| Title of Invention | "ANTIFOULING PAINT COMPOSITION, ANTIFOULING COATING FILM, SUBSTRATE WITH COATING FILM, ANTIFOULING SUBSTRATE, FORMING METHOD OF COATING FILM ON THE SURFACE OF THE SUBSTRATE AND ANTIFOULING METHOD OF SUBSTRATE" |
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| Abstract | An antifouling paint composition comprising a hydrolyzable copolymer (A) and an antifouling agent (B), wherein said hydrolyzable copolymer (A) is at least one kind of hydrolyzable copolymer selected from the group consisting of (al) a copolymer containing a bond of metal salt, which is an acrylic polymer or a polyester resin and has a side chain terminal group represented by the general formula (I): -COO-M-O-COR, where M represents zinc or copper and R1 represents an organic group; (a2) a copolymer containing a bond of metal salt composed of a component unit (a21) derived from a monomer represented by the general formula (II): CH2=C(R2)-COO-M-O-CO-C(R2)=CH2, where M represents zinc or copper and R2 represents a hydrogen atom or a methyl group, and a component unit (a22) derived from other unsaturated monomer which is copolymerizable with the monomer (IT); and (a3) a silyl ester type copolymer composed of a component unit (a31) derived from a monomer represented by the general formula (III): R7-CH=C (R3>COO-SiR4R5R6 (III), where R3 represents a hydrogen atom or a methyl group, R4, R5 and R6 each independently represents a hydrocarbon group, R7 represents a hydrogen atom or R8 -O-CO-(where R8 represents an organic group or a silyl group represented by -SiR9R10R11 and R9 , R10 and R11 each independently represents a hydrocarbon group) and a component unit (a32) derived from other unsaturated monomer which is copolymerizable with the monomer (III) and zinc sulfide is contained at an amount of 10 to 500 parts by weight with respect to 100 parts by weight of the hydrolyzable acrylate copolymer as said antifouling agent (B). |
| Full Text | TECHNICAL FIELD The present invention relates to an antifouling paint composition, an antifouling coating film, a substrate with a coating film, an antifouling substrate, a forming method of coating film on a surface of the substrate and an antifouling method of the substrate. More particularly, the present invention relates to an antifouling paint composition, an antifouling coating film formed from the antifouling paint composition, which can effectively prevent the attachment of marine organisms when formed on the surface of the body of a ship by a synergetic effect of the improvement in antibacterial action and renewability of coating film (the synergetic effect is obtained by adding zinc sulfide to a hydrolizable antifouling paint composition), a substrate with a coating film, an antifouling substrate, a forming method of a coating film on a surface of the substrate and an antifouling method of the substrate. More particularly, the present invention relates to an antifouling paint composition, an antifouling coating film formed from the antifouling paint composition, which can effectively prevent the attachment of marine organisms when formed on the surface of the body of a ship by a synergetic effect of the improvement in antibacterial action and renewability of coating film (the synergetic effect is obtained by adding zinc sulfide to a hydrolizable antifouling paint composition) , a substrate with a coating film, an antifouling substrate, a forming method of a coating film on a surface of the substrate and an antifouling method of the substrate. BACKGROUND ART The bottom of ship, submerged structures, fishing nets and the like may be damaged in their appearance and function as the result of the attachment and the proliferation of various aquatic organisms such as animals like oysters, mussels and barnacles, plants like lavers or bacteria on their surface upon the exposure in marine water for a long period of time. In the case when such aquatic organisms attach especially to the ship bottom and proliferate, the surface roughness of the whole ship increases, possibly leading to a decreased ship speed and increased fuel consumption. Moreover, a huge amount of labor and working hours are required for removing such aquatic organisms from the ship bottom. Furthermore, the strength and function of the submerged structures are deteriorated and the longevity of the submerged structures is significantly decreased if decomposition is caused by the attachment and proliferation of bacteria on submerged structures, followed by attachment of slimes (sludgy materials) thereto, and further if the coating film for corrosion proof of the submerged structures such as steel structures is damaged by the attachment and proliferation of large organisms. Conventionally, in order to prevent such damages, various antifouling paints have been applied to the ship bottom and the like, and various types of antifouling paints have been proposed, which are described in (1) to (9) as mentioned below. (1) In Japanese Patent Laid-Open Publication No. 522734/2003, an antibacterial composition having a biocidal effect comprising pyrithione or a pyrithione complex and zinc, copper or silver or a compound thereof (for example, salts, oxides, hydroxides, sulfates, chlorides, complexes and the like) is disclosed, and zinc sulfide is specifically disclosed as a zinc compound, wherein it is described that the antibacterial composition may be used by adding to an elastomer such as a styrene-butadiene copolymer, polyacrylate and silicone rubber and also may be used as a marine paint. However, a combination system of these compounds and a hydrolyzable metal polymer is not disclosed. (2) In WO No. 2004/057964 pamphlet, an antimicrobial composition comprising pyrithione or a pyrithione complex, a zinc compound (such as zinc sulfide) and an organic amine is disclosed and is suggested to be applicable for antifouling of the body of ship. However, no description is made for a coating film forming polymer. (3) In Japanese Patent Laid-Open Publication No. 508639/1998, a marine antifouling paint containing a binder based composition (such as rosin) and a fiber is disclosed. It is described that a self-polishing polymer may be used as a binder and a zinc sulfide fiber is specifically exemplified as a fiber. Moreover, it is also described that zinc sulfide may be contained as a pigment as necessary. However, although there are expressions of the self-polishing polymer and the hydrolysable polymer, there is no concrete disclosures and examples for the polymer. In addition, the zinc sulfide fiber is exemplified but no concrete examples are presented in which the polymers are blended. (4) In Japanese Patent Laid-Open Publication No. 346329/2004, which is a divisional application of the above (2), there is a similar description to the above (2). (5) In Japanese Patent Laid-Open Publication No. 510891/2000, a marine antifouling paint comprising rosin, a fiber, and a polymer flexibility imparting agent is disclosed, and it is described that the paint has excellent weather resistance. In addition, as the flexibility imparting agent, there is mentioned a poly (meth) acrylate, a polyester resin and the like. However, although a technical idea that a rosin metal salt which is one type of self-polishing polymers is used as the binder resin, there is no technical idea that a self-polishing polymer such as an acryl polymer and a polyester resin and the like having a metal salt based side chain is used and a self-polishing polymer such as (meth)acrylate ester based polymer having a silyl ester based side chain is used as is the case of the present invention. (6) Furthermore, in Japanese Patent Laid-Open Publication No. 502473/2003, there is described a self-polishing antifouling marine paint composition containing a binder copolymer having a side chain terminal group represented by the following Formula (I) : and a fiber, and a zinc sulfide fiber is specifically described as the fiber. In addition, it is described that zinc sulfide may be contained as a pigment as necessary. (Formula Removed) I), R1 to R5 each independently represents an alkyl group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms, X is >C(=0) and n is an integer 0, 1 or more. ] Moreover, as the monomer for the synthesis of said binder copolymer, there may be mentioned tri (isopropyl) silylacrylate, methoxyethylmethacrylate, methylmethacrylate and butylmethacrylate and the like. However, there are problems in the antifouling paint compositions described in the above publications that the resulting coating film may not fully exhibits an antifouling effect because of its low hydrolyzability (the elution property of the resin), causes problems such as poor adhesion and the like at the time of recoating at repair work and the like because of the deposition of an inactive layer on the surface of the coating film. (7) Japanese Patent Laid-Open Publication No. 302989/2001, an antifouling paint, which contains as a binder a resin having a silylated phosphonate group represented by the formula (1), -S (0) 2-0- [Si (R4) (R5) -0]n-Si (R1) (R2) R3, [where R1, R2, R3, R4 and R5 each independently represents a hydrocarbon group such as an alkyl group having 1 to 18 carbon atoms and an alkoxy group having 1 to 18 carbon atoms and the like and n is an integer of 0 to 200.], is disclosed, and a metal pyrithione containing metal (Cu, Zn and the like) is exemplified as an antifouling agent. In addition, zinc sulfide and the like are exemplified as a pigment and it is described that they are blended at 1 to 60% of the solid content volume of the paint. (8) In addition, in Japanese Patent Laid-Open Publication No. 5692/2000, zinc sulfide is exemplified as a coloring pigment that may be blended in a paint used for film thickness determination utilizing the color difference between a coating film containing coloring pigments and a coated material. Furthermore, a hydrolyzable acryl-modified resin or a polyester-modified resin and the like are exemplified as a resin component contained in the paint. It is described that the hydrolyzable acryl-modified resin or the polyester-modified resin have a group represented by formula (1) : -COO-M-Yy (with the proviso that y represents the valence number of M -1, M represents a metal of Cu, Zn, Si and the like, Y represents an alkyl group , a hydroxyl group, a group represented by OOCR1 (R1 is a hydrocarbon group having 10 or more carbon atoms) or a group represented by R2-CO-CH2~CO-R3 (R2 is a divalent group comprising an alkylene group or a phenyl derivative and R3 is a monovalent group comprising an alkyl group or a phenyl derivative)), a group represented by the formula (2) : -N=CHR4 (R4 is a hydrocarbon having 6 or more carbon atoms) or the formula -SOa-NH-R5 (R5 is a hydrogen atom or an alkyl group) in the side chain. In the publication, there is an example in which a metal-containing copolymer paint "Ecoloflex" having a hydrolysable, self-polishing side chain terminal, -COO-M-OOCR1 as a film thickness determination paint is used, but there is no example in which zinc sulfide of a coloring pigment is blended. (9) In Japanese Patent Laid-Open Publication No. 327914/2001, it is described that a first coating may contain a coloring pigment when a silicone rubber final coating film is directly applied on a first coating film comprising a blockpolymer consisted of an organosiloxane unit and an alkyleneoxide unit without via an intermediate coating film, and zinc sulfide is exemplified as a pigment which may be blended. However, there is no examples in which zinc sulfide is blended. In this way, in the inventions described in the above (1) to (9) , although a hydrolysable resin comprising rosin and a crosslinkable metal salt copolymer is exemplified as a resin and zinc sulfide is exemplified as a coloring agent, any of which is not a disclosure of a technical idea in which attention is paid to the antifouling effect of zinc sulfide itself but is limited to the use of the function as a coloring pigment. In short, in these prior literatures, there are no technical ideas that the antibacterial action of zinc sulfide in the antifouling coating film obtained by a combination of the zinc sulfide and a hydrolysable resin such as a particular crosslinkable copolymer containing a bond of metal salt is favorably exerted to improve the antifouling properties by paying attention to the safety to the environment and the antibacterial action of zinc sulfide as is the case of the present invention. Patent Literature 1: Japanese Patent Laid-Open Publication No. 522734/2003 Patent Literature 2: WO 2004/057964 Pamphlet Patent Literature 3: Japanese Patent Laid-Open Publication No. 508639/1998 Patent Literature 4: Japanese Patent Laid-Open Publication No. 346329/2004 Patent Literature 5: Japanese Patent Laid-Open Publication No. 510891/2000 Patent Literature 6: Japanese Patent Laid-Open Publication No. 502473/2003 Patent Literature 7: Japanese Patent Laid-Open Publication No. 302989/2001 Patent Literature 8: Japanese Patent Laid-Open Publication No. 5692/2000 Patent Literature 9: Japanese Patent Laid-Open Publication No. 327914/2001 DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION An objective of the present invention is to solve the problems associated with the conventional technology as mentioned above, and to provide an antifouling paint composition which is especially excellent in a balance between antibacterial action and renewability of a coating film and may effectively prevent the attachment of marine organisms when it is applied to the surface of the substrate of the ship body and the like and cured to form an antifouling coating film. Another objective of the present invention is to provide an antifouling paint which does not contain especially cuprous oxide and is copper free (not containing copper), and which is excellent in self-polishing property (consumption property of a coating film) for a long period of time, antifouling performance for a long period of time and antifouling performance (stationary antifouling performance) in a highly polluted sea area, compared with a paint containing cuprous oxide. Still another objective of the present invention is to provide an antifouling coating film, a substrate with the coating film and an antifouling substrate which are obtained by applying and curing the above-mentioned antifouling paint composition and are excellent in the balance between antibacterial action and renewability of the coating film. And still another objective of the present invention is to provide a safe and efficient method of forming a coating film having above-mentioned properties on the surface of the substrate and an antifouling method of the substrate. MEANS TO SOLVE THE PROBLEMS An antifouling paint composition relating to the present invention is a antifouling paint composition comprising; (A) a hydrolysable copolymer and (B) an antifouling agent, in which said hydrolysable copolymer (A) is at least one kind of hydrolysable copolymer selected from the group consisting of (al) a copolymer containing a bond of metal salt (which may be referred to as a side chain terminal structure metal salt copolymer), which is an acrylic polymer or a polyester resin, has a side chain terminal group represented by the general formula (I): -COO-M-0-COR1 (I) [in the Formula (I) , M represents zinc or copper, R1 represents an organic group, with the proviso that the case where R1 corresponds to -C(R2)=CH2 is excluded.]: (a2) a copolymer containing a bond of metal salt composed of a component unit (a21) derived from a monomer represented by the general formula (II): (Formula Removed) [in the Formula (II), M represents zinc or copper and R2 represents a hydrogen atom or a methyl group.] and a component unit (a22) derived from other unsaturated monomer which is copolymerizable with said monomer (II); and (a3) a silyl ester based copolymer composed of a component unit (a31) derived from a monomer represented by the general formula (III) : (Formula Removed) [in the Formula (III), R3 represents a hydrogen atom or a methyl group, R4, R5 and R6 each independently represents a hydrocarbon group, R7 represents a hydrogen atom or R8-0-CO- (with the proviso that R8 represents an organic group or a silyl group represented by -SiR9R10R11, and R9, R10 and R11 each independently represents a hydrocarbon group.)] and a component unit (a32) derived from other unsaturated monomer which is copolymerizable with said monomer (III); and zinc sulfide is contained at an amount of 10 to 500 parts by weight with respect to 100 parts by weight of the hydrolysable copolymer (A) as said antifouling agent (B). In the present invention, said antifouling paint composition preferably does not substantially contain cuprous oxide. In the present invention, said antifouling agent (B) preferably consists of zinc sulf ide and an organic antifouling agent (b2). In the present invention, said organic antifouling agent (b2) is preferably at least one kind of organic antifouling agent selected from the group consisting of a pyrithione compound, tri-organic boron and amine complex thereof, and 4,5-dichloro-N-octylisothiazolin-3-one. In the present invention, said organic antifouling agent (b2) is preferably at least one kind selected from the group consisting of zinc pyrithione, a triphenylboron-pyridine complex, a dimethylphenylboron- (4-isopropyl) pyridine complex and 4,5-dichloro-N-octylisothiazolin-3-one. In the present invention, when said organic antifouling agent (b2) is contained together with cuprous copper as said antifouling agent (B) , said organic antifouling agent (b2) is preferably contained at an amount of 20 to 500 parts by weight with respect to 100 parts by weight of zinc sulfide. In the present invention, furthermore, zinc oxide is preferably contained as an extender pigment. In the present invention, when zinc oxide is contained as mentioned above, zinc oxide is preferably contained at an amount of 10 to 300 parts by weight with respect to 100 parts by weight of said hydrolyzable copolymer (A). Moreover, in the present invention, zinc oxide is preferably contained at an amount of 1 to 40 % by weight in the antifouling paint composition. In the present invention, in addition, talc is preferably contained in the antifouling paint composition as an extender pigment. In the case where talc is contained, talc is preferably contained at an amount of 5 to 300 parts by weight with respect to 100 parts by weight of said hydrolyzable copolymer (A) . In addition, in such a case that talc is contained, talc is preferably contained at an amount of 0.5 to 40 % by weight in the antifouling paint composition. In the present invention, furthermore, chlorinated paraffin is preferably contained as a plasticizer in the antifouling paint composition. In the present invention, chlorinated paraffin is preferably contained at an amount of 0.05 to 40 parts by weight with respect to 100 parts by weight of said hydrolyzable copolymer (A). In the present invention, chlorinated paraffin is preferably contained at an amount of 1 to 5 % by weight in the antifouling paint composition. In the present invention, furthermore, it is preferable that at least one kind of pigment selected from the group consisting of red iron oxide, titanium white, yellow iron oxide and an organic pigment is contained. In the present invention, the organic group R1 of said copolymer (al) containing a bond of metal salt is preferably an organic acid residue of a monobasic acid, which is a monovalent saturated aliphatic hydrocarbon group having 2 to 30 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 18 carbon atoms or a substituent thereof. In the present invention, the organic group R1 of said copolymer (al) containing a bond of metal salt is preferably an organic acid residue of a monobasic acid, which is a monovalent saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms or a substituent thereof. In the present invention, said copolymer (al) containing a bond of metal salt is preferably a copolymer containing a bond of metal salt having, at -COO- of an acrylic acid copolymer via copper or zinc, a side chain terminal group represented by the general formula (IV): -0-COR1 (IV) [in the Formula (IV), R1 represents an organic acid residue of a monobasic acid, the residue consisting of a monovalent saturated or unsaturated aliphatic hydrocarbon group with the carbon atom number of 10 to 20, a saturated or unsaturated alicyclic hydrocarbon group with the carbon atom number of 3 to 20 or a substitution product thereof] In the present invention, the organic group R1 of said copolymer (al) containing a bond of metal salt is preferably an organic acid residue formed from at least one kind of a 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, said copolymer (al) containing a bond of metal salt is preferably a copolymer of two kinds or more of monobasic acid metal (meth)acrylates represented by the general formula (V): (Formula Removed) [in the Formula (V) , R1, R2 and M are the same as mentioned before] In the present invention, the organic group R1 of a component unit derived from the monobasic acid metal (meth)acrylate represented by said general formula (V) is preferably an organic acid residue of a monobasic acid comprising a monovalent saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms or a substituent thereof. In the present invention, the organic group R1 of a component unit derived from a monobasic acid metal (meth)acrylate represented by said general formula (V) is preferably an organic acid residue formed from at least one kind of a 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, said copolymer (al) containing a bond of metal salt is preferably a copolymer containing a component unit derived from said monobasic acid metal (meth)acrylate and a component unit derived from at least one kind of unsaturated monomer selected from the group consisting of alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate and hydroxyalkyl (meth)acrylate. In the present invention, the content of zinc and/or copper originated from a structure of the general formula (I) in said copolymer (al) containing a bond of metal salt is preferably 0.5 to 20 % by weight. In the present invention, a monomer represented by the general formula (II): (Formula Removed) [where M and R2 are the same as above.], which can induce the component unit (a21) in said copolymer (a2) containing a bond of metal salt, is preferably at least one kind of a monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate. In the present invention, the other unsaturated monomer which can induce the component unit (a22) in said copolymer (a2) containing a bond of metal salt is preferably at least one kind of unsaturated monomer selected from the group consisting of alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate and hydroxyalkyl(meth)acrylate. In the present invention, a monomer represented by the general formula (II): (Formula Removed) [where M and R2 are the same as above.], which can induce the component unit (a21) in said copolymer (a2) containing a bond of metal salt, is preferably at least one kind of unsaturated monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer which can induce the component unit (a22) in said copolymer (a2) containing a bond of metal salt is preferably at least one kind of unsaturated monomer selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate and 2-hydroxyethyl(meth)acrylate. In the present invention, a monomer represented by the general formula (II): (Formula Removed) [where M and R2 are the same as above.], which can induce the component unit (a21) in said copolymer (a2) containing a bond of metal salt, is preferably at least one kind of unsaturated monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomer which can induce the component unit (a22) in said copolymer (a2) containing a bond of metal salt is preferably a monobasic acid metal (meth)acrylate represented by the general formula (V) : (Formula Removed) (V) [where R1, R2 and M are the same as above.]. In the present invention, a monomer represented by the general formula (II): (Formula Removed) (II) [where M and R2 are the same as above.], which can induce the component unit (a21) in said copolymer (a2) containing a bond of metal salt, is preferably at least one kind of unsaturated monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomers which can induce the component unit (a22) in said copolymer (a2) containing a bond of metal salt are preferably a monobasic acid metal (meth)acrylate represented by the general formula (V) : (Formula Removed) (V) [where R1, R2 and M are the same as above.] and at least one kind of unsaturated monomer selected from the group consisting of alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate, and hydroxyalkyl(meth)acrylate. In the present invention, a monomer represented by the general formula (II): (Formula Removed) (II) [where M and R2 are the same as above.], which can induce the component unit (a21) in said copolymer (a2) containing a bond of metal salt, is preferably at least one kind of unsaturated monomer selected from the group consisting of zinc diacrylate, zinc dimethacrylate, copper diacrylate and copper dimethacrylate, and the other unsaturated monomers which can induce the component unit (a22) in said copolymer (a2) containing a bond of metal salt are preferably a monobasic acid metal (meth)acrylate represented by the general formula (V) : (Formula Removed) ame as above.] and at least one kind of unsaturated monomer selected from the group consisting of methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate and 2-hydroxyethyl(meth)acrylate. In the present invention, the organic group R1 of the component unit derived from a monobasic acid metal (meth)acrylate represented by said general formula (V) is preferably an organic acid residue of a monobasic acid comprising of a monovalent saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms or a substituent thereof. In the present invention, the organic group R1 of the component unit derived from a monobasic acid metal (meth)acrylate represented by said general formula (V) is preferably an organic acid residue formed from at least one kind of a 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,the content of zinc and/or copper originated from a structure of the general formula (II) in said copolymer (a2) containing a bond of metal salt is preferably 0.5 to 20 % by weight. In the present invention, the component unit (a31) derived from a monomer represenred by said general formula (III) is preferably a component unit derived from trialkylsilyl(meth)acrylate. In the present invention, the component unit (a31) derived from a monomer represented by said general formula (III) is preferably a component unit derived from triisopropylsilyl(meth)acrylate. In the present invention, the component unit (a32) derived from "the other unsaturated monomer" which is copolymerizable with a monomer represented by said general formula (III) is preferably a component unit derived from at least one kind of unsaturated monomer selected from the group consisting of alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate, and hydroxyalkyl(meth)acrylate. In the present invention, the component unit (a32) derived from "the other unsaturated monomer" which is copolymerizable with a monomer represented by said general formula (III) is preferably a component unit derived from at least one kind of 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. An antifouling coating film according to the present invention is characterized in that said film is formed from an antifouling paint composition described in any of the above paragraphs. A substrate with a coating film according to the present invention is characterized in that the surface of the substrate is coated by a coating film formed by curing an antifouling paint composition described in any of the above paragraphs. An antifouling substrate according to the present invention is characterized in that the surface of the substrate which comes in contact with marine water or fresh water is coated by a coating film formed by curing an antifouling paint composition described in any of the above paragraphs. In the antifouling substrate according to the present invention, said substrate as a base is preferably any of submerged structures, outside boards of a ship, fishing nets and fishing implements. A method of forming a coating film according to the present invention is characterized in that an antifouling paint composition described in any of the above paragraphs is applied or impregnated to the surface of the substrate and then is cured to form said coating film. An antifouling method of a substrate according to the present invention is characterized in that the antifouling paint composition described in any of the above paragraphs is applied or impregnated to the surface of the substrate and then is cured to form said antifouling coating film. In the present invention, said substrate as the subject of an antifouling method is preferably any of submerged structures, outside boards of a ship, fishing nets and fishing implements. In the present invention, when the amount (weight) of the copolymer is represented or the amount ratio of the copolymer to zinc sulfide and the like is represented, the amount of the copolymer is basically represented by the solid content value which does not contain solvents and the like. However, in embodiments and comparative examples, when a heating residue (% by weight) as well as a solid content (%) are specified as shown in Table 1 to 4, or a volatile component is specified, the amount of the copolymer (polymer) represents the amount that includes not only the resin content which is a film forming component, but also a volatile component (solvents, disperse medium). Similarly, in the antifouling paint compositions described in Table 5 to 10 in which the copolymers described in Table 1 to 4 were blended, the indication of the amount of the copolymer blended is the amount including a volatile component such as the solvent and the like. EFFECTS OF THE INVENTION According to the present invention, when an antifouling coating film is formed on the surface of the substrate such as a ship body and the like by applying and curing a paint, especially a hydrolysable type antifouling paint composition, there is provided an antifouling paint composition which is especially excellent in the balance between antibacterial action and renewability of a coating film, and can effectively prevent the attachment of marine organisms, especially algae. According to the present invention, there is provided a copper free (not containing copper) antifouling paint which does not substantially contain cuprous oxide and is excellent in safety for the environment. According to the present invention, with the addition of zinc sulfide as an antifouling agent to an hydrolyzable self-polishing resin and especially in a preferred embodiment, by the use of zinc sulfide and an organic antifouling agent (e.g., boron based and pyrithione based) in combination, there is provided an antifouling paint composition which is able to form a coating film with a more improved antifouling properties, such as excellence in self-polishing property (consumption property of a coating film) for a long period of time, excellence in antifouling performance for a long period of time and excellence in antifouling performance (stationary antifouling performance) in a highly polluted sea area, as compared with a conventional antifouling paint containing cuprous oxide. Furthermore, according to the present invention, there are provided an antifouling coating film which is excellent in the balance between antibacterial action (stationary antifouling performance) and renewability of a coating film, a substrate with a coating film and an antifouling substrate which are obtained by applying and curing said antifouling paint composition. Moreover, according to the present invention, there are provided a safe and effective forming method of a coating film having said properties on the surface of the substrate and an antifouling method of the substrate. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, there are specifically explained an antifouling paint composition, an antifouling coating film, a substrate with a coating film, an antifouling substrate, a method of forming a coating film on the surface of the substrate and an antifouling method of the substrate according to the present invention. [Antifouling Paint Composition] The antifouling paint composition according to the present invention contains the following specified (A) hydrolyzable copolymer and the following specified (B) antifouling agent. In the present invention, it is preferable that said antifouling paint composition does not substantially contain cuprous oxide from a view point to reduce an adverse effect to the environment as well as from the functional aspect of the paint such as storage stability of the paint and reduction in discoloration of the coating film. As said hydrolyzable copolymers (A) , there are mentioned said copolymers (al) and (a2) that contain a bond of metal salt, and a silylester based copolymer (a3). These hydrolyzable copolymers (A) may be used alone or in combination with two or more thereof. Moreover, in the present invention, any one of said copolymers (al) and (a2) that contain a bond of metal salt, and the silylester based copolymer (a3) may be used alone as said hydrolyzable copolymers (A) , depending on the application of the resultant antifouling paint composition and the navigation areas of ships, for example, the silyl ester based copolymer (a3) may be used alone from the view point to prevent the attachment of algae, or two or more of them may be used from the view point of stability over a long period of time, for example, a combination of said copolymers (al), (or (a2)) containing a bond of metal salt and the silyl ester based copolymer (a3) may be used in combination at any ratio of the amount as appropriate. (al) a copolymer containing a bond of metal salt, which is an acrylic copolymer or a polyester resin, having a side chain terminal group represented by the general formula (I) : (Formula Removed) [in the Formula (I) , M represents zinc or copper and R1 represents an organic group.] (a2) a copolymer containing a bond of metal salt composed of a component unit (a21) derived from a monomer represented by the general formula (II): (Formula Removed) (II) [in the Formula (II), M represents zinc or copper and R2 represent a hydrogen atom or a methyl group.] and a component unit (a22) derived from the other unsaturated monomer which is copolymerizable with said monomer. (a3) a silylester based copolymer composed of a component unit (a31) derived from a monomer represented by the general formula (III): (Formula Removed) (III) [in the Formula (III) , R3 represents a hydrogen atom or a methyl group, R4, R5 and R6each independently represents a hydrocarbon group, R7 represents a hydrogen atom or R8-0-CO- (with the proviso that R8 represents an organic group or a silyl group represented by -SiR9R10R11, and R9, R10 and R11 each independently represents a hydrocarbon group)] and a component unit (a32) derived from the other unsaturated monomer which is copolymerizable with said monomer (III). Copolymers (al) and (a2) that contain a bond of metal salt, and a silyl ester based copolymer (a3) are specifically explained hereinafter. As such copolymers (al) and (a2) that contain a bond of metal salt, and a silyl ester based copolymer (a3), there has been used a conventionally known copolymer, which includes, for example, (i) a hydrolyzable self-polishing resin having a group represented by the formula "-X-O-Cu-Y" (where X represents > C=0, Y represents an organic acid residue and may be an alkylsilyloxy group and the like.) in the side chain which is described in [0010] to [0017] of Japanese Patent Laid-Open Publication No. 298454/1998; (ii) a hydrolyzable acrylic resin or polyester resin having a group represented by the formula "-COO-M-Yy"(1) ( with the proviso that y is a valence number of M -1, M represents any metal among Cu, Zn, Si, ( in the case where y is 2 or more, Y may be the same or different from each other) and Y is an alkyl group, a hydroxyl group, a group represented by -OCOR1 (with the proviso that R1 represents a hydrocarbon group having 10 or more carbon atoms) or a group represented by -R2-CO-CH2-CO-R3 (with the proviso that R2 is a divalent group comprising an alkylene group or a phenyl derivative and R3 is a monovalent group comprising an alkyl group or a phenyl derivative) in the side chain which is described in [0010] to [0017] of Japanese Patent Laid-Open Publication No. 5692/2000; (iii) a hydrolyzable copolymer (especially a metal-containing copolymer) described in [0039] to [0068] of Japanese Patent Laid-Open Publication No. 196957/2004 and a polymerizable unsarurated carboxylic acid silyl ester copolymer described in [0069] to [0092] of the same publication, which have been previously proposed by the applicants of the present invention; and (iv) a hydrolyzable copolymer (especially a metal containing copolymer) described in [0051] to [0091] of Japanese Patent Laid-Open Publication No. 97400/2005 and a polymerizable unsarurated carboxylic acid silyl ester copolymer described in [0092] to [0124] of the same publication, which have been previously proposed by the applicants of the present invention; and the like. Said copolymers (al) and (a2) that contain a bond of metal salt, and a silyl ester based copolymer (a3) which are especially preferable in achieving the objectives of the present invention are explained in detail hereinafter. (Copolymer (al) Containing a Bond of Metal Salt) The copolymer (al) containing a bond of metal salt (also referred to as a side chain terminal structure metal salt copolymer) is an acryl polymer or a polyester resin as a base resin,and is a (co)polymer having a structure in which a side chain terminal group represented by the general formula (I) is bonded: (Formula Removed) [in the Formula (I) , M represents zinc or copper, R1 represents an organic group (with the proviso that a vinyl group (-CH=CH2) and isopropyl group (-C (CHa) =CH2) are excluded from the organic group R1 in the formula (I) to avoid overlapping of (al) with (a2) below mentioned).] Organic Group R1; As the organic group R1, there is mentioned an organic acid residue of a monobasic acid, the residue consisting of a hydrocarbon group such as a monovalent saturated aliphatic group having 2 to 30 carbon atoms, preferably 10 to 20 carbon atoms; a monovalent 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, or a substituent thereof. It is preferable in terms of resin viscosity, elution property of the resin in the coating film and storage stability of the paint that among these organic groups R1, R1 is an organic acid residue of a monobasic acid, the residue consisting of a monovalent saturated or unsaturated aliphatic hydrocarbon group having 10 to 20 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms or a substituent thereof. It is preferable in terms of an easiness of the synthesis of a copolymer (al) containing a bond of metal salt, a gradual hydrolysis of the copolymer (al) containing a bond of metal salt from a film comprising the resulting antifouling paint composition thereby exhibiting an antifouling property as well as giving less burden to the environment upon hydrolysis, high durability of an antifouling effect, excellent surface renewability and excellent recoating property at coating for repairing and the like that such an organic group R1 is an organic acid residue formed from a monobasic acid including 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 and the like. It is preferable in terms of the elution and durability of a resin that the copolymer (al) containing a bond of metal salt having such an organic group R1 is a copolymer containing one or two or more component units derived from a monobasic acid metal (meth) acrylate represented by the following general formula (V). (Formula Removed) (V) [where R1, R2 and M are the same as above.] That is, in the formula (V) , M represents zinc or copper, R2 represents a hydrogen atom or a methyl group, and R1 represents the same organic group as that in the above formula (I) and the same group as mentioned above is preferable for the sae reason. As a monobasic acid metal (meth)acrylate (V) which is a metal containing monomer, there are specifically mentioned, for example, versatic acid zinc (meth)acrylate, isostearic acid zinc (meth) acrylate, versatic acid copper (meth) acrylate, ispstearic acid copper (meth)acrylate and the like. These monobasic acid metal (meth) acrylate (V) are used alone or in combination of two or more kinds thereof. Further, in the present invention, even though a monobasic acid metal (meth)acrylate (V) is not necessarily used as a monomer in the production of the copolymer (al) containing a bond of metal salt, as long as the similar component unit to a component unit (component unit (V) ) originated from said monomer (V) is present in the resultant copolymer, a production method of the copolymer (al) is not specifically limited. Moreover, the copolymer (al) containing a bond of metal salt preferably contains the component unit (a12) derived from the "other unsaturated monomer (a12)" in addition to said monobasic acid metal (meth)acrylate component unit (V), and as the "other unsaturated monomer (a12)", alkyl (meth) acrylate in which the alkyl group has 1 to 20 carbon atoms, alkoxyalkyl(meth)acrylate in which the alkoxy group has 1 to 20 carbon atoms and the alkylene group has 1 to 20 carbon atoms, and hydroxyalkyl(meth)acrylate in which the hydroxyalkyl group has 1 to 20 carbon atoms are preferable. Among these "other unsaturated monomer (a12)", as alkyl(meth)acrylate, there are specifically mentioned, for example, methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate and the like. As said alkoxyalkyl(meth)acrylate, there are specifically mentioned, for example, methoxymethyl(meth)acrylate, 2-methoxyethyl(meth)acrylate, ethoxymethyl(meth)acrylate, ethoxyethyl(meth)acrylate, butoxymethyl(meth)acrylate, 3-methoxybutyl(meth)acrylate, 3-methyl-3-methoxybutyl(meth)acrylate and the like. As said hydroxyalkyl(meth)acrylate, there are specifically mentioned, for example, 2-hydroxyethyl(meth)acrylate and the like. Among these "other unsaturated monomer (a12)", methyl(meth)acrylate, ethyl(meth)acrylate butyl(meth)acrylate and 2-hydroxyethyl(meth)acrylate are preferable in terms of the coating film property and the elution durability of a resin from the coating film. These "other unsaturated monomer (a!2)" is used alone or in combination of two or more thereof. In such copolymers (al) containing a bond of metal salt, it is preferable in terms of the resin viscosity, the resin elution property in the coating film and the water resistance of the coating film and the like that said monobasic acid metal (meth)acrylate component unit (V) is contained at an amount of typically 10 to 100 mol %, preferably 10 to 90 mol % and the component unit (a!2) originated from the "other unsaturated monomer (a!2)" is contained at the residual amount, that is, at an amount of typically 0 to 90 mol %, preferably 10 to 90 mol %, in said copolymer (100 mol %). Furthermore, it is preferable in terms of the resin viscosity, the storage stability of the paint, the resin elution rate in the coating film and the like that the number average molecular weight Mn (a polystyrene conversion value, which is the same hereinafter, as determined by GPC. measurement conditions: column: Super H2000+H4000) of the copolymer (al) containing a bond of metal salt is typically 1,000 to 100,000, preferably 1,000 to 50,000. Moreover, in the copolymer (al) containing a bond of metal salt, it is preferable in terms of the excellent resin viscosity, the storage stability of the paint, the resin elution property from the coating film that the content of zinc (Zn) and/or copper (Cu) originated from the structure of general formula (I) in the copolymer (al) containing a bond of metal salt is typically 0.5 to 20 % by weight, preferably 5 to 20 % by weight. Any of the following copolymer (a2) containing a bond of metal salt and a silyl ester based copolymer (a3) in addition to this copolymer (al) containing a bond of metal salt can be conventionally produced by a known method, for example, by a method described in said (i) Japanese Patent Laid-Open Publication No. 298454/1998 and (ii) Japanese Patent Laid-Open Publication No. 5692/2000, or a method described in (iii) Japanese Patent Laid-Open Publication No. 196957/2004 and (iv) Japanese Patent Laid-Open Publication No. 97400/2005 which were proposed by the applicants of the present invention. (Copolymer (a2) Containing a Bond of Metal Salt) The copolymer (a2) containing a bond of metal salt is a copolymer containing a bond of metal salt composed of a component unit (a21) derived from a monomer represented by the general formula (II): (Formula Removed) (II) [where M and R2 are the same as those in the formula (V) . That is, in the formula (II), M represents zinc or copper and R2 represents a hydrogen atom or a methyl group.], and a component unit (a22) derived from the "other unsaturated monomer" which is copolymerizable with this monomer (II). Still further, in the present invention, as is the case of the copolymer (al) containing a bond of metal salt, even though metal di (meth) acrylate (II) is not necessarily used as a monomer in the production of the copolymer (a2) containing a bond of metal salt, as long as the similar component unit to a component unit (component unit (II) ) originated from said monomer (II) is present in the resultant copolymer, a production method of the copolymer (a2) is not specifically limited. As the monomer (II) , that is, metal di (meth) acrylate (II) , zinc diacrylate: (CH2=CHCOO)2Zn, zinc dimethacrylate: (CH2=C(CH3)COO)2Zn, copper diacrylate: (CH2=CHCOO) 2Cu and copper dimethacrylate: (CH2=C (CH3) COO) 2Cu are mentioned and zinc di (meth) acrylate is preferable as a monomer (II) in terms of the resin viscosity, the storage stability of the paint, the resin elution property in the coating film and the like, In the present invention, these monomers (II) may be used alone or in combination of two or more thereof. Furthermore, it is preferable in terms of the adjustment of resin elution rate that there are the component unit (a22) derived from the "other unsaturated monomer (a22)" which is copolymerizable with this monomer (II) in addition to the component unit (II) derived from said metal di(meth)acrylate (II) in the copolymer (a2) containing a bond of metal salt. As this "other unsaturated monomer (a22)", there are mentioned monobasic acid metal (meth)acrylate (V) which is used in the production of said copolymer (al) containing a bond of metal salt and/or the "other unsaturated monomer (a!2)" which is a monomer used in the production of said copolymer (al) containing a bond of metal salt, as necessary. That is, in the copolymer (a2) containing a bond of metal salt, the monobasic acid metal (meth) acrylate component unit (V) in the copolymer (al) containing a bond of metal salt may be present in addition to said essential metal di(meth)acrylate component unit (II), as well as a component unit (a!2) originated from the "other unsaturated monomer (a!2)", and both these component unit (V) and component unit (a!2) may be present. Moreover, as the "other unsaturated monomer (a!2)", alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate and hydroxyalkyl(meth)acrylate are preferable. In said copolymer (a2) containing a bond of metal salt, it is preferable in terms of easiness of adjustment of resin elution rate in the coating film that said metal di(meth)acrylate component unit (a21) is contained at an amount of typically 10 to 100 mol %, preferably 10 to 90 mol % and the component unit (a22) originated from the "other unsaturated monomer (a22) " is contained at the residual amount, that is, at an amount of typically 0 to 90 mol %, preferably 10 to 90 mol %, in said copolymer (100 mol %). In addition, the monobasic acid metal (meth) acrylate component unit (V) may be contained at an amount of typically 0 to 100 mol %, preferably 0 to 90 mol % and the component unit (a12) originated from the "other unsaturated monomer (a12)" may be contained at the residual amount, that is, at an amount of typically 100 to 0 mol %, preferably 10 to 90 mol %, in the component unit (a22) 100 mol % originated from the "other unsaturated monomer (a22)". Furthermore, it is preferable in terms of the resin viscosity and the resin elution rate in the coating film that the number average molecular weight Mn (a polystyrene conversion value, which is the same hereinafter, as determined by GPC, measurement conditions: column: Super H2000+H4000) of the copolymer (a2) containing a bond of metal salt is typically 1,000 to 100,000, preferably 1,000 to 10,000. Moreover, in the copolymers (a2) containing a bond of metal salt, it is preferable in terms of the excellence in resin viscosity, the storage stability of the paint, the resin elution property from the coating film that the content of Zinc (Zn) and/or copper (Cu) originated from the structure of general formula (I) in said copolymers (a2) is typically 0.5 to 20 % by weight, preferably 5 to 20 % by weight. (Silyl Ester Based Copolymer (a3)) The silyl ester based copolymer (a3) is, as mentioned above, a copolymer composed of a component unit (a31) (which is also referred to as a silyl based component unit) derived from a monomer represented by the following general formula (III) (which is referred to as a silyl ester based monomer, monomer (III)), and a component unit (a32) derived from the other unsaturated monomer which is copolymerizable with this monomer (III). (Formula Removed) (III) [in the Formula (III) , R3 represents a hydrogen atom or a methyl group, R4, R5 and R6 each independently represents a hydrocarbon group and R7 represents a hydrogen atom or R8-0-CO- (with the proviso that R8 represents an organic group or a silyl group represented by -SiR9R10Ru and R9, R10 and R11 each independently represents a hydrocarbon group.] In the case where R7 is a hydrogen atom (H) among said silyl ester based monomers (III), the monomer is represented by Formula (IIIa): (Formula Removed) (Ilia) [with the proviso that R3, R4, R5 and R6 in the formula (Ilia) are the same as those in the case of formula (III)] Said R4, R5 and R6 are an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, and more specifically, methyl group, ethyl group, propyl group and i-propyl group and the like are preferable. Specific examples of such a silyl ester based monomer (Ilia) include, for example, a trialkylsilyl(meth)acrylate ester such as trimethylsilyl(meth)acrylate, triethylsilyl(meth)acrylate, tri(i-propyl)silyl(meth)acrylate and the like, among which tri(i-propyl)silyl(meth)acrylate is preferable in terms of excellence in the resin elution property in the coating film, the elution persistence and physical properties of the coating film such as crack resistance and the like. In addition, among silyl ester based monomers (III), in the case where R7 is "R8-0-CO-(with the proviso that R8 is the same as the case of said formula (III))", the monomer is represented by the formula (Illb): (Formula Removed) (Illb) [with the proviso that R3, R4, R5, R6 and R8 in the formula (Illb) are the same as in the case of (III)] Specific examples of such a silyl ester based monomer (Illb) include, for example, maleic acid ester (a monomer in case of R3=H in the formula (Illb)) and the like. "Other unsaturated monomer (a32)" which is copolymerizable with this monomer (III) (or a monomer (Ilia) and/or (Illb)) includes the similar "other unsaturated monomer (a!2) and (s22)" to those used in the production of said copolymers (al) and (a2). As the "other unsaturated monomer (a32), alkyl(meth)acrylate, alkoxyalkyl(meth)acrylate and hydroxyalkyl(meth)acrylate are preferable. In this silyl ester based copolymers (a3), it is preferable in terms of the excellence in the resin viscosity in the coating film (that is, crack resistance), the storage stability of the paint, the resin elution property in the coating film and the like that the silyl ester based monomer (III) is contained at an amount of typically 10 to 100 mol %, preferably 10 to 90 mol % and the component unit (a32) originated from the the "other unsaturated monomer (a32)" is contained at the residual amount, that is, at an amount of typically 0 to 90 mol %, preferably 10 to 90 mol %, in said copolymer (100 mol %). Furthermore, it is preferable in terms of said resin viscosity, storage stability and resin elution property from the coating film that the number average molecular weight Mn (a polystyrene conversion value, which is the same hereinafter, as determined by GPC, measurement conditions: column: Super H2000+H4000) of the silyl ester based copolymers (a3) is typically 1,000 to 200,000, preferably 1,000 to 100,000. In the present invention, as said antifouling agent (B) , zinc sulfide (ZnS) is contained as an essential component. It is preferable in terms of the excellence in the antifouling property of the resultant coating film and the physical properties of the coating film such as especially cracking resistance that the zinc sulfide is contained at an amount of typically 10 to 500 parts by weight, preferably 50 to 200 parts by weight with respect to (the solid content) 100 parts by weight of the hydrolyzable copolymer (A') which is a total amount of said polymers (al) to (a3) . Meanwhile, if the zinc sulfide content is lower than the range mentioned above, there is a tendency that the coating film may not exhibit sufficient antifouling effect and the renewal property of the coating film surface is disturbed, and if the content exceeds the range, physical problems such as cracking tend to occur. In the present invention, it is preferable in terms of the persistence of the antifouling effect and the surface renewability that said antifouling agent (B) comprises zinc sulfide and an organic antifouling agent (b2), allowing the resultant coating film to exhibit an antifouling power especially in a highly polluted sea area where the coating film is liable to be soiled seriously. In the present invention, it is preferable in terms of excellence in the antifouling property of a coating film and the storage stability of the paint that said organic antifouling agent (b2) is at least one of organic antifouling agents selected from the group consisting of a metal-pyrithione represented by the following formula [VI] and a derivative thereof, tri-organic boron and amine complex thereof, and 4,5-dichloro-N-octylisothiazolin-3-one. (Formula Removed) [in formula [VI], R1 to R4 each independently represents a hydrogen atom, an alkyl group, an alkoxy group and a halogenated alkyl group, M represents a metal such as Cu, Na, Mg, Zn, Ca, Ba, Pb, Fe, Al and the like, and M is preferably Zn in consideration of the durability of the consumption degree of a coating film, n represents a valence number.] In the present invention, it is preferable in condideration of the excellent in the storage stability of a paint and in the balance between consumption property of the coating film and durability of the antifouling property that said organic antifouling agent (b2) is at least one kind of organic antifouling agents selected from the group consisting of zinc pyrithione, triphenylboron-pyridine complex, dimethylphenylboron-(4-isopropyl)pyridine complex and 4,5-dichloro-N-octylisothiazolin-3-one. In the present invention, it is preferable in terms of excellence in antifouling property of the resultant antifouling coating film especially in its durability (which means small consumption degree of the coating film), less burden to the environment and excellence in water resistance of a coating film that an organic antifouling agent, especially said organic antifouling agent as mentioned above is contained in said antifouling agent (B) at an amount of 20 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of zinc sulfide. Further, as the antifouling agent, a conventionally known antifouling agent may be used in view of exerting a sufficient antifouling property. However, it is preferable that an antifouling agent that has a relatively large environmental burden, for example, cuprous oxide etc. is not substantially used. As coloring agents, various organic and inorganic pigments which are conventionally known can be used. As organic pigments, carbon black, naphthol red, phthalocyanine blue and the like can be mentioned. As inorganic pigments, for example, red iron oxide, barites, zinc oxide (ZnO, zinc white), titanium white, yellow iron oxide and the like can be mentioned. Moreover, various coloring agents such as dyes may be contained. In the present invention, as inorganic coloring pigments, any of red iron oxide, titanium white and yellow iron oxide is especially preferable in terms of tinting strength. Said organic pigments are also preferable in the point that they may provide a coating film having a brilliant color and cause less discoloration. An extender pigment is a pigment which has a small refractive index and may not hide a coated surface because it is transparent when blending with oil and varnish. As such extender pigments, there are mentioned, for example, talc, silica, mica, clay, zinc oxide, calcium carbonate which is also used as an antiprecipitation agent, kaolin, aluminum white, white carbon which is also used as a frosting agent, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate and the like, among which an extender pigment selected from the group consisting of zinc oxide, talc, silica, mica, clay, calcium carbonate, kaolin and barium sulfate are preferable. Especially when zinc oxide is blended, it is preferable in consideration of the durability of the consumption property and attachment property of the resultant coating film that said zinc oxide is contained at an amount of typically 10 to 300 parts by weight with respect to 100 parts by weight of the copolymer (A) solid content, and is contained at an amount of 1 to 40 % by weight in the antifouling paint composition. These extender pigments are used alone or in combination of two or more thereof. In addition, the consumption degree of a coating film may be adjusted depending on the kind of extender pigments. In the present invention, when talc is contained as an extender pigment in the antifouling paint composition in consideration of a cost reduction and extending effect of the resultant paint, and the transparency and covering property of the resultant coating film, it is preferable that talc is contained at an amount of 5 to 300 parts by weight, preferably 5 to 200 parts by weight with respect to 100 parts by weight of a hydrolyzable copolymer (A). In addition, when talc is contained in this way, it is preferable in terms of absence of adverse effects on the physical and antifouling property of the coating film that talc is contained at an amount of 0.5 to 40 % by weight, preferably 0.5 to 20 % by weight in the antifouling paint composition. In the present invention, furthermore, it is preferable that chlorinated paraffin or terpene phenol is contained as a plasticizer in the antifouling paint composition. As a plasticizer, there are mentioned TCP (tricresilphosphate), chlorinated paraffin, polyvinylethylether, terpene phenol and the like. These plasticizers may be used alone or in combination of two or more thereof. These plasticizers contribute to the improvement in cracking resistance of the coating film (antifouling coating film) formed from the resultant antifouling paint compositions, among which plasticizers, chlorinated paraffin (paraffin chloride) is preferably used. A chlorinated paraffin (paraffin chloride) blended as a plasticizer to the antifouling paint composition of the present invention may be linear or branched and may be liquid or solid (powder) at room temperature. With regard to this chlorinated paraffin, the average number of caron atoms is typically from 8 to 30, preferably 10 to 26, the number average molecular weight is typically 200 to 1200, preferably 300 to 1100, the viscosity is typically 1 or more (poise/25'C ) , preferably 1.2 or more (poise/25°C) , and the specific gravity is 1.05 to 1.80/25°C, preferably 1.10 to 1.70/25°C. A coating film with less cracking and peeling can be formed by using the antifouling paint composition, if a chlorinated paraffin with these carbon number is used. Incidentally, if the average number of carbon atoms of the chlorinated paraffin is less than 8, the suppression effect of cracking may be insufficient, and if said number exceeds 30, the consumption property (renewability) and antifouling property of the resultant coating film surface may be poor. Moreover, the chlorination ratio (chlorine content) of the chlorinated paraffin is typically 35 to 75%, preferably 35 to 65%. If a chlorinated paraffin having such chlorination ratio is used, a coating film with less racking and peeling can be formed by using the resultant antifouling paint composition. As such a chlorinated paraffin, there are mentioned "ToyoparaxlSO", "ToyoparaxA-70" and the like produced by Tosoh Corp. In the present invention, when a plasticizer represented by a chlorinated paraffin is blended, it is preferable in terms of the reduction of cracking resistance, reduction in discoloration and the improvement in water resistance of a coating film that such a plasticizer is contained at an amount of 0.05 to 40 % by weight with respect to 100 parts by weight of said hydrolyzable copolymer (A). Furthermore, in the present invention, it is preferable that a plasticizer represented by a chlorinated paraffin is contained at an amount of 1 to 5 % by weight in an antifouling paint composition (that is, in which a volatile component such as a solvent is included). [Production of Antifouling Paint Composition] Such an antifouling paint composition relating to the present invention may be produced as follows. The antifouling paint composition may be produced by adding zinc sulfide (B) as an antifouling agent to a hydrolyzable copolymer (A) of said copolymer containing a bond of metal salt and the like with the use of a method which has been conventionally known, as appropriate. The antifouling paint composition of the present invention may be produced, for example, by blending a copolymer containing a bond of metal salt or a silyl ester based copolymer as a hydrolyzable copolymer (A), zinc sulfide (B) , zinc oxide, talc and "the other component" as described below simultaneously or in a given sequence, followed by stirring and mixing. An antifouling agent, a thixotropy imparting agent, a plasticizer, an inorganic dehydrating agent (stabilizer), an antisagging and antiprecipitating agent (thickening agent), a coloring pigment, a dye, the other coating film forming component, a solvent (for example, butyl acetate, ethylcyclohexane, xylene), a germicide, a fungicide, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, a heat conduction improver agent, an adhesion imparting agent and the like are added simultaneously or in a given sequence at a given ratio and stirred and mixed, followed by dissolving and dispersing in a solvent. Moreover, when said blended components are stirred and mixed, a conventionally known mixing and stirring equipment, for example, a Ross mixer, a planetary mixer, a versatile Shinagawa mixer and the like is used, as appropriate. As the antisagging and antiprecipitating agents (an thixotropic agent), an organic clay-based and an organic wax-based antisagging and antiprecipitating agent and the like may be mixed at any amount. As such antisagging and antiprecipitating agents, there are mentioned salts such as an organic clay-based Al, Ca or Zn salt of amine, stearic acid, lecithin, alkylsulfonic acid and the like, a polyethylene wax, an amide wax, a hydrogenated castor oil wax based agent, a polyamide wax based agent and a mixture of the salt base agent and the wax based agent, synthetic fine powder silica, an oxygenated polyethylene based wax, among which the polyamide wax, the synthetic fine powder silica, the oxygenated polyethylene based wax and the organic clay-based agent are preferable. Such antisagging and antiprecipitating agents are exemplified by the products under the trade name of, for example, "Disparon305", "Disparon4200-20" and "DisparonA630-20X" and the like produced by Kusumoto Chemicals, Ltd. which are commercially available. As the coating film forming components, a resin other than said copolymer (A) may be contained in a range that is not against to the objective of the present invention. Such "the other coating film forming component" is exemplified by a hardly water-soluble or water-insoluble resin, which includes, for example, acrylic resin, acrylsilicone resin, unsaturated polyester resin, fluorocarbon resin, polybutene resin, silicone rubber, urethane resin (rubber), epoxy resin, polyamide resin, vinyl chloride based copolymer resin, chlorinated rubber (resin) , chlorinated olefin resin, styrene butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarone resin, terpene phenol resin, and petroleum resin and the like. As the water-soluble resin, there are mentioned rosin (for example, trade name of "Rosin WW"), monocarboxylic acid and a salt thereof. The monocarboxylic acid includes, for example, a fatty acid having about 9 to 19 carbon atoms and naphthenic acid. The salt of monocarboxylic acid includes Cu salt, Zn salt, Ca salt and the like. The rosin includes gum rosin, wood rosin and tall oil rosin and the like, any of which may be used in the present invention. These water soluble resins may be used alone or in combination of two or more kinds thereof. In an antif ouling paint of the present invention, various components mentioned above are dissolved or dispersed in a solvent. As the solvent used here, various solvents that are typically blended to the antifouling paint are used which include, for example, an aliphatic-based solvent, an aromatic-based solvent, a ketone-based solvent, an ester-based solvent, an ether-based solvent and the like. Said aromatic-based solvent includes, for example, xylene and tluene and the like, said ketone-based solvent includes, for example, MIBK and the like, and ether-based solvent includes, for example, propylene glycol monomethyl ether, propylene glycol momomethylether acetate (PMAC) and the like. [Antifouling Coating Film, Substrate with Coating Film, etc.] The antifouling coating film according to the present invention is characterized by to be formed from the antifouling paint composition described in any of the above paragraphs. The substrate with the coating film according to the present invention is characterized in that the surface of the substrate is coated with a coating film formed by curing the antifouling paint composition described in any of the above paragraphs. The antifouling substrate according to the present invention is characterized in that the surface of the substrate which comes into contact with marine water or fresh water is coated with a coating film formed by curing the antifouling paint composition described in any of the above paragraphs. As for the antifouling substrate according to the present invention, said substrate as a base is preferably any of submerged structures, outside boards of a ship, fishing nets and fishing implements. A method of forming the coating film on the surface of the substrate according to the present invention is characterized in that the surface of the substrate is coated or impregnated with the antifouling paint composition described in any of the above paragraphs and then cured to form the coating film. An antifouling method of the substrate according to the present invention is characterized in that the surface of the substrate is coated or impregnated with the antifouling paint composition described in any of the above paragraphs and then said antifouling paint is cured to form the antifouling coating film. In the present invention, said substrate as the subject of the antifouling method is preferably any of submerged structures, outside boards of a ship, fishing nets and fishing implements. Explaining in detail, when the antifouling paint composition as mentioned above is applied once or multiple times in accordance with the conventional method to the surface of various formed bodies such as a submerged structure of water supply and drain lines at a thermal and atomic power station, coastal roads, submarine tunnels, coastal facilities, sludge spread prevention film of various ocean civil engineering works such as canals and channels, ships, fishing materials (for example, ropes, fishing nets, fishing equipment, floater, buoy) , a ship, a submerged structure and the like coated with the antifouling coating film having excellent antifouling properties, sustained release properties of the antifouling component over a long period of time, appropriate flexibility even with a thick coating of the composition and excellent crack resistance can be obtained. That is, the antifouling coating film formed by applying and curing such antifouling paint composition according to the present invention on the surface of various formed bodies is excellent in such antifouling properties that it can persistently prevent aquatic organisms such as sea lettuce, barnacle, green string lettuce, serpula, oyster and Bugla neritina from attaching to the surface of the formed bodies for long periods. Even when the material of the ship, etc. is FRP, steel, wood, aluminum alloy and the like, especially said antifouling paint composition adheres well on the surface of these material, In case of a steel vessel or alumina vessel, the antifouling paint of the present invention is applied on the material surface on which a primer, an anticorrosion paint and a binder paint are coated as necessary. In addition, said antifouling paint composition may be overpainted on the existing antifouling coating film surface. Furthermore, for example, if said antifouling paint composition is applied on the surface of submerged structures, an attempt may be made to prevent the attachment of aquatic organisms, thereby making it possible to maintain the function of said structure over a long period of time. If said antifouling paint composition is applied to the fishing nets, the blockage of the mesh of the fishing nets may be prevented and moreover, environmental pollution is not likely to occur. Furthermore, the antifouling paint composition according to the present invention may be directly applied to the fishing nets or may be applied to the surface of a ship or submerged structures and the like which is coated with a base material such as an anticorrosive agent or a primer in advance. In addition, the antifouling paint composition of the present invention may be overpainted as a repair on the surface of the ship (especially the FRP vessels) or submerged structures on which painting with the conventional antifouling paint the antifouling paint composition of the present invention has been already done. The thickness of the antifouling coating film formed on the surface of the ship and submerged structures in this manner is not specifically limited, but, for example, is approximately 30 to 150µm/time. The antifouling coating film or the coating film of the water contacting parts of the ship and submerged structures according to the present invention obtained as mentioned above is formed from the antifouling paint composition as mentioned above and is excellent in long-term antifouling properties against a wide variety of organisms which attach to the ship and submerged structures with less possibility of environmental pollution. Effects of the Invention According to the present invention, there can be provided an antifouling paint composition that may form the antifouling coating film suitable for an ocean vessel which is excellent in antifouling properties with less burden to the environment and is excellent in consumption properties (where the coating film is uniformly consumed at a constant rate over a long period of time) and furthermore is excellent in antifouling properties (where excellent antifouling performance may be maintained for a long period of time) , an antifouling coating film formed from said antifouling paint composition, and a ship, submerged structures, fishing implements or fishing nets coated with said antifouling coating film. Especially when a conventional hydolyzable antifouling paint composition is combined with an organic antifouling agent (for example, a boron-based or pyrithione-based agent) and zinc sulfide, the synergistic effect of the antibacterial effect of zinc sulfide and the improvement of renewability of the coating film is produced, thereby the preventing effect for the attachment of marine organisms, especially algae is significantly improved. Embodiments Hereinafter, the present invention is explained more specifically with reference to the embodiments, but the present invention is not limited thereto. Moreover, in the following embodiments and comparative examples and the like, "parts" represents parts by weight, as long as it is not against to the purpose of the present invention. Furthermore, when the term, "copolymer (A) " and the like is simply used in the present invention including the following tables, it is basically used to represent the resin content which is the coating film forming component. In addition to this, in the case where the heating residue is described and the solid content is indicated for the copolymer (A) and the like, they are also used to mean a resin solution or dispersing solution which contains not only the resin content that is the coating film forming component but also a volatile component such as a solvent. [Production Example 1] (Production of Copolymer (al-1) Containing a Bond of Metal Salt at the Side Chain Terminal) To a four-neck flask equipped with a condenser, a thermometer, a dropping funnel and a stirrer was charged 30 parts by weight of PGM (polypropyleneglycol monomethylether) and 40 parts by weight of xylene, and the solution was heated to 100°C with stirring. And then, to the resultant solution was added dropwisely a mixture comprising a monomer and a polymerization initiator listed in Table 1 at a constant rate from the dropping funnel over 3 hours. After the completion of dropwise addition, to the mixture solution was added dropwisely 1 part by weight of t-butylper oxide and 10 parts by weight of xylene over 2 hours, and after stirring for 2 hours, to the resultant mixture solution was added 20 parts by weight of xylene to obtain the copolymer (al-1) containing a bond of metal salt at the side chain terminal having characteristic values shown in Table 1. The Gardner viscosity and the solid content (%) were evaluated which are physical properties of a reaction mixture containing the resultant copolymer containing a bond of side chain terminal metal salt (which is also referred to as a side chain terminal structure metal salt copolymer) or said copolymer. The results are shown in Table 1. Measurement Conditions of Gardner Viscosity> The Gardner viscosity was measured at the 35 % by weight concentration of the resin content at 25°C in accordance with 4.3 of JIS K7233, as described in Japanese Patent Laid-Open Publication No. 55890/2003. The solid content is referred to as a heating residue at the time when a reaction mixture, a paint and an uncured coating film and the like in which a polymer and a solvent and the like are contained are heated and dried to volatilize the solvent and the like. The heating residue contains a pigment in addition to the resin content and typically becomes a coating film forming composition. In addition, the calculation is made by including a monomer and the like (for example, Table 2), which is contained in the paint and can react to form the resin (the solid content), as the solid content. Measurements of Number Average Molecular Weight (Mn) and Weight Average Molecular Weight (Mw)> The weight average molecular weight (Mw) of a resin such as a metal-containing resin was measured by HLC-8120GPC with two separation columns (α-M) of TSK-gel a Type using DMF (dimethylformamide) to which 20mL of LiBr is blended as an eluent. The weight average molecular weight (Mw) was determined in terms of polystyrene conversion. Furthermore, the number average molecular weight (Mn) of a resin was determined by the above-mentioned GPC in terms of polystyrene conversion. [Production Examples 2 to 3] Except that the blended components were changed as shown in Table 1 in Production Example 1, a side chain terminal structure metal salt copolymers (al-2) to (al-3) were produced in a similar manner to Production Example (al-1). The physical properties of a reaction mixture containing the resultant side chain terminal structure metal salt copolymers or said copolymers were evaluated in a similar manner to Production Example (al-1). The results are shown in Table 1. Best View in Resolution of 1024x768 or later. Enable Javascript for Better Performance. |
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6938-delnp-2007-Abstract-(15-12-2011).pdf
6938-delnp-2007-Claims-(15-12-2011).pdf
6938-DELNP-2007-Correspodence Others-(27-06-2011).pdf
6938-delnp-2007-Correspondence Others-(15-12-2011).pdf
6938-DELNP-2007-Correspondence-Other.pdf
6938-delnp-2007-descripiton (complete).pdf
6938-delnp-2007-Description (Complete)-(15-12-2011).pdf
6938-DELNP-2007-Form-3-(27-06-2011).pdf
6938-delnp-2007-GPA-(15-12-2011).pdf
6938-delnp-2007-Petition-137-(15-12-2011).pdf
| Patent Number | 250603 | ||||||||
|---|---|---|---|---|---|---|---|---|---|
| Indian Patent Application Number | 6938/DELNP/2007 | ||||||||
| PG Journal Number | 03/2012 | ||||||||
| Publication Date | 20-Jan-2012 | ||||||||
| Grant Date | 12-Jan-2012 | ||||||||
| Date of Filing | 07-Sep-2007 | ||||||||
| Name of Patentee | CHUGOKU MARINE PAINTS, LTD. | ||||||||
| Applicant Address | 1-7, MEIJISHINKAI, OHTAKE-SHI, HIROSHIMA 7390652, JAPAN. | ||||||||
Inventors:
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| PCT International Classification Number | C09D 133/00 | ||||||||
| PCT International Application Number | PCT/JP2006/316965 | ||||||||
| PCT International Filing date | 2006-08-29 | ||||||||
PCT Conventions:
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