HK1118075B

HK1118075B - Stain-proof coating composition, stain-proof coating film, substrate having coating film, stain-proof substrate, method for formation of coating film on surface of substrate, and method for stain-proofing of substrate

Info

Publication number: HK1118075B
Application number: HK08108476.8A
Authority: HK
Inventors: 仁井本顺治
Original assignee: 中国涂料株式会社
Priority date: 2005-09-01
Filing date: 2006-08-29
Publication date: 2011-12-23

Description

Antifouling coating composition, antifouling coating film, substrate with coating film, antifouling substrate, method for forming coating film on substrate surface, and method for preventing fouling of substrate

Technical Field

The present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with a coating film, an antifouling substrate, a method for forming a coating film on a substrate surface, and a method for preventing fouling of a substrate.

More specifically, the present invention relates to an antifouling coating composition, an antifouling coating film, a substrate with a coating film, an antifouling substrate, a method for forming a coating film on a substrate surface, and a method for antifouling of a substrate, which can effectively prevent adhesion of marine organisms by adding zinc sulfide to a hydrolysis type antifouling coating composition to exhibit a synergistic effect of an improvement in antibacterial action and an improvement in renewability of the coating film when a coating film formed from the obtained antifouling coating composition is formed on a surface of a ship hull or the like.

Background

When a ship bottom, an underwater structure, a fishing net, etc. are exposed to water for a long time and animals such as oysters, mussels, barnacles, etc., plants such as sea sedges, etc., or various aquatic organisms such as bacteria, etc. are attached to and propagated on the surface of the ship bottom, the underwater structure, the fishing net, etc., the appearance may be deteriorated, and the functions may be deteriorated.

In particular, if such aquatic organisms adhere to and propagate on the bottom of the ship, the surface roughness of the entire ship increases, which may lead to a decrease in ship speed, an increase in fuel consumption, and the like. In addition, a large amount of manpower and working time are required to remove such aquatic organisms from the bottom of the ship. Further, if bacteria adhere to and propagate in an underwater structure or the like, and further slime (slurry) adheres thereto to cause putrefaction, or large scale adhering organisms adhere to and propagate on the surface of an underwater structure such as a steel structure to damage an anticorrosive coating film of the underwater structure, there is a possibility that the strength and function of the structure in water are deteriorated, and the life of the structure is remarkably reduced.

Conventionally, in order to prevent such damage, various antifouling paints as shown in the following (1) to (9) have been proposed for coating a ship bottom or the like with the antifouling paint.

(1) Japanese patent laid-open No. 2003-522734 discloses an antibacterial composition containing pyrithione (pyrithione) or a pyrithione complex and zinc, copper, silver, or a compound thereof (for example, a salt, an oxide, a hydroxide, a sulfate, a chloride, a complex, etc.) having an effect of killing organisms, specifically zinc sulfide is disclosed as a zinc compound, and a technical content is described in which the antibacterial composition can be used by adding it to an elastomer such as a styrene-butadiene copolymer, a polyacrylate, a silicone rubber, or the like, or the composition can be used as a marine coating. However, there is no disclosure of the combination of these compounds with a hydrolyzable metal polymer.

(2) The document WO2004/057964 discloses an antimicrobial composition containing pyrithione or a pyrithione complex and a zinc compound (zinc sulfide or the like), an organic amine, and also suggests that it can be used for antifouling of ship hulls. However, there is no description of the film-forming polymer.

(3) Japanese patent application laid-open No. 10-508639 discloses an antifouling paint for marine use containing a binder component (rosin or the like) and fibers. The publication describes that the binder may be a self-polishing polymer, and the fiber specifically exemplifies a zinc sulfide fiber. Further, it is described that zinc sulfide may be contained as a pigment as required.

However, as the binder resin, a self-polishing polymer and a hydrolyzable polymer are mentioned, but there is no specific disclosure and no example. Further, while zinc sulfide fibers are illustrated, no specific examples thereof are added.

(4) Japanese patent laid-open No. 2004-346329 is a divisional application of the above (2), and the same technical contents as those of the above (2) are described in the publication.

(5) Japanese patent application laid-open No. 2000-510891 discloses an antifouling paint for marine use containing rosin, fiber, and a polymer flexibility imparting agent component, and describes that the antifouling paint has good weather resistance. Further, examples of the polymer flexibility imparting agent component include poly (meth) acrylate and polyester resin. However, although the technical idea of using 1 kind of rosin metal salt as a self-polishing polymer as a binder resin is disclosed, there is no technical idea of using a self-polishing polymer such as an acrylic polymer or a polyester resin having a metal salt side chain or a self-polishing polymer such as a (meth) acrylate polymer having a silyl ester side chain as in the present invention.

(6) In addition, Japanese patent laid-open publication No. 2003-502473 discloses a compound having the formula (I):

(in the formula (I), R₁～R₅A binder copolymer having side chain terminal groups represented by C1 to C20, and C1 to C20, wherein X is > C (═ 0), and n is an integer of 0 or 1 or more, and a fiber, and specifically a zinc sulfide fiber. Further, it is described that zinc sulfide may be contained as a pigment as required.

Examples of the monomer for synthesizing the adhesive copolymer include tri (isopropyl) silyl acrylate, methoxyethyl methacrylate, methyl methacrylate, and butyl methacrylate.

However, the antifouling paint composition disclosed in the above publication has problems that the obtained coating film has poor hydrolyzability (elution property of resin) and cannot sufficiently exhibit an antifouling effect, and that an inert layer is deposited on the surface of the coating film and adhesion is not good at the time of double coating such as repair.

(7) Japanese patent laid-open No. 2001-302989 discloses a composition comprising a compound represented by the formula (1): -S (O)₂-O-[Si(R⁴)(R⁵)-O]_n-Si(R¹)(R²)R³(in the formula, R¹、R²、R³、R⁴And R⁵Independently a hydrocarbon group such as an alkyl group of C1 to C18 or an alkoxy group of C1 to C18, and n is an integer of 0 to 200) as a binder, and examples of the antifouling agent include metal pyrithione salts containing a metal (e.g., Cu or Zn). Further, the pigment is exemplified by zinc sulfide, etc., and is described to be incorporated in an amount of 1 to 60% by volume of the solid content of the coating material.

(8) Further, in Japanese patent laid-open No. 2000-5692, zinc sulfide is exemplified as an example of a color pigment that can be added to a coating material for film thickness determination that utilizes the difference in color between a coating film containing a color pigment and an object to be coated.

Further, as the resin component contained in the coating material, a hydrolysis type acrylic modified resin, a polyester modified resin, or the like is exemplified. Wherein the hydrolysis type acrylic modified resin or polyester modified resin has a side chain represented by the formula (1): -COO-M-Y_y… (1) (wherein Y represents the valence of M-1, M represents a metal such as Cu, Zn, Si, etc., and Y represents an alkyl group, a hydroxyl group, OOCR¹A group of (R)¹A hydrocarbon group having 10 or more carbon atoms) or R²-CO-CH₂-CO-R³A group of (R)²Represents alkyleneRadical or 2-valent radical composed of phenyl derivatives, R³Represents an alkyl group or a 1-valent group composed of a phenyl derivative), formula (2): -N ═ CHR⁴…(2)(R⁴A hydrocarbon group having 6 or more carbon atoms) or formula (3): -SO₃-NH-R⁵…(3)(R⁵Hydrogen atom or alkyl group).

This publication discloses the use of a hydrolyzable self-polishing side chain terminal-COO-MOOCR as a coating material for determining film thickness¹The example of the metal-containing copolymer coating "エコフレックス", but no example incorporating zinc sulfide as a coloring pigment.

(9) Japanese patent laid-open No. 2001-327914 discloses that when a silicone rubber top coating film is directly applied to a base coating film comprising a block copolymer comprising organosiloxane units and alkylene oxide units without interposing an intermediate coating film, the base coating film may contain a coloring pigment, and zinc sulfide is an example of the coloring pigment that can be added. However, there is no example incorporating zinc sulfide.

As described above, in the inventions described in the above (1) to (9), the resin is exemplified by a hydrolyzable resin formed of a rosin or a crosslinkable metal salt copolymer, and zinc sulfide is exemplified as the coloring pigment, but none of them discloses a technical idea of paying attention to the antifouling effect of zinc sulfide itself, and is limited to the application in terms of the function as the coloring pigment.

In short, these conventional documents do not have a technical idea of focusing on the safety of zinc sulfide to the environment and the antibacterial action as in the present invention, and combining the zinc sulfide with a hydrolyzable resin such as a specific copolymer containing a crosslinkable metal salt bond to exhibit the antibacterial action of zinc sulfide in the obtained antifouling coating film well, thereby improving the antifouling property.

Patent document 1: japanese patent laid-open publication No. 2003-522734

Patent document 2: WO2004/057964

Patent document 3: japanese patent laid-open publication No. Hei 10-508639

Patent document 4: japanese patent laid-open No. 2004-346329

Patent document 5: japanese patent laid-open publication No. 2000-510891

Patent document 6: japanese patent laid-open publication No. 2003-502473

Patent document 7: japanese patent laid-open No. 2001-302989

Patent document 8: japanese patent laid-open No. 2000-5692

Patent document 9: japanese patent laid-open No. 2001-327914

Disclosure of The Invention

In order to solve the problems associated with the prior art as described above, an object of the present invention is to provide an antifouling coating composition which is a coating material, particularly a hydrolysis type antifouling coating composition, and which, when applied and cured on the surface of a substrate such as a ship hull to form an antifouling coating film, has an antibacterial action and excellent renewability of the coating film in particular, and can effectively prevent the adhesion of marine organisms.

The present invention has an object to provide an antifouling paint which is excellent in self-polishing property (coating film consumption) for a long period of time, antifouling performance for a long period of time, and antifouling performance in a highly fouling sea area (static antifouling performance) as compared with a paint containing cuprous oxide, particularly an antifouling paint containing no cuprous oxide and no copper.

It is another object of the present invention to provide an antifouling coating film, a substrate with a coating film, and an antifouling substrate, which are excellent in balance between the antibacterial action and the renewability of the coating film obtained by applying and curing the antifouling coating composition.

Further, another object of the present invention is to provide a method for safely and efficiently forming a coating film having the above characteristics on a surface of a substrate, and a method for preventing stains on a substrate.

The antifouling paint composition of the present invention is an antifouling paint composition comprising (a) a hydrolyzable copolymer and (B) an antifouling agent, wherein the hydrolyzable copolymer (a) is an acrylic polymer or a polyester resin selected from (a1) having a general formula (I):

-COO-M-O-COR¹·····(I)

[ in the formula (I), M represents zinc or copper, R¹Represents an organic group, but as R¹Excluding the group corresponding to formula (II) — C (R)²)＝CH₂In the case of]The copolymer containing a metal salt bond of a side chain terminal group (also referred to as a side chain terminal structure metal salt copolymer), (a2) is represented by the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group]A copolymer containing a metal salt bond formed from a constituent unit (a21) derived from the monomer represented by (a) and a constituent unit (a22) derived from another unsaturated monomer copolymerizable with the monomer, and (a3) a copolymer represented by the general formula (III):

R⁷-CH＝C(R³)-COO-SiR⁴R⁵R⁶·····(III)

[ in the formula (III), R³Represents a hydrogen atom or a methyl group, R⁴、R⁵And R⁶Each independently represents a hydrocarbon group, R⁷Represents a hydrogen atom or R⁸-O-CO- (wherein, R⁸Representing an organic radical or represented by-SiR⁹R¹⁰R¹¹Silyl group represented by R⁹、R¹⁰And R¹¹Each independently represents a hydrocarbon group)]At least 1 hydrolyzable copolymer of a silyl ester copolymer comprising a constituent unit (a31) derived from the monomer and a constituent unit (a32) derived from another unsaturated monomer copolymerizable with the monomer (III), wherein the amount of zinc sulfide as the antifouling agent (B) is 10 to 500 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A).

In the present invention, it is preferable that the antifouling paint composition does not substantially contain cuprous oxide.

In the present invention, it is preferable that the antifouling agent (B) is composed of zinc sulfide and an organic antifouling agent (B2).

In the present invention, it is preferred that the organic antifouling agent (b2) is at least 1 organic antifouling agent selected from the group consisting of pyrithione compounds, triorganoborons and amine complexes thereof, and 4, 5-dichloro-n-octylisothiazolin-3-one.

In the present invention, it is preferred that the organic antifouling agent (b2) is at least 1 selected from the group consisting of zinc pyrithione, triphenylboron pyridine complex, methyldiphenylboron 4-isopropylpyridine complex and 4, 5-dichloro-n-octylisothiazolin-3-one.

In the present invention, when the antifouling agent (B) contains both cuprous oxide and the organic antifouling agent (B2), the content of the organic antifouling agent (B2) is preferably 20 to 500 parts by weight based on 100 parts by weight of zinc sulfide.

In the present invention, zinc oxide is preferably further contained as a filler pigment.

In the present invention, when zinc oxide is contained as described above, the content of zinc oxide is preferably 10 to 300 parts by weight based on 100 parts by weight of the above-mentioned hydrolyzable copolymer (A).

In the present invention, the content of zinc oxide is preferably 1 to 40% by weight in the antifouling paint composition.

In the present invention, it is preferred that the antifouling paint composition further contains talc as a filler pigment. When talc is contained in this manner, the content of talc is preferably 5 to 300 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A). When talc is contained in this manner, the content of talc is preferably 0.5 to 40% by weight in the antifouling paint composition.

In the present invention, it is preferable that the antifouling paint composition further contains chlorinated paraffin as a plasticizer.

In the present invention, the content of the chlorinated paraffin is preferably 0.05 to 40 parts by weight based on 100 parts by weight of the above-mentioned hydrolyzable copolymer (A).

In the present invention, the content of the chlorinated paraffin is preferably 1 to 5% by weight in the antifouling paint composition.

In the present invention, it is preferable to further contain at least 1 coloring pigment selected from the group consisting of red iron oxide, titanium white, yellow iron oxide and organic pigments.

In the present invention, the organic group R of the above-mentioned copolymer (a1) containing a bond of a metal salt is preferred¹Is a monobasic acid organic acid residue formed by univalent saturated aliphatic group with 2-30 carbon atoms, unsaturated aliphatic group with 2-30 carbon atoms, alicyclic group with 3-20 carbon atoms, aromatic hydrocarbon group with 6-18 carbon atoms or a substitute thereof.

In the present invention, the organic group R of the above-mentioned copolymer (a1) containing a bond of a metal salt is preferred¹Is a monobasic acid organic acid residue formed by univalent saturated or unsaturated aliphatic with 10-20 carbon atoms, saturated or unsaturated alicyclic hydrocarbon with 3-20 carbon atoms or a substituent thereof.

In the present invention, it is preferable that the copolymer (a1) containing a bond of a metal salt is an acrylic copolymer having a structure represented by the general formula (IV):

-O-COR¹ ·····(IV)

[ in the formula (IV), R¹An organic acid residue of a monobasic acid comprising a C10-20 monovalent saturated or unsaturated aliphatic, C3-20 saturated or unsaturated alicyclic hydrocarbon group or a substituent thereof]The copolymer having a metal salt bond at the side chain terminal group is shown.

In the present invention, the organic group R of the above-mentioned copolymer (a1) containing a bond of a metal salt is preferred¹Is prepared from tertiary carbonic acid (Versatic acid), palmitic acid, stearic acid, oleic acid, linoleic acid, and linoleic acidAnd (2) organic acid residues formed by at least 1 monobasic acid of the oleic acid, the abietic acid, the neoabietic acid, the pimaric acid, the dehydroabietic acid, the 12-hydroxystearic acid and the naphthenic acid.

In the present invention, it is preferable that the copolymer (a1) containing a bond of a metal salt is represented by the general formula (V):

CH2＝C(R²)-COO-M-O-COR¹ ·····(V)

[ in the formula (V), R¹、R²And M is as previously described]A copolymer of 2 or more monoacid metal (meth) acrylates.

In the present invention, the organic group R of the constituent unit derived from the monobasic acid metal (meth) acrylate represented by the formula (V) is preferably an organic group¹Is a monobasic acid organic acid residue formed by univalent saturated or unsaturated aliphatic with 10-20 carbon atoms, saturated or unsaturated alicyclic hydrocarbon with 3-20 carbon atoms or a substituent thereof.

In the present invention, the organic group R of the constituent unit derived from the monoacid metal (meth) acrylate represented by the formula (V) is preferably an organic group¹Is an organic acid residue formed from at least 1 monobasic acid selected from the group consisting of versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid.

In the present invention, it is preferable that the copolymer (a1) containing a bond of a metal salt is a copolymer containing a constituent unit derived from the copolymer of the monobasic acid metal (meth) acrylate and a constituent unit derived from at least 1 unsaturated monomer selected from the group consisting of an alkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate and a hydroxyalkyl (meth) acrylate.

In the present invention, it is preferable that the content of zinc and/or copper based on the structure of the general formula (I) in the copolymer (a1) containing a metal salt bond is 0.5 to 20% by weight.

In the present invention, the constituent unit (a21) of the copolymer (a2) containing a metal salt bond is preferably one derived from the copolymer represented by the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ formula (II) < CHEM > M, R²As described above]The monomer represented is at least 1 monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate.

In the present invention, it is preferable that the other unsaturated monomer from which the constituent unit (a22) in the above-mentioned copolymer (a2) containing a metal salt bond can be derived is at least 1 unsaturated monomer selected from the group consisting of alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ formula (II) < CHEM > M, R²As described above]The monomer represented is at least 1 monomer selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is at least 1 unsaturated monomer selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ formula (II) < CHEM > M, R²As described above]The monomer is selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and dimethylAt least 1 monomer of copper acrylate, and the other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is represented by the general formula (V):

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

[ in the formula (V), R¹、R²And M is as previously described]Monobasic acid metal (meth) acrylates are shown.

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ formula (II) < CHEM > M, R²As described above]The monomer represented is at least 1 monomer selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is selected from the group consisting of monomers represented by the general formula (V):

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

[ in the formula (V), R¹、R²And M is as previously described]At least 1 unsaturated monomer of monobasic acid metal (meth) acrylate, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate.

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ formula (II) < CHEM > M, R²As described above]The monomer represented is at least 1 monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylateThe other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is selected from those represented by the general formula (V):

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

[ in the formula (V), R¹、R²And M is as previously described]The monobasic acid metal (meth) acrylate and at least 1 unsaturated monomer of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.

In the present invention, the organic group R of the constituent unit derived from the monoacid metal (meth) acrylate represented by the formula (V) is preferably an organic group¹Is a monobasic acid organic acid residue formed by univalent saturated or unsaturated aliphatic with 10-20 carbon atoms, saturated or unsaturated alicyclic hydrocarbon with 3-20 carbon atoms or a substituent thereof.

In the present invention, it is preferable that the content of zinc and/or copper based on the structure of the general formula (II) in the copolymer (a2) containing a metal salt bond is 0.5 to 20% by weight.

In the present invention, it is preferred that the constituent unit (a31) derived from the monomer represented by the general formula (III) is a constituent unit derived from a trialkylsilylalkyl (meth) acrylate.

In the present invention, it is preferred that the constituent unit (a31) derived from the monomer represented by the general formula (III) is a constituent unit derived from triisopropylsilyl (meth) acrylate.

In the present invention, it is preferable that the constituent unit (a32) derived from the "other unsaturated monomer" copolymerizable with the monomer represented by the general formula (III) is a constituent unit derived from at least 1 unsaturated monomer selected from the group consisting of alkyl (meth) acrylates, alkoxyalkyl (meth) acrylates and hydroxyalkyl (meth) acrylates.

In the present invention, it is preferable that the constituent unit (a32) derived from the "other unsaturated monomer" copolymerizable with the monomer represented by the general formula (III) is a constituent unit derived from at least 1 unsaturated monomer selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.

The antifouling coating film of the present invention is characterized by being formed from any one of the above-described antifouling paint compositions.

The substrate with a coating film of the present invention is characterized in that the surface of the substrate is coated with a coating film obtained by curing the antifouling paint composition described in any one of the above.

The antifouling substrate of the present invention is characterized in that the surface of the substrate which is in contact with seawater or fresh water is coated with a coating film obtained by curing the antifouling coating composition described in any one of the above.

The antifouling substrate of the present invention is preferably one of an underwater structure, a ship outer plate, a fishing net and a fishing tackle as a base.

The method of forming a coating film on a surface of a substrate of the present invention is characterized in that the antifouling paint composition described in any one of the above is applied to or impregnated into the surface of a substrate, and the coating film is formed by curing the composition.

The antifouling method of the present invention is characterized in that the antifouling coating composition described in any one of the above is applied to or impregnated into the surface of a substrate, and the antifouling coating is cured to form an antifouling coating film.

In the present invention, the substrate to be subjected to the antifouling method is preferably any one of an underwater structure, a ship outer plate, a fishing net, and a fishing tackle.

In the present invention, when the amount (weight) of the copolymer or the amount ratio of the copolymer to zinc sulfide or the like is expressed, the amount of the copolymer is substantially represented by a solid content value not containing a solvent or the like.

However, in examples, comparative examples and the like, as shown in tables 1 to 4, when the residual component (% by weight) and the solid component (%) are particularly noted or the volatile component is noted, the amount of the copolymer (polymer) is indicated by including the amount of the resin component as the coating film forming component and the amount of the volatile component (solvent, dispersion medium). Similarly, in the antifouling paint compositions described in tables 5 to 10 and the like, in which the copolymers described in tables 1 to 4 were blended, the amount of the blended copolymer also indicates the amount of volatile components including a solvent and the like.

The present invention provides an antifouling coating composition which, when a coating material, particularly a hydrolyzable antifouling coating composition, is applied and cured on the surface of a substrate such as a ship hull to form an antifouling coating film, has a particularly good balance between an antibacterial action and the renewability of the coating film, and can effectively prevent the adhesion of marine organisms, particularly algae.

The present invention can provide a copper-free antifouling paint which is particularly safe to the environment and substantially free of cuprous oxide.

According to the present invention, zinc sulfide as an antifouling agent is incorporated into a hydrolyzable self-polishing resin, and particularly, in a preferred embodiment thereof, by using zinc sulfide as an antifouling agent in combination with an organic antifouling agent (e.g., boron-based or pyrithione-based), an antifouling coating composition capable of forming a coating film having excellent self-polishing properties (coating film wear properties) for a long period of time, and further improved antifouling properties such as antifouling properties for a long period of time and antifouling properties in a highly fouling sea area (static antifouling properties) can be provided, as compared with conventional antifouling coatings containing cuprous oxide.

The present invention also provides an antifouling coating film, a substrate with a coating film, and an antifouling substrate, which are obtained by applying and curing the antifouling coating composition and have an antibacterial effect and a coating film having a good renewal property.

Further, according to the present invention, it is possible to provide a method for safely and efficiently forming a coating film having the above-described characteristics on a surface of a base material and a method for preventing stains on a base material.

Best Mode for Carrying Out The Invention

The antifouling coating composition, antifouling coating film, substrate with coating film, antifouling substrate, method for forming coating film on substrate surface, and method for preventing fouling of substrate of the present invention will be specifically described below.

[ antifouling paint composition]

The antifouling paint composition of the present invention comprises (A) a specific hydrolyzable copolymer and (B) an antifouling agent.

In the present invention, it is preferable that the antifouling paint composition does not substantially contain cuprous oxide from the viewpoint of reducing the adverse effect on the environment, the storage stability of the paint, and the paint function such as discoloration of the coating film.

<(A) Hydrolyzable copolymer>

Examples of the hydrolyzable copolymer (A) include the copolymers (a1), (a2) containing a metal salt bond and the silyl ester-based copolymer (a 3). These hydrolyzable copolymers (A) may be used in combination of 1 kind or 2 or more kinds. In the present invention, as the hydrolyzable copolymer (a), any 1 of the copolymers (a1), (a2) and the silyl ester based copolymer (a3) containing a metal salt bond can be used depending on the use of the obtained antifouling paint composition, the sea area in which ships are used, and the like, and for example, the silyl ester based copolymer (a3) may be used alone from the viewpoint of preventing adhesion of algae, or 2 or more of them may be used from the viewpoint of long-term stability, and for example, the copolymer (a1) (or (a2)) containing a metal salt bond and the silyl ester based copolymer (a3) may be used in an appropriate combination at an arbitrary amount ratio.

(a1) As acrylic polymer or polyester resin having a general formula (I):

-COO-M-O-COR¹·····(I)

[ in the formula (I), M represents zinc or copper, R¹Represents an organic group]The copolymer having a metal salt bond at the side chain terminal group is shown.

(a2) Consisting of a compound of the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group]A copolymer containing a metal salt bond formed from the constituent unit (a21) derived from the monomer shown in the above and the constituent unit (a22) derived from another unsaturated monomer copolymerizable with the monomer.

(a3) Consisting of a compound of the general formula (III):

R⁷-CH＝C(R³)-COO-SiR⁴R⁵R⁶·····(III)

[ in the formula (III), R³Represents a hydrogen atom or a methyl group, R⁴、R⁵And R⁶Each independently represents a hydrocarbon group, R⁷Represents a hydrogen atom or R⁸-O-CO- (wherein, R⁸Representing an organic radical or represented by-SiR⁹R¹⁰R¹¹Silyl group represented by R⁹、R¹⁰And R¹¹Each independently represents a hydrocarbon group)]A silyl ester copolymer comprising a constituent unit (a31) derived from the monomer(s) and a constituent unit (a32) derived from another unsaturated monomer copolymerizable with the monomer (III).

The copolymer (a1), (a2) containing a metal salt bond and the silyl ester copolymer (a3) will be specifically described below.

As such a copolymer (a1), (a2) and silyl ester copolymer (a3) containing a bond of a metal salt, conventionally known copolymers can be used, and examples thereof include (I) Japanese patent laid-open publication No. H10-298454 [0010 ]]～[0017]The hydrolyzable self-polishing resin having a group represented by the formula-X-O-Cu-Y (wherein X represents > C ═ O and Y represents an organic acid residue, and may be an alkylsilyloxy group) in the side chain as described in (1), (II) Japanese patent laid-open No. 2000-]～[0017]Having the formula-COO-M-Y in the side chain as described in (1)_y… (1) (wherein Y represents the valence of M-1, M represents any metal selected from Cu, Zn and Si (when Y is 2 or more, Y may be the same or different), Y represents an alkyl group, a hydroxyl group, or-OCOR¹A group represented by (wherein, R¹Represents a hydrocarbon group having 10 or more carbon atoms) or represented by the formula-R²-CO-CH₂-CO-R³A group represented by (wherein, R²Is alkylene or a 2-valent radical composed of phenyl derivatives, R³Alkyl group or 1-valent group composed of a phenyl derivative)), and a hydrolysis type acrylic resin or polyester resin, and [0039 ] of Japanese patent application laid-open No. 2004-196957 previously proposed by the present applicant]～[0068]The hydrolyzable copolymer (particularly, a metal-containing copolymer) described in (1) and [0069 ] of the same publication]～[0092]The polymerizable unsaturated carboxylic acid silyl ester copolymer described in (1), and [0051 ] of Japanese patent laid-open No. 2005-97400]～[0091]The hydrolyzable copolymer (particularly, a metal-containing copolymer) described in (1) and [0092 ] of the same publication]～[0124]The polymerizable unsaturated carboxylic acid silyl ester copolymer described in (1).

The copolymer (a1), (a2) and silyl ester copolymer (a3) containing a metal salt bond, which are particularly preferable for achieving the object of the present invention, will be described in detail below.

(copolymer (a1) having bond of Metal salt)

The copolymer (a1) containing a metal salt bond, also referred to as a side chain terminal structure metal salt copolymer, is an acrylic polymer or a polyester resin as a base resin, and is a copolymer obtained by combining a copolymer represented by the general formula (I):

-COO-M-O-COR¹·····(I)

[ in the formula (I), M represents zinc or copper, R¹Represents an organic group](Co) polymers having the structure of the side chain terminal group shown. { wherein, in order to avoid repetition of (a1) with (a2) described below, the organic group R in the formula (I)¹Excluding vinyl groups (-CH ═ CH)₂) And isopropenyl (-C (CH)₃)＝CH₂)}

Organic radical R¹：

As organic radicals R¹Examples of the organic acid residue include organic acid residues of monobasic acids comprising a monovalent saturated aliphatic group having 2 to 30 carbon atoms, preferably 10 to 20 carbon atoms, an unsaturated aliphatic group having 2 to 30 carbon atoms, preferably 10 to 20 carbon atoms, a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, an aromatic group having 6 to 18 carbon atoms and the like, or a substitution product thereof.

These organic radicals R¹In (2), R is R from the viewpoints of resin viscosity, resin elution from a coating film, and storage stability of a coating material¹Preferably a monovalent organic acid residue of a monovalent saturated or unsaturated aliphatic group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a substituent thereof.

Such an organic group R is good in terms of easiness of synthesis of the copolymer (a1) containing a metal salt bond, capability of exerting antifouling property by slowly hydrolyzing a coating film formed from the obtained antifouling paint composition and having a small load on the environment after hydrolysis, durability of the antifouling effect, surface renewability, and overcoatability in repair coating or the like, and the like¹Preferably an organic acid residue formed from a monobasic acid such as versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, naphthenic acid, or the like.

This is true from the viewpoint of elution and persistence of the resinOrganic radical R of¹The copolymer (a1) containing a metal salt bond of (A) is preferably a copolymer containing 1 or 2 or more constituent units derived from a monobasic acid metal (meth) acrylate represented by the following formula (V).

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

[ in the formula (V), R¹、R²And M is as previously described]

That is, in the formula (V), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group, R¹The same organic group as in the above formula (I) is shown, and the same group as in the above is preferable for the same reason as described above.

Specific examples of the monobasic acid metal (meth) acrylate (V) as the metal-containing monomer include zinc (meth) versatate, zinc (meth) isostearate, copper (meth) versatate, and copper (meth) isostearate. These monoacid metal (meth) acrylates (V) may be used in combination of 1 kind or 2 or more kinds.

In the present invention, when the copolymer (a1) containing a metal salt bond is produced, the monobasic acid metal (meth) acrylate (V) is not necessarily used as the monomer, and the production method of the copolymer (a1) is not particularly limited as long as the same constituent unit as that derived from the monomer (V) (constituent unit (V)) is present in the obtained copolymer.

The copolymer (a1) containing a bond of a metal salt preferably contains a constituent unit derived from "another unsaturated monomer (a 12)" in addition to the monobasic acid metal (meth) acrylate constituent unit (V), "the other unsaturated monomer (a 12)" preferably being an alkyl (meth) acrylate having an alkyl group with 1 to 20 carbon atoms, an alkoxyalkyl (meth) acrylate having an alkoxy group with 1 to 20 carbon atoms and an alkylene group with 1 to 20 carbon atoms, or a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group with 1 to 20 carbon atoms.

Among these "other unsaturated monomers (a 12)", specific examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate.

Specific examples of the alkoxyalkyl (meth) acrylate include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, ethoxymethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxymethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, and 3-methyl-3-methoxybutyl (meth) acrylate.

Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate and the like.

Among these "other unsaturated monomers (a 12)", methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate are preferable from the viewpoint of the coating film properties and the resin elution durability from the coating film.

These "other unsaturated monomers (a 12)" may be used in combination of 1 kind or 2 or more kinds.

In the copolymer (a1) containing a bond of a metal salt, the content of the monobasic acid metal (meth) acrylate component unit (V) in the copolymer (100 mol%) is usually 10 to 100 mol%, preferably 10 to 90 mol%, and the content of the component unit (a12) derived from the "other unsaturated monomer (a 12)" is the remaining amount, that is, usually 0 to 90 mol%, preferably 10 to 90 mol%, from the viewpoints of the viscosity of the resin, the elution property of the resin in the coating film, the water resistance of the coating film, and the like.

Further, the number average molecular weight Mn (polystyrene equivalent, hereinafter, the same, measured by GPC under the column: Super H2000+ H4000) of the copolymer (a1) containing a metal salt bond is usually 1000 to 100000(10 ten thousand), preferably 1000 to 50000(5 ten thousand), from the viewpoints of resin viscosity, storage stability of a coating material, elution rate of a resin in a coating film, and the like.

In addition, the content of zinc and/or copper based on the structure of the general formula (I) in the copolymer (a1) containing a metal salt bond is usually 0.5 to 20% by weight, preferably 5 to 20% by weight, from the viewpoint of satisfactory resin viscosity, storage stability of a paint, and elution from a resin in a coating film, of the copolymer (a1) containing a metal salt bond.

In addition to the copolymer (a1) containing a metal salt bond, the copolymer (a2) containing a metal salt bond and the silyl ester-based copolymer (a3) described below can be produced by conventionally known methods, for example, the methods described in the aforementioned Japanese patent application laid-open (first) No. 10-298454, Japanese patent application laid-open (second) No. 2000-1965692, Japanese patent application laid-open (third) No. 2004-196957, and Japanese patent application laid-open (fourth) No. 2005-97400.

(copolymer (a2) having bond of Metal salt)

The copolymer (a2) containing a bond of a metal salt is represented by the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

[ formula (II) < CHEM > M, R²The same as in formula (V), i.e., formula (II) wherein M represents zinc or copper, R²Represents a hydrogen atom or a methyl group]A copolymer containing a metal salt bond formed from the constituent unit (a21) derived from the monomer shown in the above and the constituent unit (a22) derived from the "other unsaturated monomer" copolymerizable with the monomer (II).

In the present invention, in the production of the copolymer (a2) containing a metal salt bond, as in the case of the copolymer (a1) containing a metal salt bond, the metal di (meth) acrylate (II) is not necessarily used as a monomer, and the production method of the copolymer (a2) is not particularly limited as long as the same constituent unit as that derived from the monomer (II) (constituent unit (II)) is present in the obtained copolymer.

Examples of the monomer (II), i.e., the metal di (meth) acrylate (II), include zinc diacrylate: (CH)₂＝CHCOO)₂Zn, zinc dimethacrylate: (CH)₂＝C(CH₃)COO)₂Zn, copper diacrylate: (CH)₂＝CHCOO)₂Cu, copper dimethacrylate: (CH)₂＝C(CH₃)COO)₂Cu is preferably zinc di (meth) acrylate from the viewpoints of resin viscosity, storage stability of the coating material, elution property of the resin in the coating film, and the like. In the present invention, these monomers (II) may be used in combination of 1 or 2 or more.

In addition, in the copolymer (a2) containing a metal salt bond, it is preferable that a component unit (a22) derived from "another unsaturated monomer (a 22)" copolymerizable with the monomer (II) is present in addition to the component unit (II) derived from the metal di (meth) acrylate (II) from the viewpoint of adjustment of the elution rate of the resin.

Examples of the "other unsaturated monomer (a 22)" include a monoacid metal (meth) acrylate (V) used in the production of the copolymer (a1) having a metal salt bond and/or an "other unsaturated monomer (a 12)" which is a monomer used as needed in the production of the copolymer (a1) having a metal salt bond.

That is, in the copolymer (a2) containing a metal salt bond, in addition to the essential metal di (meth) acrylate component unit (II), a monoacid metal (meth) acrylate component unit (V) in the copolymer (a1) containing a metal salt bond or a component unit (a12) derived from another unsaturated monomer (a12) may be present, or both the component unit (V) and the component unit (a12) may be present. The other unsaturated monomer (a12) is preferably an alkyl (meth) acrylate, an alkoxyalkyl (meth) acrylate, or a hydroxyalkyl (meth) acrylate as described above.

In the copolymer (a2) containing a metal salt bond, the content of the metal di (meth) acrylate component unit (a21) is usually 10 to 100 mol%, preferably 10 to 90 mol%, and the content of the component unit (a22) derived from the "other unsaturated monomer (a 22)" is the remaining amount, that is, usually 0 to 90 mol%, preferably 10 to 90 mol%, in terms of easy adjustment of the elution rate of the resin in the coating film. The amount of the monoacid metal (meth) acrylate constituent unit (V) that may be present in the constituent unit (a22) derived from the "other unsaturated monomer (a 22)" in 100 mol% is 0 to 100 mol%, preferably 0 to 90 mol%, and the content of the constituent unit (a12) derived from the other unsaturated monomer (a12) is 100 to 0 mol%, preferably 10 to 90 mol%, based on the remainder.

The number average molecular weight Mn (in terms of polystyrene, hereinafter, the same applies, measured by GPC under the conditions of column: Super H2000+ H4000) of the copolymer (a2) containing a metal salt bond is usually 1000 to 100000(10 ten thousand), preferably 1000 to 10000(1 ten thousand), from the viewpoint of the resin viscosity and the elution rate of the resin in the coating film.

In addition, the content of zinc (Zn) and/or copper (Cu) based on the structure of the general formula (II) in the copolymer (a2) is usually 0.5 to 20% by weight, preferably 5 to 20% by weight, in view of good resin viscosity, storage stability of the paint, and elution property of the resin in the coating film, of the copolymer (a2) containing a metal salt bond.

(silyl ester copolymer (a3))

The silyl ester copolymer (a3) is a copolymer comprising a constituent unit (a31) (also referred to as a silyl ester constituent unit) derived from a monomer represented by the following general formula (III) (also referred to as a silyl ester monomer, monomer (III), etc.) and a constituent unit (a32) derived from another unsaturated monomer copolymerizable with the monomer (III), as described above.

General formula (III):

R⁷-CH＝C(R³)-COO-SiR⁴R⁵R⁶·····(III)

[ in the formula (III), R³Represents a hydrogen atom or a methyl group, R⁴、R⁵And R⁶Each independently represents a hydrocarbon group, R⁷Represents a hydrogen atom or R⁸-O-CO- (wherein, R⁸Representing an organic radical or represented by-SiR⁹R¹⁰R¹¹Silyl group represented by R⁹、R¹⁰And R¹¹Each independently represents a hydrocarbon group)]

In the above silyl ester monomer (III), R⁷In the case of a hydrogen atom (H), the monomer is represented by the formula (IIIa): CH (CH)₂＝C(R³)-COO-SiR⁴R⁵R⁶·····(IIIa)

{ therein, R in the formula (IIIa)³、R⁴、R⁵And R⁶The same as in the case of formula (III).

R is as defined above⁴、R⁵And R⁶Preferably an alkyl group having 1 to 10, preferably 1 to 5 carbon atoms, more specifically an alkyl group such as methyl, ethyl, propyl or isopropyl.

Examples of the silyl ester monomer (IIIa) include trialkylsilyl (meth) acrylates such as trimethylsilyl (meth) acrylate, triethylsilyl (meth) acrylate, and triisopropylsilyl (meth) acrylate is particularly preferred from the viewpoint of satisfactory elution properties and elution durability of the resin in the coating film, and good physical properties of the coating film such as crack resistance.

Further, in the silyl ester monomer (III), R⁷Is R⁸-O-CO- (wherein, R⁸As in the case of the above formula (III), a monomer and

formula (IIIb):

R⁸-O-CO-CH＝C(R³)-COO-SiR⁴R⁵R⁶····(IIIb)

{ therein, R in the formula (IIIb)²、R⁴、R⁵、R⁶And R⁸The same as in the case of formula (III).

Specific examples of the silyl ester monomer (IIIb) include maleic acid ester (R in the formula (IIIb))³H), etc.

Examples of the other unsaturated monomer copolymerizable with the monomer (III) (or the monomer (IIIa) and/or the monomer (IIIb)) include "other unsaturated monomers (a12) and (a 22)" similar to the monomers used in the production of the copolymers (a1) and (a 2).

As the "other unsaturated monomer (a 32)", the alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate described above are preferable.

In the silyl ester based copolymer (a3), the content of the silyl ester based monomer (III) in the copolymer (100 mol%) is usually 10 to 100 mol%, preferably 10 to 90 mol%, and the content of the component unit (a32) derived from the "other unsaturated monomer (a 32)" is the remaining amount, that is, usually 0 to 90 mol%, preferably 10 to 90 mol%, from the viewpoints of the resin viscosity (i.e., crack resistance) in the coating film, the storage stability of the coating material, and the elution property of the resin in the coating film.

Further, the number average molecular weight Mn (in terms of polystyrene, hereinafter, the same applies, measured by GPC under the conditions of column: Super H2000+ H4000) of the silyl ester copolymer (a3) is usually 1000 to 200000(20 ten thousand), preferably 1000 to 100000(10 ten thousand), from the viewpoints of the viscosity of the resin, storage stability, and elution property from the resin of the coating film.

<(B) Antifouling agent>

In the present invention, the antifouling agent (B) contains zinc sulfide (ZnS) as an essential component. From the viewpoint of satisfactory antifouling properties and coating film physical properties, particularly satisfactory crack resistance, of the resulting coating film, the content of the zinc sulfide is preferably 10 to 500 parts by weight, preferably 50 to 200 parts by weight, based on 100 parts by weight of the hydrolyzable copolymer (a) (solid content) which is the total amount of the polymers (a1) to (a 3). If the zinc sulfide content is less than the above range, the antifouling effect of the coating film cannot be sufficiently exhibited, and the renewability of the coating film surface tends to be suppressed; if the content is higher than the above range, problems in physical properties such as cracking tend to occur.

In the present invention, it is preferable that the antifouling agent (B) is composed of zinc sulfide and an organic antifouling agent (B2) from the viewpoint that the obtained coating film exhibits antifouling ability, durability of antifouling effect, and surface renewal property particularly in a highly fouling sea area where fouling is severe.

In the present invention, it is particularly preferable that the organic antifouling agent (b2) is selected from the following formulae [ VI ] in view of good antifouling property of the coating film and storage stability of the coating material:

[ formula [ VI ]]In, R¹～R⁴Each independently represents hydrogen, an alkyl group, an alkoxy group or a haloalkyl group, M represents a metal such as Cu, Na, Mg, Zn, Ca, Ba, Pb, Fe or Al, and preferably, M represents Zn, n represents a valence number, from the viewpoint of the durability of the coating film consumption]At least 1 organic antifouling agent of metal pyrithione salt and its derivative (pyrithione compound), triorganoboron and its amine complex, 4, 5-dichloro-n-octylisothiazolin-3-one.

In the present invention, it is preferable that the organic antifouling agent (b2) is at least 1 selected from the group consisting of zinc pyrithione, triphenylboron pyridine complex, methyldiphenylboron 4-isopropylpyridine complex and 4, 5-dichloro-n-octylisothiazolin-3-one, from the viewpoint of well-balanced storage stability of the coating material, coating film wear-out property and durability of antifouling property.

In the present invention, the content of the organic antifouling agent (B), particularly the organic antifouling agent, is preferably 20 to 500 parts by weight, more preferably 20 to 300 parts by weight, based on 100 parts by weight of zinc sulfide, from the viewpoints that the obtained antifouling coating film has good antifouling properties, particularly good durability (low coating film consumption), low environmental load, and good coating film water resistance.

In addition, as the antifouling agent, conventionally known antifouling agents can be used from the viewpoint of sufficiently exhibiting antifouling performance, and it is preferable that an antifouling agent having a large environmental load such as cuprous oxide is not substantially added.

< colored pigment >

As the coloring pigment, various organic and inorganic pigments known in the art can be used.

Examples of the organic pigment include carbon black, naphthol red, and phthalocyanine blue.

Examples of the inorganic pigment include red iron oxide, barite powder, zinc oxide (ZnO, zinc oxide), titanium white, and yellow iron oxide. In addition, various colorants such as dyes may be contained.

In the present invention, the inorganic coloring pigment is particularly preferably any of red iron oxide, titanium white and yellow iron oxide from the viewpoint of coloring power; the organic pigment is also preferable from the viewpoint of providing a coating film having a particularly vivid color and reducing discoloration.

< filled pigment >

The extender pigment is a pigment having a small refractive index and being transparent without covering the coated surface when blended with oil or varnish, and examples of the extender pigment include talc, silica, mica, clay, zinc oxide, calcium carbonate, kaolin, alumina white, white carbon ink, aluminum hydroxide, magnesium carbonate, barium sulfate, etc., which are also used as a precipitant, and among them, preferred are extender pigments selected from the group consisting of zinc oxide, talc, silica, mica, clay, calcium carbonate, kaolin, and barium sulfate.

Particularly, when zinc oxide is incorporated, the amount of zinc oxide is preferably 10 to 300 parts by weight per 100 parts by weight of the solid content of the copolymer (A) or 1 to 40% by weight in the antifouling paint composition, in view of the durability of the erodibility and the adhesion of the resulting coating film.

These extender pigments may be used in combination of 1 kind or 2 or more kinds. Further, the degree of consumption of the coating film can be adjusted by the kind of the filler pigment.

In the present invention, when talc is contained as a filler pigment in the antifouling paint composition, the content of talc is preferably 5 to 300 parts by weight, more preferably 5 to 200 parts by weight, based on 100 parts by weight of the hydrolyzable copolymer (A), in view of cost reduction and an extending effect of the obtained paint, and transparency and film thickness of the obtained coating film. In addition, when talc is contained as described above, the content of talc is preferably 0.5 to 40% by weight, more preferably 0.5 to 20% by weight, in the antifouling paint composition, from the viewpoint of not adversely affecting the physical properties and antifouling properties of the coating film.

In the present invention, it is preferable that the antifouling paint composition further contains chlorinated paraffin and terpene phenol as plasticizers.

< plasticizers such as chlorinated Paraffin >

Examples of the plasticizer include TCP (tricresyl phosphate), chlorinated paraffin, polyvinyl ethyl ether, and terpene phenol. These plasticizers may be used in combination of 1 kind or 2 or more kinds.

These plasticizers contribute to the improvement of the crack resistance of the coating film (antifouling coating film) formed from the obtained antifouling coating composition, and among these plasticizers, chlorinated paraffin is preferably used.

The chlorinated paraffin which can be incorporated as a plasticizer in the antifouling paint composition of the present invention may be linear or branched and may be liquid or solid (powder) at room temperature, and it is preferable to use a chlorinated paraffin having an average carbon number of usually 8 to 30, preferably 10 to 26, and it is preferable to use a chlorinated paraffin having a number average molecular weight of usually 200 to 1200, preferably 300 to 1100, and a viscosity of usually 1 or more (poise/25 ℃ C.), preferably 1.2 or more (poise/25 ℃ C.), and a specific gravity of 1.05 to 1.80/25 ℃ C, preferably 1.10 to 1.70/25 ℃. When such a chlorinated paraffin having a carbon number is used, a coating film having less cracks and less peeling can be formed using the obtained antifouling paint composition. If the carbon number of the chlorinated paraffin is less than 8, the effect of suppressing cracking is insufficient, and if the carbon number exceeds 30, the wear-out property (renewability) of the surface of the obtained coating film may be deteriorated, and the antifouling property may be deteriorated. Further, the chlorination rate (chlorine content) of the chlorinated paraffin is preferably 35 to 75%, more preferably 35 to 65%. When the chlorinated paraffin having such a chlorination rate is used, a coating film having less cracks and less peeling can be formed using the obtained antifouling paint composition. Examples of the chlorinated paraffin include "TOYOPARAX 150" and "TOYOPARAX A-70" available from Tosoh corporation.

In the present invention, when a plasticizer represented by chlorinated paraffin is added, the content of such plasticizer is preferably 0.05 to 40 parts by weight based on 100 parts by weight of the above hydrolyzable copolymer (A) from the viewpoints of crack resistance, reduction in discoloration, improvement in water resistance, and the like of a coating film.

In the present invention, the content of the plasticizer represented by chlorinated paraffin is 1 to 5% by weight in the antifouling paint composition (that is, including volatile components such as a solvent).

[ production of antifouling paint composition]

The antifouling paint composition of the present invention as described above can be produced as follows.

The antifouling paint composition of the present invention can be produced by a conventionally known method using zinc sulfide (B) as an antifouling agent in the above-mentioned hydrolyzable copolymer (a) such as a copolymer containing a metal salt bond. For example, the antifouling paint composition of the present invention can be produced by blending the hydrolyzable copolymer (a) containing a metal salt bond or the silyl ester-based copolymer, zinc sulfide (B), zinc oxide, talc, and "other components" shown below, all at once or in any order, stirring and mixing them, and the like.

< other ingredients >

The anti-fouling agent, thixotropy imparting agent, plasticizer, inorganic dehydrating agent (stabilizer), anti-sagging agent/anti-settling agent (thickener), coloring pigment, dye, other coating film forming components, solvent (for example, butyl acetate, ethylcyclohexane, xylene), bactericide, antifungal agent, antiaging agent, antioxidant, antistatic agent, flame retardant, heat conduction improving agent, adhesion imparting agent, etc. may be added at once or in any order at a predetermined ratio, stirred, mixed, and dissolved/dispersed in the solvent.

In addition, when the above-mentioned components are mixed and mixed, conventionally known mixing and stirring apparatuses such as a ross mixer (ロスミキサ a), a planetary mixer, a universal pinkish mixer, and the like can be suitably used.

< anti-sagging/anti-settling agent (thixotropic agent) >

As the anti-sagging/anti-setting agent (thixotropic agent), an organic clay, an organic wax, or the like may be blended in an arbitrary amount. Examples of such anti-sagging/anti-setting agents include organic clay salts such as stearates, lecithin salts and alkylsulfonates of Al, Ca and Zn, polyethylene waxes, amide waxes, hydrogenated castor oil waxes, polyamide waxes and mixtures thereof, synthetic fine white carbon black, oxidized polyethylene waxes and the like, and preferably polyamide waxes, synthetic fine white carbon black, oxidized polyethylene waxes and organic clays are used.

Examples of such anti-sagging/anti-setting agents include those marketed under the trade names "Disbaron 305", "Disbaron 4200-20" and "Disbaron A630-20X" by Nanguozhizu Kabushiki Kaisha.

< other coating film-forming ingredients >

The coating film-forming component may contain a resin other than the copolymer (a) within a range not departing from the object of the present invention, and examples of such "other coating film-forming component" include water-insoluble or water-insoluble resins such as acrylic resins, acrylic silicone resins, unsaturated polyester resins, fluorine-containing resins, polybutene resins, silicone rubbers, urethane resins (rubbers), epoxy resins, polyamide resins, vinyl chloride-based copolymer resins, chlorinated rubbers (resins), chlorinated olefin resins, styrene-butadiene copolymer resins, ethylene-vinyl acetate copolymer resins, polyvinyl chloride resins, alkyd resins, coumarone resins, terpene resins, petroleum resins, and the like.

Examples of the water-soluble resin include rosin (trade name: rosin WW), monocarboxylic acids, and salts thereof. Examples of the monocarboxylic acid include fatty acids having about 9 to 19 carbon atoms and naphthenic acids. Examples of the salt of the monocarboxylic acid include a Cu salt, a Zn salt, and a Ca salt. Examples of the rosin include gum rosin, wood rosin, tall oil rosin, and the like, and any of them can be used in the present invention. These water-soluble resins may be used in combination of 1 kind or 2 or more kinds.

< solvent >

In the antifouling paint of the present invention, the above-mentioned various components can be dissolved or dispersed in a solvent as required. Examples of the solvent used herein include various solvents that are usually used in antifouling paints, such as aliphatic, aromatic, ketone, ester, and ether solvents. Examples of the aromatic solvent include xylene and toluene, examples of the ketone solvent include MIBK and cyclohexanone, and examples of the ether solvent include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PGMAC).

[ antifouling coating film, substrate with coating film, and the like]

Specifically, if the above-mentioned antifouling coating composition is applied to the surfaces of underwater structures such as water supply ports and water discharge ports of thermal or nuclear power plants, antifouling mud spreading films for various marine civil engineering works such as coastal roads, submarine tunnels, harbor facilities, canals and waterways, and various molded bodies such as ships and fishery materials (e.g., ropes, fishing nets, buoys and life buoys) by a usual method 1 to several times, ships or underwater structures coated with an antifouling coating film having excellent antifouling properties, which can release an antifouling component slowly over a long period of time, and which have appropriate flexibility and excellent crack resistance even when the coating thickness is large, can be obtained.

That is, the antifouling coating film obtained by applying and curing the antifouling paint composition of the present invention on the surface of various molded articles has excellent antifouling properties, and can prevent the adhesion of aquatic organisms such as ulva, barnacle, enteromorpha, serpula, oyster, and bryozoans for a long period of time.

In particular, the antifouling paint composition adheres well to the surface of a material such as a ship even when the material is FRP, steel, wood, an aluminum alloy, or the like. In the case of steel ships and aluminum ships, the antifouling paint of the present invention is usually applied to the surface of a substrate coated with a primer, an anticorrosive paint, and a binder paint if necessary. The antifouling paint composition can be applied to the surface of an existing antifouling coating film.

Further, for example, when the antifouling paint composition is applied to the surface of a marine structure, adhesion of marine organisms can be prevented, the function of the structure can be maintained for a long time, and when the antifouling paint composition is applied to a fishing net, the net pores of the fishing net can be prevented from being closed, and environmental pollution is less likely to occur.

The antifouling paint composition of the present invention may be applied directly to a fishing net, or may be applied to the surface of a ship, an underwater structure, or the like, to which a primer such as a rust inhibitor or a primer has been applied in advance. The antifouling paint composition of the present invention can be applied to the surface of a ship, particularly an FRP ship, an underwater structure, or the like, which has been coated with a conventional antifouling paint or with the antifouling paint composition of the present invention, for repair. The thickness of the antifouling coating film formed on the surface of a ship, an underwater structure, or the like is not particularly limited, and is, for example, about 30 to 150 μm/time.

The antifouling coating film of the present invention or the coating film on the surface of the water receiving part of a ship or underwater structure obtained as described above is formed from the antifouling coating composition described above, and is less likely to cause environmental pollution and has excellent long-term antifouling properties against organisms attached to a wide range of ships or underwater structures.

The antifouling coating composition and antifouling coating film according to the present invention can provide an antifouling coating film which can form an antifouling coating film suitable for an outer boat, a ship, an underwater structure, a fishing tackle or a fishing net coated with the antifouling coating film, which has a small load on the environment, has excellent antifouling properties, can uniformly wear the coating film at a constant rate over a long period of time, has excellent uniform wear properties of the coating film, can maintain excellent antifouling performance over a long period of time, and has excellent long-term antifouling property maintaining performance of the coating film.

In particular, if an organic antifouling agent (e.g., boron-based or pyrithione-based) and zinc sulfide are used in combination in a conventional hydrolysis-type antifouling paint composition, the synergistic effect of the antibacterial action of zinc sulfide and the improvement in the renewability of the coating film can be exhibited, and the effect of preventing the adhesion of marine organisms, particularly algae, is remarkably improved.

[ examples ]

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

In the following examples and comparative examples, "part" means part by weight unless otherwise specified.

In the present invention, the following table, including the tables, is used to basically indicate the resin component as the coating film forming component, such as simply "copolymer (a)". In addition, when the copolymer (a) and the like are described as residual components by heating or as solid components, the resin solution or dispersion liquid containing a volatile component such as a solvent in addition to the resin component as a coating film forming component is also described.

Production example 1

(preparation of copolymer (a1-1) having Metal salt bond at end of side chain)

To a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, 30 parts by weight of PGM (propylene glycol monomethyl ether) and 40 parts by weight of xylene were charged, and the temperature was raised to 100 ℃ while stirring. Subsequently, a mixture composed of the monomers and the polymerization initiator shown in table 1 was uniformly dropped from the dropping funnel over 3 hours. After completion of the dropwise addition, 1 part by weight of t-butyl peroctoate and 10 parts by weight of xylene were dropwise added over 2 hours, and after further stirring for 2 hours, 20 parts by weight of xylene was added to obtain a copolymer (a1-1) containing a metal salt bond at the end of a side chain having characteristic values shown in Table 1.

The properties of the resulting copolymer having a metal salt bond at the end of a side chain (also referred to as a side chain-end metal salt copolymer) or a reaction mixture containing the copolymer, i.e., the Gardner viscosity and the solid content (%), were evaluated.

The results are shown in Table 1.

< conditions for measuring Gardner viscosity >

As described in Japanese patent laid-open No. 2003-55890 and the like, the Gardner viscosity was measured at 25 ℃ at a resin component concentration of 35% by weight in accordance with 4.3 of JIS K7233.

< solid content >

The solid component is a heating residual component obtained by heating and drying a reaction mixture containing a polymer, a solvent and the like, a coating material, an uncured coating film and the like to volatilize the solvent and the like, and generally the resin component further contains a pigment and the like and becomes a coating material forming component. In addition, the amount of monomers and the like (example: Table 2) which are contained in the coating material and the like and which react to form a resin (solid content) is also included in the solid content.

< measurement of number average molecular weight Mw, Mn >

The weight average molecular weight Mw of a resin such as a metal-containing resin was measured by HLC-8120GPC using 2 TSK-gel α type separation columns (. alpha. -M) and DMF (dimethylformamide) containing 20mM LiBr added as an eluent. The weight average molecular weight (Mw) was determined in terms of polystyrene.

The number average molecular weight Mn of the resin was determined by GPC as described above in terms of polystyrene.

Production examples 2 to 3

In production example 1, the side chain terminal structure metal salt copolymers (a1-2) to (a1-3) were produced in the same manner as in production example (a1-1) except that the blending components were changed as shown in Table 1.

The physical properties of the resulting side chain terminal structure metal salt copolymer or the reaction mixture containing the copolymer were evaluated in the same manner as in production example (a 1-1).

The results are shown in Table 1.

<TABLE 1>Preparation example of side chain terminal Structure Metal salt copolymer (a1)

		Production example 1	Production example 2	Production example 3
					Side chain terminal structure metal salt copolymer (a1) component complex unit (parts by weight)		a1-1	a1-2	a1-3
Metal-containing monomer (i)	Acrylic acid zinc salt	8
					Methacrylic acid zinc salt	8
	Acrylic acid copper salt			16
					Metal-containing monomer (ii)	Tertiary zinc carbonate methacrylate		35
Zinc isostearate acrylate	12
				Isostearic acid zinc methacrylate		12
Copper carbonate tert-acrylate			24
				Polymerizable monomer (iii)		2-Methoxyethyl acrylate	13	10	10
3-Methoxybutyl acrylate		30	40
					Unsaturated monomer (iv)	Methacrylic acid methyl ester	13
Acrylic acid ethyl ester	34	25	10
				Polymerization initiator		Tert-butyl peroxide	5	6	7

Characteristic value	Gardner viscosity	-Y	+Z	+Z1
					Solid content (%)	49.7	50.5	51.1

Production example 4

(production of Metal-containing monomer A)

To a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, 85.4 parts of propylene glycol monomethyl ether (PGM) and 40.7 parts of zinc oxide were charged, and the temperature was raised to 75 ℃ while stirring. Subsequently, a mixture of 43.1 parts of Methyl Methacrylate (MMA), 36.1 parts of Acrylic Acid (AA) and 5 parts of water was uniformly dropped from the dropping funnel over 3 hours. After the completion of the dropwise addition, the reaction solution was changed from a milky white state to a transparent one. After stirring for another 2 hours, 36 parts of propylene glycol monomethyl ether (PGM) was added to obtain a transparent mixture solution a containing a metal-containing monomer.

The solid content (metal-containing monomer A) in the resulting mixture solution was 44.8% by weight. (solid content: remarks column in Table 2, etc.)

The compounding composition and the like are shown in Table 2.

Production example 5

Production example 4 (production example of metal-containing monomer (a)) a transparent mixture solution (B) containing a metal-containing monomer was produced in the same manner as in production example 4, except that the compounding ingredients were changed as shown in table 2.

The compounding composition and the like are shown in Table 2.

< Table 2> production example of mixture of Metal-containing monomers

	Amount added (molar ratio)				Volatile content (%)		Solid content (%) tangle-solidup
									MMA	AA	ZnO	Water (W)	PGM	N-BuOH	Xylene	Water (W)
Production example 4(A)	0.5	0.5	0.5	0.27	53.2	2	44.8
								Production example 5(B)	0.5	0.5	0.5	0.27		9.9	43.2	2	44.9
(remarks): MMA/methyl methacrylate, AA/acrylic acid, PGM/propylene glycol monomethyl ether, N-BuOH/N-butanol. Solid component (%) or the amount of the copolymer in the reaction mixture containing a solvent or the like in addition to the copolymer obtained by reacting the charged raw materials.

Production example 6

(production of Metal-containing copolymer (a 2-1))

To a four-necked flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer, 15 parts of propylene glycol monomethyl ether, 57 parts of xylene and 4 parts of ethyl acrylate were charged, and the temperature was raised to 100 ℃ while stirring. Subsequently, a transparent mixture composed of 1 part of Methyl Methacrylate (MMA), 66.2 parts of Ethyl Acrylate (EA), 5.4 parts of 2-methoxyethyl acrylate (2-MEA), 52 parts of the mixture solution A obtained in production example 4, 10 parts of xylene, 1 part of a chain transfer agent (manufactured by NOF corporation, "ノフマ -MSD"), 2.5 parts of AIBN (azobisisobutyronitrile, Nippon hydrazine Kabushiki Kaisha) and 7 parts of AMBN (azobismethylbutyronitrile, Nippon hydrazine Kabushiki Kaisha) was uniformly dropped from a dropping funnel over 6 hours.

After completion of the dropwise addition, 0.5 part of t-butyl peroxide (TBPO) and 7 parts of xylene were added dropwise over 30 minutes, followed by stirring for 1 hour and 30 minutes, and then 4.4 parts of xylene were added to obtain a pale yellow transparent resin composition containing the copolymer (a2-1) containing a metal salt bond. The resin composition had a residual content under heating of 45.6%, a Gardner viscosity (concentration of the resin component: 35% by weight, measured at 25 ℃) of "-Y", a number average molecular weight Mn of the resin, determined by GPC, of 1950, a weight average molecular weight Mw of 5200, and no insoluble matter in the composition.

The physical properties (Gardner viscosity, solid content (%), molecular weight Mn and Mw) of the obtained copolymer (a2-1) containing a metal salt bond or the reaction mixture containing the copolymer are also shown in Table 3.

Production example 7

A crosslinkable copolymer (a2-2) having metal salt bonds was produced in the same manner as in production example 6, except that the compounding ingredients in production example 6 were changed as shown in Table 3.

The physical properties of the resulting copolymer crosslinked with a metal salt bond or the reaction mixture containing the copolymer were evaluated in the same manner as in production example 6 (production example of copolymer (a 2-1)).

The results are shown in Table 3.

< Table 3> production example of crosslinkable copolymer containing Metal salt bond (a2)

		Production example 6	Production example 7
				The crosslinkable copolymer (a2) containing metal salt bond (in parts by weight) constituting a complex constituent unit		a2-1	a2-2
Metal-containing reactant mixture solution	A (production example 4)	52
				B (production example 5)		37.8
	Comonomer	MMA	1				18
EA				66.2	65
		2-MEA	5.4

Initiator	AIBN	2.5	2.5
				AMBN	7	7
	TBPO	0.5	0.5
				Chain transfer agent	ノフマ A MSD	1	1
Characteristic value	Gardner viscosity	-Y	+Y
				Solid content (%)	45.6	46.2
	Molecular weight (Mn)	1950	2200
				Molecular weight (Mw)	5200	5600

Production example 8

Production example of (meth) acrylic acid silyl ester copolymer (a3-1)

100 parts of xylene was charged into a reaction vessel equipped with a stirrer, a condenser, a thermometer, a dropping device, a nitrogen inlet tube, and a heating/cooling jacket, and heated and stirred at 85 ℃ under a nitrogen stream. While maintaining the same temperature, a mixture of 60 parts of triisopropylsilyl acrylate, 40 parts of methyl methacrylate and 0.3 part of 2, 2' -azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours to the above reaction vessel by means of a dropping device. Then, after stirring at the same temperature for 4 hours, 0.4 part of 2, 2' -azobisisobutyronitrile was added, and further stirring was carried out at the same temperature for 4 hours to obtain a colorless and transparent reaction solution containing the silyl (meth) acrylate copolymer (a 3-1).

The resulting copolymer (a3-1) had a residual component on heating (residual component on heating after drying in a hot air dryer at 105 ℃ for 3 hours) of 51.2% by weight, a viscosity at 25 ℃ of 408cps, a number-average molecular weight (Mn) of 9735 and a weight-average molecular weight (Mw) of 55650 as measured by GPC.

The dropping components at the time of producing the copolymer, properties of the product, and the like are shown in Table 4.

Production examples 9 to 10

In production example 8, silyl ester copolymers (a3-2) to (a3-3) were produced in the same manner as in production example (a3-1) except that the compounding ingredients (dropwise addition ingredients) were changed as shown in Table 4.

The physical properties of the resulting silyl (meth) acrylate copolymer or the reaction mixture containing the copolymer were evaluated in the same manner as in production example 8 (production example of silyl ester copolymer (a 3-1)).

The results are shown in Table 4.

< Table 4> production example of silyl ester copolymer (a3)

[ examples 1 to 43]

Antifouling paint compositions having the formulation shown in examples 1 to 43 of tables 5 to 7 (i.e., tables 8 to 10) were prepared by a usual method using the crosslinkable metal salt copolymer having a metal salt bond of a side chain terminal structure (a1-1) to (a1-3) obtained in production examples 1 to 3 shown in table 1, the crosslinkable copolymer having a metal salt bond (a2-1) and (a2-2) obtained in production examples 6 to 7 shown in table 3, or the silyl ester copolymer (a3-1) to (a3-3) obtained in production example 8 to 10 shown in table 4.

The antifouling paint compositions having the formulation shown in tables 5 to 7 obtained as described above were directly applied to a hard polyvinyl chloride resin plate (50mm × 50mm × 1.5mm) which had not been subjected to primer coating treatment by a coater under the condition that the dry film thickness thereof was 150 μm thick, and the test plates with coating films obtained were set in seawater (of Nagasaki bay, Nagasaki prefecture) and mounted on a rotating drum so as to rotate at a peripheral speed of 15 seas, and the degree of coating film consumption per 1 month (the total amount of the film thickness consumed from the time of installation, μm, the degree of coating film consumption) was measured within 6 months.

The results are summarized in tables 5 to 7.

(preparation of test plate)

An epoxy anticorrosive paint (epoxy AC paint, trade name "BANNOH 500", manufactured by China paint Co., Ltd.) was applied in advance to a sand blast-treated steel sheet (length 300 mm. times. width 100 mm. times. thickness 3.2mm) in such a manner that the dry film thickness became 150 μm thick, and an epoxy adhesive paint (trade name "BANNOH 500N", manufactured by China paint Co., Ltd.) was applied in such a manner that the dry film thickness became 100 μm thick.

Subsequently, an antifouling paint composition having a compounding composition shown in tables 8 to 10 (the same compounding composition as in tables 5 to 7) was applied 1 time under the condition that the dry film thickness thereof became 150 μm thick, and dried to prepare a test plate with a coating film. In addition, the coating interval was 1 day/1 coating between each coating material (example: "BANNOH 500") and the coating material coated on the surface thereof (example: "BANNOH 500N").

(method of testing static antifouling Property)

After the test plate was dried for 7 days, it was left to stand and immersed in Nagasaki bay, Nagasaki county, for 6 months, and the area (%) of attached organisms was examined every 1 month.

The results are summarized in tables 8 to 10.

Comparative examples 1 to 33

In example 1, the coating film consumption and the static antifouling property were measured in the same manner as in example 1 except that the compounding composition of the antifouling paint composition was changed as shown in tables 11 to 13 and 17 (or tables 14 to 16 and 18) when the coating film consumption and the static antifouling property were measured.

The results are summarized in tables 11 to 18.

< ingredients to be blended, evaluation criteria, etc. >

In the tables and the like, the components shown in the composition are the following products and the like.

Chlorinated paraffin:

the trade name "TOYOPARAX 150" (average carbon number: 14.5, chlorine content (amount) 50%, viscosity: 12 poise/25 ℃ C., specific gravity: 1.25/25 ℃ C., manufactured by Tosoh Corp.).

Zinc oxide: the trade name is "Zuniu No. 3" (manufactured by Kyushu white Water Co., Ltd.).

Talc: the trade name "TTK talc" (manufactured by Diatom chemical Co., Ltd.).

1-oxo-2-pyridinethiol zinc salt: the trade name "AF-Z" (manufactured by Gilford chemical engineering Co., Ltd.).

Zinc sulfide: the trade name is "Sachtolith HD" (manufactured by SACHTLEBEN CHEMIE Co., Ltd.).

4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one: trade name "SEA-none 211" (manufactured by rochon corporation), solid content: 30% by weight.

Oxidized polyethylene wax: the trade name is "Dispalon 4200-20(Dispal 4200-20X)" (manufactured by Nanguo Kabushiki Kaisha), and 20% xylene paste.

Aliphatic polyamide wax: trade name "Dispalon A630-20X (Dispaly A630-20X)" (manufactured by Nanben Kabushiki Kaisha), 20% xylene paste.

Propylene glycol monomethyl ether: the trade name "Kuraray PGM" (manufactured by Cola corporation); a solvent.

The main components of the above formulation are shown in Table 19.

The evaluation criteria for the attachment area of aquatic organisms are as follows.

Evaluation criteria

< evaluation Standard of area to which aquatic organisms attach (evaluation Standard of static antifouling Property) >

0 point … … no aquatic organisms attached.

The adhering area of 0.5 minute … … aquatic organisms was about 10%.

The settlement area of 1 minute … … aquatic organisms is about 20%.

The 2-point … … attachment area of aquatic organisms is about 30%.

The 3-point … … attachment area of aquatic organisms is about 40%.

The 4-point … … attachment area of aquatic organisms is about 50%.

The settlement area of 5 minutes … … aquatic organisms is about 100%.

In the table, "-" indicates that the content ratio of the organic antifouling agent component (b2)/ZnS, for example, could not be calculated.

< TABLE 5> (measurement of degree of consumption of coating film)

	Examples
																Compounding composition (parts by weight) of antifouling paint composition	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15
Side chain terminal Structure Metal salt copolymer a1-1 (solid content 49.7%)	30	30	35	40	38	40	35	32	40	38	35
																Side chain terminal Structure Metal salt copolymer a1-2 (solid content: 50.5%)												30	35
Side chain terminal Structure Metal salt copolymer a1-3 (solid content 51.1%)														32	35
																TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	3	2	2	2	2	2	2	2	2
Talc FC-1	15	7	5	4	2	2	5	7	5	2	5	10	2	5	2
																Zhanghua No. 3 (ZnO)	12	8	5	5	10	3	10	8	10	3	10	10	5	10	3
Zinc sulfide (ZnS)	9	17	24	18	24	33	18	17	17	30	23	20	30	22	30
																Red moonlight of iron oxideBB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0 5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0 5	0.5
																Dis4200	1	1	1	1	1	1	1	1	1	1	1	1	1	1	1
Copper pyrithione
																Zinc pyrithione	2	5	2	2	2	3	2	2	2	5	1	2	2	2	1
Triphenylboron pyridine	6	10	6	6	6	5					5	5	5	5	4
																4-isopropylpyridine-diphenylmethyl borane									6	5
SEA-NINE 211							10	10
																Xylene	18	15	15	15	10	6	11	16	12	10	12	15	13	16	17
Dis630-20XC	3	3	3	3	3	3	3	3	3	3	3	3	3	3	3
																Calcined Gypsum (FT-2)											1
Total up to	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100

After 1 month from the consumption of the film thickness (in total, μm)	4.9	5.5	6.1	6.7	5.6	6.8	5.2	6.4	4.9	6.1	6.3	3.1	6.7	4.9	6.3
																After 2 months	9 7	10.4	9 7	131	11.3	11.2	8.9	10.2	10.1	9.8	10.4	7.1	12.1	8.8	10.4
After 3 months	16.7	16.4	18.3	20.2	19.8	18.4	13.3	15.3	16.1	16.1	16.1	13.8	18.5	15.1	16.1
																After 4 months	22.3	22.7	26.3	28.5	28.9	22.3	20.8	21.9	24.5	22.6	21.3	19.3	24.5	19.4	21.3
After 5 months	27.1	29.1	33 6	35.9	36.8	28.1	26.3	27.8	30.9	31.1	27.9	24.3	30.9	24.5	27.9
																After 6 months	32.4	35.3	40.6	43.1	42.6	35.3	33.3	35.5	36.7	38.7	33.4	29.7	36.7	29.7	33.4
ZnS/copolymer (a1) solid content	60.4	114.0	138.0	90.5	127.1	166.0	103.5	106.9	85.5	158.8	132.2	132.0	169.7	134.5	167.7
																Organic antifouling agent component (b 2)/Zinc sulfide	88.9	88.2	33.3	44.4	33.3	24.2	22.2	23.5	47.1	33.3	26.1	35.0	23.3	31.8	16.7
ZnO/copolymer (a1) solid content	80.5	53.7	28.7	25.2	52.9	15.1	57.5	50.3	50.3	15.9	57.5	66.0	28.3	61.2	16.8
																Talc/copolymer (a1) solid content	100.6	46.9	28.7	20.1	10.6	10.1	28.7	44.0	25.2	10.6	28.7	66.0	11.3	30.6	11.2
Chlorinated paraffin/copolymer (a1) solid content	13.4	13.4	11.5	20.1	10.6	10.1	17.2	12.6	10.1	10.6	11.5	13.2	11.3	12.2	11.2

< Table 6> (measurement of degree of consumption of coating film)

	Examples
														Compounding composition (parts by weight) of antifouling paint composition	16	17	18	19	20	21	22	23	24	25	26	27	28
Cross-linkable Metal copolymer a2-1 (solid content: 45.6%)	30	30	35	40	38	40	35	32	40	38	35
														Cross-linkable Metal copolymer a2-2 (solid content: 46.2%)												30	35
TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	3	2	2	2	2	2	2
														Talc FC-1	15	7	5	4	2	2	5	7	5	2	5	10	2
Zn Hua No. 3	12	8	5	5	10	3	10	8	10	3	10	10	5
														Zinc sulfide (ZnS)	9	17	24	18	24	33	18	17	17	30	23	20	30
Iron oxideRed moon light BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0.5	1.5	1.5	1.5
														Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Dis4200	1	1	1	1	1	1	1	1	1	1	1	1	1
														Copper pyrithione
Zinc pyrithione	2	5	2	2	2	3	2	2	2	5	1	2	2
														Triphenylboron pyridine	6	10	6	6	6	5					5	5	5
4-isopropylpyridine-diphenylmethyl borane									6	5
														SEA-NINE 211							10	10
Xylene	18	15	15	15	10	6	11	16	12	10	12	15	13
														Dis630-20XC	3	3	3	3	3	3	3	3	3	3	3	3	3
Slaked lime FT-2											1
														Total up to	100	100	100	100	100	100	100	100	100	100	100	100	100

After 1 month from the consumption of the film thickness (in total, μm)	5.2	5.5	6.1	6.8	5.5	8.3	5.2	6.1	6.3	5.5	5.6	3.8	4.4
														After 2 months	9.7	10.3	9.8	13.1	10.3	15.4	8.9	9.7	10.4	9.7	11.3	6.9	9.7
After 3 months	14.3	16.4	17.3	19.4	14.3	22.6	13.3	15.3	16.1	15.1	14.3	12.4	15.8
														After 4 months	20.2	22.2	24.3	26.7	20.9	31.9	20.8	22.6	21.3	21.9	22.8	18.9	19.4
After 5 months	26.3	28.3	31.3	33.2	27.9	37.4	26.3	30.1	27.9	26.4	28.9	25.3	24.3
														After 6 months	31.2	34	39	42.1	32.3	55.1	33.3	38.4	33.4	32	33.4	31.3	29.6
ZnS/copolymer (a2) solid content	65.8	124.3	150.4	98.7	138.5	180.9	112.8	116.5	93.2	173.1	144.1	144.3	185.5
														Organic antifouling agent component (b 2)/Zinc sulfide	88.9	88.2	33.3	44.4	33.3	24.2	22.2	23.5	47.1	33.3	26.1	35.0	23.3
ZnO/copolymer (a2) solid content	87.7	58.5	31.3	27.4	57.7	16.4	62.7	54.8	54.8	17.3	62.7	72.2	30.9
														Talc/copolymer (a2) solid content	109.6	51.2	31.3	21.9	11.5	11.0	31.3	48.0	27.4	11.5	31.3	72.2	12.4
Chlorinated paraffin/copolymer (a2) solid content	14.6	14.6	12.5	21.9	11.5	11.0	18.8	13.7	11.0	11.5	12.5	14.4	12.4

< TABLE 7> (measurement of degree of consumption of coating film)

	Examples
																Compounding composition (parts by weight) of antifouling paint composition	29	30	31	32	33	34	35	36	37	38	39	40	41	42	43
Copolymer a3-1 (heating residue 51.2%)	30	30	35	40	38	40	35	32	40	38	35
																Copolymer a3-2 (heating residual component 50.1%)												30	35
Copolymer a3-3 (heating residual component 49.5%)														32	35
																TOYOPARAX150 (oxidized paraffin)	2	2	2	4	2	2	3	2	2	2	2	2	2	2	2
Talc FC-1	15	7	5	4	2	2	5	7	5	2	5	10	2	5	2
																Zhanghua No. 3 (ZnO)	12	8	5	5	10	3	10	8	10	3	10	10	5	10	3
Zinc sulfide (Zn5)	9	17	24	18	24	33	18	17	17	30	23	20	30	22	30
																Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
																Dis4200	1	1	1	1	1	1	1	1	1	1	1	1	1	1	1
Copper pyrithione
																Zinc pyrithione	2	5	2	2	2	3	2	2	2	5	1	2	2	2	1
Triphenyl radicalBoron pyridine	6	10	6	6	6	5					5	5	5	5	4
																4-isopropylpyridine-diphenylmethyl borane									6	5
SEA-NINE 211							10	10
																Xylene	18	15	15	15	10	6	11	16	12	10	12	15	13	16	17
Dis630-20XC	3	3	3	3	3	3	3	3	3	3	3	3	3	3	3

Calcined Gypsum (FT-2)											1
																Total up to	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
After 1 month from the consumption of the film thickness (in total, μm)	2.4	3.3	5.3	31	41	5.9	3.2	3.3	3.8	61	42	2.1	3.1	1.9	3.3
																After 2 months	4.5	6.6	11.4	5.8	8.3	11.5	7.1	7.2	8.1	11.9	8.4	3.7	5.9	3.7	6.1
After 3 months	8.4	12.3	17.1	9.1	16.1	18.7	11.4	12.1	11.9	18.6	15.9	7.9	11.1	7.3	11.1
																After 4 months	11.3	17.1	22.9	12.1	19.8	23.4	15.4	17.9	16.7	27.3	20.3	10.5	15.9	9.5	14.9
After 5 months	16.3	23.1	28.6	17.9	22.8	29.4	20.6	22.4	21.9	33.3	24.9	14.3	20.3	13.2	20.9
																After 6 months	21.2	29.5	33.6	23.1	29.5	35.4	24.5	29.5	28.3	39.7	29.5	19.6	25.6	16.7	25.9
ZnS/copolymer (a3) solid content	58.6	110.7	133.9	87.9	123.4	161.1	100.4	103.8	83.0	154.2	128.3	133.1	171.1	138.9	173.2
																Organic antifouling agent component (b 2)/Zinc sulfide	88.9	88.2	33.3	44.4	33.3	24.2	22.2	23.5	47.1	33.3	26.1	35.0	23.3	31.8	16.7
ZnO/copolymer (a3) solid content	78.1	52.1	27.9	24.4	51.4	14.6	55.8	48.8	48.8	15.4	55.8	66.5	28.5	63.1	17.3
																Talc/copolymer (a3) solid content	97.7	45.6	27.9	19.5	10.3	9.8	27.9	42.7	24.4	10.3	27.9	66.5	11.4	31.6	11.5
Chlorinated paraffin/copolymer (a3) solid content	13.0	13.0	11.2	19.5	10.3	9.8	16.7	12.2	9.8	10.3	11.2	13.3	11.4	12.6	11.5

< Table 8> (measurement of static antifouling Property)

	Examples
																Compounding composition (parts by weight) of antifouling paint composition	1	2	3	4	5	6	7	8	9	10	11	12	13	14	15
Side chain terminal Structure Metal salt copolymer a1-1 (solid content 49.7%)	30	30	35	40	38	40	35	32	40	38	35
																Side chain terminal Structure Metal salt copolymer a1-2 (solid content: 50.5%)												30	35
Side chain terminal Structure Metal salt copolymer a1-3 (solid content 51.1%)														32	35
																TOYOPARAX 150	2	2	2	4	2	2	3	2	2	2	2	2	2	2	2
Talc FC-1	15	7	5	4	2	2	5	7	5	2	5	10	2	5	2
																Zn Hua No. 3	12	8	5	5	10	3	10	8	10	3	10	10	5	10	3
Zinc sulfide	9	17	24	18	24	33	18	17	17	30	23	20	30	22	30
																Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
																Dis4200	1	1	1	1	1	1	1	1	1	1	1	1	1	1	1
Copper pyrithione
																Zinc pyrithione	2	5	2	2	2	3	2	2	2	5	1	2	2	2	1
Triphenylboron pyridine	6	10	6	6	6	5					5	5	5	5	4
																4-isopropylpyridine-diphenylmethyl borane									6	5
SEA-NINE 211							10	10
																Xylene	18	15	15	15	10	6	11	16	12	10	12	15	13	16	17
Dis630-20XC	3	3	3	3	3	3	3	3	3	3	3	3	3	3	3

Calcined Gypsum (FT-2)											1
																Total up to	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
Evaluation of the area of attachment of aquatic organisms (based on the aforementioned criteria) after 1 month	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
																After 2 months	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
After 3 months	0.5	0	0	0	0	0.5	0	0.5	0	0	0	0	0	0.5	0
																After 4 months	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0	0.5	0.5	0	0.5	0.5	0.5
After 5 months	1	0.5	0.5	0.5	0.5	1	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
																After 6 months	1	0.5	0.5	1	0.5	1	0 5	1	0.5	1	1	1	0.5	1	0.5

< Table 9> (measurement of static antifouling Property)

	Examples
														Compounding composition (parts by weight) of antifouling paint composition	16	17	18	19	20	21	22	23	24	25	26	27	28
Cross-linkable Metal copolymer a2-1 (solid content: 45.6%)	30	30	35	40	38	40	35	32	40	38	35
														Cross-linkable Metal copolymer a2-2 (solid content: 46.2%)												30	35
TOYOPARAX150	2	2	2	4	2	2	3	2	2	2	2	2	2
														Talc FC-1	15	7	5	4	2	2	5	7	5	2	5	10	2
Zn Hua No. 3	12	8	5	5	10	3	10	8	10	3	10	10	5
														Zinc sulfide	9	17	24	18	24	33	18	17	17	30	23	20	30
Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0.5	1.5	1.5	1.5
														Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Dis4200	1	1	1	1	1	1	1	1	1	1	1	1	1

Copper pyrithione
														Zinc pyrithione	2	5	2	2	2	3	2	2	2	5	1	2	2
Triphenylboron pyridine	6	10	6	6	6	5					5	5	5
														4-isopropylpyridine-diphenylmethyl borane									6	5
SEA-NINE 211							10	10
														Xylene	18	15	15	15	10	6	11	16	12	10	12	15	13
Dis630-20XC	3	3	3	3	3	3	3	3	3	3	3	3	3
														Slaked lime FT-2											1
Total up to	100	100	100	100	100	100	100	100	100	100	100	100	100
														Evaluation of the area of attachment of aquatic organisms (based on the aforementioned criteria) after 1 month	0	0	0	0	0	0	0	0	0	0	0	0	0
After 2 months	0	0	0	0	0	0.5	0	0	0	0	0	0	0
														After 3 months	0.5	0	0	0	0	0.5	0	0	0	0	0	0.5	0
After 4 months	0.5	0.5	0.5	0.5	0	0.5	0.5	0.5	0.5	0	0.5	0.5	0
														After 5 months	1	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
After 6 months	1	1	0.5	0.5	0.5	1	0.5	1	0.5	0.5	0.5	0.5	0.5

< TABLE 10> (measurement of static antifouling Property)

	Examples
																Compounding composition (parts by weight) of antifouling paint composition	29	30	31	32	33	34	35	36	37	38	39	40	41	42	43
Copolymer a3-1 (heating residue 51.2%)	30	30	35	40	38	40	35	32	40	38	35
																Copolymer a3-2 (heating residual component 50.1%)												30	35
Copolymer a3-3 (heating residual component 49.5%)														32	35
																TOYOPARAX 150	2	2	2	4	2	2	3	2	2	2	2	2	2	2	2
Talc FC-1	15	7	5	4	2	2	5	7	5	2	5	10	2	5	2
																Zn Hua No. 3	12	8	5	5	10	3	10	8	10	3	10	10	5	10	3
Zinc sulfide	9	17	24	18	24	33	18	17	17	30	23	20	30	22	30
																Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	0.5	1.5	1.5	1.5	1.5	1.5

Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
																Dis4200	1	1	1	1	1	1	1	1	1	1	1	1	1	1	1
Copper pyrithione
																Zinc pyrithione	2	5	2	2	2	3	2	2	2	5	1	2	2	2	1
Triphenylboron pyridine	6	10	6	6	6	5					5	5	5	5	4
																4-isopropylpyridine-diphenylmethyl borane									6	5
SEA-NINE 211							10	10
																Xylene	18	15	15	15	10	6	11	16	12	10	12	15	13	16	17
Dis630-20XC	3	3	3	3	3	3	3	3	3	3	3	3	3	3	3

Calcined Gypsum (FT-2)											1
																Total up to	100	100	100	100	100	100	100	100	100	100	100	100	100	100	100
Evaluation of the area of attachment of aquatic organisms (based on the aforementioned criteria) after 1 month	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
																After 2 months	0	0	0	0	0	0	0	0	0	0	0	0	0	0	0
After 3 months	0.5	0	0	0	0	0.5	0	0	0	0	0	0	0	0	0
																After 4 months	0.5	0.5	0.5	0.5	0	0.5	0.5	0	0.5	0	0.5	0.5	0	0.5	0
After 5 months	1	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
																After 6 months	1	0.5	0.5	1	0.5	1	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5

< TABLE 11> (measurement of degree of consumption of coating film)

	Comparative example
										Compounding composition (parts by weight) of antifouling paint composition	1	2	3	4	5	6	7	8	9
Side chain terminal Structure Metal salt copolymer a1-1 (solid content 49.7%)	30	30	35	40	35	40
										Side chain terminal Structure Metal salt copolymer a1-2 (solid content: 50.5%)							35	35
Side chain terminal Structure Metal salt copolymer a1-3 (solid content 51.1%)									35
										TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	2	2	2
Talc FC-1	20	15	10	7	18	17	10	18	10
										Zhanghua No. 3 (ZnO)	16	17	24	20	20	20	24	19	24
Zinc sulfide (ZnS)	0	0	0	0	0	0	0	0	0
										Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
										Dis4200	1	1	1	1	1	1	1	1	1
Copper pyrithione
										Zinc pyrithione	2	5	2	2	1		2	2	2

Triphenylboron pyridine	6	10	6	6	3		6	5	6
										4-isopropylpyridine-diphenylmethyl borane
SEA-NINE 211
										Xylene	18	15	15	15	15	15	15	13	15
Dis630-20XC	3	3	3	3	3	3	3	3	3
										Hydrated limeFT-2
Total up to	100	100	100	100	100	100	100	100	100
										After 1 month from the consumption of the film thickness (total: μm)	4.5	4.3	3.9	4.4	4.8	3.9	3.2	4.2	3
After 2 months	8.9	6.8	5.8	6.7	7.1	7.1	6.2	7.9	5.8
										After 3 months	12.2	10.4	9.7	9.9	11.1	10.3	9.3	10.3	9.4
After 4 months	18.4	15.3	14.3	14.5	15	14.1	13.3	14.3	13.3
										After 5 months	23.2	20.2	19.8	19.1	19.8	17.1	16.9	18.9	16.7
After 6 months	28.4	26.1	24.3	23.3	24.3	22.3	20.3	23.4	18.9

ZnS/copolymer (a1) solid content	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0
										Organic antifouling agent component (b 2)/Zinc sulfide	-	-	-	-	-	-	-	-	-
ZnO/copolymer (a1) solid content	107.3	114.0	138.0	100.6	115.0	100.6	135.8	107.5	134.2
										Talc/copolymer (a1) solid content	134.1	100.6	57.5	35.2	103.5	85.5	56.6	101.8	55.9
Chlorinated paraffin/copolymer (a1) solid content	13.4	13.4	11.5	20.1	11.5	10.1	11.3	11.3	11.2

< TABLE 12> (measurement of degree of consumption of coating film)

	Comparative example
									Compounding composition (parts by weight) of antifouling paint composition	10	11	12	13	14	15	16	17
Cross-linkable Metal copolymer a2-1 (solid content: 45.6%)	30	30	35	40	35	40
									Cross-linkable Metal copolymer a2-2 (solid content: 46.2%)							35	35
T0YOPARAX 150 (chlorinated paraffin)	2	2	2	4	2	2	2	2
									Talc FC-1	20	15	10	17	18	17	10	18
Zhanghua No. 3 (ZnO)	16	17	24	20	20	20	24	19
									Zinc sulfide (ZnS)	0	0	0	0	0	0	0	0
Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
									Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Dis4200	1	1	1	1	1	1	1	1
									Copper pyrithione
Zinc pyrithione	2	5	2	2	1		2	2
									Triphenylboron pyridine	6	10	6	6	3		6	5
4-isopropylpyridine-diphenylmethyl borane

SEA-NINE 211
									Xylene	18	15	15	15	15	15	15	13
Dis630-20XC	3	3	3	3	3	3	3	3
									Slaked lime FT-2
Total up to	110	111	112	113	114	115	116	117
									After 1 month from the consumption of the film thickness (in total, μm)	4.3	4.1	3.8	4.3	4.8	3.9	3.1	3.9
After 2 months	8.7	7.8	5.8	7.1	6.9	6.7	5.9	7.8
									After 3 months	11.9	10.4	9.6	9.8	11.1	10.3	10.1	12.1
After 4 months	17.9	15.5	14.3	13.2	14.7	14.1	l4.1	15.3
									After 5 months	22.2	2.8	18.7	18.8	19.8	17.1	17.3	19.5
After 6 months	28.9	26.7	22.3	23.4	22.7	23.3	21.7	24.3
									ZnS/copolymer (a2) solid content	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0

Organic deficiency preventive ingredient (b 2)/zinc sulfide	-	-	-	-	-	-	-	-
									ZnO/copolymer (a2) solid content	117.0	124.3	150.4	109.6	125.3	109.6	148.4	117.5

Talc/copolymer (a2) solid content	146.2	109.6	62.7	38.4	112.8	93.2	61.8	111.3
									Chlorinated paraffin/copolymer (a2) solid content	14.6	14.6	12.5	21.9	12.5	11.0	12.4	12.4

< TABLE 13> (measurement of film consumption)

	Comparative example
									Compounding composition (parts by weight) of antifouling paint composition	18	19	20	21	22	23	24	25
Copolymer a3-1 (heating residue 51.2%)	30	30	35	40	35	40
									Copolymer a3-2 (heating residual component 50.1%)							35
Copolymer a3-3 (heating residual component 49.5%)								35
									TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	2	2
Talc FC-1	20	15	10	7	18	17	0	18
									Zhanghua No. 3 (ZnO)	16	17	24	20	20	20	24	19
Zinc sulfide (ZnS)	0	0	0	0	0	0	0	0
									Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
									Dis4200	1	1	1	1	1	1	1	1
Copper pyrithione
									Zinc pyrithione	2	5	2	2	1		2	2
Triphenylboron pyridine	6	10	6	6	3		6	5

4-isopropylpyridine-diphenylmethyl borane
									SEA-NINE 211
Xylene	18	15	15	15	15	15	5	13
									Dis630-20XC	3	3	3	3	3	3	3	3
Slaked lime FT-2
									Total up to	100	100	100	100	100	100	100	100
After 1 month from the consumption of the film thickness (in total, μm)	2.4	2.7	2.1	3.1	2.9	2.7	2.1	2
									After 2 months	4.7	4.1	3.9	5.9	6.9	5.9	3.6	3.1
After 3 months	9.7	9.9	10.1	10.3	11.4	10.4	8.7	6.9
									After 4 months	14.4	13.9	14.1	15.3	14.5	13.9	1.5	10.3
After 5 months	17.9	17.9	18.3	18.8	18.7	17.3	5.4	13.3
									After 6 months	21.7	21.3	22.3	23.5	21.9	21.5	8.7	16.7
ZnS/copolymer (a3) solid content	0.0	0.0	0.0	0.0	0.0	0.0	0.0	0.0

Organic antifouling agent component (b 2)/Zinc sulfide	-	-	-	-	-	-	-	-
									ZnO/copolymer (a3) solid content	104.2	110.7	133.9	97.7	111.6	97.7	136.9	109.7
Talc/copolymer (a3) solid content	130.2	97.7	55.8	34.2	100.4	83.0	57.0	103.9
									Chlorinated paraffin/copolymer (a3) solid content	13.0	13.0	11.2	19.5	11.2	9.8	11.4	11.5

< TABLE 14> (measurement of static antifouling Property)

	Comparative example
										Compounding composition (parts by weight) of antifouling paint composition	1	2	3	4	5	6	7	8	9
Side chain terminal Structure Metal salt copolymer a1-1 (solid content 49.7%)	30	30	35	40	35	40
										Side chain terminal Structure Metal salt copolymer a1-2 (solid content: 50.5%)							35	35
Side chain terminal Structure Metal salt copolymer a1-3 (solid content 51.1%)									35
										TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	2	2	2
Talc FC-1	20	15	10	7	18	17	10	18	10
										Zhanghua No. 3 (ZnO)	16	17	24	20	20	20	24	19	24
Zinc sulfide (ZnS)	0	0	0	0	0	0	0	0	0
										Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
										Dis4200	1	1	1	1	1	1	1	1	1
Copper pyrithione

Zinc pyrithione	2	5	2	2	1		2	2	2
										Triphenylboron pyridine	6	10	6	6	3		6	5	6
4-isopropylpyridine-diphenylmethyl borane
										SEA-N NE 211
Xylene	18	15	15	15	15	15	15	13	15
										Dis630-20XC	3	3	3	3	3	3	3	3	3
Slaked lime FT-2
										Total up to	100	100	100	100	100	100	100	100	100
Evaluation of the area of attachment of aquatic organisms (based on the aforementioned criteria) after 1 month	0	0	0	0	0.5	2	0	0	0
										After 2 months	0.5	0	0.5	0	0.5	3	0.5	0	0
After 3 months	1	0.5	0.5	0.5	1	5	0.5	0.5	0.5
										After 4 months	1	1	0.5	1	2	5	1	1	1
After 5 months	2	2	2	1	4	5	2	2	2
										After 6 months	2	2	2	2	4	5	2	2	2

< TABLE 15> (measurement of static antifouling Property)

	Comparative example
									Compounding composition (parts by weight) of antifouling paint composition	10	11	12	13	14	15	16	17
Cross-linkable Metal copolymer a2-1 (solid content: 45.6%)	30	30	35	40	35	40
									Cross-linkable Metal copolymer a2-2 (solid content: 46.2%)							35	35
TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	2	2
									Talc FC-1	20	15	10	7	18	17	10	18
Zhanghua No. 3 (ZnO)	16	17	24	20	20	20	24	19
									Zinc sulfide (ZnS)	0	0	0	0	0	0	0	0
Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
									Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Dis4200	1	1	1	1	1	1	1	1
									Copper pyrithione
Zinc pyrithione	2	5	2	2	1		2	2
									Triphenylboron pyridine	6	10	6	6	3		6	5

4-isopropylpyridine-diphenylmethyl borane
									SEA-NINE 211
Xylene	18	15	15	15	15	15	15	13
									Dis630-20XC	3	3	3	3	3	3	3	3
Slaked lime FT-2
									Total up to	110	111	112	113	114	115	116	117
Evaluation of the area of attachment of aquatic organisms (based on the aforementioned criteria) after 1 month	0	0	0	0	0.5	2	0	0
									After 2 months	0.5	0.5	0.5	0	1	3	0.5	0.5
After 3 months	1	1	1	0.5	2	4	1	1
									After 4 months	2	1	1	1	2	5	2	2
After 5 months	3	2	2	2	3	5	2	3
									After 6 months	3	3	2	3	4	5	2	3

< TABLE 16> (measurement of static antifouling Property)

	Comparative example
									Compounding composition (parts by weight) of antifouling paint composition	18	19	20	21	22	23	24	25
Copolymer a3-1 heating residual component 51.2%)	30	30	35	40	35	40
									Copolymer a3-2 (heating residual component 50.1%)							35
Copolymer a3-3 (heating residual component 49.5%)								35
									TOYOPARAX150 (chlorinated paraffin)	2	2	2	4	2	2	2	2
Talc FC-1	20	15	10	7	18	17	10	18
									Zhanghua No. 3 (ZnO)	16	17	24	20	20	20	24	19
Zinc sulfide (ZnS)	0	0	0	0	0	0	0	0
									Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
									Dis4200	1	1	1	1	1	1	1	1
Copper pyrithione
									Zinc pyrithione	2	5	2	2	1		2	2

Triphenylboron pyridine

6

10

6

3

6

5

4-isopropylpyridine-diphenylmethyl borane
									SEA-NINE 211
Xylene	18	15	15	15	15	15	15	13
									Dis630-20XC	3	3	3	3	3	3	3	3
Slaked lime FT-2
									Total up to	100	100	100	100	100	100	100	100
Evaluation of the area of attachment of aquatic organisms (based on the aforementioned criteria) after 1 month	0	0	0	0	0.5	2	0	0
									After 2 months	0.5	0	0	0	2	4	0	0
After 3 months	0.5	0.5	0.5	0.5	3	5	0.5	0.5
									After 4 months	1	1	0.5	1	3	5	1	1
After 5 months	2	2	1	2	3	5	2	1
									After 6 months	3	3	2	3	4	5	2	2

< TABLE 17> (measurement of film consumption)

	Comparative example
									Compounding composition of antifouling paint composition	26	27	28	29	30	31	32	33
Rosin	11	11	11	11	11	11	11	11
									Laroflex MP-15	9	9	9	9	9
Polyethylene resin VYHH						9	9	9
									TOYOPARAX150 (chlorinated paraffin)	2	2	2	2	2	2	2	2
Talc FC-1	6	6	6	6	6	6	6	6
									Zhanghua No. 3 (ZnO)	25	20	10	11	15	25	20	10
Zinc sulfide (ZnS)	5	10	20	23	23	5	10	20
									Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
									Dis4200	1	1	1	1	1	1	1	1
Copper pyrithione
									Zinc pyrithione	2	2	2	1		2	2	2
Triphenylboron pyridine	6	6	6	3		6	6	6

4-isopropylpyridine-diphenylmethyl borane
									SEA-NINE 211
Xylene	28	28	28	28	28	28	28	28
									Dis 630-20XC	3	3	3	3	3	3	3	3
Slaked lime FT-2
									Total up to	100	100	100	100	100	100	100	100
Consumption of the coating film after 1 month	7.5	8.1	9.1	10.3	6.7	7.7	8.9	9.9
									After 2 months	13.2	15.3	17.3	17.3	12.3	14.3	16.3	18.3
After 3 months	14.7	16.7	19.4	19.3	13.3	15.1	18.3	20.3
									After 4 months	15.3	18.1	20.7	20.7	14.7	15.9	19.7	21.3

After 5 months	16.7	19.7	21.3	21.3	15.5	16.7	20.3	22.7
									After 6 months	17.7	20.2	22.5	22.8	16.4	18.1	21.3	23.1

< TABLE 18> (measurement of static antifouling Property)

Comparative example

Compounding composition of antifouling paint composition	26	27	28	29	30	31	32	33
									Rosin	11	11	11	11	11	11	11	11
Laroflex MP-15	9	9	9	9	9
									Polyethylene resin VYHH						9	9	9
TOYOPARAX150 (chlorinated paraffin)	2	2	2	2	2	2	2	2
									Talc FC-1	6	6	6	6	6	6	6	6
Zhanghua No. 3 (ZnO)	25	20	10	11	15	25	20	10
									VulcanizationZinc (ZnS)	5	10	20	23	23	5	10	20
Iron oxide red moonlight BB	1.5	1.5	1.5	1.5	1.5	1.5	1.5	1.5
									Permanent Red F5RK	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
Dis4200	1	1	1	1	1	1	1	1
									Copper pyrithione
Zinc pyrithione	2	2	2	1		2	2	2
									Triphenylboron pyridine	6	6	6	3		6	6	6
4-isopropylpyridine-diphenylmethyl borane
									SEA-NINE 211
Xylene	28	28	28	28	28	28	28	28
									Dis630-20XC	3	3	3	3	3	3	3	3
Total up to	100	100	100	100	100	100	100	100
									Antifouling property after 1 month	0	0	0	0	0.5	0	0	0
After 2 months	0.5	0	0	0.5	2	0	0	0
									After 3 months	0.5	0.5	0.5	0.5	3	0.5	0.5	0.5
After 4 months	1	1	1	1	3	0.5	1	1
									After 5 months	2	2	2	2	3	1	2	3

After 6 months

3

2

3

4

2

3

< Table 19>

Mainly uses raw materials

Name of article	Manufacturer(s)	Traits and others	Remarks for note
				TOYOPARAX 150	Dongcao	Chlorinated paraffin	Average carbon number: 14.5, chlorine content (amount) 50%, viscosity: 12 poise/25 ℃, specific gravity: 1.25/25 ℃.
Talc FC-1	Fugang talc	Filled pigments
				Zn Hua No. 3	Kyushu white water chemistry	Filled pigments
Zinc sulfide Saxhtolith HD	Shaharliban chemical company Limited (Germany)	Filled pigments
				Iron oxide red moonlight BB	Household field industry	Coloured pigments
Permanent Red F5RK	Clariant North America	Organic red pigments
				Laroflex MP-15	BASF	Vinyl chloride/vinyl acetate copolymer
Polyethylene resin VYHH	BASF	Vinyl chloride/vinyl acetate copolymer
				Dis4200	Cost-reducing method for Nanmu	Anti-settling agent
Dis630-20XC	Cost-reducing method for Nanmu	Anti-sagging agent
				DisA630-20X	Cost-reducing method for Nanmu	Anti-sagging agent	20% xylene paste
Copper omazine	Jifu medicine preparation	Organic antifouling agent	Copper salt of 1-oxo-2-pyridinethiol
				PK boron	HOKKO CHEMICAL INDUSTRY Co.,Ltd.	Organic antifouling agent	Triphenylboron pyridine
KM-2	KI-FORMED JUSH	Organic antifouling agent	4-isopropylpyridine-diphenylmethyl borane
				Zinc pyrithione	Jifu medicine preparation	Organic antifouling agent
Soluble anhydrous gypsum D-1	Zewu Co.,Ltd.	Inorganic dehydrating agent
				Calcined Gypsum (FT-2)	Zewu Co.,Ltd.	Inorganic dehydrating agent
SEA-NINE 211	Rohm and Haas Co.		4, 5-dichloro-2-n-octyl-4-isothiazolin-3-one
				Xylene
N-BuOH			N-butanol
				Cuprous oxide redcopp 97	American Chemet	Cuprous oxide	Stearic acid treatment

Claims

1. An antifouling paint composition comprising (A) a hydrolyzable copolymer and (B) an antifouling agent, wherein the hydrolyzable copolymer (A) is an acrylic polymer or a polyester resin selected from the group consisting of (a1) having a general formula (I):

-COO-M-O-COR¹·····(I)

the copolymer containing a metal salt bond of a side chain terminal group (a2) represented by the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

a copolymer containing a metal salt bond formed from a constituent unit (a21) derived from the monomer represented by (I) and a constituent unit (a22) derived from another unsaturated monomer copolymerizable with the monomer (II), and (a3) a copolymer of a monomer represented by the general formula (III):

R⁷-CH＝C(R³)-COO-SiR⁴R⁵R⁶·····(III)

at least 1 hydrolyzable copolymer of a silyl ester copolymer comprising a constituent unit (a31) derived from the monomer(s) and a constituent unit (a32) derived from another unsaturated monomer copolymerizable with the monomer (III), wherein the amount of zinc sulfide as the antifouling agent (B) is 10 to 500 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A); in the formula (I), M represents zinc or copper, R¹Represents an organic group; in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group; in the formula (III), R³Represents a hydrogen atom or a methyl group, R⁴、R⁵And R⁶Each independently represents a hydrocarbon group, R⁷Represents a hydrogen atom or R⁸-O-CO-, wherein R⁸Representing an organic radical or represented by-SiR⁹R¹⁰R¹¹Silyl group represented by R⁹、R¹⁰And R¹¹Each independently represents a hydrocarbon group.

2. The antifouling coating composition of claim 1, wherein cuprous oxide is substantially absent.

3. The antifouling paint composition as claimed in claim 1, wherein the antifouling agent (B) comprises zinc sulfide and an organic antifouling agent (B2).

4. The antifouling paint composition as claimed in claim 3, wherein the organic antifouling agent (b2) is at least 1 organic antifouling agent selected from the group consisting of pyrithione compounds, triorganoborons and amine complexes thereof, 4, 5-dichloro-n-octylisothiazolin-3-one.

5. The antifouling paint composition as claimed in claim 3, wherein the organic antifouling agent (b2) is at least 1 selected from the group consisting of zinc pyrithione, triphenylboron pyridine complex, methyldiphenylboron 4-isopropylpyridine complex and 4, 5-dichloro-n-octylisothiazolin-3-one.

6. The antifouling paint composition as claimed in claim 3, wherein the organic antifouling agent (B2) is contained in an amount of 20 to 500 parts by weight based on 100 parts by weight of zinc sulfide as the antifouling agent (B).

7. The antifouling paint composition as claimed in claim 1, further comprising zinc oxide as a coloring pigment.

8. The antifouling paint composition as claimed in claim 7, wherein the zinc oxide is contained in an amount of 10 to 300 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A).

9. The antifouling paint composition as claimed in claim 7, wherein the zinc oxide is contained in the antifouling paint composition in an amount of 1 to 40 wt.%.

10. The antifouling paint composition as claimed in claim 1, wherein the antifouling paint composition further comprises talc as a filler pigment.

11. The antifouling paint composition as claimed in claim 10, wherein the talc is contained in an amount of 5 to 300 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A).

12. The antifouling paint composition as claimed in claim 10, wherein the talc is contained in an amount of 0.5 to 40% by weight in the antifouling paint composition.

13. The antifouling paint composition as claimed in claim 1, wherein the antifouling paint composition further comprises chlorinated paraffin as a plasticizer.

14. The antifouling paint composition as claimed in claim 13, wherein the content of the chlorinated paraffin is 0.05 to 40 parts by weight based on 100 parts by weight of the hydrolyzable copolymer (A).

15. The antifouling paint composition as claimed in claim 13, wherein the chlorinated paraffin is contained in an amount of 1 to 5% by weight in the antifouling paint composition.

16. The antifouling paint composition according to claim 1, further comprising at least 1 coloring pigment selected from the group consisting of red iron oxide, titanium white, yellow iron oxide and organic pigments.

17. The antifouling paint composition as claimed in claim 1, wherein the organic group R of the copolymer (a1) containing a metal salt bond¹Is a monobasic acid organic acid residue formed by univalent saturated aliphatic group with 2-30 carbon atoms, unsaturated aliphatic group with 2-30 carbon atoms, alicyclic group with 3-20 carbon atoms, aromatic hydrocarbon group with 6-18 carbon atoms or a substitute thereof.

18. The antifouling paint composition as claimed in claim 1, wherein the organic group R of the copolymer (a1) containing a metal salt bond¹Is a monobasic acid organic acid residue formed by univalent saturated or unsaturated aliphatic with 10-20 carbon atoms, saturated or unsaturated alicyclic hydrocarbon with 3-20 carbon atoms or a substituent thereof.

19. The antifouling paint composition as claimed in claim 1, wherein the copolymer (a1) containing a metal salt bond is a copolymer having the general formula (IV) in which-COO-in an acrylic copolymer is intercalated with copper or zinc:

-O-COR¹·····(IV)

a copolymer containing a metal salt bond of the side chain terminal group represented; in the formula (IV), R¹An organic acid residue of a monobasic acid comprising a C10-20 saturated or unsaturated aliphatic group, a C3-20 saturated or unsaturated alicyclic hydrocarbon group, or a substituent thereof.

20. The antifouling paint composition as claimed in claim 1, wherein the organic group R of the copolymer (a1) containing a metal salt bond¹Is an organic acid residue formed from at least 1 monobasic acid selected from the group consisting of versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid.

21. The antifouling paint composition as claimed in claim 1, wherein the copolymer (a1) containing a metal salt bond is represented by the general formula (V):

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

a copolymer of 1 or 2 or more monoacid metal (meth) acrylates represented by the formula; in the formula (V), R¹Represents an organic group, R²Represents a hydrogen atom or a methyl group, and M represents zinc or copper.

22. The antifouling paint composition as claimed in claim 21, wherein the organic group R of the constituent unit derived from the monobasic acid metal (meth) acrylate represented by the general formula (V)¹Is a monobasic acid organic acid residue formed by univalent saturated or unsaturated aliphatic with 10-20 carbon atoms, saturated or unsaturated alicyclic hydrocarbon with 3-20 carbon atoms or a substituent thereof.

23. The antifouling paint composition as claimed in claim 21, wherein the metal monoacid (methyl group) represented by the formula (V)) Organic radical R of constituent units derived from acrylic esters¹Is an organic acid residue formed from at least 1 monobasic acid selected from the group consisting of versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid.

24. The antifouling paint composition as claimed in claim 21, wherein the copolymer (a1) containing a metal salt bond is a copolymer comprising constituent units derived from a copolymer of monobasic acid metal (meth) acrylate represented by the general formula (V) and constituent units derived from at least 1 unsaturated monomer selected from alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and hydroxyalkyl (meth) acrylate.

25. The antifouling paint composition as claimed in claim 1, wherein the zinc and/or copper content in the copolymer (a1) containing a metal salt bond based on the structure of the general formula (I) is 0.5 to 20% by weight.

26. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a21) of the copolymer (a2) containing a metal salt bond is derived according to the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

the monomer represented is at least 1 monomer selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate; in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group.

27. The antifouling paint composition as claimed in claim 1, wherein the other unsaturated monomer from which the constituent unit (a22) of the copolymer (a2) containing a metal salt bond can be derived is at least 1 unsaturated monomer selected from the group consisting of alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and hydroxyalkyl (meth) acrylate.

28. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a21) of the copolymer (a2) containing a metal salt bond is derived according to the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

the monomer represented is at least 1 monomer selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is at least 1 unsaturated monomer selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate; in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group.

29. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a21) of the copolymer (a2) containing a metal salt bond is derived according to the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

the monomer represented is at least 1 monomer selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is represented by the general formula (V):

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

monobasic acid metal (meth) acrylates of the formula; in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group; in the formula (V), R¹Represents an organic group, R²Represents a hydrogen atom or a methyl group and M represents zinc or copper.

30. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a21) of the copolymer (a2) containing a metal salt bond is derived according to the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

the monomer represented is at least 1 monomer selected from zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer from which the constituent unit (a22) in the copolymer (a2) containing a metal salt bond can be derived is selected from the group consisting of monomers represented by the general formula (V):

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

at least 1 unsaturated monomer of monobasic acid metal (meth) acrylate and alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, and hydroxyalkyl (meth) acrylate; in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group; in the formula (V), R¹Represents an organic group, R²Represents a hydrogen atom or a methyl group and M represents zinc or copper.

31. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a21) of the copolymer (a2) containing a metal salt bond is derived according to the general formula (II):

CH₂＝C(R²)-COO-M-O-CO-C(R²)＝CH₂·····(II)

CH₂＝C(R²)-COO-M-O-COR¹·····(V)

at least 1 unsaturated monomer of monobasic acid metal (meth) acrylate and methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate; in the formula (II), M represents zinc or copper, R²Represents a hydrogen atom or a methyl group; in the formula (V), R¹Represents an organic matterRadical, R²Represents a hydrogen atom or a methyl group and M represents zinc or copper.

32. The antifouling paint composition as claimed in claim 29, wherein the organic group R of the constituent unit derived from the monobasic acid metal (meth) acrylate represented by the general formula (V)¹Is a monobasic acid organic acid residue formed by univalent saturated or unsaturated aliphatic with 10-20 carbon atoms, saturated or unsaturated alicyclic hydrocarbon with 3-20 carbon atoms or a substituent thereof.

33. The antifouling paint composition as claimed in claim 29, wherein the organic group R of the constituent unit derived from the monobasic acid metal (meth) acrylate represented by the general formula (V)¹Is an organic acid residue formed from at least 1 monobasic acid selected from the group consisting of versatic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, abietic acid, neoabietic acid, pimaric acid, dehydroabietic acid, 12-hydroxystearic acid, and naphthenic acid.

34. The antifouling paint composition as claimed in claim 1, wherein the zinc and/or copper content in the copolymer (a2) containing a metal salt bond based on the structure of the general formula (II) is 0.5 to 20% by weight.

35. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a31) derived from the monomer represented by the general formula (III) is a constituent unit derived from trialkylsilylalkyl (meth) acrylate.

36. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a31) derived from the monomer represented by the general formula (III) is a constituent unit derived from triisopropylsilyl (meth) acrylate.

37. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a32) derived from another unsaturated monomer copolymerizable with the monomer represented by the general formula (III) is a constituent unit derived from at least 1 unsaturated monomer selected from the group consisting of alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate and hydroxyalkyl (meth) acrylate.

38. The antifouling paint composition as claimed in claim 1, wherein the constituent unit (a32) derived from another unsaturated monomer copolymerizable with the monomer represented by the general formula (III) is a constituent unit derived from at least 1 unsaturated monomer selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-methoxyethyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.

39. An antifouling coating film comprising the antifouling paint composition according to any one of claims 1 to 38.

40. A substrate with a coating film, wherein the surface of the substrate is coated with a coating film obtained by curing the antifouling paint composition according to any one of claims 1 to 38.

41. An antifouling substrate, wherein the surface of the substrate which comes into contact with seawater or fresh water is coated with a coating film obtained by curing the antifouling coating composition according to any one of claims 1 to 38.

42. The antifouling substrate as claimed in claim 41, wherein said substrate is any one of an underwater structure, a ship outer plate, a fishing net and a fishing tackle.

43. A method for forming a coating film on a surface of a substrate, comprising applying or impregnating the antifouling paint composition according to any one of claims 1 to 38 on the surface of the substrate, and curing the coating film.

44. A method for antifouling a substrate, comprising applying or immersing the antifouling coating composition according to any one of claims 1 to 38 on the surface of a substrate, and curing the antifouling coating to form an antifouling coating film.

45. The method for preventing fouling of a substrate according to claim 44, wherein the substrate is any one of an underwater structure, a ship outer plate, a fishing net and a fishing tackle.