JP4154345B2 - 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 coating composition has been proposed in which a copolymer containing a polymerizable monomer as a constituent component is used as a vehicle component and contains an antifouling component.

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 hardly exhibited, recoatability is poor, and there is a problem that antifouling property is lowered when a pigment is blended.

  The object of the present invention is to exhibit an antifouling effect in seawater for a long time even when it does not contain an antifouling chemical component, and is excellent in adhesion and recoatability, and even when a pigment is blended. It is providing the coating composition used as the antifouling paint which expresses antifouling property, and the copolymer suitable for forming it.

  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 provides both terminal (meth) acryl-modified silicone-containing polymerizable monomer (a) units and a metal atom-containing polymerizable containing divalent metal atom monomer (c) units and the including co a polymer, wherein both ends (meth) acryl-modified silicone-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.

Wherein R ¹ and R ⁶ are hydrogen atoms or methyl groups, k and p are integers of 2 to 5, l and q are 0 to 50, m and o are integers of 2 to 5, n is 3 to 80, R ^{2 to} R ^{5 each} represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group)

(Wherein R ¹¹ and R ²² are hydrogen atoms or methyl groups, k ′ and p ′ are integers of 2 to 5, l ′ and q ′ are 0 to 50, m ′ and o ′ are integers of 2 to 5, r and s are 0 to 20, and R ^{12 to} R ²¹ are alkyl groups)
The content of the polymerizable monomer (a) at both ends (meth) acryl-modified silicon with respect to the copolymer component contained in the monomer mixture for forming the copolymer is 0.1 to 30% by mass. It is preferable that the content of the divalent metal atom contained in the copolymer is 1 to 25% by mass.

Moreover, it is preferable that the said monomer mixture further contains the one terminal (meth) acryl modified | denatured silicon containing polymeric monomer (b). The one-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) contains at least one of (b ₁ ) represented by the following formula (III) and (b ₂ ) represented by the following formula (IV). It is preferable to do.

Wherein R ⁴¹ 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 ^{42 to} R ⁴⁶ are alkyl groups, (Indicates any of alkoxy group, phenyl group, substituted phenyl group, phenoxy group and substituted phenoxy group)

Wherein R ⁵¹ 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, R ^{52 to} R ⁵⁴ are alkyl groups, R ⁵⁵ { R ⁵⁵ is ^{- (- O-SiR 56 R} 57 -) y -OSiR 58 R 59 R 60 (y 0-20 integer, R ⁵⁶ to R ⁶⁰ is an alkyl group)}, and, R ⁶¹ {R ⁶¹ is —R ⁶² — (— OC ₂ H ₄ ) _{y ′} —OR ⁶³ (y ′ is an integer of 1 to 20, R ⁶² and R ⁶³ are alkyl groups)}
The terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) and the one-terminal (meth) acryl-modified silicon-containing polymerization with respect to the copolymer component contained in the monomer mixture for forming the copolymer The total content of the functional monomer (b) is preferably 1 to 60% by mass.

Before Symbol metal atom-containing polymerizable monomer (c) is, two metal atom-containing polymerizable monomer having an unsaturated group (c ₁₎ and the metal atom-containing polymerizable monomer represented by the following formula (V) It is preferable to include at least one of the monomer (c ₂ ).

(Wherein R ⁷¹ is a hydrogen atom or a methyl group, M is Mg, Zn or Cu, and R ⁷² is 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, the adhesiveness and recoatability with the substrate are good, and even when a pigment is blended, long-term antifouling properties are exhibited, which is very useful industrially.

  Both terminal (meth) acryl-modified 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 by using this, Even when it does not contain an antifouling agent, it tends to make it difficult for organisms to adhere and develop recoat properties, and even when a pigment is blended, it imparts an effect of developing long-term antifouling properties.

  The content of the terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) relative to the copolymer component contained in the monomer mixture for forming the copolymer is not particularly limited, It is preferable that it is the range of 0.1-30 mass%. This is because when it is 0.1% by mass or more, a long-term antifouling effect is exhibited even when it does not contain an antifouling agent, and recoatability tends to be good, and by setting it to 30% by mass or less. This is because a copolymer tends to be obtained without proceeding to gelation by crosslinking. More preferably, it is the range of 0.5-25 mass%, Most preferably, it is the range of 1-20 mass%.

Examples of the both-terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) include (a ₁ ) represented by the following formula (I), (a ₂ ) represented by the following formula (II), and the like. Monomers can be used. (A ₁ ) and (a ₂ ) may contain at least one, or may contain both (a ₁ ) and (a ₂ ).

Wherein R ¹ and R ⁶ are hydrogen atoms or methyl groups, k and p are integers of 2 to 5, l and q are 0 to 50, m and o are integers of 2 to 5, n is 3 to 80, R ^{2 to} R ^{5 each} represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group)

(Wherein R ¹¹ and R ²² are hydrogen atoms or methyl groups, k ′ and p ′ are integers of 2 to 5, l ′ and q ′ are 0 to 50, m ′ and o ′ are integers of 2 to 5, r and s are 0 to 20, and R ^{12 to} R ²¹ are alkyl groups)
The both-end (meth) acryl-modified silicon-containing polymerizable monomer (a ₁ ) represented by the formula (I) may be used alone or in combination of two or more. Note that R ^{1 to} R ⁶ , 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.

  In formula (I), l and q are average polymerization degrees of the polyether structure and may be 0, but are 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 and p in the formula (I) are preferably integers of 2 to 5, and 2 or 3 is more preferable because of low cost. It is also possible to use those having k and p of 2 and 3.

  M and o in the formula (I) are preferably integers of 2 to 5, and more preferably 2 or 3.

  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 ⁵ in the 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 double-terminal (meth) acryl-modified silicon-containing polymerizable monomer (a ₁ ) represented by the formula (I) include, for example, FM-7711 manufactured by Chisso Corporation, assuming that l and q are 0. FM-7721, FM-7725 (above, trade name), Nihon Unicar F2-311-02 (trade name), and the like. Examples of those in which l and q are larger than 0 include F2-354-04 (trade name) manufactured by Nihon Unicar.

The both-end (meth) acryl-modified silicon-containing polymerizable monomer (a ₂ ) represented by the formula (II) may be used alone or in combination of two or more. R ^{11 to} R ²² , k ′, l ′, m ′, o ′, p ′, q ′, r, and s are independent of each other, and when the same code exists in or between molecules, They can be different.

  In formula (II), l 'and q' are average degrees of polymerization of the polyether structure and may be 0, but are 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.

  In the formula (II), k ′ and p ′ are preferably integers of 2 to 5, and 2 or 3 is more preferable because of low cost. It is also possible to use those having k 'and p' of 2 and 3 in combination.

  M 'and o' in formula (II) are preferably integers of 2 to 5, 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.

As an alkyl group which can be selected by R < ¹² > -R < ²¹ > of Formula (II), a methyl group, an ethyl group, n-propyl group, n-butyl group etc. are mentioned, for example. A methyl group or an ethyl group is preferable, and a methyl group is more preferable.

  Specific examples of the compound represented by the formula (II) include, for example, F2-312-01 (trade name) manufactured by Nihon Unicar Co., Ltd., where l ′ and q ′ are 0. Examples of those in which l 'and q' are larger than 0 include F2-212-04 (trade name) manufactured by Nihon Unicar.

  Further, when both terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) and one terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) are used in combination, even when no antifouling agent is contained, It is more preferable because the coating film to be formed is provided with sufficient and long-term antifouling properties and a good balance of adhesion with the base.

  When both end (meth) acryl-modified silicon-containing polymerizable monomer (a) and one end (meth) acryl-modified silicon-containing polymerizable monomer (b) are used in combination, both end (meth) acryl-modified The ratio ((a) / (b)) of the content of the silicon-containing polymerizable monomer (a) and the one-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) is 1/99 to 80/20. A range of (molar ratio) is preferable. This is because, when the ratio is 80/20 or less, the coating film properties excellent in crack resistance and adhesion tend to be obtained. Further, by setting the ratio to 1/99 or more, the antifouling property of the formed coating film is maintained for a long time and the recoating property tends to be good. More preferably, it is the range of 3 / 97-60 / 40.

  When both end (meth) acryl-modified silicon-containing polymerizable monomer (a) and one-end (meth) acryl-modified silicon-containing polymerizable monomer (b) are used in combination, a single unit for forming a copolymer is used. The content of both terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) and one terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) with respect to the copolymer component contained in the monomer mixture Although total is not specifically limited, It is preferable that it is the range of 1-60 mass%. This tends to develop a long-term 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 can be obtained. This is because it tends to be balanced with the above. More preferably, it is the range of 5-50 mass%, Most preferably, it is the range of 10-40 mass%.

Examples of the one-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) include (b ₁ ) represented by the following formula (III), (b ₂ ) represented by the following formula (IV), and the like. Monomers can be used. (B ₁ ) and (b ₂ ) may contain at least one, or may contain both (b ₁ ) and (b ₂ ).

Wherein R ⁴¹ 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 ^{42 to} R ⁴⁶ are alkyl groups, (Indicates any of alkoxy group, phenyl group, substituted phenyl group, phenoxy group and substituted phenoxy group)

Wherein R ⁵¹ 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, R ^{52 to} R ⁵⁴ are alkyl groups, R ⁵⁵ { R ⁵⁵ is ^{- (- O-SiR 56 R} 57 -) y -OSiR 58 R 59 R 60 (y 0-20 integer, R ⁵⁶ to R ⁶⁰ is an alkyl group)}, and, R ⁶¹ {R ⁶¹ is —R ⁶² — (— OC ₂ H ₄ ) _{y ′} —OR ⁶³ (y ′ is an integer of 1 to 20, R ⁶² and R ⁶³ are alkyl groups)}
The single terminal (meth) acryl-modified silicon-containing polymerizable monomer (b ₁ ) represented by the formula (III) may be used alone or in combination of two or more. Note that R ^{41 to} R ⁴⁶ , u, v, w, and x are independent of each other, and when the same symbol exists in the molecule or between the molecules, they may be different.

  V in the formula (III) 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.

  U in Formula (III) 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 u in combination of 2 and 3.

  W in formula (III) is preferably an integer of 2 to 5, more preferably 2 or 3.

  X in the formula (III) is an average polymerization degree 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 ^{42 to} R ⁴⁶ in formula (III) 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.

  As specific examples of the compound represented by the formula (III), for example, assuming that v 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 v greater than 0 include Nihon Unicar F2-254-04, F2-254-14 (trade name), and the like.

The single-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b ₂ ) represented by the formula (IV) may be used alone or in combination of two or more. Note that R ^{51 to} R ⁶³ , u ′, v ′, w ′, y, and y ′ are independent of each other, and may be different when the same symbol exists in or between molecules.

  In the formula (IV), v ′ 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.

  U 'in the formula (IV) 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 having u 'of 2 and 3.

  W 'in formula (IV) is preferably an integer of 2 to 5, more preferably 2 or 3.

  In formula (IV), y and y 'are the average degree of polymerization of the silicon-containing structure introduced into the side chain, and more preferably 20 or less. 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.

Examples of the alkyl group that can be selected from R ^{52 to} R ⁵⁴ , R ^{56 to} R ⁶⁰ , R ^62, and R ⁶³ in the formula (IV) include a methyl group, an ethyl group, an n-propyl group, and an 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 the formula (IV) 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 v ′ is 0. ), F2-250-01, F2-302-01 (trade name) manufactured by Nippon Unicar Co., Ltd., and the like. Examples of v 'greater than 0 include F2-302-04 (trade name) manufactured by Nihon Unicar.

  The copolymer of the present invention also contains a divalent metal atom. The content of metal atoms contained in the copolymer is preferably 1 to 25% by mass. 3-20 mass% is more preferable, and 5-15 mass% is especially preferable.

  As a method for producing a copolymer containing a divalent metal atom, for example, a high acid value obtained by copolymerization using acrylic acid, which is a polymerizable monomer capable of introducing a divalent metal atom, as a copolymerization component. A method of adding a divalent metal atom to a resin or a monomer mixture containing a divalent metal atom-containing polymerizable monomer that is a polymerizable monomer capable of introducing a divalent metal atom is copolymerized. There is a way to get it. In order to maintain a stable self-polishing property over a long period of time for the antifouling coating film, it is preferable to copolymerize and produce a monomer mixture containing a divalent metal atom-containing polymerizable monomer (c). . As the divalent metal atom, Mg, Zn or Cu is preferable.

The divalent metal atom-containing polymerizable monomer (c), which is preferably used in the monomer mixture for forming the copolymer, is a component that improves the adhesion to the base. In addition, it is a component for imparting a high self-polishing property to the obtained coating film for a long period of time and exhibiting an excellent antifouling effect. Preferably those containing at least one of the metal atom-containing polymerizable monomer having two unsaturated groups (c ₁₎ and the metal atom-containing polymerizable monomer represented by the following formula (V) (c ₂₎ .

(Wherein R ⁷¹ is a hydrogen atom or a methyl group, M is Mg, Zn or Cu, and R ⁷² is an organic acid residue or an alcohol residue)
The metal atom-containing polymerizable monomer (c ₁ ) having two unsaturated groups can maintain the self-polishing property of the formed coating film for a long period of time by using this monomer. The content of the metal atom-containing polymerizable monomer (c ₁ ) having two unsaturated groups with respect to the copolymer component contained in the monomer mixture for forming the copolymer is not particularly limited. However, it is preferably in the range of 1 to 50% by mass. By setting it to 1% by mass or more, the adhesiveness with the base is improved, and the self-polishing property of the coating film to be formed tends to be maintained for a longer period. By setting it to 50% by mass or less This is because the effect of improving the balance between crack resistance and adhesion after immersion in seawater becomes prominent, long-term self-polishing properties are 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 (c ₁ ) having two unsaturated groups 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 a method for producing the metal atom-containing polymerizable monomer (c ₁ ) having these two unsaturated groups, an inorganic metal compound, a carboxyl group-containing radical polymerizable monomer such as (meth) acrylic acid, Is preferable to react with water in an organic solvent containing an alcohol compound. This is because the reactant containing the metal atom-containing polymerizable monomer (c ₁ ) having two unsaturated groups obtained by this method is used as an organic solvent or other component for forming a copolymer ( This is because it is excellent in compatibility with a silicon-containing polymerizable monomer and other copolymerizable unsaturated monomers described later), and using this tends to facilitate copolymerization. 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 metal atom-containing polymerizable monomer (c ₂ ) represented by the above formula (V) can improve the antifouling effect of the formed coating film by using it. The content of the metal atom-containing polymerizable monomer (c ₂ ) represented by the formula (V) with respect to the copolymer component contained in the monomer mixture for forming the copolymer is not particularly limited. Is preferably in the range of 1 to 60% by mass. This tends to be excellent in crack resistance and peelability of the coating film by setting it to 1% by mass or more, and tends to be excellent in self-polishing property and antifouling effect of the coating film by setting it to 60% by mass or less. Because there is. More preferably, it is the range of 5-40 mass%.

  Specific examples of the compound represented by the above formula (V) include, for example, magnesium acetate (meth) acrylate, zinc acetate (meth) acrylate, copper acetate (meth) acrylate, monochloromagnesium acetate (meth) acrylate, and 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, isostearic acid Magnesium (meth) acrylate, Zinc isostearate (meth) acrylate, Copper isostearate (meth) acrylate, Magnesium palmitate (meth) acrylate, Palmitic acid Lead (meth) acrylate, copper palmitate (meth) acrylate, magnesium cresotate (meth) acrylate, zinc cresate (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 (meth) Acrylate, copper linoleate (meth) acrylate, magnesium linolenate (meth) acrylate, zinc linolenate (meth) acrylate, copper linolenate (meth) acrylate, stearole acid magnesium (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, zinc α-naphthoate (meth) acrylate Rate, 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 carboxylate mug Cium (meth) acrylate, quinolinecarboxylate zinc (meth) acrylate, quinolinecarboxylate copper (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 (c ₂ ) represented by the formula (V) include an inorganic metal compound and a carboxyl group-containing radical polymerizable monomer such as (meth) acrylic acid. And a non-polymerizable organic acid can be reacted in an organic solvent containing an alcohol compound.

Further, as the metal atom-containing polymerizable monomer (c), a metal atom-containing polymerizable monomer having two unsaturated groups (c ₁ ) and a metal atom-containing polymerizable monomer represented by the formula (V) When the body (c ₂ ) is used in combination, sufficient and long-term hydrolyzability is imparted to the formed coating film, and the balance between the crack resistance and the peel resistance of the coating film is improved, which is further preferable. In particular, a metal atom-containing polymerizable monomer (c) represented by the formula (V) using zinc (meth) acrylate as the metal atom-containing polymerizable monomer (c ₁ ) having two unsaturated groups. ₂ ) When zinc oleate (meth) acrylate or zinc versatate (meth) acrylate is used, the above-mentioned effect tends to be particularly excellent, which is very preferable.

When used in combination with the metal atom-containing polymerizable monomer (c ₁₎ and a metal atom-containing polymerizable monomer represented by the formula (V) (c ₂₎ is having two unsaturated groups, copolycondensates contained in the monomer mixture to form a combined, metal atom-containing polymerizable monomer represented by the formula (V) (c ₂₎ and the metal atom-containing polymerizable monomer having two unsaturated groups The ratio of the content to (c ₁ ) ((c ₂ ) / (c 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.

  Moreover, the above-mentioned both terminal (meth) acryl modified silicone containing polymerizable monomer (a) used for the monomer mixture for forming a copolymer, and one terminal (which is a preferred form) In addition to the (meth) acryl-modified silicon-containing polymerizable monomer (b) and the metal atom-containing polymerizable monomer (c), an unsaturated monomer (d) copolymerizable with these can be used.

  The copolymerizable unsaturated monomer (d) can be appropriately used as necessary and is not necessarily used, but is included in the monomer mixture for forming the copolymer. The content of the copolymerizable unsaturated monomer (d) with respect to the resin component 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 (d) 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, when a metal atom-containing polymerizable monomer (c ₁ ) having two unsaturated groups is used, a chain transfer agent is used in order to achieve high solids and improve productivity, in particular, to suppress the formation of cullet during polymerization. It is particularly preferred to use From the viewpoint of compatibility with the metal atom-containing polymerizable monomer (c), 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, that the terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) represented by the above formula (I) contained in the monomer mixture is a copolymer obtained by copolymerization, for example, It can be confirmed using ¹ H-NMR, ICP emission analysis, or the like. 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 in the case of using an antifouling agent or a pigment component is usually 20 to 30% by mass (solid content) as a resin component in the coating composition. It is preferable to use within a range. By appropriately containing the resin component, the coating film performance such as crack resistance becomes good, and by not containing it excessively, the good antifouling ability is maintained and the crack resistance is well balanced. It is because it tends to become.

  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 coating composition of the present invention may contain pigments such as extender pigments and coloring pigments, plasticizers, various coating additives, other resins, and the like as necessary. Examples of the pigment include titanium oxide, talc, precipitated barium, and bengara. The pigment may be used alone or in combination of two or more.

  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 the examples, “part” represents “part by mass”.

[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 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-7711 (trade name, manufactured by Chisso Corporation), and a metal atom-containing polymerizable monomer mixture described in Production Example M1 from the dropping funnel 21. 7 parts, 10 parts of xylene, 2 parts of chain transfer agent (Nofmer MSD (trade name), α-methylstyrene dimer manufactured by NOF Corporation), 2.5 parts of azobisisobutyronitrile (AIBN), azobismethylbutyro A transparent mixture consisting of 7.5 parts of nitrile (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. A pale yellow transparent metal atom-containing resin composition P1 having a Gardner viscosity + W 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 5400. 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, using a dropping pump, 32.3 parts of methyl methacrylate, 33.9 parts of ethyl acrylate, 20 parts of FM-7721 (trade name, manufactured by Chisso Corporation), metal atom-containing polymerizable monomer described in Production Example M1 A transparent mixture composed of 21.7 parts of a mixture, 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 parts of AMBN was constant 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, and then 10.1 parts of xylene was added thereto. A cloudy metal atom-containing resin composition P2 having a Gardner viscosity + U 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 6200.

[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), 59 parts of xylene and 4 parts of ethyl acrylate and heated to 100 ° C. with stirring. Subsequently, using a dropping pump, 26.4 parts of methyl methacrylate, 40.5 parts of ethyl acrylate, 15 parts of F2-354-04 (trade name, manufactured by Nihon Unicar Company), metal atom-containing polymerizability described in Production Example M1 A transparent mixture comprising 31.3 parts of a monomer mixture, 10 parts of xylene, 2 parts of a chain transfer agent (NOFMER MSD (trade name) manufactured by NOF Corporation), 2.5 parts of AIBN, 8 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. Then, 10.8 parts of xylene was added, and the heating residue was 46.4%, A cloudy metal atom-containing resin composition P3 having a Gardner viscosity + R 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 5600.

[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), 59 parts of xylene and 4 parts of ethyl acrylate and heated to 100 ° C. with stirring. Subsequently, using a dropping pump, 26.4 parts of methyl methacrylate, 35.5 parts of ethyl acrylate, 20 parts of F2-212-01 (trade name, manufactured by Nihon Unicar Co., Ltd.), metal atom-containing polymerization described in Production Example M1 A transparent mixture comprising 31.3 parts of a monomer mixture, 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 7.5 parts of AMBN. It was dropped at a constant rate in 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 45.8%. A cloudy metal atom-containing resin composition P4 having a Gardner viscosity -W 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 5500.

[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 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, 13.9 parts of ethyl acrylate, 5 parts of FM-7711 (trade name, manufactured by Chisso), 35 parts of FM-0711 (trade name, manufactured by Chisso) from the dropping funnel, production example It consists of 21.7 parts of the metal atom-containing polymerizable monomer mixture described in M1, 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 4 parts of AMBN. A transparent mixture consisting of 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, and then 10.1 parts of xylene was added, and the heating residue was 45.6%. A light yellow transparent metal atom-containing resin composition P5 having a Gardner viscosity + V 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 9000.

[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 35 parts of PGM (propylene glycol methyl ether) and 31 parts of xylene and heated to 100 ° C. while stirring. Subsequently, 18 parts of methyl methacrylate, 25 parts of ethyl acrylate, 10 parts of FM-7721 (trade name, manufactured by Chisso), 30 parts of X-24-8201 (trade name, manufactured by Shin-Etsu Chemical), metal described in Production Example M2 A transparent mixture comprising 28.4 parts of an atom-containing polymerizable monomer mixture, 30 parts of xylene, 2.5 parts of AIBN, and 2.5 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. After that, 4.6 parts of xylene was added, and the heating residue was 45.4%. A slightly cloudy metal atom-containing resin composition P6 having a Gardner viscosity of -V 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 7200.

[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 40 parts of PGM (propylene glycol methyl ether) and 31 parts of xylene and heated to 100 ° C. while stirring. Subsequently, using a dropping pump, 18 parts of methyl methacrylate, 15 parts of ethyl acrylate, 10 parts of FM-7711 (trade name, manufactured by Chisso Corporation), 10 parts of FM-7721 (trade name, manufactured by Chisso Corporation), FM-0711 (Trade name, manufactured by Chisso Corporation) 30 parts, a transparent mixture comprising 42.5 parts of a metal atom-containing polymerizable monomer mixture described in Production Example M3, 10 parts of xylene, 2.5 parts of AIBN, 4.5 parts 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 45.6%. A slightly cloudy 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 6400.

[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, using a dropping pump, 26.4 parts of methyl methacrylate, 15.5 parts of ethyl acrylate, 2 parts of F2-212-04 (trade name, manufactured by Nihon Unicar), F2-302-04 (trade name, Japan) 38 parts by Unicar), 31.3 parts by weight of the metal atom-containing polymerizable monomer mixture described in Production Example M1, 10 parts by xylene, 1.2 parts by chain transfer agent (NOFMER MSD (trade name) by NOF Corporation), A transparent mixture consisting of 2.5 parts of AIBN and 5.5 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 cloudy metal atom-containing resin composition P8 having a Gardner viscosity -T 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 5600.

[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 35 parts of PGM (propylene glycol methyl ether) and 31 parts of xylene and heated to 100 ° C. while stirring. Subsequently, 18 parts of methyl methacrylate, 45 parts of ethyl acrylate, 10 parts of F-312-04 (trade name, manufactured by Nihon Unicar), 10 parts of TM-0701 (trade name, manufactured by Chisso), metal described in Production Example M2 A transparent mixture consisting of 28.4 parts of an atom-containing polymerizable monomer mixture, 30 parts of xylene, 2.5 parts of AIBN, and 5 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. Then, 4.6 parts of xylene was added, and the heating residue was 45.6%. A slightly cloudy metal atom-containing resin composition P9 having a Gardner viscosity + W 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 6000.

[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 120 parts of xylene and 30 parts of n-butanol and heated to 100 ° C. while stirring. Subsequently, 20 parts ethyl acrylate, 25 parts 2-ethylhexyl acrylate, 15 parts acrylic acid, 5 parts FM-7711 (trade name, manufactured by Chisso), FM-0711 (trade name, manufactured by Chisso) from the dropping funnel A mixture consisting of 35 parts and 4 parts of azobisisobutyronitrile was added dropwise at a constant rate over 3 hours. After completion of the dropwise addition, 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 + G.

  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 P10 having a heating residue of 50.4% and a Gardner viscosity of -M 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 9800.

[Production Example P11: Production of Resin Composition P11]
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 50 parts of xylene and heated to 110 ° C. while stirring. Subsequently, 42.1 parts of methyl methacrylate, 37.9 parts of ethyl acrylate, 20 parts of FM-7721 (trade name, manufactured by Chisso Corporation), 10 parts of xylene, 11.9 parts of PGM, 20 parts of xylene, chain transfer agent (Nippon Oils and Fats) A transparent mixture consisting of 3 parts of NOFMER MSD (trade name) manufactured by the company, 2.5 parts of AIBN, and 7 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. After that, 5.1 parts of xylene was added, and the heating residue was 45.1%. A cloudy resin composition P11 having a Gardner viscosity + J was obtained.

  When the obtained resin composition P11 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), the weight average molecular weight of the copolymer contained in the resin composition P11 was 9400. there were.

[Production Example P12: Production of 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) and 70 parts of xylene and heated to 110 ° C. while stirring. Subsequently, 42.1 parts of methyl methacrylate, 17.9 parts of ethyl acrylate, 10 parts of FM-7711 (trade name, manufactured by Chisso), 30 parts of FM-0711 (trade name, manufactured by Chisso), xylene 10 A transparent mixture consisting of 1 part of PGM, 11.9 parts of PGM, 3 parts of chain transfer agent (NOFMER MSD (trade name) manufactured by NOF Corporation), 2.5 parts of AIBN and 7 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. After that, 5.1 parts of xylene was added, and the heating residue was 45.5%. A transparent resin composition P12 having a Gardner viscosity + E was obtained.

  The obtained resin composition P12 was analyzed by GPC (HLC-8120GPC (trade name) manufactured by Tosoh Corporation, eluent: dimethylformamide), and the weight average molecular weight of the copolymer contained in the resin composition P12 was 8600. there were.

  Table 1 shows preparation amounts (molar ratio) of metal atom-containing polymerizable monomer mixtures (M1 to M3) of production examples M1 to M3, volatile components and metal atom contents in the metal atom-containing polymerizable monomer mixture. (% By mass) and solid content (% by mass) are described.

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 P9, and the charged amounts (parts by mass) of each component when producing the resin compositions of P11 and P12, the obtained metal atom-containing resin compositions or The viscosity (Gardner) and solid content (mass%) of the resin composition were described.

FM-7711 (trade name, manufactured by Chisso Corporation): in formula (I), l and q = 0, m and o = 3, R ^{1 to} R ⁶ are methyl groups, n = 10
FM-7721 (trade name, manufactured by Chisso Corp.): in formula (I), l and q = 0, m and o = 3, R ^{1 to} R ⁶ are methyl groups, n = 65
F2-354-04 (trade name, Nippon Unicar Co., Ltd.): In the formula (I), l and q = 10, k and p are a mixture of 2 and 3, and the molar ratio is 5: 5, m and o = 3, R ^{1 to} R ⁶ are methyl groups, n = 10
F2-212-01 (trade name, Nippon Unicar Co., Ltd.): In formula (II), l ′ and q ′ = 0, m ′ and o ′ = 3, R ^{11 to} R ²² are methyl groups, r and s = 3
F2-212-04 (trade name, Nippon Unicar Co., Ltd.): In the formula (II), l ′ and q ′ = 10, k ′ and p ′ are a mixture of 2 and 3, and the molar ratio is 5: 5, m ′ and o ′ = 3, R ^{11 to} R ²² are methyl groups, r and s = 3
FM-0711 (trade name, manufactured by Chisso Corporation): in formula (III), v = 0, R ^{41 to} R ⁴⁶ are methyl groups, w = 3, x = 10
X-24-8201 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.): in formula (III), v = 0, R ^{41 to} R ⁴⁶ are methyl groups, w = 3, x = 25
TM-0701 (trade name, manufactured by Chisso Corporation): In formula (IV), v ′ = 0, w ′ = 3, R ^{51 to} R ⁵⁴ are methyl groups F2-302-04 (trade name, Nippon Unicar ( Co., Ltd.): In formula (IV), v ′ = 10, w ′ = 3, R ⁵¹ is a methyl group, R ^{52 to} R ⁵⁴ are R ⁵⁵ (y = 3, R ^{56 to} R ⁶⁰ are methyl groups)
AIBN: azobisisobutyronitrile AMBN: azobismethylbutyronitrile novmer MSD (trade name, manufactured by NOF Corporation): 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 1-3 was prepared by the compounding ratio shown in Table 3 using resin composition P11, P12.

* 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 an adhesion 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 (adhesion test)
On the following substrate (1) and substrate (2), the antifouling coating compositions of Examples 1 to 12 and Comparative Examples 1 to 3 were applied so that the dry film thickness was 120 μm, respectively, and the test plate (1 ) And (2) were created. 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 coating film having a film thickness of 120 μm by the antifouling paint compositions of Examples 1 to 12 and Comparative Examples 1 to 3 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.

  For coating compositions (Comparative Examples 1 to 3) using metal atom-containing resin compositions P11 and P12 containing a copolymer of silicon-containing polymerizable monomers that do not contain metal atoms, in the coating film wear test No self-polishing property was observed, antifouling property was low, and adhesion was poor.

  On the other hand, a coating composition using metal atom-containing resin compositions P1 to P9 including a copolymer using both terminal (meth) acryl-modified silicon-containing polymerizable monomers and metal atom-containing polymerizable monomers (implementation) About Examples 1-9, 11-12) While self-polishing property is seen over a long period of time, adhesion with the base and recoatability are good, and long-term antifouling properties are obtained when no antifouling agent is used. Even when the pigment was blended, the antifouling property for a long time was good. Moreover, the coating composition which uses the metal atom containing resin composition P10 which added the metal atom to the copolymer which copolymerized the polymerizable monomer containing the both-terminal (meth) acryl modified silicon-containing polymerizable monomer Regarding Example 10 as well, when no antifouling agent was used, the antifouling property was good for a long period of time, self-polishing property was seen, and the adhesion to the ground was good.

Claims (9)

A copolymer comprising both terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) units and a metal atom-containing polymerizable monomer (c) unit containing a divalent metal atom,
Wherein both terminal (meth) acryl-modified silicone-containing polymerizable monomer (a) is a co-polymer you characterized by containing the by (a ₁₎ of the following formula (I).

Wherein R ¹ and R ⁶ are hydrogen atoms or methyl groups, k and p are integers of 2 to 5, l and q are 0 to 50, m and o are integers of 2 to 5, n is 3 to 80, R ^{2 to} R ^{5 each} represents an alkyl group, an alkoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, or a substituted phenoxy group) A copolymer comprising both terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) units and a metal atom-containing polymerizable monomer (c) unit containing a divalent metal atom,
Wherein both terminal (meth) acryl-modified silicone-containing polymerizable monomer (a) is a co-polymer you characterized by containing (a ₂₎ represented by the following formula (II).

(Wherein R ¹¹ and R ²² are hydrogen atoms or methyl groups, k ′ and p ′ are integers of 2 to 5, l ′ and q ′ are 0 to 50, m ′ and o ′ are integers of 2 to 5, r and s are 0 to 20, and R ^{12 to} R ²¹ are alkyl groups) The content of the polymerizable monomer (a) at both ends (meth) acryl-modified silicon with respect to the copolymer component contained in the monomer mixture for forming the copolymer is 0.1 to 30% by mass. There, and copolymer of claim 1 or 2, wherein the content of the divalent metal atoms contained in the copolymer is 1 to 25 mass%. The copolymer according to claim 3, wherein the monomer mixture further comprises a one-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b). The copolymer according to claim 4, wherein the one-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) contains (b ₁ ) represented by the following formula (III).

Wherein R ⁴¹ 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 ^{42 to} R ⁴⁶ are alkyl groups, (Indicates any of alkoxy group, phenyl group, substituted phenyl group, phenoxy group and substituted phenoxy group) 6. The copolymer according to claim 4, wherein the one-terminal (meth) acryl-modified silicon-containing polymerizable monomer (b) contains (b ₂ ) represented by the following formula (IV). .

Wherein R ⁵¹ 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, R ^{52 to} R ⁵⁴ are alkyl groups, R ⁵⁵ { R ⁵⁵ is ^{- (- O-SiR 56 R} 57 -) y -OSiR 58 R 59 R 60 (y is 0 to 20 integer, R ⁵⁶ to R ⁶⁰ is an alkyl group)}, and, R ⁶¹ {R ⁶¹ is —R ⁶² — (— OC ₂ H ₄ ) _{y ′} —OR ⁶³ (y ′ is an integer of 1 to 20, R ⁶² and R ⁶³ are alkyl groups)} The terminal (meth) acryl-modified silicon-containing polymerizable monomer (a) and the one-terminal (meth) acryl-modified silicon-containing polymerization with respect to the copolymer component contained in the monomer mixture for forming the copolymer The copolymer according to any one of claims 4 to 6 , wherein the total content of the polymerizable monomer (b) is 1 to 60% by mass. The metal atom-containing polymerizable monomer (c) is a metal atom-containing polymerizable monomer having two unsaturated groups (c ₁ ) and a metal atom-containing polymerizable monomer represented by the following formula (V) copolymer of any one claims 1 to 7, characterized in that it comprises at least one of the body (c _2).

(Wherein R ⁷¹ is a hydrogen atom or a methyl group, M is Mg, Zn or Cu, and R ⁷² is an organic acid residue or an alcohol residue) A coating composition containing the copolymer according to claim 1 as a vehicle.