.

Polymerization of monomer mixture:
As a polymerization method of the monomer mixture, for example, a known polymerization method such as a solution polymerization method, a suspension polymerization method, a bulk polymerization method, and an emulsion polymerization method can be applied. The solution polymerization method is preferable in terms of productivity and coating film performance.
The polymerization may be performed by a known method using a known polymerization initiator. For example, a method of reacting the above monomer mixture in the presence of a radical initiator at a reaction temperature of 60 to 120 ° C. for 4 to 14 hours can be mentioned. In the polymerization, a chain transfer agent may be used as necessary.

Known radical initiators can be used, for example, 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methyl). Butyronitrile), benzoyl peroxide, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate and the like.
The content of the polymerization initiator is not particularly limited and can be set as appropriate. Typically, it is about 0.1-20 mass parts with respect to 100 mass parts of polymerizable monomers.

As the chain transfer agent, known ones can be used, and examples thereof include mercaptans such as n-dodecyl mercaptan, thioglycolic acid esters such as octyl thioglycolate, α-methylstyrene dimer, terpinolene and the like.
The content of the chain transfer agent is not particularly limited and can be set as appropriate. Typically, it is about 0.0001-10 mass parts with respect to 100 mass parts of polymerizable monomers.

  As a solvent used in the solution polymerization, for example, a general organic solvent such as toluene, xylene, methyl isobutyl ketone, n-butyl acetate can be used.

"Manufacturing method (β)"
In the production method (β), first, a monomer mixture containing the monomer (m0) and the monomer (m2) is polymerized to obtain a copolymer (A0) having a carboxy group. The monomer mixture may further contain a monomer (m3).
The monomer (m0), monomer (m2), and monomer (m3) are the same as described above.
The preferable ranges of the contents of the monomer (m0) and the monomer (m2) in the monomer mixture are the monomer (m1) and the monomer in the monomer mixture in the production method (α). (M2) It is the same as the preferable range of each content. The preferable range of the content of the oxyethylene group-containing (meth) acrylic acid ester monomer and other monomers (m3) is the same as described above.
Polymerization of the monomer mixture can be carried out in the same manner as in the production method (α).

Next, the copolymer (A) is obtained by converting the carboxy group of the copolymer (A0) into the structure (I).
Examples of the method for converting the carboxy group of the copolymer (A0) into the structure (I) include a method in which the copolymer (A0) and the compound (B) are reacted (addition reaction).
The reaction between the copolymer (A0) and the compound (B) can be carried out in the same manner as the reaction between the monomer (m0) and the compound (B).

(Function and effect)
Since the copolymer (A) has a structure (I) in which a carboxy group is protected by a specific group, it can be hydrolyzed in seawater or the like. Therefore, the coating film containing the copolymer (A) exhibits self-polishing properties in seawater or the like. That is, the copolymer (A) has the structure (I) and does not dissolve in seawater in this state, but when the structure (I) is hydrolyzed by contact with seawater, a carboxy group or the like is generated, Dissolves in seawater. The coating surface gradually dissolves in seawater and is renewed (self-polishing).
Further, since the copolymer (A) has a polysiloxane group, marine organisms and other dirt are difficult to adhere to the surface of the coating film. Therefore, the coating film containing the copolymer (A) exhibits an excellent antifouling effect even when the antifouling agent is not included. When the antifouling agent is included, the surface of the coating film is renewed, so that the antifouling agent is always exposed on the surface of the coating film, and the antifouling effect by the antifouling agent is stably exhibited over a long period of time.
In addition, since the copolymer (A) has the structure (I) as a hydrolyzable structure, the coating (A) is more coated than the case of using a copolymer having a structure containing a divalent metal as the hydrolyzable structure. Excellent water resistance of the film. In particular, by combining a polysiloxane group with the structure (I), these effects become more excellent. This is considered to be due to the fact that the hydrophilicity of the coating film is lowered by the polysiloxane group, thereby suppressing the swelling and excessive dissolution of the coating film. Since the water resistance of the coating film is excellent, an excellent antifouling effect is stably exhibited over a long period of time.
The coating film has a sufficiently high hardness and is unlikely to cause damage or peeling of the coating film that causes a decrease in the antifouling effect. Also from this point, the excellent antifouling effect is stably exhibited over a long period of time.
The resin composition containing the copolymer (A) and the coating film of the antifouling coating composition also have the same effects as described above.
Further, the copolymer (A) can be made into a solution having a high solid content and a low viscosity when an organic solvent is added. If the resin composition containing the copolymer (A) and the organic solvent has a high solid content and a low viscosity, it is possible to apply paint without adding an organic solvent to the resin composition at the time of producing the antifouling coating composition. It is possible to obtain an antifouling paint composition having Further, when an antifouling agent or the like is added, it can be mixed well with the antifouling agent or the like without adding an organic solvent. Therefore, an antifouling paint composition having a low VOC content can be obtained.
Therefore, the copolymer (A) is suitable for an antifouling coating composition.

(Resin composition)
The second aspect of the present invention is a resin composition containing the copolymer (A). The copolymer (A) contained in the resin composition of this embodiment may be one type or two or more types.

Although content of the copolymer (A) in the resin composition of this aspect is not specifically limited, 45 mass% or more is preferable with respect to the whole quantity of a resin composition, 50 mass% or more is more preferable, 55 mass% The above is more preferable, 60% by mass or more is particularly preferable, and 64% by mass or more is most preferable. If content of a copolymer (A) is more than the said lower limit, an antifouling paint composition with little VOC content can be obtained easily.
The upper limit of content of a copolymer (A) is not specifically limited, 100 mass% may be sufficient. When the resin composition contains a solvent, an amount is preferably such that the viscosity of the resin composition measured with a B-type viscometer at 25 ° C. is less than 5,000 mPa · s (more preferably less than 3,000 mPa · s), Although it varies depending on the weight average molecular weight, glass transition temperature, presence or absence of a crosslinked structure, etc., the copolymer (A) is preferably 80% by mass or less, more preferably 85% by mass or less.

It is preferable that the resin composition of this embodiment further includes at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent. Thereby, the storage stability of the resin composition and the antifouling coating composition containing the resin composition is improved.
In the copolymer (A), the structure (I) may be unintentionally decomposed during storage. When structure (I) decomposes, a carboxylic acid is produced. As a result, the glass transition temperature of the copolymer (A) is increased, or the carboxylic acid and other components in the coating form a crosslinked structure, so that the viscosity of the solution of the copolymer (A) and the coating including the same is increased. Or rise. In addition, when free carboxylic acid is generated, dissolution stability and water resistance in an organic solvent are reduced. Further, the generated carboxylic acid catalyzes the hydrolysis reaction as an acid, whereby the structure (I) is further decomposed. By including a compound that reacts with an acid in the resin composition, when the structure (I) in the copolymer (A) is decomposed to produce a carboxylic acid, the carboxylic acid is captured by the compound that reacts with the acid. , Storage stability is improved.
Further, in the high pH region and the low pH region, the storage stability is lowered by promoting the decomposition of the structure (I). In the high pH region, the storage stability also decreases due to a decrease in the reactivity between the compound (B) and the carboxylic acid. By adjusting the pH of the resin composition by adding a basic compound or an acidic compound, decomposition of the structure (I) can be suppressed, and a decrease in storage stability can be suppressed.
In addition, moisture promotes decomposition (hydrolysis) of structure (I). By containing a dehydrating agent in the resin composition, moisture in the resin composition can be captured and deterioration in storage stability can be suppressed.

Examples of the compound that reacts with an acid include the aforementioned compound (B), a basic compound, and a compound having an epoxy group.
Examples of the basic compound include dimethylamine, diethylamine, trimethylamine, triethylamine, aniline, pyridine and the like.
Examples of the compound containing an epoxy group include 2-ethyloxirane, 2,3-dimethyloxirane, 2,2-dimethyloxirane, glycidyl (meth) acrylate, glycidyl α-ethylacrylate, and (meth) acrylic acid 3,4. -Epoxy butyl etc. are mentioned.
The compound that reacts with the acid is preferably the compound (B) from the viewpoint of storage stability. Among the compounds listed above, the compound (B) is preferably a 1-alkenyl alkyl ether in which X in the formula (31) is —O— in terms of more excellent storage stability. More preferred are vinyl ethers such as vinyl ether and isobutyl vinyl ether.

Examples of the basic compound for adjusting pH include the same compounds as those described above.
Acidic compounds include abietic acid, neoabietic acid, parastrinic acid, pimaric acid, isopimaric acid, levopimaric acid, dextropimaric acid, sandaracopimaric acid, acetic acid, propionic acid, butyric acid, lauric acid, stearic acid, linoleic acid, oleic acid Chloroacetic acid, fluoroacetic acid and the like.

  Examples of the dehydrating agent include silicate-based, isocyanate-based, orthoester-based, and inorganic-based materials. More specifically, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, orthoborate ester, tetraethyl orthosilicate, anhydrous gypsum, calcined gypsum, synthetic zeolite (molecular sieve) and the like can be mentioned. Molecular sieve is particularly preferable.

These additives can be used alone or in combination of two or more.
Examples of combinations of two or more additives include a combination of a compound (B) and a dehydrating agent, a combination of a compound (B), an acidic compound and a dehydrating agent, a compound (B), a basic compound, an acidic compound and a dehydrating agent. A combination with an agent, a combination of a basic compound and a dehydrating agent, and the like.

  When the compound (B) is contained in the resin composition, the content of the compound (B) in the resin composition is 20 mol% or more based on the structure (I) of the copolymer (A). Preferably, 30 to 1000 mol% is more preferable, and 40 to 800 mol% is more preferable. If content of a compound (B) is in the said range, the improvement effect of storage stability will be more excellent.

When the basic compound or / and acidic compound is contained in the resin composition, the content of the basic compound and / or acidic compound in the resin composition is such that the pH measured in water is 2 from the viewpoint of storage stability. The amount of basic compound at a concentration of ˜12 is preferred, and the amount of basic compound at a concentration of 6-9 is more preferred.
Here, the pH measured in water is specifically a value measured by adding a basic compound in water. The pH is a value at 23 ° C.

  When the resin composition contains a dehydrating agent, the content of the dehydrating agent in the resin composition is preferably 0.1 to 40% by mass and more preferably 1 to 20% by mass with respect to the total mass of the resin composition. . If content of a dehydrating agent is more than the lower limit of the said range, storage stability will be more excellent. If content of a dehydrating agent is below the upper limit of the said range, melt | dissolution stability will be favorable.

<Silicone oil>
The resin composition of the present invention preferably further contains silicone oil. When the resin composition contains silicone oil, the antifouling property of the formed coating film is more excellent.
Examples of the silicone oil include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, and methylhydrogen silicone oil, and modified silicone oils. The modified silicone oil is a silicone oil in which an organic group other than a methyl group and a phenyl group (hereinafter also referred to as “modified group”) is introduced into a part of silicon atoms of a straight silicone oil. Examples of the modifying group include a chlorophenyl group, a methylstyrene group, a long chain alkyl group (for example, an alkyl group having 2 to 18 carbon atoms), a polyether group, a carbinol group, an aminoalkyl group, an epoxy group, a (meth) acryloyl group, and the like. Is mentioned. These silicone oils can be used alone or in combination of two or more. Among the above, as the silicone oil, a polyether-modified silicone oil having a polyether group as a modifying group is preferable from the viewpoint of antifouling properties.

  A commercially available product can be used as the silicone oil. Examples of commercially available silicone oils include “KF-96”, “KF-50”, “KF-54”, “KF-56”, “KF-6016” (above, manufactured by Shin-Etsu Chemical Co., Ltd.), “ "TSF451" (made by Momentive Performance Materials), "Fluid47" (made by Rhone Plan (France)), "SH200", "SH510", "SH550", "SH710", "DC200", "ST-114PA" "," FZ209 "(manufactured by Toray Dow Corning).

  When the silicone oil is contained in the resin composition, the content of the silicone oil in the resin composition is preferably 0.1 to 40% by mass and more preferably 1 to 20% by mass with respect to the total mass of the resin composition. . If the content of the silicone oil is not less than the lower limit of the above range, the antifouling property is more excellent. If content of silicone oil is below the upper limit of the said range, melt | dissolution stability will be more excellent.

<Organic solvent>
The resin composition of this embodiment preferably contains an organic solvent. When the resin composition contains an organic solvent, the coating suitability of the antifouling coating composition using the resin composition, the water resistance of the formed coating film, the film forming property, etc. are further improved.
The organic solvent is not particularly limited as long as it can dissolve the copolymer (A). For example, hydrocarbon solvents such as toluene and xylene; the compound (B), propylene glycol monomethyl ether-2-acetate, etc. Examples include ether solvents; ketone solvents such as methyl isobutyl ketone; ester solvents such as n-butyl acetate; Any of these may be used alone or in combinations of two or more.

The content of the organic solvent in the resin composition of this embodiment is preferably 60% by mass or less, and preferably 50% by mass or less, based on the total amount of the resin composition, from the viewpoint of reducing the VOC content of the antifouling coating composition. More preferably, it is more preferably 45% by mass or less, and particularly preferably 40% by mass or less.
The content of the organic solvent is preferably such that the viscosity measured with a B-type viscometer at 25 ° C. of the resin composition is not more than the preferred upper limit described later, and the weight average molecular weight of the copolymer (A), glass transition Although it varies depending on the temperature and the presence or absence of a crosslinked structure, it is preferably 15% by mass or more, and more preferably 20% by mass or more.
The compound (B) can also function as an organic solvent. Therefore, when a resin composition contains a compound (B), content of a compound (B) is contained in content of an organic solvent.

<Other ingredients>
The resin composition of this embodiment may further contain other components other than the copolymer (A), a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, silicone oil, and an organic solvent.
Examples of the other components include the same components as the other components in the antifouling coating composition described later.
The content of other components is preferably 200% by mass or less, and may be 0% by mass with respect to the copolymer (A).

<Solid content>
The solid content of the resin composition of this embodiment is preferably 40% by mass or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and particularly preferably 60% by mass or more. When the solid content of the resin composition is not less than the lower limit of the above range, the VOC content of the antifouling coating composition is sufficiently low.
The upper limit of the solid content of the resin composition is not particularly limited, and may be 100% by mass. When the resin composition contains an organic solvent, the content is preferably 85% by mass or less, and more preferably 80% by mass or less from the viewpoint of the viscosity of the resin composition.
The solid content of the resin composition is measured by the measurement method described in Examples described later.

<Viscosity>
When the resin composition of this embodiment contains a solvent, the viscosity of the resin composition measured with a B-type viscometer at 25 ° C. (hereinafter also referred to as “B-type viscosity”) is preferably less than 5000 mPa · s. It is more preferably less than 3000 mPa · s, even more preferably less than 2,000 mPa · s, and particularly preferably less than 1,000 mPa · s.
The viscosity (hereinafter also referred to as “Gardner viscosity”) measured by a Gardner bubble viscometer at 25 ° C. of the resin composition is preferably W or less, and more preferably V or less.
If the viscosity (B-type viscosity or Gardner viscosity) of the resin composition is less than or equal to the above upper limit, an antifouling agent or the like may be blended or applied without adding a solvent for dilution to the resin composition. Thus, an antifouling coating composition having a low VOC content can be obtained.
It is preferable that the resin composition has a viscosity at a solid content of at least 50% by mass, not more than the preferable upper limit.
The lower limit of the viscosity of the resin composition is not particularly limited. From the viewpoint of suppressing the sagging of the paint during coating, the B-type viscosity at 25 ° C. is preferably 100 mPa · s or more.
Accordingly, the B-type viscosity at 25 ° C. of the resin composition is preferably 100 mPa · s or more and less than 5,000 mPa · s, more preferably 100 mPa · s or more and less than 3,000 mPa · s, and more preferably 100 mPa · s or more and 2,000 mPa · s. Less than s is more preferable, and 100 mPa · s or more and less than 1,000 mPa · s is particularly preferable.

  The viscosity of the resin composition depends on the solid content of the resin composition (contents of the copolymer (A) and other components), the weight average molecular weight of the copolymer (A), the glass transition temperature, the presence or absence of a crosslinked structure, and the like. Can be adjusted. For example, the lower the solid content, particularly the content of the copolymer (A), the lower the viscosity. Moreover, there exists a tendency for it to become low viscosity, so that the weight average molecular weight of a copolymer (A) is small or a glass transition temperature is low.

<Decomposition rate of structure (I)>
In the resin composition of this embodiment, the decomposition rate of the structure (I) in the copolymer (A) after storage at 40 ° C. for 30 days is preferably 20% or less, and preferably 7% or less. More preferably, it is 4% or less, more preferably 3% or less, and most preferably 2% or less. If the decomposition rate of the structure (I) after storing the resin composition at 40 ° C. for 30 days is not more than the above upper limit value, the storage stability of the resin composition and the antifouling coating composition containing the resin composition is excellent. Moreover, when a resin composition contains the organic solvent, it is excellent also in the melt stability with respect to the organic solvent of a copolymer (A). The lower the decomposition rate, the better. The lower limit may be 0%.
The decomposition rate of structure (I) after storage at 40 ° C. for 30 days can be reduced to 20% or less, for example, by adding a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, or the like to the resin composition.

In the measurement of the decomposition rate of the structure (I), the storage of the resin composition means that the resin composition is sealed in a glass bottle and left in a dry environment in a shielded environment.
The decomposition rate of the structure (I) is determined when the structure (I) contained in the copolymer (A) is not completely decomposed from the measured solid acid value (a) of the resin composition (after storage at 40 ° C. for 30 days). The value obtained by subtracting the theoretical solid acid value (b) is defined as the following value divided by the theoretical solid acid value (c) when the structure (I) contained in the copolymer (A) is completely decomposed.
(Decomposition rate) = {(Measured solid acid value (a)) − (Theoretical solid acid value (b))} / (Theoretical solid acid value (c)) × 100
The measured solid acid value will be described later in the item of acid value measurement.
The theoretical solid acid value can be calculated by the following formula.
(Theoretical solid acid value) = Σ (561 × 100 / Mw _i × w _i )
w _i represents the mass fraction of the monomer i with acid functionality of the monomers constituting the copolymer (A), Mw _i represents the molecular weight of a monomer having an acid functional group . The acid functional group is a functional group such as carboxylic acid.
The acid value at the time of decomposition is calculated as a monomer having an acid functional group.
The acid value when not decomposed is calculated as a monomer having no acid functional group.

(Production method of resin composition)
The resin composition of this embodiment can be produced using a known method. For example, the copolymer (A) is produced by the production method (α) or (β) described above, and if necessary, the obtained copolymer (A) can be reacted with an acid, a basic compound, an acidic compound. A resin composition can be prepared by blending a compound, a dehydrating agent, an organic solvent, other components, and the like.
When the resin composition of this aspect contains a compound (B), the timing which mix | blends a compound (B) may be the time of manufacture of a copolymer (A), and after manufacture of a copolymer (A). There may be, and it is not specifically limited. For example, in the production method (α), the compound (B) may coexist during the polymerization of the monomer mixture, or the compound (B) may be added after the polymerization is completed. In the production method (β), after the polymerization of the monomer mixture is completed, the copolymer (A0) is obtained by reacting the produced copolymer (A0) with the compound (B) to obtain the copolymer (A0). The compound (B) exceeding the equivalent amount with respect to the carboxy group of) may be added so that the unreacted compound (B) remains. When the compound (B) is allowed to coexist during the polymerization reaction, a part of the compound (B) undergoes radical polymerization. Therefore, a method of adding the compound (B) after the completion of the polymerization is preferable.

The resin composition of this embodiment can be used as it is or mixed with an antifouling agent or the like as necessary to obtain an antifouling coating composition.
In addition to the antifouling paint composition, the resin composition of this embodiment can also be used in an antifogging paint composition and the like.

(Function and effect)
Since the resin composition of this embodiment contains the copolymer (A), the coating film containing the resin composition of this embodiment exhibits self-polishing properties in seawater or the like as described above. Moreover, even when it does not contain an antifouling agent, it exhibits an excellent antifouling effect and is excellent in water resistance. This coating film has a sufficiently high hardness.
Moreover, the resin composition of this aspect can be made into the solution form of a high solid content low viscosity. Therefore, by using the resin composition of this embodiment, an antifouling paint composition having a low VOC content can be obtained.
Furthermore, when the resin composition of this embodiment contains at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent, in addition to the copolymer (A). In addition, the resin composition can exhibit excellent storage stability. For example, the decomposition rate of the structure (I) in the copolymer (A) after storage at 40 ° C. for 30 days can be reduced to 20% or less. Moreover, when the resin composition further contains an organic solvent, the increase in the viscosity of the resin composition over time can be suppressed. It is excellent also in the dissolution stability with respect to the organic solvent of the copolymer (A) in a resin composition.
Therefore, the resin composition of this embodiment is suitable for an antifouling coating composition.

[Anti-fouling paint composition]
The third aspect of the present invention is an antifouling paint composition containing the resin composition of the second aspect. Therefore, the antifouling coating composition of this embodiment contains the copolymer (A).
The antifouling coating composition of this embodiment further comprises at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent, from the viewpoint of the storage stability of the antifouling coating composition. It is preferable. Examples of the compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent are the same as those described above. The preferable content is also the same.
It is preferable that the antifouling coating composition of this embodiment further contains silicone oil from the viewpoint of the antifouling property of the coating film. Examples of the silicone oil are the same as described above. The preferable content is also the same.
The antifouling paint composition of this embodiment may contain an organic solvent. Examples of the organic solvent are the same as described above.
The antifouling coating composition of this embodiment may further contain an antifouling agent.
The antifouling paint composition of this embodiment further comprises other components other than the copolymer (A), a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, a silicone oil, an organic solvent, and an antifouling agent. But you can.
When the antifouling paint composition contains a compound that reacts with an acid, a basic compound, an acidic compound, a dehydrating agent, a silicone oil, an organic solvent, other components, etc., these components are derived from the resin composition, respectively. It may be, may not be derived (mixed at the time of manufacturing the antifouling paint composition), or a mixture thereof.

<Anti-fouling agent>
Examples of the antifouling agent include inorganic antifouling agents, organic antifouling agents, and the like, and one or more types can be appropriately selected and used according to the required performance.
Antifouling agents include, for example, copper-based antifouling agents such as cuprous oxide, thiocyanic copper and copper powder, compounds of other metals (lead, zinc, nickel, etc.), amine derivatives such as diphenylamine, nitrile compounds, benzothiazole Compounds, maleimide compounds, pyridine compounds, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  More specifically, as an antifouling agent, 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile, manganese ethylenebisdithiocarbamate, zinc dimethyldithio Carbamate, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroisophthalonitrile, N, N-dimethyldichlorophenylurea, zinc ethylenebisdithiocarbamate Rhodan copper, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, N- (fluorodichloromethylthio) phthalimide, N, N′-dimethyl-N′-phenyl- (N-fluorodichloro) Methylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt ( Zinc pyrithione ”), tetramethylthiuram disulfide, Cu-10% Ni solid solution alloy, 2,4,6-trichlorophenylmaleimide 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutyl carbamate, diiodomethyl paratolyl sulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) -benzimidazole, medetomidine, pyridine triphenyl Examples include borane.

Among the above, the antifouling agent is cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2 in terms of antifouling properties. At least one selected from the group consisting of-(4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile (hereinafter also referred to as “antifouling agent (b1)”) and medetomidine. It is preferable to include.
When combining cuprous oxide and antifouling agent (b1), the blending ratio (mass ratio) is preferably cuprous oxide / antifouling agent (b1) = 80/20 to 99/1, 90/10 to 99 / 1 is more preferable.
At least one selected from the group consisting of cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, antifouling agent (b1) and medetomidine; You may combine with antifouling agent.

  When the antifouling coating composition contains an antifouling agent, the content of the antifouling agent in the antifouling coating composition is not particularly limited, but is 10 to 200 masses per 100 parts by mass of the copolymer (A). Part is preferable, and 50 to 150 parts by mass are more preferable. When the content of the antifouling agent is not less than the lower limit of the above range, the antifouling effect of the formed coating film is more excellent. When the content of the antifouling agent is not more than the upper limit of the above range, the coating film properties are excellent.

<Other ingredients>
Examples of other components include other polymers than the copolymer (A). Another polymer is a polymer which does not have structure (I), for example.
Examples of other polymers include thermoplastic resins (thermoplastic polymers) other than the copolymer (A). It is preferable that the antifouling coating composition of this embodiment contains a thermoplastic resin other than the copolymer (A). When the antifouling coating composition contains a thermoplastic resin other than the copolymer (A), the coating film properties such as crack resistance and water resistance are improved.

Examples of the thermoplastic resin other than the copolymer (A) include chlorinated paraffin; chlorinated polyolefin such as chlorinated rubber, chlorinated polyethylene, and chlorinated polypropylene; polyvinyl ether; polypropylene sebacate; partially hydrogenated terphenyl; Vinyl acetate; (meth) methyl acrylate copolymer, (meth) ethyl acrylate copolymer, (meth) propyl acrylate copolymer, (meth) butyl acrylate copolymer, (meth) Poly (meth) acrylic acid alkyl ester such as cyclohexyl acrylate copolymer; 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 Vinyl chloride resins such as ter copolymers and vinyl chloride-ethyl vinyl ether copolymers; waxes; oils and fats that are solid at room temperature other than wax; oils and fats such as castor oil; and refined products thereof; petrolatum; liquid paraffin; And rosin, hydrogenated rosin, naphthenic acid, fatty acid, and divalent metal salts thereof. Examples of the wax include animal-derived waxes such as beeswax; plant-derived waxes; semi-synthetic waxes such as amide waxes; synthetic waxes such as oxidized polyethylene waxes. These thermoplastic resins may be used alone or in combination of two or more.
Chlorinated paraffin is preferable in that it functions as a plasticizer and can improve the crack resistance and peel resistance of the coating film.
Organic waxes such as semi-synthetic wax and synthetic wax are preferred in that they function as an anti-settling agent and an anti-sagging agent, and an effect of improving the storage stability and pigment dispersibility of the antifouling coating composition is obtained. Oxidized polyethylene wax and polyamide wax are more preferred.

  The content of the thermoplastic resin other than the copolymer (A) in the antifouling coating composition is not particularly limited, but is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A). 0.1-10 mass parts is more preferable. If the content of the thermoplastic resin other than the copolymer (A) is not less than the lower limit of the above range, the coating film properties such as crack resistance and water resistance are more excellent, and if not more than the upper limit of the above range, More hydrolyzable.

  The antifouling paint composition of this embodiment is provided with a silicone compound such as dimethylpolysiloxane (excluding silicone oil), fluorinated hydrocarbons for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms. Fluorine-containing compounds such as

  The antifouling coating composition of this embodiment is composed of various pigments, antifoaming agents, leveling agents, pigment dispersants (eg anti-settling agents), anti-sagging agents, matting agents, ultraviolet absorbers, antioxidants, and improved heat resistance. Agents, slip agents, preservatives, plasticizers, viscosity control agents and the like may be included.

Examples of the pigment include zinc oxide, talc, silica, barium sulfate, potassium feldspar, aluminum hydroxide, magnesium carbonate, mica, carbon black, dial, titanium oxide, phthalocyanine blue, kaolin, gypsum and the like. In particular, zinc oxide and talc are preferable.
Examples of anti-settling agents and anti-sagging agents other than thermoplastic resins include bentonite-based, finely divided silica-based, stearate salt, lecithin salt, alkyl sulfonate, and the like.

  Examples of plasticizers other than thermoplastic resins include phthalate plasticizers such as dioctyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, and diisodecyl phthalate; aliphatic dibasic ester plasticizers such as isobutyl adipate and dibutyl sebacate ; Glycol ester plasticizers such as diethylene glycol dibenzoate and pentaerythritol alkyl ester; phosphate ester plasticizers such as tricresyl phosphate (TCP), triaryl phosphate and trichloroethyl phosphate; epoxy soybean oil, octyl epoxy stearate, etc. Epoxy plasticizers of the above; organic tin plasticizers such as dioctyltin laurate and dibutyltin laurate; trioctyl trimellitic acid, triacetylene and the like. By adding a plasticizer to the antifouling coating composition, the crack resistance and peel resistance of the coating film can be enhanced. Among the above, TCP is preferable as the plasticizer.

The VOC content of the antifouling coating composition of this embodiment is preferably 410 g / L or less, more preferably 400 g / L or less, and even more preferably 380 g / L or less.
The VOC content is calculated from the following formula using the specific gravity of the antifouling paint composition and the value of the solid content (heating residue).
VOC content (g / L) = specific gravity of composition × 1000 × (100−solid content) / 100
The specific gravity of the antifouling coating composition is calculated by filling the antifouling coating composition in a specific gravity cup having a capacity of 100 mL at 25 ° C. and measuring the mass.
The solid content (heating residue) of the antifouling coating composition is measured by the method described in Examples described later.
The VOC content can be adjusted by the content of the organic solvent.

55-100 mass% is preferable, as for solid content of the antifouling coating composition of this aspect, 60-90 mass% is more preferable, and 65-80 mass% is further more preferable.
If the solid content of the antifouling coating composition is at least the lower limit of the above range, the VOC content will be sufficiently low. If solid content is below the upper limit of the said range, it will be easy to make the viscosity of an antifouling coating composition low.

The B-type viscosity at 25 ° C. of the antifouling coating composition of this embodiment is preferably less than 5,000 mPa · s, more preferably less than 3,000 mPa · s, and even more preferably less than 1,000 mPa · s. If the viscosity of the antifouling coating composition is not more than the above upper limit value, coating is easy.
The lower limit of the B-type viscosity of the antifouling coating composition is not particularly limited, but is preferably 100 mPa · s or more in terms of physical properties of the coating film.
The viscosity of the antifouling coating composition can be adjusted by the viscosity of the resin composition, the amount of organic solvent added to the resin composition, and the like.

  The antifouling coating composition of this embodiment can be prepared by preparing the resin composition of this embodiment as described above, adding an antifouling agent, other components, and an organic solvent as necessary, and mixing them.

The antifouling paint composition of this aspect is for forming a paint film (antifouling paint film) on the surface of a base material such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base. Can be used.
A coating film using the antifouling coating composition of this embodiment can be formed on the substrate surface directly or via a base coating film.
The undercoat film can be formed using a wash primer, a primer such as a chlorinated rubber or an epoxy, an intermediate coating, or the like.
The coating film can be formed by a known method. For example, an antifouling coating composition is applied to the surface of a substrate or a base coating on the substrate by means of brush coating, spray coating, roller coating, immersion coating, or the like, and dried to dry the coating film. Can be formed.
The application amount of the antifouling coating composition can generally be set to an amount that results in a dry coating film thickness of 10 to 400 μm.
The coating film can be usually dried at room temperature, and may be heat-dried as necessary.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited at all by these examples. In addition, the part in an Example represents a mass part.
Evaluation in the examples was performed by the following methods.

(Solid content (heating residue))
0.50 g of a measurement sample (resin composition or antifouling paint composition) was weighed on an aluminum dish, 3 mL of toluene was added with a dropper and spread evenly on the bottom of the dish, and preliminary drying was performed. Pre-drying is a process for extending the measurement sample over the entire dish and facilitating volatilization of the solvent in the main drying. In the preliminary drying, the measurement sample and toluene were dissolved by heating in a water bath at 70 to 80 ° C. and evaporated to dryness. After preliminary drying, main drying was performed for 2 hours with a hot air dryer at 105 ° C. The solid content (heating residue) was determined from the mass of the measurement sample before preliminary drying (mass before drying) and the mass after main drying (mass after drying) according to the following formula.
Solid content (mass%) = mass after drying / mass before drying × 100

(B type viscosity)
The viscosity of the measurement sample was measured with a B-type viscometer at 25 ° C., and the value was shown as the B-type viscosity.

(Gardner viscosity)
A measurement sample was put in a dried Gardner bubble viscosity tube (hereinafter also simply referred to as a viscosity tube) up to the indication line of the viscosity tube, and the tube was stoppered with a cork stopper. The viscosity tube from which the sample was collected was immersed vertically in a constant temperature water bath adjusted to a specified temperature (25.0 ± 0.1 ° C.) for at least 2 hours to make the sample constant temperature. The viscosity tube was rotated 180 ° at the same time, and the viscosity (Gardner viscosity) was determined by comparing the milling speed of the sample with the reference tube.

(Decomposition rate of structure (I) after storage at 40 ° C for 30 days)
100 g of the produced resin composition was put in a 150 mL glass bottle and sealed, and left in a drying cabinet at 40 ° C. for 30 days in a shielded environment. Thereafter (after storage at 40 ° C. for 30 days), the measured solid acid value (a) of the resin composition was measured by the following procedure, and the decomposition rate (%) was calculated by the following formula. The theoretical solid acid values (b) and (c) are as described above.
Decomposition rate (%) = {(Measured solid acid value (a)) − (Theoretical solid acid value (b))} / (Theoretical solid acid value (c)) × 100

(Measured solid acid value)
About 4.0 g of a sample (resin composition) was precisely weighed in a beaker (A (g)), and 50 mL was added at a ratio of toluene / 95% ethanol solution = 50/50. After stirring for 5 minutes in a sealed container, 0.5 mol / L hydroxylation with a factor (f) of 1.003 at 20 ° C. manufactured by Kishida Chemical Co., Ltd. using a Hiranuma automatic titrator (AUTO TITRATOR COM-1600). Potentiometric titration was performed with a potassium solution (ethanol solution), and the maximum slope point of the titration curve was set as the end point (titration amount = B (mL), titer of KOH solution = f). A blank measurement was performed in the same manner (titrated amount = C (mL)), and calculation was performed according to the following formula.
Measurement solid acid value (mgKOH / g) = {(BC) × 0.5 × 56.11 × f} / A / solid content

(Weight average molecular weight (Mw), number average molecular weight (Mn))
The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured using gel permeation chromatography (GPC) (manufactured by Tosoh Corporation, HLC-8220). TSKgelα-M (Tosoh Corp., 7.8 mm × 30 cm) and TSKguardcolumn α (Tosoh Corp., 6.0 mm × 4 cm) were used as columns. A calibration curve was prepared using F288 / F1 / F28 / F80 / F40 / F20 / F2 / A1000 (manufactured by Tosoh Corporation, standard polystyrene) and a styrene monomer.

(VOC content)
The VOC content of the antifouling coating composition was calculated from the following formula.
VOC content (g / L) = specific gravity of composition × 1000 × (100−solid content) / 100
The method for measuring the solid content is as described above. The specific gravity was calculated by filling a specific gravity cup having a capacity of 100 mL with the antifouling coating composition at 25 ° C. and measuring the mass.

(Paintability)
The smoothness of the coating film after coating was confirmed visually, and coating suitability was evaluated according to the following criteria.
○: The coating film is smooth.
X: Streaks remain in the coating film.

(Paint viscosity change rate)
The B-type viscosity (B-type viscosity before storage) (mPa · s) of the produced antifouling coating composition was measured. This antifouling paint composition was placed in a 150 mL glass bottle and stored at 40 ° C. for 30 days. Thereafter, the B-type viscosity (B-type viscosity after storage at 40 ° C. for 30 days) (mPa · s) of the antifouling coating composition was measured, and the paint viscosity change rate (%) was calculated by the following formula.
Paint viscosity change rate (%) = B-type viscosity after storage at 40 ° C. for 30 days / B-type viscosity before storage × 100

(Coating hardness)
On the glass substrate, the resin composition was applied with a 500 μm applicator and dried at 25 ° C. for 1 week to form a coating film to obtain a test plate. About the coating film of this test board, Martens hardness (HM) was measured with the ultra micro hardness meter (The product made from Fisher Instruments, brand name: HM2000). The measurement conditions were dQRST (F) / dt = constant, F (test force) = 10 mN / 10 seconds, C (maximum load creep time) = 5 seconds, maximum indentation load 10 mN, and maximum indentation depth 6 μm. Martens hardness (HM) was measured at three different locations of the same coating film, and the average value thereof was defined as the coating film hardness, which was evaluated according to the following criteria.
A: The coating film hardness is 10.0 N / mm ² or more.
○: the coating film hardness is 5.0 N / mm ² or more 10.0 N / mm less than ^2.
△: Coating film hardness of 1.2 N / mm ² or more 5.0 N / mm less than ^2.
X: The coating film hardness is less than 1.2 N / mm ² .

(Water resistance of the coating film of the resin composition)
On the glass substrate, the resin composition was applied with a 500 μm applicator and dried at room temperature for 1 week to form a coating film to obtain a test plate. After immersing this test plate in sterilized filtered seawater for one month, the test plate was dried at room temperature of 20 ° C. for one week. About the whitening degree, the coating-film surface of this test plate was observed visually. Evaluation was performed according to the following criteria.
A: Almost no whitening is observed.
○: Slight whitening is observed.
Δ: Some whitening is observed.
X: Fair whitening is observed.

(Water resistance of coating film of antifouling paint composition)
A test plate was prepared by applying an antifouling coating composition on a glass plate substrate so that the dry film thickness was 120 μm. After immersing the test plate in sterilized filtered seawater for 3 months, the test plate was dried at room temperature of 20 ° C. for 1 week, and the surface of the coating film was observed. Evaluation was performed according to the following criteria.
(Double-circle): A crack and peeling are not observed at all.
○: Cracks are partially observed.
(Triangle | delta): A crack and peeling are observed in part.
X: Cracks and peeling are observed on the entire surface.

(Standing antifouling property)
The antifouling coating composition was applied to a sandblasted steel plate to which a rustproof coating had been applied in advance with a brush so that the dry film thickness was 200 to 300 μm, dried to form a coating film, and a test plate was obtained. . After leaving this test plate in the Seto Inland Sea for 6 months, the ratio of the area where marine organisms adhered to the total area of the coating (the area where marine organisms adhered) was examined. evaluated.
A: The adhesion area of seawater organisms is 10% or less.
○: The adhesion area of seawater organisms is more than 10% and 20% or less.
(Triangle | delta): The adhesion area of seawater organisms is more than 20% and 40% or less.
X: The adhesion area of seawater organisms exceeds 40%.

(Paint consumption test)
The antifouling paint composition was applied to a hard vinyl chloride plate of 50 mm × 50 mm × 2 mm (thickness) with an applicator so as to have a dry film thickness of 120 μm, dried to form a coating film, and a test plate was obtained. . The test plate was attached to a rotating drum installed in seawater and rotated at a peripheral speed of 7.7 m / s (15 knots). This state was maintained for 6 months, and the film thickness (μm) of the coating film was measured after 3 months and 6 months after installation. From the measured film thickness, the consumable film thickness (120 μm—measured film thickness) was calculated after 3 months and 6 months, and the value was defined as the degree of wear (after 3 months and 6 months).
The ratio of the degree of wear after 3 months (μm) to the degree of wear after 6 months (μm) (after 3 months / 6 months) was calculated. The closer this ratio is to 2.0, the smaller the change in the degree of wear of the coating film over time, which is preferable.

The meanings of the abbreviations used in the following examples are as follows.
Monomer (M1): 1-butoxyethyl methacrylate (synthetic product synthesized in Production Example M1 described later).
Monomer (M2): 1-isobutoxyethyl methacrylate (synthetic product synthesized in Production Example M2 described later).
Monomer (M3): 1- (cyclohexyloxy) ethyl methacrylate (synthetic product synthesized in Production Example M3 described later).
Monomer (M4): 1- (2-ethylhexyloxy) ethyl methacrylate (synthetic product synthesized in Production Example M4 described later).
Monomer (M5): 2-tetrahydropyranyl methacrylate (synthetic product synthesized in Production Example M5 described later).

FM-0711: trade name, manufactured by Chisso Corporation (v = 0 in the above formula (m2-3), R ^{3a to} R ^3f = methyl group, w = 3, x = 10 one-end polysiloxane macromonomer) .
X-24-8201: Trade name, manufactured by Shin-Etsu Chemical Co., Ltd. (v = 0 in the formula (m2-3), R ^{3a to} R ^3f = methyl group, w = 3, x = 25).
FM-0721: trade name, manufactured by Chisso Corporation (v = 0, R ^{3a to} R ^3f = methyl group, w = 3, x = 65 in the formula (m2-3)).
X-22-174DX: Trade name, manufactured by Shin-Etsu Chemical Co., Ltd. (v = 0 in the formula (m2-3), R ^{3a to} R ^3f = methyl group, w = 3, reactive group equivalent 4600 g / mol).
FM-7711: trade name, manufactured by Chisso Corporation (l and q = 0 in the formula (m2-1), m and о = 3, R ^{1a to} R ^1f = methyl group, n = 10).
FM-7721: trade name, manufactured by Chisso Corporation (l and q = 0 in the formula (m2-1), m and о = 3, R ^{1a to} R ^1f = methyl group, n = 65).
MMA: methyl methacrylate.
EA: ethyl acrylate.
2-MTA: 2-methoxyethyl acrylate.
2-MTMA: 2-methoxyethyl methacrylate.
MAA: methacrylic acid.
TIPX: Triisopropylsilyl acrylate.
Monomer (N1): An ethylenically unsaturated monomer mixture containing a divalent metal (a synthetic product synthesized in Production Example N1 described later).

AIBN: 2,2′-azobisisobutyronitrile.
AMBN: 2,2′-azobis (2-methylbutyronitrile).
NOFMER MSD: trade name, manufactured by NOF Corporation, α-methylstyrene dimer.
Additive (a): Disparon (registered trademark) 4200-20 (manufactured by Enomoto Kasei Co., Ltd., oxidized polyethylene wax).
Additive (b): Disparon A603-20X (manufactured by Enomoto Kasei Co., Ltd., polyamide wax).
Additive (c): Toyoparax (registered trademark) 150 (manufactured by Tosoh Corporation, chlorinated paraffin).
KF-6016: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., polyether-modified silicone oil.
ST-114PA: trade name, manufactured by Toray Dow Corning, polyether-modified silicone oil.
FZ209: Trade name, manufactured by Toray Dow Corning, methylphenyl silicone oil.
KF-56: trade name, manufactured by Shin-Etsu Chemical Co., Ltd., methyl phenyl silicone oil.
Antifouling agent (1): 4-bromo-2- (4-chlorophenyl) -5- (trifluoromethyl) -1H-pyrrole-3-carbonitrile.
Antifouling agent (2): pyridine triphenylborane (manufactured by Hokuko Chemical Co., Ltd., trade name: PK).
Antifouling agent (3): 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (Rohm and Haas, trade name: Cine Nine 211).

[Production Example M1]
150.2 parts (1.5 mol) of butyl vinyl ether, 0.24 part of hydroquinone, and 0.47 part of phenothiazine were stirred at room temperature and mixed until uniform. While blowing air (10 mL / min), 86.1 parts (1.0 mol) of methacrylic acid was added dropwise so that the temperature of the reaction solution was kept at 60 ° C. or lower. After the dropping, the temperature of the reaction solution was raised to 80 ° C. and reacted for 5 hours. To the reaction solution, 264.5 parts (3.0 mol) of t-butyl methyl ether was added and mixed, and the organic phase was washed once with 350 parts of a 20 mass% aqueous potassium carbonate solution. To the organic phase, 0.06 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and a low boiling point component was distilled off using an evaporator. The obtained residue was distilled under reduced pressure to obtain 166.9 parts (0.91 mol) of 1-butoxyethyl methacrylate (monomer (M1)) having a boiling point of 70 ° C./5 torr (667 Pa).

[Production Example M2]
90.1 parts (0.9 mol) of isobutyl vinyl ether, 0.14 part of hydroquinone, and 0.28 part of phenothiazine were mixed at room temperature until uniform. While blowing air (10 ml / min), 51.7 parts (0.6 mol) of methacrylic acid was added dropwise so as to keep the temperature of the reaction solution at 60 ° C. or lower. After the dropping, the temperature of the reaction solution was raised to 80 ° C. and reacted for 6 hours. To the reaction solution, 158.7 parts (1.8 mol) of t-butyl methyl ether was added and mixed, and the organic phase was washed once with 200 parts of a 20 mass% aqueous potassium carbonate solution. To the organic phase, 0.03 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and a low boiling point component was distilled off using an evaporator. The obtained residue was distilled under reduced pressure to obtain 97.5 parts (0.52 mol) of 1-isobutoxyethyl methacrylate (monomer (M2)) having a boiling point of 60 ° C./3 torr.

[Production Example M3]
138.8 parts (1.1 mol) of cyclohexyl vinyl ether, 0.28 part of hydroquinone, and 0.53 part of phenothiazine were stirred at room temperature and mixed until uniform. While blowing air (10 ml / min), 86.1 parts (1.0 mol) of methacrylic acid was added dropwise so that the temperature of the reaction solution was kept at 60 ° C. or less. After the dropping, the temperature of the reaction solution was raised to 80 ° C. and reacted for 5 hours. To the reaction solution, 220.4 parts (2.5 mol) of t-butyl methyl ether was added and mixed, and the organic phase was washed once with 135 parts of a 20 mass% aqueous potassium carbonate solution. To the organic phase, 0.06 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and a low boiling point component was distilled off using an evaporator. The obtained residue was distilled under reduced pressure to obtain 160.0 parts (0.75 mol) of 1- (cyclohexyloxy) ethyl methacrylate (monomer (M3)) having a boiling point of 92 ° C./5 torr.

[Production Example M4]
171.9 parts (1.1 mol) of 2-ethylhexyl vinyl ether, 0.32 part of hydroquinone, and 0.61 part of phenothiazine were mixed at room temperature until uniform. While blowing air (10 ml / min), 86.1 parts (1.0 mol) of methacrylic acid was added dropwise so that the temperature of the reaction solution was kept at 60 ° C. or less. After dripping, the temperature of the reaction solution is raised to 80 ° C,
The reaction was allowed for 5 hours. To the reaction solution, 264.5 parts (3.0 mol) of t-butyl methyl ether was added and mixed, and the organic phase was washed once with 135 parts of a 20 mass% aqueous potassium carbonate solution. To the organic phase, 0.07 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and a low boiling point component was distilled off using an evaporator. The obtained residue was distilled under reduced pressure to obtain 207.0 parts (0.85 mol) of 1- (2-ethylhexyloxy) ethyl methacrylate (monomer (M4)) having a boiling point of 99 ° C./3 torr.

[Production Example M5]
75.7 parts (0.9 mol) of 3,4-dihydro-2H-pyran, 0.13 part of hydroquinone, and 0.26 part of phenothiazine were mixed at room temperature until uniform. While blowing air (10 ml / min), 51.7 parts (0.6 mol) of methacrylic acid (MAA) was added dropwise so that the temperature of the reaction solution was kept at 60 ° C. or lower. After the dropping, the temperature of the reaction solution was raised to 80 ° C. and reacted for 12 hours. To the reaction solution, 158.7 parts (1.8 mol) of t-butyl methyl ether was added and mixed, and the organic phase was washed once with 200 parts of a 20 mass% aqueous potassium carbonate solution. To the organic phase, 0.03 part of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl was added, and a low boiling point component was distilled off using an evaporator. The obtained residue was distilled under reduced pressure to obtain 75.7 parts (0.44 mol) of 2-tetrahydropyranyl methacrylate (monomer (M5)) having a boiling point of 76 ° C./3 torr.

[Production Example N1]
A reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel was charged with 85.4 parts of PGM (propylene glycol methyl ether) and 40.7 parts of zinc oxide and heated to 75 ° C. while stirring. Subsequently, a mixture consisting of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 5 parts of water was dropped from the dropping funnel at a constant rate over 3 hours. After further stirring for 2 hours, 36 parts of PGM was added to obtain a transparent divalent metal atom-containing monomer mixture (monomer (N1)) having a solid content of 44.8% by mass.

[Production Example B-1]
A reaction vessel equipped with a stirrer, a temperature controller, and a dropping device was charged with 75 parts of xylene and heated to 90 ° C. while stirring. Subsequently, a mixture of 25 parts of monomer (M2), 20 parts of FM-0711, 35 parts of MMA, 20 parts of EA and 1.6 parts of AMBN as an initiator from the dropping funnel over 4 hours. It was dropped at a constant speed. After the addition, 10 parts of xylene was added, and 2.0 parts of AMBN and 4.0 parts of xylene were added dropwise at a constant rate over 30 minutes. After further stirring for 2 hours, 6.7 parts of isobutyl vinyl ether, 1.3 parts of xylene and 3 parts of butyl acetate were added to obtain a resin composition B-1 having a solid content of 51% by mass and containing a copolymer. It was.

[Production Examples B-2 to B-4, B-11 to B-26, B-32 to B-33]
The types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) added after polymerization are shown in Tables 1-3, and the theory Resin compositions B-2 to B-4 in the same manner as in Production Example B-1, except that the amount of xylene after completion of dropping was adjusted according to the amount of additive so that the solid content was 50% by mass. B-11 to B-26 and B-32 to B-33 were produced.

[Production Examples B-5 to B-10, B-34, B-35]
Table 1 or Table 3 shows the types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) added after polymerization, Resin composition was the same as in Production Example B-1, except that the amount of xylene at the end of the dropping was omitted and the initial amount of xylene was adjusted according to the amount of additive so that the theoretical solid content was 65% by mass. Products B-5 to B-10, B-34 and B-35 were produced.

[Production Examples B-28 to B-31]
Table 3 shows the types and amounts of monomers and initiators, and the types and amounts of additives (compound (B), basic compound, acidic compound, dehydrating agent) to be added after polymerization. In the same manner as in Production Example B-1, except that the amount of xylene was omitted and the initial amount of xylene was adjusted according to the amount of additive so that the theoretical solid content was 55% by mass, the resin composition B- 28-B-31 was produced.

[Production Example B-27]
A reaction vessel equipped with a stirrer, a temperature controller, and a dropping device was charged with 44.4 parts of propylene glycol monomethyl ether acetate and heated to 90 ° C. while stirring. Subsequently, a mixture of 30 parts of X-24-8201, 45 parts of MMA, 11.6 parts of MAA, and 1.5 parts of AIBN as an initiator was dropped from the dropping funnel over a period of 4 hours. After the completion of dropping, 2.0 parts of AMBN and 2.0 parts of xylene were dropped at a constant rate over 30 minutes. After further stirring for 2 hours, 67 parts of isobutyl vinyl ether was added dropwise at a constant rate over 30 minutes, followed by further stirring for 15 hours. As a result, the carboxyl group in the X-24-8201 / MMA / MAA copolymer was reacted with isobutyl vinyl ether to obtain a resin composition B-27 containing a copolymer having a solid content of 50.1% by mass. Obtained.

[Production Example B-36]
A reaction vessel equipped with a stirrer, a temperature controller, and a dropping funnel was charged with 15 parts of PGM (propylene glycol methyl ether), 65 parts of xylene and 4 parts of ethyl acrylate, and heated to 100 ° C. while stirring. Subsequently, 24 parts of MMA, 11.3 parts of EA, 50 parts of FM-0711, 23.9 parts of monomer (N1), 10 parts of xylene, 1.2 parts of Nofmer MSD, AIBN from the dropping funnel A transparent mixture consisting of 2.5 parts and 1 part of AMBN was added dropwise at a constant rate over 6 hours. After completion of dropping, 9 parts of xylene were added, 0.5 parts of t-butyl peroctoate and 10 parts of xylene were added 4 times at 30 minute intervals, and further stirred for 1 hour, and then 10.1 parts of xylene was added. Thus, a resin composition B-36 containing a copolymer having a solid content of 45% by mass was obtained.

Tables 1 to 3 show characteristics of the obtained resin compositions B-1 to B-36 (solid content (mass%), B-type viscosity, Gardner viscosity, decomposition rate of structure (I) after storage at 40 ° C. for 30 days) Evaluation of the number average molecular weight (Mn) and weight average molecular weight (Mw) of the copolymer contained in each resin composition, and the performance (water resistance, coating hardness) of the coating film formed from each resin composition The results are listed.
Production Examples B-1 to B-31 are Examples, and Production Examples B-32 to B-36 are Comparative Examples.

In Tables 1 to 3, the numerical values described in the columns of the monomer and the initiator indicate the charged amount (parts). Regarding the charged amount of the monomer (N1), the value shown in parentheses is the charged amount in solid content, and the value described above is the charged amount in the total amount including the solvent.
About resin composition B-35, since it was adhesiveness, the coating-film hardness was not able to be measured.

[Examples 1 to 34, Comparative Examples 1 to 5]
According to the formulation shown in Tables 4-8, each component was mixed with a high speed disper to obtain an antifouling paint composition.
Coating properties (solid content, B-type viscosity, VOC content), coating suitability, coating viscosity change rate, coating film performance (stationary antifouling property, water resistance, coating film consumption test) of the obtained antifouling coating composition The evaluation results are shown in Tables 4-8.

  In Tables 4-8, the numerical value described in the column of composition shows a compounding quantity (part). The compounding quantity of a resin composition is the quantity of the whole resin composition.

The antifouling paint compositions of Examples 1 to 34 had a low viscosity even at a high solid content, and good paintability. Moreover, the viscosity change at the time of storage is small, and it can be judged from the results of Production Examples B-1, B-5 to B-9 that the decomposition rate of the structure (I) at the time of storage is low, and the storage stability is excellent. there were.
Moreover, the coating film of the antifouling coating composition of Examples 1 to 34 was excellent in stationary antifouling property and water resistance. This can be confirmed from the results of Production Examples B-1 to B-31. Further, this coating film had an appropriate degree of wear.
On the other hand, the coating film of the antifouling coating composition of Comparative Example 1 using the resin composition containing the copolymer having the structure (I) and not having the polysiloxane group has a static antifouling property and water resistance. It was inferior.
The coating film of the antifouling coating composition of Comparative Example 2 containing a copolymer having a higher structure (I) ratio than that of Comparative Example 1 was improved in static antifouling property but decreased in water resistance.
The coating film of the antifouling coating composition of Comparative Example 3 containing a copolymer having a triorganosilyloxycarbonyl group as a hydrolyzable structure (having a constitutional unit derived from TIPX) was inferior in static antifouling properties. . From the results of Production Example B-35, it can be determined that this coating film has extremely low coating film hardness and is insufficient as the film strength.
Although the antifouling coating composition of Comparative Example 5 containing a copolymer having a higher proportion of triorganosilyloxycarbonyl groups and a lower proportion of polysiloxane groups than Comparative Example 3 had an improved coating viscosity change rate, The static antifouling property of the membrane was still inferior. From the results of Production Example B-34, it can be determined that this coating film has low coating film hardness and is insufficient as the film strength.
The coating film of the antifouling coating composition of Comparative Example 4 containing a copolymer having a structure containing a divalent metal as a hydrolyzable structure was inferior in water resistance. Moreover, this antifouling paint composition had a high viscosity and was inferior in coating suitability.

  The (meth) acrylic copolymer and the resin composition of the present invention can be used for an antifouling coating composition, an antifogging coating composition, and the like, respectively, and particularly preferably for an antifouling coating composition.

Claims (12)

The (meth) acrylic-type copolymer which has at least 1 sort (s) of structure (I) represented by following formula (1), following formula (2), or following formula (3), and a polysiloxane group.

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, and R ¹ and R ² represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively. R ³ and R ⁵ each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R ⁴ and R ⁶ each represents an alkylene group having 1 to 10 carbon atoms.) The (meth) acrylic copolymer according to claim 1, comprising a structural unit derived from the following monomer (m1) and a structural unit derived from the following monomer (m2).
Monomer (m1): A monomer having at least one of the structures (I) and an ethylenically unsaturated bond.
Monomer (m2): A monomer having the polysiloxane group and an ethylenically unsaturated bond.   The resin composition containing the (meth) acrylic-type copolymer of Claim 1 or 2.   The resin composition according to claim 3, wherein a decomposition rate of the structure (I) in the (meth) acrylic copolymer after storage at 40 ° C for 30 days is 20% or less.   The resin composition according to claim 3 or 4, further comprising at least one selected from the group consisting of a compound that reacts with an acid, a basic compound, an acidic compound, and a dehydrating agent. The compound that reacts with the acid is at least one selected from the group consisting of a compound represented by the following formula (31), a compound represented by the following formula (32), and a compound represented by the following formula (33). The resin composition according to claim 5, which is the compound (B).

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, R ⁷ represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms, R ⁸ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ⁹ and R ¹¹ each represents an alkyl group, a cycloalkyl group or an aryl group having 1 to 20 carbon atoms, and R ¹⁰ represents a single bond Or an alkylene group having 1 to 9 carbon atoms, and R ¹² represents an alkylene group having 1 to 9 carbon atoms.)   The resin composition according to any one of claims 3 to 6, further comprising silicone oil.   An antifouling paint composition comprising the resin composition according to any one of claims 3 to 7.   The antifouling paint composition according to claim 8, further comprising an antifouling agent.   The antifouling agent is cuprous oxide, pyridine triphenylborane, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one, 4-bromo-2- (4-chlorophenyl) -5- ( The antifouling paint composition according to claim 9, comprising at least one selected from the group consisting of (trifluoromethyl) -1H-pyrrole-3-carbonitrile and medetomidine.   The antifouling paint composition according to any one of claims 8 to 10, further comprising a thermoplastic resin other than the (meth) acrylic copolymer. A method for producing a (meth) acrylic copolymer, wherein a monomer mixture containing the following monomer (m1) and the following monomer (m2) is polymerized to obtain a (meth) acrylic copolymer.
Monomer (m1): A monomer having at least one structure (I) represented by the following formula (1), the following formula (2) or the following formula (3) and an ethylenically unsaturated bond.
Monomer (m2): A monomer having a polysiloxane group and an ethylenically unsaturated bond.

(In the formula, X represents —O—, —S— or —NR ¹⁴ —, R ¹⁴ represents a hydrogen atom or an alkyl group, and R ¹ and R ² represent a hydrogen atom or an alkyl having 1 to 10 carbon atoms, respectively. R ³ and R ⁵ each represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, and R ⁴ and R ⁶ each represents an alkylene group having 1 to 10 carbon atoms.)