JP4154344B2 - Coating composition and copolymer - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a coating composition having antifouling properties and a copolymer suitable for forming the same, and more specifically, prevents adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms. The present invention relates to a coating composition capable of forming a coating film to be formed and a copolymer suitable for forming the coating composition.

  Conventionally, an antifouling paint has been applied to a flooded portion of a ship or offshore structure for the purpose of preventing corrosion due to adhesion of marine organisms such as barnacles, snails, and algae and preventing a decrease in navigation speed of the ship. The aquaculture net is also painted in the same way for the purpose of preventing the lethality of seafood due to the attachment of marine organisms.

  The coating film formed from the antifouling paint exhibits an antifouling effect when the antifouling chemical component contained therein elutes into the sea. When a disintegrating antifouling paint film using a rosin compound is immersed in the sea for a long time, the amount of elution gradually decreases and the amount of non-elution increases, and the coating surface becomes uneven. Therefore, the effect of preventing the attachment of organisms such as marine organisms is significantly reduced. On the other hand, a coating film formed from a hydrolyzable paint gradually dissolves and renews the surface (self-polishing). By using a large amount of antifouling chemical components in the coating film, The antifouling component is always exposed and a long-term antifouling effect is exhibited. However, a large amount of antifouling chemical components are currently used in these paints, and even if the amount of antifouling chemical components used is reduced or no antifouling chemical components are used, the antifouling chemical components are protected for a long time in the sea. Development of paints that form a coating film that exhibits a fouling function has been carried out.

  As hydrolyzable antifouling paints, for example, Patent Document 1 and Patent Document 2 contain a copolymer having a metal atom-containing group at the end of the side chain, and Patent Document 3 and Patent Document 4 contain a metal atom. A self-polishing antifouling paint composition containing a copolymer having a polymerizable monomer as a constituent component as a vehicle component and containing an antifouling component has been proposed.

On the other hand, Patent Document 5, Patent Document 6, Patent Document 7 and Patent Document 8 propose a reaction-curing silicone rubber containing silicone oil, a hydroxyl group-containing silicone resin, or a polysiloxane containing a silanol group. Patent Document 9 proposes a coating composition using polydimethylsiloxane in the polymer side chain and utilizing low surface tension. Patent Document 10 proposes a copolymer having a polysiloxane structure in the polymer side chain and a metal salt of a specific organic acid in the side chain as a copolymer that exhibits antifouling performance even when no antifouling agent is used. Has been.
JP-A-62-57464 JP-A-62-84168 JP 11-35877 A JP 2002-012630 A JP-A-62-252480 Japanese Patent Laid-Open No. 63-2959 Japanese Patent Laid-Open No. 5-78617 Japanese Patent Laid-Open No. 5-287203 JP 62-156172 A JP 2001-72869 A

  However, antifouling paints using metal atom-containing copolymers such as those described in Patent Document 1, Patent Document 2, Patent Document 3 and Patent Document 4 have a separate antifouling property in order to develop an antifouling effect. It is necessary to use a large amount of drugs.

  On the other hand, antifouling paints utilizing low surface tension as described in Patent Document 5, Patent Document 6, Patent Document 7, Patent Document 8 and Patent Document 9 maintain a constant surface tension for a long time in seawater. There is a problem that it is difficult to achieve long-term antifouling effects and is particularly poor in adhesion to the substrate.

  In Patent Document 10, a monovalent organic acid residue and a divalent metal oxide are reacted with a copolymer having a silicon structure and a carboxyl group in the polymer side chain, and a metal is present in the carboxyl group of the polymer side chain. Since it is difficult to add, there is a problem that long-term polishing stability is low, long-term antifouling effect is difficult to be exhibited, and recoatability is poor.

  An object of the present invention is to provide a coating composition which can exhibit an antifouling effect in seawater for a long period of time even when it does not contain an antifouling chemical component, and which becomes an antifouling paint excellent in adhesion and recoatability, and It is to provide a copolymer suitable for forming the same.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a coating composition having a specific copolymer as a vehicle component exhibits excellent performance and can achieve the above-mentioned object, thereby completing the present invention. .

That is, the present invention relates to a silicon-containing polymerizable monomer (a) unit and a metal atom-containing polymerizable monomer (b ₁ ) having two unsaturated groups and containing a metal atom of Mg, Zn or Cu. ) and the unit a including both the polymer, the silicon-containing polymerizable monomer (a) is represented by the following formula (I) (a ₁₎ or the following formula (II) (a ₂ ) copolymers characterized by containing, and to a paint composition you containing the copolymer as a vehicle.

（式中、Ｒ¹は水素原子またはメチル基、ｋは２〜５の整数、ｌは０〜５０、ｍは２〜５の整数、ｎは３〜８０、Ｒ²〜Ｒ⁶はアルキル基、アルコキシ基、フェニル基、置換フェニル基、フェノキシ基及び置換フェノキシ基のいずれかを示す）

(In the formula, R ¹ is a hydrogen atom or a methyl group, k is an integer of 2 to 5, l is 0 to 50, m is an integer of 2 to 5, n is 3 to 80, R ^{2 to} R ⁶ are alkyl groups, (Indicates any of alkoxy group, phenyl group, substituted phenyl group, phenoxy group and substituted phenoxy group)

（式中、Ｒ⁷は水素原子またはメチル基、ｏは２〜５の整数、ｐは０〜５０、ｑは２〜５の整数、Ｒ⁸、Ｒ⁹及びＲ¹⁰はアルキル基、Ｒ¹¹｛Ｒ¹¹は−（−Ｏ−ＳｉＲ¹²Ｒ¹³−）_r−ＯＳｉＲ¹⁴Ｒ¹⁵Ｒ¹⁶（ｒは０〜２０の整数、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶はアルキル基）｝、及び、Ｒ¹⁷｛Ｒ¹⁷は−Ｒ¹⁸−（−ＯＣ₂Ｈ₄）_s−ＯＲ¹⁹（ｓは１〜２０の整数、Ｒ¹⁸及びＲ¹⁹はアルキル基）｝のいずれかを示す）
前記共重合体を形成するための単量体混合物に含まれる共重合成分に対する、前記シリコン含有重合性単量体（ａ）の含有量が１〜６０質量％であり、前記金属原子含有重合性単量体（ｂ₁）の含有量が１〜５０質量％であることが好ましい。

Wherein R ⁷ is a hydrogen atom or a methyl group, o is an integer of 2 to 5, p is 0 to 50, q is an integer of 2 to 5, R ⁸ , R ⁹ and R ¹⁰ are alkyl groups, R ¹¹ { R ¹¹ is — (— O—SiR ¹² R ¹³ —) _r —OSiR ¹⁴ R ¹⁵ R ¹⁶ (r is an integer of 0 to 20, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are alkyl groups)} And R ¹⁷ {R ¹⁷ is -R ¹⁸ -(-OC ₂ H ₄ ) _s -OR ¹⁹ (s is an integer of 1 to 20, R ¹⁸ and R ¹⁹ are alkyl groups)}
The content of the silicon-containing polymerizable monomer (a) is 1 to 60% by mass relative to the copolymer component contained in the monomer mixture for forming the copolymer, and the metal atom-containing polymerizable property it is preferable that the content of the monomer (b ₁₎ is from 1 to 50% by weight.

Further, the monomer mixture preferably further contains the metal atom-containing polymerizable monomer represented by the following formula (III) and (b _2). The ratio of the content of said metal atom-containing polymerizable monomer (b ₂₎ and the metal atom-containing polymerizable monomer _{(b 1) ((b 2} ) / (b 1)) is 20/80 The range is preferably 80/20 (molar ratio). Content of the metal-containing polymerizable monomer (b ₁ ) and the metal-containing polymerizable monomer (b ₂ ) with respect to the copolymer component contained in the monomer mixture for forming the inside of the copolymer Is preferably 1 to 50% by mass.

（式中、Ｒ²⁰は水素原子またはメチル基、ＭはＭｇ、ＺｎまたはＣｕ、Ｒ²¹は有機酸残基またはアルコール残基を示す）

(Wherein R ²⁰ represents a hydrogen atom or a methyl group, M represents Mg, Zn or Cu, and R ²¹ represents an organic acid residue or an alcohol residue)

  The antifouling paint using the coating composition of the present invention and a copolymer suitable for forming the same can maintain an excellent antifouling effect for a long time even when it contains no antifouling chemical component. In addition, since it has good adhesion to the base and recoatability, it is very useful industrially.

  The silicon-containing polymerizable monomer (a) is used as a constituent component of a copolymer which is a vehicle component of the coating composition of the present invention, and does not contain an antifouling agent by using this. Even in the case, the effect of making it difficult for organisms to adhere is imparted.

  The content of the silicon-containing polymerizable monomer (a) with respect to the copolymer component contained in the monomer mixture for forming the copolymer is not particularly limited, but is in the range of 1 to 60% by mass. It is preferable that This tends to develop an antifouling effect even when it contains no antifouling agent by setting it to 1% by mass or more. By setting it to 60% by mass or less, long-term antifouling properties and adhesiveness This is because it tends to be balanced. More preferably, it is the range of 5-50 mass%, Most preferably, it is the range of 10-40 mass%.

As the silicon-containing polymerizable monomer (a), for example, a monomer represented by (a ₁ ) represented by the following formula (I), (a ₂ ) represented by the following formula (II), or the like is used. be able to. (A ₁ ) and (a ₂ ) may contain at least one, or may contain both (a ₁ ) and (a ₂ ).

（式中、Ｒ¹は水素原子またはメチル基、ｋは２〜５の整数、ｌは０〜５０、ｍは２〜５の整数、ｎは３〜８０、Ｒ²〜Ｒ⁶はアルキル基、アルコキシ基、フェニル基、置換フェニル基、フェノキシ基及び置換フェノキシ基のいずれかを示す）

(In the formula, R ¹ is a hydrogen atom or a methyl group, k is an integer of 2 to 5, l is 0 to 50, m is an integer of 2 to 5, n is 3 to 80, R ^{2 to} R ⁶ are alkyl groups, (Indicates any of alkoxy group, phenyl group, substituted phenyl group, phenoxy group and substituted phenoxy group)

（式中、Ｒ⁷は水素原子またはメチル基、ｏは２〜５の整数、ｐは０〜５０、ｑは２〜５の整数、Ｒ⁸、Ｒ⁹及びＲ¹⁰はアルキル基、Ｒ¹¹｛Ｒ¹¹は−（−Ｏ−ＳｉＲ¹²Ｒ¹³−）_r−ＯＳｉＲ¹⁴Ｒ¹⁵Ｒ¹⁶（ｒは０〜２０の整数、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶はアルキル基）｝、及び、Ｒ¹⁷｛Ｒ¹⁷は−Ｒ¹⁸−（−ＯＣ₂Ｈ₄）_s−ＯＲ¹⁹（ｓは１〜２０の整数、Ｒ¹⁸及びＲ¹⁹はアルキル基）｝のいずれかを示す）
式（Ｉ）で示される（ａ₁）は単独でも良く、複数種を組合わせて使用しても良い。なお、Ｒ¹〜Ｒ⁶、ｋ、ｌ、ｍ及びｎはそれぞれ独立であり、また、分子中又は分子間において同一符号が存在する場合、それらは異なっていても良い。

Wherein R ⁷ is a hydrogen atom or a methyl group, o is an integer of 2 to 5, p is 0 to 50, q is an integer of 2 to 5, R ⁸ , R ⁹ and R ¹⁰ are alkyl groups, R ¹¹ { R ¹¹ is — (— O—SiR ¹² R ¹³ —) _r —OSiR ¹⁴ R ¹⁵ R ¹⁶ (r is an integer of 0 to 20, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are alkyl groups)} And R ¹⁷ {R ¹⁷ is -R ¹⁸ -(-OC ₂ H ₄ ) _s -OR ¹⁹ (s is an integer of 1 to 20, R ¹⁸ and R ¹⁹ are alkyl groups)}
(A ₁ ) represented by formula (I) may be used alone or in combination of two or more. Note that R ^{1 to} R ⁶ , k, l, m, and n are independent of each other, and they may be different when the same symbol exists in the molecule or between molecules.

  In formula (I), l is the average degree of polymerization of the polyether structure and may be 0, but is preferably larger than 0 because recoatability with the old coating film tends to be good. Further, 50 or less is preferable because water resistance tends to be good, and by setting it to 30 or less, recoatability with an old coating film is excellent, and more preferable. More preferably, it is the range of 3-25, Most preferably, it is the range of 5-20.

  K in the formula (I) is preferably an integer of 2 to 5, and 2 or 3 is more preferable because it is inexpensive. It is also possible to use those in which k is 2 and 3.

  M in the formula (I) is preferably an integer of 2 to 5, and 2 or 3 is more preferable because it is inexpensive.

  N in formula (I) is the average degree of polymerization of the silicon-containing structure, and is preferably in the range of 3-80. By setting it to 3 or more, there is a tendency to exhibit an antifouling effect even when it does not contain an antifouling agent. By setting it to 80 or less, it is compatible with other polymerizable monomers and obtained. This is because the copolymer tends to be soluble in common organic solvents. More preferably, it is the range of 5-50, Most preferably, it is the range of 8-40.

R ^{2 to} R ⁶ in formula (I) are preferably any of an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, and a substituted phenoxy group. An alkyl group having 1 to 18 carbon atoms is more preferable, a methyl group or an ethyl group is further preferable, and a methyl group is particularly preferable.

  Specific examples of the compound represented by the formula (I) include, for example, those in which l is 0, FM-0711, FM-0721, FM-0725 (trade name) manufactured by Chisso Corporation, Shin-Etsu Chemical Co., Ltd. X-24-8201, X-22-174DX, X-22-2426 (above, trade name), and the like. Examples of those where l is greater than 0 include F2-254-04 and F2-254-14 (above, trade names) manufactured by Nihon Unicar.

(A ₂ ) represented by formula (II) may be used alone or in combination of two or more. Note that R ^{7 to} R ¹⁹ , o, p, q, r, and s are independent of each other, and they may be different when the same symbol exists in the molecule or between molecules.

  P in the formula (II) is an average degree of polymerization of the polyether structure and may be 0, but is preferably larger than 0 because recoatability with the old coating film tends to be good. Further, 50 or less is preferable because water resistance tends to be good, and by setting it to 30 or less, recoatability with an old coating film is excellent and more preferable. More preferably, it is the range of 3-25, Most preferably, it is the range of 5-20.

  O in the formula (II) is preferably an integer of 2 to 5, and 2 or 3 is more preferable because it is inexpensive. It is also possible to use a combination of o and 2 and 3.

  Q in the formula (II) is preferably an integer of 2 to 5, and more preferably 2 or 3.

  In formula (II), r and s are the average degree of polymerization of the silicon-containing structure introduced into the side chain, and those in the range of 20 or less are more preferred. This is because by making it 20 or less, it is compatible with other polymerizable monomers, and the resulting copolymer tends to be dissolved in a general organic solvent. More preferably, it is the range of 10 or less, Especially preferably, it is the range of 5 or less.

The ^{R 8 ~R 10, R 12 ~R} 16, R 18 and the alkyl group may be selected by the R ¹⁹ of Formula (II), for example, a methyl group, an ethyl group, n- propyl group, and n- butyl group Can be mentioned. A methyl group or an ethyl group is preferable, and a methyl group is more preferable.

  Specific examples of the compound represented by formula (II) include, for example, TM-0701 (trade name) manufactured by Chisso Corporation and X-22-2404 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., assuming that p is 0. F2-250-01, F2-302-01 (trade name) manufactured by Nippon Unicar Co., Ltd., and the like. Examples of p greater than 0 include F2-302-04 (trade name) manufactured by Nihon Unicar.

A metal atom-containing polymerizable monomer having two unsaturated groups and containing a metal atom of Mg, Zn or Cu with respect to the copolymer component contained in the monomer mixture for forming the copolymer of the present invention. the content of mer (b ₁₎ is not particularly limited, is preferably in the range of 1 to 50 mass%. When the content is 1% by mass or more, the adhesion to the base is improved, and the self-polishing property of the formed coating film tends to be stably maintained for a long period of time. This is because the effect of improving the balance between the crack resistance and the adhesiveness after immersion in seawater becomes remarkable, the long-term self-polishing property is maintained, and the physical properties of the coating film tend to be improved. More preferably, it is the range of 5-30 mass%.

Examples of the metal atom-containing polymerizable monomer (b ₁ ) include magnesium acrylate [(CH ₂ ═CHCOO) ₂ Mg], magnesium methacrylate [(CH ₂ ═C (CH ₃ ) COO) ₂ Mg], Zinc acrylate [(CH ₂ ═CHCOO) ₂ Zn], zinc methacrylate [(CH ₂ ═C (CH ₃ ) COO) ₂ Zn], copper acrylate [(CH ₂ ═CHCOO) ₂ Cu], copper methacrylate [(CH ₂ ═C (CH ₃ ) COO) ₂ Cu] and the like. These can be used by appropriately selecting one kind or two or more kinds as necessary. Above all, when zinc (meth) acrylate is used, the color of the coated film tends to be beautiful due to the high transparency of the resulting polymerized product, and the solubility in commonly used organic solvents is also high. Since it is high, workability tends to be good, which is preferable. “(Meth) acryl” means acryl or methacryl (hereinafter the same including similar expressions).

As the method for producing the metal atom-containing polymerizable monomer (b ₁ ), an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer such as (meth) acrylic acid are used as an organic compound containing an alcohol compound. A method of reacting with water in a solvent is preferred. This is because the reaction product containing the metal atom-containing polymerizable monomer (b ₁ ) obtained by this method is an organic solvent or other component for forming a copolymer (silicon-containing polymerizable monomer or This is because it is excellent in compatibility with other copolymerizable unsaturated monomers described later and the copolymerization tends to be facilitated by using this. In this case, it is preferable to produce such that the water content in the reaction product is in the range of 0.01 to 30% by mass.

The monomer mixture for forming the copolymer of the present invention can further contain a metal atom-containing polymerizable monomer (b ₂ ) represented by the following formula (III). When the metal atom-containing polymerizable monomer (b ₂ ) represented by the formula (III) is used in combination, sufficient and long-term hydrolyzability is imparted to the formed coating film, and the coating film has crack resistance. This is preferable because the balance with the peel resistance is improved.

（式中、Ｒ²⁰は水素原子またはメチル基、ＭはＭｇ、ＺｎまたはＣｕ、Ｒ²¹は有機酸残基またはアルコール残基を示す）
上記の式（ＩＩＩ）で表される化合物の具体例としては、例えば、酢酸マグネシウム（メタ）アクリレート、酢酸亜鉛（メタ）アクリレート、酢酸銅（メタ）アクリレート、モノクロル酢酸マグネシウム（メタ）アクリレート、モノクロル酢酸亜鉛（メタ）アクリレート、モノクロル酢酸銅（メタ）アクリレート、モノフルオロ酢酸マグネシウム（メタ）アクリレート、モノフルオロ酢酸亜鉛（メタ）アクリレート、モノフルオロ酢酸銅（メタ）アクリレート、プロピオン酸マグネシウム（メタ）アクリレート、プロピオン酸亜鉛（メタ）アクリレート、プロピオン酸銅（メタ）アクリレート、カプロン酸マグネシウム（メタ）アクリレート、カプロン酸亜鉛（メタ）アクリレート、カプロン酸銅（メタ）アクリレート、カプリル酸マグネシウム（メタ）アクリレート、カプリル酸亜鉛（メタ）アクリレート、カプリル酸銅（メタ）アクリレート、２−エチルヘキシル酸マグネシウム（メタ）アクリレート、２−エチルヘキシル酸亜鉛（メタ）アクリレート、２−エチルヘキシル酸銅（メタ）アクリレート、カプリン酸マグネシウム（メタ）アクリレート、カプリン酸亜鉛（メタ）アクリレート、カプリン酸銅（メタ）アクリレート、バーサチック酸マグネシウム（メタ）アクリレート、バーサチック酸亜鉛（メタ）アクリレート、バーサチック酸銅（メタ）アクリレート、イソステアリン酸マグネシウム（メタ）アクリレート、イソステアリン酸亜鉛（メタ）アクリレート、イソステアリン酸銅（メタ）アクリレート、パルミチン酸マグネシウム（メタ）アクリレート、パルミチン酸亜鉛（メタ）アクリレート、パルミチン酸銅（メタ）アクリレート、クレソチン酸マグネシウム（メタ）アクリレート、クレソチン酸亜鉛（メタ）アクリレート、クレソチン酸銅（メタ）アクリレート、オレイン酸マグネシウム（メタ）アクリレート、オレイン酸亜鉛（メタ）アクリレート、オレイン酸銅（メタ）アクリレート、エライジン酸マグネシウム（メタ）アクリレート、エライジン酸亜鉛（メタ）アクリレート、エライジン酸銅（メタ）アクリレート、リノール酸マグネシウム（メタ）アクリレート、リノール酸亜鉛（メタ）アクリレート、リノール酸銅（メタ）アクリレート、リノレン酸マグネシウム（メタ）アクリレート、リノレン酸亜鉛（メタ）アクリレート、リノレン酸銅（メタ）アクリレート、ステアロール酸マグネシウム（メタ）アクリレート、ステアロール酸亜鉛（メタ）アクリレート、ステアロール酸銅（メタ）アクリレート、リシノール酸マグネシウム（メタ）アクリレート、リシノール酸亜鉛（メタ）アクリレート、リシノール酸銅（メタ）アクリレート、リシノエライジン酸マグネシウム（メタ）アクリレート、リシノエライジン酸亜鉛（メタ）アクリレート、リシノエライジン酸銅（メタ）アクリレート、ブラシジン酸マグネシウム（メタ）アクリレート、ブラシジン酸亜鉛（メタ）アクリレート、ブラシジン酸銅（メタ）アクリレート、エルカ酸マグネシウム（メタ）アクリレート、エルカ酸亜鉛（メタ）アクリレート、エルカ酸銅（メタ）アクリレート、α−ナフトエ酸マグネシウム（メタ）アクリレート、α−ナフトエ酸亜鉛（メタ）アクリレート、α−ナフトエ酸銅（メタ）アクリレート、β−ナフトエ酸マグネシウム（メタ）アクリレート、β−ナフトエ酸亜鉛（メタ）アクリレート、β−ナフトエ酸銅（メタ）アクリレート、安息香酸マグネシウム（メタ）アクリレート、安息香酸亜鉛（メタ）アクリレート、安息香酸銅（メタ）アクリレート、２，４，５−トリクロロフェノキシ酢酸マグネシウム（メタ）アクリレート、２，４，５−トリクロロフェノキシ酢酸亜鉛（メタ）アクリレート、２，４，５−トリクロロフェノキシ酢酸銅（メタ）アクリレート、２，４−ジクロロフェノキシ酢酸マグネシウム（メタ）アクリレート、２，４−ジクロロフェノキシ酢酸亜鉛（メタ）アクリレート、２，４−ジクロロフェノキシ酢酸銅（メタ）アクリレート、キノリンカルボン酸マグネシウム（メタ）アクリレート、キノリンカルボン酸亜鉛（メタ）アクリレート、キノリンカルボン酸銅（メタ）アクリレート、ニトロ安息香酸マグネシウム（メタ）アクリレート、ニトロ安息香酸亜鉛（メタ）アクリレート、ニトロ安息香酸銅（メタ）アクリレート、ニトロナフタレンカルボン酸マグネシウム（メタ）アクリレート、ニトロナフタレンカルボン酸亜鉛（メタ）アクリレート、ニトロナフタレンカルボン酸銅（メタ）アクリレート、プルビン酸マグネシウム（メタ）アクリレート、プルビン酸亜鉛（メタ）アクリレート、プルビン酸銅（メタ）アクリレート等が挙げられる。これらは、１種または２種以上を必要に応じて適宜選択して使用することができる。中でも、有機酸残基が脂肪酸系のものを使用すると、長期にわたりクラックや剥離のない塗膜を維持することができる傾向にあり好ましい。亜鉛を含有するものを使用すると、得られる重合生成物の透明性が高いため塗装された塗膜の色調が美しくなる傾向にあり、また一般的に使用される有機溶剤への溶解性が高いため作業性が良好となる傾向にあり好ましい。特に、可塑性の高いオレイン酸亜鉛（メタ）アクリレートやバーサチック酸亜鉛（メタ）アクリレートの重合性単量体が好ましい。

(Wherein R ²⁰ represents a hydrogen atom or a methyl group, M represents Mg, Zn or Cu, and R ²¹ represents an organic acid residue or an alcohol residue)
Specific examples of the compound represented by the above formula (III) include, for example, magnesium acetate (meth) acrylate, zinc acetate (meth) acrylate, copper acetate (meth) acrylate, monochloromagnesium acetate (meth) acrylate, monochloroacetic acid Zinc (meth) acrylate, monochloro copper acetate (meth) acrylate, magnesium monofluoroacetate (meth) acrylate, zinc monofluoroacetate (meth) acrylate, copper monofluoroacetate (meth) acrylate, magnesium propionate (meth) acrylate, propion Zinc (meth) acrylate, copper propionate (meth) acrylate, magnesium caproate (meth) acrylate, zinc caproate (meth) acrylate, copper caproate (meth) acrylate, magnesium caprylate (Meth) acrylate, zinc caprylate (meth) acrylate, copper caprylate (meth) acrylate, magnesium 2-ethylhexylate (meth) acrylate, zinc 2-ethylhexylate (meth) acrylate, copper 2-ethylhexylate (meth) Acrylate, magnesium caprate (meth) acrylate, zinc caprate (meth) acrylate, copper caprate (meth) acrylate, magnesium versatate (meth) acrylate, zinc versatate (meth) acrylate, copper versatate (meth) acrylate, Magnesium isostearate (meth) acrylate, zinc isostearate (meth) acrylate, copper isostearate (meth) acrylate, magnesium palmitate (meth) acrylate, palmiti Zinc acid (meth) acrylate, copper palmitate (meth) acrylate, magnesium cresotate (meth) acrylate, zinc cresotate (meth) acrylate, copper cresate (meth) acrylate, magnesium oleate (meth) acrylate, zinc oleate (Meth) acrylate, copper oleate (meth) acrylate, magnesium elaidate (meth) acrylate, zinc elaidate (meth) acrylate, copper elaidate (meth) acrylate, magnesium linoleate (meth) acrylate, zinc linoleate (meta ) Acrylate, copper linoleate (meth) acrylate, magnesium linolenate (meth) acrylate, zinc linolenate (meth) acrylate, copper linolenate (meth) acrylate, stearolic acid magne Cium (meth) acrylate, zinc stearolate (meth) acrylate, copper stearolate (meth) acrylate, magnesium ricinoleate (meth) acrylate, zinc ricinoleate (meth) acrylate, copper ricinoleate (meth) acrylate, ricino Magnesium elaidate (meth) acrylate, zinc ricinoelaidate (meth) acrylate, copper ricinoelaidate (meth) acrylate, magnesium brassinate (meth) acrylate, zinc brassinate (meth) acrylate, copper brassinate (meth) Acrylate, magnesium erucate (meth) acrylate, zinc erucate (meth) acrylate, copper erucate (meth) acrylate, magnesium α-naphthoate (meth) acrylate, α-naphthoic acid zinc (meth) a Chlorate, α-naphthoic acid copper (meth) acrylate, β-naphthoic acid magnesium (meth) acrylate, β-naphthoic acid zinc (meth) acrylate, β-naphthoic acid copper (meth) acrylate, magnesium benzoate (meth) acrylate, Zinc benzoate (meth) acrylate, copper benzoate (meth) acrylate, 2,4,5-trichlorophenoxyacetate magnesium (meth) acrylate, 2,4,5-trichlorophenoxyacetate zinc (meth) acrylate, 2,4,5 5-trichlorophenoxyacetate copper (meth) acrylate, 2,4-dichlorophenoxyacetate magnesium (meth) acrylate, 2,4-dichlorophenoxyacetate zinc (meth) acrylate, 2,4-dichlorophenoxyacetate copper (meth) acrylate, Quinoline carboxylic acid Gnesium (meth) acrylate, zinc quinolinecarboxylate (meth) acrylate, copper quinolinecarboxylate (meth) acrylate, magnesium nitrobenzoate (meth) acrylate, zinc nitrobenzoate (meth) acrylate, copper nitrobenzoate (meth) acrylate , Magnesium nitronaphthalenecarboxylate (meth) acrylate, Zinc nitronaphthalenecarboxylate (meth) acrylate, Copper nitronaphthalenecarboxylate (meth) acrylate, Magnesium puruvate (meth) acrylate, Zinc puruvate (meth) acrylate, Copper puruvate (Meth) acrylate etc. are mentioned. These can be used by appropriately selecting one kind or two or more kinds as necessary. Among them, it is preferable to use a fatty acid-based organic acid residue because it tends to maintain a coating film free from cracks and peeling over a long period of time. If zinc-containing material is used, the resulting polymerized product is highly transparent, so the color of the coated film tends to be beautiful, and it is highly soluble in commonly used organic solvents. This is preferable because workability tends to be good. In particular, polymerizable monomers such as zinc oleate (meth) acrylate and zinc versatate (meth) acrylate having high plasticity are preferable.

Examples of the method for producing the metal atom-containing polymerizable monomer (b ₂ ) include an inorganic metal compound, a carboxyl group-containing radical polymerizable monomer such as (meth) acrylic acid, a non-polymerizable organic acid, Can be reacted in an organic solvent containing an alcohol compound.

Ratio of content of metal atom-containing polymerizable monomer (b ₂ ) and metal atom-containing polymerizable monomer (b ₁ ) contained in the monomer mixture for forming the copolymer ((b ₂ ) / (b ₁ )) is preferably in the range of 20/80 to 80/20 (molar ratio). This is because when the ratio is 80/20 or less, there is a tendency that the coating film properties excellent in crack resistance and adhesion are obtained, while on the other hand, the coating formed is formed when the ratio is 20/80 or more. This is because the self-polishing property of the film tends to be maintained for a long time. More preferably, it is the range of 30 / 70-70 / 30.

Further, the total content of the metal-containing polymerizable monomer (b ₁ ) and the metal-containing polymerizable monomer (b ₂ ) with respect to the copolymer component contained in the monomer mixture for forming the copolymer Is preferably in the range of 1 to 50% by mass. When the content is 1% by mass or more, the adhesion to the base is improved, and the self-polishing property of the formed coating film tends to be stably maintained for a long period of time. This is because the effect of improving the balance between the crack resistance and the adhesiveness after immersion in seawater becomes remarkable, the long-term self-polishing property is maintained, and the physical properties of the coating film tend to be improved. More preferably, it is the range of 5-30 mass%.

Further, the above-mentioned silicon-containing polymerizable monomer (a) and metal atom-containing polymerizable monomer (b ₁ ) used in the monomer mixture for forming the copolymer are preferably used. In addition to the metal atom-containing polymerizable monomer (b ₂ ) which is in the form, an unsaturated monomer (c) copolymerizable with these can be used.

  The component (c) can be appropriately used as necessary, and is not necessarily used, but can be copolymerized with the resin component contained in the monomer mixture for forming the copolymer. The content of the unsaturated monomer (c) is preferably in the range of 0.1 to 89% by mass. This tends to be able to balance the various properties of the resulting antifouling paint by setting it to 0.1% by mass or more. By setting it to 89% by mass or less, the coating film to be formed has a long term. This is because excellent hydrolyzability is imparted, excellent antifouling properties are exhibited even when no antifouling agent is used, and the balance with the adhesion of the coating tends to be good. More preferably, it is the range of 7-75 mass%, More preferably, it is the range of 10-70 mass%.

  Examples of such copolymerizable unsaturated monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, Phenoxyethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 3-methyl-3- Methoxybutyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenylethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenylethyl (Meth) acrylate, n- Lopyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) (Meth) acrylic acid ester monomers such as acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate; 2 -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Hydroxyl-containing monomers such as carbonates; adducts of 2-hydroxyethyl (meth) acrylate with ethylene oxide, propylene oxide, γ-butyrolactone, ε-caprolactone, etc .; 2-hydroxyethyl (meth) acrylate, 2-hydroxy Dimers or trimers such as propyl (meth) acrylate; monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate; primary and second monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide Secondary amino group-containing vinyl monomer: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, dimethyl Tertiary amino group-containing vinyl monomers such as minoethyl (meth) acrylamide and dimethylaminopropyl (meth) acrylamide; heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole; styrene, vinyltoluene , Α-methylstyrene, (meth) acrylonitrile, vinyl acetate, vinyl propionate, and other vinyl monomers.

  The method for producing the above-mentioned copolymer is not particularly limited. For example, a monomer mixture obtained by mixing the above-described monomers is prepared at a reaction temperature of 60 to 180 ° C. in the presence of a radical initiator. It can manufacture by making it react for -14 hours. Examples of the radical initiator include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis (2-methylbutyronitrile), peroxide Benzoyl, cumene hydroperoxide, lauryl peroxide, di-t-butyl peroxide, t-butylperoxy-2-ethylhexanoate and the like can be used.

In addition, a chain transfer agent can be used to achieve high solids and improve productivity, in particular, to suppress the formation of cullet during polymerization. From the viewpoint of compatibility with the metal atom-containing polymerizable monomer (b ₁ ), chain transfer agents other than mercaptans are preferable, and styrene dimers and the like are preferable. As the polymerization method, in addition to the solution polymerization method performed in an organic solvent, an emulsion polymerization method, a suspension polymerization method, and the like can be adopted, but a general organic solvent such as toluene, xylene, methyl isobutyl ketone, and n-butyl acetate is used. Adopting a solution polymerization method is advantageous in terms of productivity and performance.

Although the weight average molecular weight of the copolymer of the present invention as described above varies depending on the polymerization conditions, it is usually in the range of 1000 to 3000000. When the coating film is formed when the weight average molecular weight is 1000 or more, antifouling property can be exhibited, and when the weight average molecular weight is 3000000 or less, the copolymer is easily dispersed uniformly in the coating composition. The range of 3000-100000 is more preferable, and the range of 5000-50000 is particularly preferable. The weight average molecular weight can be measured by gel permeation chromatography (GPC). Moreover, it is confirmed using ¹ H-NMR, ICP emission analysis, etc. that the above-mentioned silicon-containing polymerizable monomer (a) contained in the monomer mixture is copolymerized. can do. Moreover, it can be confirmed, for example, by atomic absorption analysis that the copolymer contains a divalent metal atom.

  The coating composition of the present invention can retain excellent antifouling performance in the formed coating film by containing the above copolymer as a vehicle component. Furthermore, antifouling performance can be further improved by blending an antifouling agent.

  In the coating composition of the present invention, the proportion of the copolymer as a vehicle when using a pigment component or the like without using an antifouling agent is expressed as (resin solid component) / (solid component such as pigment). The ratio is preferably 0.3 or more. In the case of 0.3 or more, even when the antifouling agent is not used, it tends to be possible to develop an excellent antifouling effect. This is because the antifouling effect tends to hardly occur. More preferably, it is 0.5 or more.

  In order to further improve the antifouling performance, the antifouling agent used in the coating composition of the present invention can be appropriately selected and used according to the required performance. For example, copper-based antifouling agents such as cuprous oxide, thiocyanic copper and copper powder, other metal compounds such as lead, zinc and nickel, amine derivatives such as diphenylamine, nitrile compounds, benzothiazole compounds, maleimide compounds, Examples include pyridine compounds. These can be used alone or in combination. In particular, those selected and selected for research by the Japan Shipbuilding Industry Association, etc. are preferable. For example, Manganese ethylene bisdithiocarbamate, zinc dimethyldithiocarbamate, 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-3 (2H) isothiazolone, N- (fluorodichloromethylthio) phthalimide, N, N'-dimethyl-N'-phenyl- (N-fluorodichloromethylthio) sulfamide, 2-pyridinethiol-1-oxide zinc salt , Tetramethylthiuram disulfide, Cu-10% i solid solution alloy, 2,4,6-trichlorophenylmaleimide 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, 3-iodo-2-propynylbutylcarbamate, diiodomethyl Examples include paratrisulfone, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, phenyl (bispyridyl) bismuth dichloride, 2- (4-thiazolyl) -benzimidazole, and pyridine-triphenylborane.

  The coating composition of the present invention also includes silicon compounds such as dimethylpolysiloxane and silicone oil, and fluorine-containing compounds such as fluorocarbons for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms. Can be blended. Furthermore, the paint composition of the present invention can contain extender pigments, color pigments, plasticizers, various paint additives, other resins, and the like as necessary.

  Examples of the solvent used in the coating composition of the present invention include xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, and n-butanol. The organic solvent may be used alone or in combination of two or more.

  In order to form a coating film using the coating composition of the present invention, the coating composition described above is applied to the surface of a substrate such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base. Apply directly or on the base material with a primer such as wash primer, chlorinated rubber, epoxy, etc., intermediate coating, etc., by brushing, spraying, roller coating, submersion coating, etc. . The coating amount is generally such an amount as to give a thickness of 50 to 400 μm as a dry coating film. The coating film is generally dried at room temperature, but may be heat-dried.

  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.

[Production Example M1: Production of metal atom-containing polymerizable monomer mixture M1]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer 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 metal atom-containing polymerizable monomer mixture M1. The solid content was 44.8%.

[Production Example M2: Production of metal atom-containing polymerizable monomer mixture M2]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 72.4 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 30.1 parts of methacrylic acid, 25.2 parts of acrylic acid, and 51.6 parts of versatic acid was dropped from the dropping funnel at a constant rate over 3 hours. After further stirring for 2 hours, 11 parts of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture M2. The solid content was 59.6%.

[Production Example M3: Production of metal atom-containing polymerizable monomer mixture M3]
A four-necked flask equipped with a condenser, thermometer, dropping funnel and stirrer was charged with 60 parts of xylene, 13 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 32.3 parts of methacrylic acid, 27 parts of acrylic acid, 37.7 parts of oleic acid, 2.3 parts of acetic acid, and 5.8 parts of propionic acid was dropped from the dropping funnel at a constant rate over 3 hours. After further stirring for 2 hours, 77 parts of xylene and 46 parts of PGM were added to obtain a transparent metal atom-containing polymerizable monomer mixture M3. The solid content was 39.6%.

[Production Example M4: Production of metal atom-containing polymerizable monomer mixture M4]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 85 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 21.5 parts of methacrylic acid, 18 parts of acrylic acid and 85.5 parts of versatic acid was dropped from the dropping funnel at a constant rate over 3 hours. After further stirring for 2 hours, 10.5 parts of PGM was added to obtain a transparent metal atom-containing polymerizable monomer mixture M4. The solid content was 59.8%.

[Production Example P1: Production of metal atom-containing resin composition P1]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 65 parts of xylene and 4 parts of ethyl acrylate, and the temperature was raised to 100 ° C. while stirring. Subsequently, 32.3 parts of methyl methacrylate, 43.9 parts of ethyl acrylate, 10 parts of FM-0721 (trade name, manufactured by Chisso Corporation) and a metal atom-containing polymerizable monomer mixture described in Production Example M1 (M1) from the dropping funnel ) 21.7 parts, 10 parts of xylene, 1.2 parts of chain transfer agent (Nofmer MSD (trade name), α-methylstyrene dimer manufactured by NOF Corporation), 2.5 parts of azobisisobutyronitrile (AIBN), A transparent mixture composed of 3 parts of azobismethylbutyronitrile (AMBN) was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.1 parts of xylene was added, and the heating residue was 45.7%. A pale yellow transparent metal atom-containing resin composition P1 having a Gardner viscosity -U was obtained.

  When the obtained metal atom-containing resin composition P1 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P1 was analyzed. The weight average molecular weight was 6800. Further, a copolymer isolated from the obtained metal atom-containing resin composition P1 by methanol reprecipitation was collected in a platinum crucible, sulfuric acid was added, and the mixture was heated in a pressure decomposition vessel. After volatilizing the sulfuric acid, the copolymer was completely ashed. This ashed product was allowed to cool and then alkali-melted, and analyzed by an ICP emission analyzer (ICAP-575 MK-II (trade name) manufactured by Japan Jarrell Ash). As a result, Si atoms were confirmed. Further, when the copolymer was analyzed by an atomic absorption spectrophotometer (AA6800 (trade name) manufactured by Shimadzu Corporation), a signal derived from Zn atoms was confirmed.

[Production Example P2: Production of metal atom-containing resin composition P2]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 65 parts of xylene and 4 parts of ethyl acrylate, and the temperature was raised to 100 ° C. while stirring. Subsequently, from the dropping funnel, 32.3 parts of methyl methacrylate, 33.9 parts of ethyl acrylate, 20 parts of FM-0711 (trade name, manufactured by Chisso Corporation), metal atom-containing polymerizable monomer mixture described in Production Example M1 (M1) ) 21.7 parts, 10 parts of xylene, 1.2 parts of chain transfer agent (NOFMER MSD (trade name) manufactured by NOF Corporation), 2.5 parts of AIBN, and 2 parts of AMBN were dropped at a constant rate over 6 hours. . After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. Then, 10.1 parts of xylene was added, and the heating residue was 45.4%. A light yellow transparent metal atom-containing resin composition P2 having a Gardner viscosity + V was obtained.

  When the obtained metal atom-containing resin composition P2 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P2 was analyzed. The weight average molecular weight was 7600.

[Production Example P3: Production of metal atom-containing resin composition P3]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 65 parts of xylene and 4 parts of ethyl acrylate, and the temperature was raised to 100 ° C. while stirring. Subsequently, from the dropping funnel, 32.3 parts of methyl methacrylate, 13.9 parts of ethyl acrylate, 40 parts of FM-0711 (trade name, manufactured by Chisso Corporation), metal atom-containing polymerizable monomer mixture described in Production Example M1 (M1) ) 21.7 parts, 10 parts of xylene, 1.2 parts of chain transfer agent (NOFMER MSD (trade name) manufactured by NOF Corporation), 2.5 parts of AIBN, 0.8 parts of AMBN at a constant rate in 6 hours. It was dripped. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. After that, 10.1 parts of xylene was added, and the heating residue was 45.1%. A light yellow transparent metal atom-containing resin composition P3 having a Gardner viscosity + U was obtained.

  When the obtained metal atom-containing resin composition P3 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P3 was analyzed. The weight average molecular weight was 8800.

[Production Example P4: Production of metal atom-containing resin composition P4]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 61 parts of xylene and heated to 100 ° C. while stirring. Subsequently, from the dropping funnel, 18 parts of methyl methacrylate, 25 parts of ethyl acrylate, 40 parts of X-24-8201 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), metal atom-containing polymerizable monomer mixture (M2) described in Production Example M2 A transparent mixture consisting of 28.4 parts, 20 parts of PGM, 2.5 parts of AIBN and 1 part of AMBN was added dropwise at a constant rate over 4 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. After that, 4.6 parts of xylene was added, and the heating residue was 45.2%. A light yellow transparent metal atom-containing resin composition P4 having a Gardner viscosity + U was obtained.

  When the obtained metal atom-containing resin composition P4 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P4 was analyzed. The weight average molecular weight was 8200.

[Production Example P5: Production of metal atom-containing resin composition P5]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 35 parts of PGM (propylene glycol methyl ether) and 41 parts of xylene and heated to 100 ° C. while stirring. Subsequently, from the dropping funnel, 18 parts of methyl methacrylate, 15 parts of ethyl acrylate, 50 parts of X-24-8201 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), metal atom-containing polymerizable monomer mixture described in Production Example M3 (M3) A transparent mixture composed of 42.5 parts, 5 parts of PGM, 2.5 parts of AIBN, and 1 part of AMBN was dropped at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. After that, 5.5 parts of xylene was added, and the heating residue was 45.0%. A light yellow transparent metal atom-containing resin composition P5 having a Gardner viscosity + R was obtained.

  When the obtained metal atom-containing resin composition P5 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P5 was analyzed. The weight average molecular weight was 7200.

[Production Example P6: Production of metal atom-containing resin composition P6]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 59 parts of xylene and 4 parts of ethyl acrylate and heated to 100 ° C. with stirring. Subsequently, from the dropping funnel, 26.4 parts of methyl methacrylate, 25.5 parts of ethyl acrylate, 30 parts of F-254-04 (trade name, manufactured by Nihon Unicar), metal atom-containing polymerizable monomer described in Production Example M1 A transparent mixture composed of 31.3 parts of mixture (M1), 10 parts of xylene, 1.5 parts of chain transfer agent (NOFMER MSD (trade name) manufactured by NOF Corporation), 2.5 parts of AIBN, 4 parts of AMBN, etc. in 6 hours, etc. It was dripped quickly. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.8 parts of xylene was added, and the heating residue was 45.8%. A light yellow transparent metal atom-containing resin composition P6 having a Gardner viscosity -W was obtained.

  When the obtained metal atom-containing resin composition P6 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P6 was analyzed. The weight average molecular weight was 6400.

[Production Example P7: Production of metal atom-containing resin composition P7]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 59 parts of xylene and 4 parts of ethyl acrylate and heated to 100 ° C. with stirring. Subsequently, 21.4 parts of methyl methacrylate, 25.5 parts of ethyl acrylate, 5 parts of styrene, 30 parts of F-254-14 (trade name, manufactured by Nihon Unicar) from the dropping funnel, metal atom-containing polymerization described in Production Example M1 Transparent monomer mixture (M1) 31.3 parts, xylene 10 parts, chain transfer agent (Nofmer MSD (trade name) manufactured by NOF Corporation) 1.5 parts, AIBN 2.5 parts, AMBN 2.5 parts The mixture was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.8 parts of xylene was added, and the heating residue was 45.3%. A light yellow transparent metal atom-containing resin composition P7 having a Gardner viscosity -T was obtained.

  When the obtained metal atom-containing resin composition P7 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P7 was analyzed. The weight average molecular weight was 6900.

[Production Example P8: Production of metal atom-containing resin composition P8]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 59 parts of xylene and 4 parts of ethyl acrylate and heated to 100 ° C. with stirring. Subsequently, 26.4 parts of methyl methacrylate, 14.5 parts of ethyl acrylate, 5 parts of 2-methoxyethyl acrylate, 20 parts of FM-0711 (trade name, manufactured by Chisso Corporation), TM-0701 (trade name, Chisso) from the dropping funnel. 20 parts, 31.3 parts of the metal atom-containing polymerizable monomer mixture (M1) described in Production Example M1, 10 parts of xylene, chain transfer agent (NOFMER MSD (trade name) manufactured by NOF Corporation) 1.5 A transparent mixture consisting of 2.5 parts of AIBN, 2.5 parts of AIBN and 2.5 parts of AMBN was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.8 parts of xylene was added, and the heating residue was 45.6%. A light yellow transparent metal atom-containing resin composition P8 having a Gardner viscosity of -V was obtained.

  When the obtained metal atom-containing resin composition P8 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P8 was analyzed. The weight average molecular weight was 7000.

[Production Example P9: Production of metal atom-containing resin composition P9]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 61 parts of xylene and heated to 100 ° C. while stirring. Subsequently, from the dropping funnel, 18 parts of methyl methacrylate, 35 parts of ethyl acrylate, 30 parts of F2-302-01 (trade name, manufactured by Nihon Unicar), metal atom-containing polymerizable monomer mixture (M2) described in Production Example M2 A transparent mixture composed of 28.4 parts, 20 parts of PGM, 2.5 parts of AIBN, and 2 parts of AMBN was added dropwise at a constant rate over 4 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 4.6 parts of xylene was added, and the heating residue was 45.3%. A light yellow transparent metal atom-containing resin composition P9 having a Gardner viscosity + T was obtained.

  When the obtained metal atom-containing resin composition P9 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P9 was analyzed. The weight average molecular weight was 7700.

[Production Example P10: Production of metal atom-containing resin composition P10]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 59 parts of xylene and 4 parts of ethyl acrylate and heated to 100 ° C. with stirring. Subsequently, from the dropping funnel, 26.4 parts of methyl methacrylate, 35.5 parts of ethyl acrylate, 20 parts of F-302-04 (trade name, manufactured by Nihon Unicar), metal atom-containing polymerizable monomer described in Production Example M1 A transparent mixture comprising 31.3 parts of the mixture (M1), 10 parts of xylene, 1.5 parts of a chain transfer agent (Nofmer MSD (trade name) manufactured by NOF Corporation), 2.5 parts of AIBN, and 5.5 parts of AMBN for 6 hours At a constant speed. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.8 parts of xylene was added, and the heating residue was 45.6%. A pale yellow transparent metal atom-containing resin composition P10 having a Gardner viscosity + W was obtained.

  When the obtained metal atom-containing resin composition P10 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P10 was analyzed. The weight average molecular weight was 6000.

[Production Example P11: Production of metal atom-containing resin composition P11]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 120 parts of xylene and 30 parts of n-butanol and heated to 100 ° C. while stirring. Subsequently, a mixture comprising 20 parts of ethyl acrylate, 25 parts of 2-ethylhexyl acrylate, 15 parts of acrylic acid, 40 parts of FM-0711 (trade name, manufactured by Chisso Corporation) and 1 part of azobisisobutyronitrile from the dropping funnel. Was added dropwise at a constant rate in 3 hours. After completion of dropping, the mixture was stirred for 2 hours to obtain a varnish having a solid content of 39.4% and a characteristic value of Gardner viscosity + B.

  Next, 100 parts of the obtained varnish, 20 parts of naphthenic acid, and 7 parts of copper hydroxide were added to a four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer, and the temperature was raised to 120 ° C. After stirring for a period of time and dehydrating the water (2.6 g) produced during this time, a metal atom-containing resin composition P11 having a heating residue of 50.8% and a characteristic value of Gardner viscosity + E was obtained.

  When the obtained metal atom-containing resin composition P11 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P11 was analyzed. The weight average molecular weight was 9,200.

[Production Example P12: Production of metal atom-containing resin composition P12]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether), 65 parts of xylene and 4 parts of ethyl acrylate, and the temperature was raised to 100 ° C. while stirring. Subsequently, from the dropping funnel, 32.3 parts of methyl methacrylate, 53.9 parts of ethyl acrylate, 21.7 parts of the metal atom-containing polymerizable monomer mixture (M1) described in Production Example M1, 10 parts of xylene, a chain transfer agent ( Transparent made of NOFMER MSD (trade name), α-methylstyrene dimer (Nippon Yushi Co., Ltd.) 1.2 parts, 2.5 parts azobisisobutyronitrile (AIBN), 4 parts azobismethylbutyronitrile (AMBN) The mixture was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.1 parts of xylene was added, and the heating residue was 45.6%. A pale yellow transparent metal atom-containing resin composition P12 having a Gardner viscosity -S was obtained.

  When the obtained metal atom-containing resin composition P12 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P12 was analyzed. The weight average molecular weight was 6600.

[Production Example P13: Production of metal atom-containing resin composition P13]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 61 parts of xylene and heated to 100 ° C. while stirring. Subsequently, from the dropping funnel, 15.6 parts of methyl methacrylate, 25 parts of ethyl acrylate, 40 parts of X-24-8201 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), metal atom-containing polymerizable monomer mixture described in Production Example M2 ( M4) A transparent mixture composed of 32.3 parts, 20 parts of PGM and 1.5 parts of AIBN was added dropwise at a constant rate over 4 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. After that, 3.1 parts of xylene was added, and the heating residue was 44.8%. A pale yellow transparent metal atom-containing resin composition P13 having a Gardner viscosity + K was obtained.

  When the obtained metal atom-containing resin composition P13 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P13 was analyzed. The weight average molecular weight was 9000.

[Production Example P14: Production of Resin Composition P14]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 65 parts of xylene and heated to 100 ° C. while stirring. Subsequently, 42.1 parts of methyl methacrylate, 37.9 parts of ethyl acrylate, 20 parts of FM-0711 (trade name, manufactured by Chisso Corporation), 10 parts of xylene, 11.9 parts of PGM, chain transfer agent (Nippon Yushi Co., Ltd.) A transparent mixture comprising 1.2 parts of NOFMER MSD (trade name), 2.5 parts of AIBN, and 2 parts of AMBN was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes, and then 10.1 parts of xylene was added, and the heating residue was 44.8%. A transparent resin composition P14 having a Gardner viscosity + E was obtained.

  When the obtained metal atom-containing resin composition P14 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P14 was analyzed. The weight average molecular weight was 6200.

[Production Example P15: Production of Resin Composition P15]
A four-necked flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of PGM (propylene glycol methyl ether) and 65 parts of xylene and heated to 100 ° C. while stirring. Subsequently, 42.1 parts of methyl methacrylate, 17.9 parts of ethyl acrylate, 40 parts of FM-0711 (trade name, manufactured by Chisso Corporation), 10 parts of xylene, 11.9 parts of PGM, chain transfer agent (Nippon Yushi Co., Ltd.) A transparent mixture consisting of 1.2 parts of NOFMER MSD (trade name), 2.5 parts of AIBN, and 0.8 parts of AMBN was added dropwise at a constant rate over 6 hours. After completion of the dropwise addition, 0.5 part of t-butyl peroctoate and 10 parts of xylene were added dropwise over 30 minutes, and the mixture was further stirred for 1 hour and 30 minutes. Then, 10.1 parts of xylene was added, and the heating residue was 44.4%. A transparent resin composition P15 having a Gardner viscosity + C was obtained.

  When the obtained metal atom-containing resin composition P15 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the copolymer contained in the metal atom-containing resin composition P15 was analyzed. The weight average molecular weight was 6600.

  Table 1 shows the charged amounts (molar ratio) of the metal atom-containing polymerizable monomer mixtures (M1 to M4) of Production Examples M1 to M4, the volatile components and metal atom contents in the metal atom-containing polymerizable monomer mixture. (% By mass) and solid content (% by mass) are described.

注）表中に使用される略号は下記を表す。
ＭＡＡ：メタクリル酸、ＡＡ：アクリル酸、ＺｎＯ：酸化亜鉛、ＰＧＭ：プロピレングリコールモノメチルエーテル
＊１）金属原子含有重合性単量体混合物中の値を示す。

Note) Abbreviations used in the table represent the following.
MAA: methacrylic acid, AA: acrylic acid, ZnO: zinc oxide, PGM: propylene glycol monomethyl ether * 1) Values in the metal atom-containing polymerizable monomer mixture are shown.

  In Table 2, the metal atom-containing resin compositions of Production Examples P1 to P10, P12 and P13, and the charged amounts (parts by mass) of each component when producing the resin compositions of P14 and P15, and the metal atom content obtained The viscosity (Gardner) and solid content (mass%) of the resin composition or resin composition are described.

ＦＭ−０７１１（商品名、チッソ（株）品）：式（Ｉ）中、ｌ＝０、Ｒ¹〜Ｒ⁶はメチル基、ｍ＝３、ｎ＝１０
ＦＭ−０７２１（商品名、チッソ（株）品）：式（Ｉ）中、ｌ＝０、Ｒ¹〜Ｒ⁶はメチル基、ｍ＝３、ｎ＝６５
Ｘ−２４−８２０１（商品名、信越化学（株）品）：式（Ｉ）中、ｌ＝０、Ｒ¹〜Ｒ⁶はメチル基、ｍ＝３、ｎ＝２５
Ｆ２−２５４−０４（商品名、日本ユニカー（株）品）：式（Ｉ）中、ｌ＝１０、ｋは２と３のものの混合物でモル比率が５：５、Ｒ¹〜Ｒ⁶はメチル基、ｍ＝３、ｎ＝１０
Ｆ２−２５４−１４（商品名、日本ユニカー（株）品）：式（Ｉ）中、ｌ＝４、ｋは２と３のものの混合物でモル比率が５：５、Ｒ¹〜Ｒ⁶はメチル基、ｍ＝３、ｎ＝１０
ＴＭ−０７０１（商品名、チッソ（株）品）：式（ＩＩ）中、ｐ＝０、ｑ＝３、Ｒ⁷〜Ｒ¹⁰はメチル基
Ｆ２−３０２−０１（商品名、日本ユニカー（株）品）：式（ＩＩ）中、ｐ＝０、ｑ＝３、Ｒ⁷〜Ｒ⁹はメチル基、Ｒ¹⁰はＲ¹¹（ｒ＝３，Ｒ¹²〜Ｒ¹⁶はメチル基）
Ｆ２−３０２−０４（商品名、日本ユニカー（株）品）：一般式（ＩＩ）中、ｐ＝１０、ｏは２と３のものの混合物でモル比率が５：５、ｍ＝３、Ｒ⁷〜Ｒ¹⁰はメチル基
ＭＭＡ：メチルメタクリレート
ＥＡ：エチルアクリレート
２−ＭＴＡ：２−メトキシエチルアクリレート
Ｓｔ：スチレン
ＡＩＢＮ：アゾビスイソブチロニトリル
ＡＭＢＮ：アゾビスメチルイソブチロニトリル
ノフマーＭＳＤ（商品名、日本油脂社製）：連鎖移動剤
＊１）ガードナー泡粘度計を用い、２５℃で測定した。

FM-0711 (trade name, manufactured by Chisso Corporation): in formula (I), l = 0, R ^{1 to} R ⁶ are methyl groups, m = 3, n = 10
FM-0721 (trade name, manufactured by Chisso Corporation): in formula (I), l = 0, R ^{1 to} R ⁶ are methyl groups, m = 3, n = 65
X-24-8201 (trade name, Shin-Etsu Chemical Co., Ltd.): In formula (I), l = 0, R ^{1 to} R ⁶ are methyl groups, m = 3, n = 25
F2-254-04 (trade name, Nippon Unicar Co., Ltd.): In formula (I), l = 10, k is a mixture of 2 and 3, molar ratio is 5: 5, R ^{1 to} R ⁶ are methyl Group, m = 3, n = 10
F2-254-14 (trade name, Nippon Unicar Co., Ltd.): In formula (I), l = 4, k is a mixture of 2 and 3, molar ratio is 5: 5, R ^{1 to} R ⁶ are methyl Group, m = 3, n = 10
TM-0701 (trade name, product of Chisso Corporation): in formula (II), p = 0, q = 3, R ^{7 to} R ¹⁰ are methyl groups F2-302-01 (trade name, Nippon Unicar Co., Ltd.) goods): formula (II) in, p = 0, q = 3 , R 7 ~R 9 is a methyl group, R ¹⁰ is ^{R 11 (r = 3, R} 12 ~R 16 is methyl)
F2-302-04 (trade name, Nippon Unicar Co., Ltd.): In general formula (II), p = 10, o is a mixture of 2 and 3, molar ratio is 5: 5, m = 3, R ⁷ to R ¹⁰ is a methyl group MMA: methyl methacrylate EA: ethyl acrylate 2-MTA: 2-methoxyethyl acrylate St: styrene AIBN: azobisisobutyronitrile AMBN: azo-bis-methyl-isobutyronitrile Nof mer MSD (trade name, Nippon Oil & Fats Co., Ltd.): Chain transfer agent * 1) Measured at 25 ° C. using a Gardner foam viscometer.

  Subsequently, the coating composition (Examples 1-12) of this invention was prepared by the compounding ratio shown in Table 3 using the metal atom containing resin composition P1-P10 obtained in this way. Moreover, the coating composition of Comparative Examples 1-6 was prepared by the compounding ratio shown in Table 3 using resin composition P11-P15.

＊１）石原産業（株）のＣＲ−９０（商品名）を使用
＊２）デグッサ（株）のＯＫ−４１２（商品名）を使用
＊３）商品名、楠本化成（株）品
次いで、上記調製の各塗料組成物を用いて、下記の要領で塗膜の消耗度試験、防汚性試験、碁盤目剥離性試験を行った。

* 1) Uses CR-90 (trade name) from Ishihara Sangyo Co., Ltd. * 2) Uses OK-412 (product name) from Degussa Co., Ltd. * 3) Product name, Enomoto Kasei Co., Ltd. Using each of the prepared coating compositions, a coating film wear degree test, an antifouling test, and a cross-cut peel test were performed in the following manner.

(1) Degree of wear test of coating film Each coating composition was applied to a hard vinyl chloride plate of 50 × 50 × 2 mm (thickness) with an applicator so as to have a dry film thickness of 240 μm and placed in seawater. It was attached to a rotating drum and rotated at a peripheral speed of 15 knots, and the consumed film thickness was measured every 6 months for 24 months. The results are shown in Table 4.

(2) Antifouling test Each coating composition was applied to a sandblasted steel plate to which a rust-proof coating had been applied in advance so that the dry film thickness was 240 μm. Immersion was allowed to stand for 6 months, and the adhesion area (%) of the adherent was examined every 6 months. The results are shown in Table 4.

(3) Cross-cut peel test On the following substrate (1) and substrate (2), the coating compositions of Examples 1 to 12 and Comparative Examples 1 to 6 were applied so that the dry film thickness was 120 μm. Test plates (1) and (2) were prepared. The test plate (2) was coated with the same antifouling paint applied when the substrate (2) was prepared.
Substrate (1): Substrate substrate made of sandblasted steel plate to which a rust preventive paint has been applied in advance (2): A 120 μm thick coating film made of the antifouling paint compositions of Examples 1-12 and Comparative Examples 1-6 Substrates obtained by immersing in sterilized filtered seawater for 3 months on the substrate (1), respectively, and drying for 1 week at room temperature Test plates (1) and (2) The test plate immersed in sterile filtered seawater for 6 months was dried at room temperature of 20 ° C. for 1 week, and a cross-cut peel test was performed. The results are shown in Table 4.

In the cross-cut peel test, cross cuts reaching the base material at intervals of 2 mm were made to make 25 ² mm ² cross-cuts, and cellophane tape was stuck on them and peeled off rapidly to determine the state of the peeled cross cuts.

  The case where there is no crossing of the cross-cuts and the corners of the cross-cuts are marked ◎, and the case where only the corners of the cross-cuts are peeled off is ○, and the number of peeled cross-cuts is 1 to 12 Was marked with △, and the number of peeled grids was 13-25.

金属原子を含まない、シリコン含有重合性単量体の共重合体を含む樹脂組成物Ｐ１４、Ｐ１５を使用した塗料組成物（比較例４〜６）については、塗膜の消耗試験において自己研磨性は見られず、防汚性が低位であり、また密着性も不良であった。シリコンを含まない金属原子含有重合性単量体の共重合体を含む金属原子含有樹脂組成物Ｐ１２を使用した塗料組成物（比較例２）は、自己研磨性は見られるものの防汚性が低位であった。シリコン含有高酸価樹脂に有機酸の金属塩を付加した金属原子含有樹脂組成物Ｐ１１及び式（ＩＩＩ）の金属含有重合性単量体のＭ４だけを重合して得られたシリコン含有共重合体を含む金属原子含有樹脂組成物Ｐ１３を使用した塗料組成物（比較例１及び３）は長期の研磨性安定性と防汚性が低位であった。

For the coating compositions (Comparative Examples 4 to 6) using the resin compositions P14 and P15 containing a copolymer of silicon-containing polymerizable monomers that do not contain a metal atom, self-polishing properties in the coating film wear test No antifouling property was observed, and adhesion was poor. The coating composition (Comparative Example 2) using the metal atom-containing resin composition P12 containing a copolymer of metal atom-containing polymerizable monomers not containing silicon has a low antifouling property although self-polishing properties are observed. Met. Silicon-containing copolymer obtained by polymerizing only metal atom-containing resin composition P11 obtained by adding metal salt of organic acid to silicon-containing high acid value resin and M4 of metal-containing polymerizable monomer of formula (III) The coating compositions (Comparative Examples 1 and 3) using the metal atom-containing resin composition P13 containing low-grade abrasive stability and antifouling properties were low.

  On the other hand, containing a metal atom including a copolymer using a metal atom-containing polymerizable monomer having two unsaturated groups and containing a metal atom of Mg, Zn or Cu and a silicon-containing polymerizable monomer About the coating composition (Examples 1-12) using resin composition P1-P10, when not using an antifouling chemical | medical agent, antifouling property is favorable over a long period of time, self-polishing property is seen, and foundation | substrate Adhesion with was good. In addition, a coating composition using metal atom-containing resin compositions P6, P7, P10 containing a copolymer obtained by polymerizing a silicon-containing polymerizable monomer having a polyether bond (Examples 6, 7, For 10, 11, and 12), the recoatability was particularly good.

  The coating composition of the present invention can maintain an excellent antifouling effect for a long time even when it does not contain an antifouling chemical component, and has good adhesion and recoatability with the groundwork. It is very useful.

Claims (7)

Including a silicon-containing polymerizable monomer (a) unit and a metal atom-containing polymerizable monomer (b ₁ ) unit having two unsaturated groups and containing a metal atom of Mg, Zn or Cu A copolymer comprising:
The silicon-containing polymerizable monomer (a) is a co-polymer you characterized by containing (a ₁₎ represented by the following formula (I).

(In the formula, R ¹ is a hydrogen atom or a methyl group, k is an integer of 2 to 5, l is 0 to 50, m is an integer of 2 to 5, n is 3 to 80, R ^{2 to} R ⁶ are alkyl groups, (Indicates any of alkoxy group, phenyl group, substituted phenyl group, phenoxy group and substituted phenoxy group) A silicon-containing polymerizable monomer (a) unit and a metal atom-containing polymerizable monomer (b ₁ ) unit having two unsaturated groups and containing a metal atom of Mg, Zn or Cu A copolymer comprising:
The silicon-containing polymerizable monomer (a) is a co-polymer you characterized by containing (a ₂₎ represented by the following formula (II).

Wherein R ⁷ is a hydrogen atom or a methyl group, o is an integer of 2 to 5, p is 0 to 50, q is an integer of 2 to 5, R ⁸ , R ⁹ and R ¹⁰ are alkyl groups, R ¹¹ { R ¹¹ is — (— O—SiR ¹² R ¹³ —) _r —OSiR ¹⁴ R ¹⁵ R ¹⁶ (r is an integer of 0 to 20, R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are alkyl groups)} And R ¹⁷ {R ¹⁷ is -R ¹⁸ -(-OC ₂ H ₄ ) _s -OR ¹⁹ (s is an integer of 1 to 20, R ¹⁸ and R ¹⁹ are alkyl groups)} The content of the silicon-containing polymerizable monomer (a) is 1 to 60% by mass relative to the copolymer component contained in the monomer mixture for forming the copolymer, and the metal atom-containing polymerizable property The copolymer according to claim 1 or 2, wherein the content of the monomer (b ₁ ) is 1 to 50% by mass. The copolymer according to claim 3, wherein the monomer mixture further contains a metal atom-containing polymerizable monomer (b ₂ ) represented by the following formula (III).

(Wherein R ²⁰ represents a hydrogen atom or a methyl group, M represents Mg, Zn or Cu, and R ²¹ represents an organic acid residue or an alcohol residue) The ratio of the content of said metal atom-containing polymerizable monomer (b ₂₎ and the metal atom-containing polymerizable monomer _{(b 1) ((b 2} ) / (b 1)) is 20/80 The copolymer according to claim 4, which is in the range of 80/20 (molar ratio). Content of the metal-containing polymerizable monomer (b ₁ ) and the metal-containing polymerizable monomer (b ₂ ) with respect to the copolymer component contained in the monomer mixture for forming the inside of the copolymer The copolymer according to claim 4 or 5 , wherein the total is from 1 to 50% by mass. A coating composition containing the copolymer according to any one of claims 1 to 6 as a vehicle.