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    • 专利摘要:
    The antifouling coating composition of the present invention is an antifouling coating composition substantially free of cuprous oxide and organotin, (A) a metal-containing copolymer obtained by copolymerizing a polymerizable unsaturated monomer (a1) containing a metal with a radical polymerizable unsaturated monomer (a2) containing no metal, (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and (C) metal pyrithione compounds It is characterized by containing. According to the present invention, an antifouling coating composition having a low load on the environment, excellent antifouling property, excellent uniformity of the coating film, and excellent long-term antifouling performance of the coating film, an antifouling coating film, a vessel coated with the antifouling coating film, aquatic structures, fishing gear Or fishing nets.
    公开号:KR20040071245A
    申请号:KR10-2004-7009935
    申请日:2002-12-18
    公开日:2004-08-11
    发明作者:오키모토히로유키；무쿠노키야스오；아시다도시히코；오노마사시
    申请人:주고꾸 도료 가부시키가이샤；
    IPC主号:
    专利说明:

    Antifouling paint composition, antifouling paint films, and ships, underwater structures, fishing gear and fishing nets covered with the films}
    [2] The bottoms, underwater structures, and fishing nets are exposed to water for a long time, and their surfaces are attached to and propagate various aquatic organisms, such as oysters, mussels and shellfish, plants such as seaweed, or bacteria. The appearance may be impaired and its function may be impaired.
    [3] In particular, when these aquatic organisms adhere to and propagate on the bottom, surface roughness of the entire ship may increase, resulting in a decrease in ship speed and an increase in fuel efficiency. In addition, in order to remove these aquatic life from the bottom, a lot of effort and work time is required. In addition, bacteria adhere to and propagate in underwater structures, and furthermore, slime (sludgy matter) adheres to them, causing decay, or large adherent organisms in underwater structures such as steel structures. If it adheres and propagates on the surface and damages the anti-corrosion coating film or the like of the underwater structure, the strength or function of the underwater structure is lowered and the life may be remarkably reduced.
    [4] Conventionally, in order to prevent such damage, various antifouling paints are applied to the bottom and the like, and various antifouling paints as described below have been proposed.
    [5] For example, (1): Japanese Patent Laid-Open No. 63-128084 discloses a gas resin having an acid group and a metal salt of a low boiling organic base acid, provided that the metal is a divalent or higher metal having a lower ionization tendency than an alkali metal. ) And antifouling paints containing a metal-containing resin composition obtained by heating a high boiling point monobasic acid by removing the low boiling point organic base out of the system as a vehicle.
    [6] Further, Example 42 of the publication discloses an antifouling paint obtained by mixing tetraphenylborane pyridinium with varnish of copper (meth) acrylate MMA acrylic acid 2-ethylhexyl copolymer. The antifouling paint which mix | blended copper nitrate with the zinc oleate (meth) acrylate, MMA, ethyl acrylate copolymer varnish in Example 43 is disclosed.
    [7] In addition, (2): The applicant of the present application is Japanese Patent Laid-Open No. Hei 11-323209, (a) a (meth) acrylate metal salt copolymer and (b) a triphenyl boron amine represented by the following formula: Complex:
    [8]
    [9] (In said formula, R represents H, a C3-C30 alkyl group, the pyridyl group which may have a substituent, and the aromatic group which may have a substituent.) Or the antifouling coating composition containing pyridine triphenyl boron is proposed.
    [10] (3): An antifouling paint containing a complex composed of triphenylborane and an amine having 6 or more carbon atoms and a hydrolyzable resin is disclosed, and as a hydrolyzable resin, a formula: at the side chain end of a (meth) acrylic resin (CH 2 ) m -COO-ML n (m: an integer of 0 to 2, n: metal atom is number-1, M: zinc, copper, etc., L: alkyl group, carboxyl group, etc.) is mentioned (Japan) See Japanese Patent Application Laid-Open No. 11-302572).
    [11] However, the antifouling coating composition according to any one of the above (1) to (3) contains an antifouling agent such as copper nitrous oxide having a relatively high environmental load, and the resulting coating film is further improved in terms of reducing the environmental load. There was room.
    [12] In addition, Japanese Patent Application Laid-Open No. Hei 11-35877 and Japanese Patent Application Laid-Open No. 2002-12630 disclose antifouling paints using a resin composition containing a metal. It was required.
    [13] For this reason, the coating film is consumed at a constant speed regardless of the coating site over a longer period, it has been required to develop an antifouling coating composition that can maintain excellent antifouling performance for a long time, can be applied to the outer port, and can form an excellent antifouling coating film .
    [14] The present inventor has intensively studied in such a situation, and the specific copolymer (A) containing a metal is used as a resin powder, and 4, 5- dichloro-2-n-octyl-4- is used as an antifouling agent. When the isothiazolin-3-one (B) and the metal pyrithione compound (C) are used in combination, the coating film of the antifouling coating composition obtained has excellent antifouling performance even without compounding cuprous oxide or organotin. The load is small, and the coating film is consumed at a constant speed regardless of the coating area over a long period of time, it can maintain excellent antifouling performance for a long time, it can be applied to external ships, it is difficult to crack or peel off, pyridine-triphenylborane, etc. Compared with the coating film used, it has excellent adhesion and has various performances such as clear color and small discoloration even after water immersion and exposure. And it completed the present invention.
    [15] The present invention is to solve the problems associated with the prior art as described above, the environmental load is small, and the coating film is uniformly consumed at a constant speed over a long period of time (uniform consumption of the coating film), and further maintains excellent antifouling performance for a long time Antifouling coating composition, antifouling coating, antifouling coating, ships coated with the antifouling coating, underwater structures, fishing gear or fishing nets and their antifouling methods The purpose is to provide.
    [1] The present invention relates to an antifouling coating composition, an antifouling coating film, a vessel coated with the antifouling coating film, an underwater structure, fishing gear or a fishing net, and an antifouling method thereof. More specifically, the present invention, the environmental load is small, the coating film is uniformly consumed at a constant speed over a long period of time, and also the antifouling coating composition which can maintain an excellent antifouling performance for a long time and can form an antifouling coating film that can be applied to the outer ship, The present invention relates to an antifouling coating film, a vessel coated with the antifouling coating film, an underwater structure, a fishing gear or a fishing net, and an antifouling method thereof.
    [16] Disclosure of the Invention
    [17] The antifouling coating composition of the present invention is an antifouling coating composition substantially free of cuprous oxide and organic tin.
    [18] (A) a metal-containing copolymer obtained by copolymerizing a polymerizable unsaturated monomer (a1) containing a metal with a radical polymerizable unsaturated monomer (a2) containing no metal,
    [19] (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and
    [20] (C) metal pyrithione compounds
    [21] It is characterized by containing.
    [22] It is preferable that the antifouling coating composition of this invention does not contain a triphenyl borane compound and a tetraphenyl borane compound substantially.
    [23] In the present invention, (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one in an amount of 0.5 to 100 parts by weight relative to 100 parts by weight of the (A) metal-containing copolymer. It is preferable to contain, and it is more preferable to contain in the quantity of 1-50 weight part.
    [24] In this invention, in 100 weight part of antifouling paint compositions, it is preferable to contain (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one in the quantity of 0.1-40 weight part, It is more preferable to contain in the quantity of 0.5-20 weight part.
    [25] The antifouling coating composition of the present invention preferably contains (C) a metal pyrithione compound in an amount of 1 to 90 parts by weight, and in an amount of 5 to 55 parts by weight, based on 100 parts by weight of the (A) metal-containing copolymer. It is more preferable to do.
    [26] In this invention, it is preferable to contain (C) metal pyrithione compound in the quantity of 0.2-40 weight part in 100 weight part of antifouling paint compositions, and it is more preferable to contain it in the quantity of 1-20 weight part.
    [27] It is preferable that the antifouling paint composition of this invention contains (D) zinc oxide further, and contains (D) zinc oxide in the quantity of 5-100 weight part with respect to 100 weight part of said (A) metal containing copolymers. More preferred.
    [28] The antifouling paint composition of the present invention preferably further contains (E) extender pigments selected from the group consisting of talc, silica, mica, clay, calcium carbonate and kaolin.
    [29] In addition, the antifouling coating composition of the present invention further comprises (F) an organic antifouling agent ((B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and (C) metal pyridine). It is preferable to contain a thion compound).
    [30] In this invention, it is preferable that the polymerizable unsaturated monomer (a1) containing a metal is 1 or more types of monomers chosen from the group which consists of a metal (meth) acrylate, a metal di (meth) acrylate, and those low-polymers.
    [31] In this invention, it is preferable that the polymerizable unsaturated monomer (a1) containing a metal is a polymeric compound obtained by making an inorganic metal compound and (meth) acrylic acid react in presence of an alcoholic organic solvent and water, and an inorganic metal compound is zinc More preferably, oxides, hydroxides or chlorides of metals selected from the group consisting of copper and magnesium.
    [32] In addition, in this invention, it is preferable that the polymerizable unsaturated monomer (a1) containing a metal consists of a metal di (meth) acrylate (a11) and the metal containing monomer (a12) represented by following formula (1);
    [33]
    [34] In Formula 1, R 1 is selected from the group consisting of CH 2 = C (CH 3 )-, CH 2 = CH-, HOOC-CH = CH-, and HOOC-CH = C (CH 3 )-, and -COOH Represents an unsaturated bond-containing organic group which may form a metal salt or ester,
    [35] M represents a metal atom,
    [36] L represents an organic acid residue represented by -OCOR 2 (R 2 represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group),
    [37] n represents the number of valence number-1 of the metal M).
    [38] In the present invention, the polymerizable unsaturated monomer (a1) containing a metal preferably contains a metal selected from the group consisting of zinc, copper and magnesium.
    [39] In addition, in this invention, the radically polymerizable unsaturated monomer (a2) which does not contain a metal is a 1 or more types of monomer (a21) chosen from the group which consists of (meth) acrylic acid and (meth) acrylic acid ester represented by following General formula (2). Is preferred;
    [40]
    [41] (Wherein, R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group, a cycloalkyl group, an aryl group.).
    [42] In this invention, it is also preferable that the radically polymerizable unsaturated monomer (a2) which does not contain a metal becomes one or more types of monomers (a21) represented by the said General formula (2), and one or more types of monomers (a22) represented by the following general formula (3). Do;
    [43]
    [44] (Wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkylene group, a cycloalkylene group, an arylene group, and R 7 represents a hydroxyl group, an alkoxyl group, a cycloalkoxyl group or an aryloxyl group.).
    [45] The antifouling coating composition of the present invention is a radically polymerizable unsaturated monomer (a2) containing 2 to 50% by weight of a component unit derived from the polymerizable unsaturated monomer (a1) containing a metal (A) containing a metal. It is preferable that it is a copolymer containing 50 to 98 weight% of the component unit derived from ().
    [46] In the present invention, the metal-containing copolymer (A) is 0.1 to 49.9% by weight of the component unit derived from the metal di (meth) acrylate (a11), derived from the metal-containing monomer (a12) represented by the formula (1) It is preferable that it is a copolymer containing 0.1 to 49.9 weight% of a component unit and 50 to 98 weight% of a component unit derived from the radically polymerizable unsaturated monomer (a2) which does not contain a metal.
    [47] In the present invention, the metal-containing copolymer (A) is 0.1 to 49.9% by weight of the component unit derived from the metal di (meth) acrylate (a11), derived from the metal-containing monomer (a12) represented by the formula (1) 0.1 to 49.9 wt% of the component unit, and 0.1 to 99.9 wt% of the component unit derived from at least one monomer (a21) selected from the group consisting of (meth) acrylate and alkyl (meth) acrylate. It is preferable that it is a copolymer containing 0.1-97.9 weight% of the component units derived from the monomer (a22) shown.
    [48] The antifouling coating of the present invention is formed from the antifouling coating composition of the present invention.
    [49] The ship or the underwater structure of the present invention is coated with a coating film formed from the antifouling coating composition of the present invention.
    [50] The fishing gear or the fishing net of the present invention is coated with a coating film formed from the antifouling coating composition of the present invention.
    [51] The antifouling method of the ship or the underwater structure of the present invention is characterized by coating the surface of the ship or the underwater structure with a coating film of the antifouling coating composition of the present invention.
    [52] The antifouling method of the fishing gear or the fishing net of the present invention is characterized by coating the surface of the fishing net or the fishing net with a coating film made of the antifouling coating composition of the present invention.
    [53] Best Mode for Carrying Out the Invention
    [54] EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated concretely.
    [55] Hereinafter, the antifouling coating composition, the antifouling coating film of the present invention, a ship, an underwater structure, fishing gear or a fishing net covered with the antifouling coating film will be described in detail.
    [56] <Anti-fouling paint composition>
    [57] The antifouling coating composition of the present invention is an antifouling coating composition substantially free of cuprous oxide and organotin, comprising (A) a metal-containing copolymer and (B) 4,5-dichloro-2-n-octyl-4-isothia Zolin-3-one and (C) metal pyrithione compound.
    [58] (A) metal-containing copolymer
    [59] In the present invention, the metal-containing copolymer (A) acts as a substrate for forming a coating film and also has antifouling performance. The metal-containing copolymer (A) used in the present invention is obtained by copolymerizing a polymerizable unsaturated monomer (a1) containing a metal and a radically polymerizable unsaturated monomer (a2) containing no metal.
    [60] -Polymerizable unsaturated monomer containing a metal (a1)
    [61] As a polymerizable unsaturated monomer (a1) containing a metal, what is necessary is just to contain a metal and act as a polymerization monomer, For example, a metal di (meth) acrylate (a11), a metal (meth) acrylate, etc. are mentioned. Moreover, low polymers, such as those dimers and trimers, are also things which have a polymerization activity, and can be used combining these 1 or more types. In addition, in this specification, (meth) acryl means an acryl and / or methacryl, and (meth) acrylate means an acrylate and / or methacrylate.
    [62] As the metal di (meth) acrylate (a11), for example, magnesium acrylate: (CH 2 = CHCOO) 2 Mg, magnesium methacrylate: (CH 2 = C (CH 3 ) COO) 2 Mg, zinc acrylate :( CH 2 = CHCOO) 2 Zn, zinc methacrylate: (CH 2 = C (CH 3 ) COO) 2 Zn, copper acrylate: (CH 2 = CHCOO) 2 Cu, copper methacrylate: (CH 2 = C ( And CH 3 ) COO) 2 Cu. One or more of these may be selected and used. The metal di (meth) acrylate preferably contains a metal selected from the group consisting of zinc, copper, calcium, aluminum and magnesium as the metal, and more preferably contains a metal selected from zinc, copper and magnesium. Do.
    [63] Moreover, as a polymerizable unsaturated monomer (a1) containing a metal, the polymeric compound obtained by making an inorganic metal compound and the compound which has a carboxyl group react is mentioned. Such (a1) is obtained by reacting an inorganic metal compound and a compound having a carboxyl group in the presence of water, more preferably in the presence of an alcohol-based organic solvent and water.
    [64] The method for producing the polymerizable unsaturated monomer (a1) containing such a metal is not particularly limited. For example, the compound containing an inorganic metal compound and a carboxyl group is heated in the presence of an organic solvent and water at a decomposition temperature of the metal salt or less. It can obtain by stirring.
    [65] As the inorganic metal compound, any of those which react with a compound having a carboxyl group to form a metal salt can be used, and examples thereof include oxides of metals such as zinc oxide, aluminum oxide, calcium oxide, cupric oxide, magnesium oxide, and manganese oxide; Hydroxides of metals such as zinc hydroxide, aluminum hydroxide, calcium hydroxide, cupric hydroxide, and magnesium hydroxide; And chlorides of metals such as zinc chloride, aluminum chloride, calcium chloride, cupric chloride, magnesium chloride, and manganese chloride.
    [66] The metal of the inorganic metal compound is selected from metals such as Ib, IIa, IIb, IIIa, IIIb, IVa, IVb, Va, Vb, VIb, VIIb and VIII in the periodic table. An inorganic metal compound may be used independently and may use two or more types together as needed.
    [67] As such inorganic metal compounds, oxides, hydroxides or chlorides of metals selected from the group consisting of zinc, copper, calcium, aluminum and magnesium can be preferably used, and more preferably selected from the group consisting of zinc, copper and magnesium. Preferred are metals, oxides, hydroxides or chlorides.
    [68] When using a compound of copper as an inorganic metal compound, when using a compound of zinc together, since copolymerizability with an acrylic monomer rises, it is preferable.
    [69] Moreover, when the compound of zinc, magnesium, calcium, or aluminum is used, since the resin obtained tends to be excellent in transparency, it is preferable. In particular, the use of a divalent zinc or magnesium compound is preferable because the increase in viscosity can be suppressed at the time of resin production.
    [70] In the case of using a compound of zinc or magnesium, the transparency of the resulting metal-containing copolymer (A) tends to be high and the color tone of the coating film tends to be beautiful, and these compounds have high solubility in organic solvents that are commonly used. It is more preferable because the property tends to be good. Moreover, when the compound of zinc is used, water resistance of the metal-containing copolymer (A) obtained becomes favorable and it is especially preferable.
    [71] Examples of the compound having a carboxyl group include methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, monoalkyl itaconic acid (for example, methyl, ethyl, butyl, 2-ethylhexyl, etc.) and monoalkyl maleate. (For example, methyl, ethyl, butyl, 2-ethylhexyl, etc.) etc. are mentioned, These 1 type, or 2 or more types of combination can be used. As the compound having a carboxyl group, double (meth) acrylic acid is preferably used and methacrylic acid is particularly preferably used.
    [72] When preparing the polymerizable unsaturated monomer (a1) containing a metal using an organic solvent, it is preferable that the organic solvent to be used contains an alcohol type compound. As an alcohol type compound, alcohol solvents, such as ethanol, isopropanol, butanol, and propylene glycol monomethyl ether, are preferable.
    [73] In addition, the organic solvent used in order to obtain (a1) may contain the organic solvent other than an alcoholic compound as needed with an alcoholic compound. Examples of organic solvents other than alcohol compounds include aliphatic hydrocarbon solvents such as pentane, hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ester solvents such as ethyl acetate, butyl acetate and isobutyl acetate, methyl ethyl ketone, Ketone solvents, such as methyl isobutyl ketone and cyclohexanone, etc. are mentioned. In the case where an organic solvent other than an alcohol compound is mixed with an alcohol compound, the alcohol compound is preferably 5% by weight or more, preferably 25% by weight or more in the total amount of the organic solvent. The use of an organic solvent containing an alcohol-based compound in such an amount is preferable because the solubility of the polymerizable unsaturated monomer (a1) containing a metal in the solvent is improved, and crystals are not produced and storage stability is expressed.
    [74] Although metal content in the polymerizable unsaturated monomer (a1) containing a metal changes with kinds of metal, 0.1-60 weight% is preferable and 3-25 weight% is more preferable. If it is 60 weight% or less, since it becomes possible to melt | dissolve in an organic solvent and to mix and polymerize with an acrylic monomer, it is preferable. Moreover, when it is 0.1 weight% or more, since a metal containing polymer (A) can be manufactured efficiently, it is preferable.
    [75] Although the ratio of the inorganic metal compound and the compound which has a carboxyl group at the time of obtaining the polymerizable unsaturated monomer (a1) containing a metal by the above-mentioned method is not specifically limited, The inorganic metal compound is 0.6 with respect to 1 mol of compounds which have a carboxyl group. If it is a molar ratio or less, since the transparency of the metal-containing polymer (A) obtained is excellent, it is preferable. Moreover, since the coating film formed by the antifouling paint obtained when an inorganic metal compound is 0.1 mol or more with respect to 1 mol of compounds which have a carboxyl group is excellent in water resistance, it is preferable.
    [76] When obtaining the polymerizable unsaturated monomer (a1) containing a metal by reaction of an inorganic metal compound and the compound which has a carboxyl group, as mentioned above, the compound containing an inorganic metal compound and a carboxyl group is heated in presence of an organic solvent and water. It is preferable to carry out by stirring. In this reaction, the amount of water (excluding the amount of water generated during the reaction) is 0.01 to 30% by weight, preferably 0.2 to 15% by weight, based on the total amount of the inorganic metal compound, the compound containing the carboxyl group, the organic solvent and the water. Is preferably. Since the polymerizable unsaturated monomer (a1) containing the metal which is a reactant obtained when it is 0.01 weight% or more in water in a reaction system is obtained in solution state, the radical containing no metal and the polymerizable unsaturated monomer (a1) containing a metal Copolymerization with a polymerizable unsaturated monomer (a2) can be performed efficiently.
    [77] When the polymerizable unsaturated monomer (a1) containing a metal is obtained by reacting an inorganic metal compound with a compound having a carboxyl group in the presence of an alcoholic organic solvent and water, the metal is usually contained in the form of a mixture of (a1), the organic solvent and water. It is provided for the copolymerization reaction with the radically polymerizable unsaturated monomer (a2) which does not. In this case, when copolymerizing with (a2), the mixture containing (a1) preferably contains water in the range of 0.01 to 30% by weight, preferably 0.2 to 15% by weight. When the amount of this water is 30% by weight or less, solubility with a radically polymerizable unsaturated monomer (a2) containing no metal such as an acrylic monomer, an organic solvent, or the like becomes good, and copolymerization of (a1) and (a2) can be efficiently performed. have. The water contained in the mixture containing the polymerizable unsaturated monomer (a1) containing this metal may be only water added in the reaction system for preparing (a1), and further includes water added after preparing (a1). You may be. In addition, the amount of water contained in the mixture containing this (a1) is preferably in the range of 0.01 to 5 times, more preferably 0.05 to 3 times (molar ratio), relative to the number of moles of the inorganic metal compound. Preferred at
    [78] As a polymerizable unsaturated monomer (a1) containing such a metal, the compound (a12) represented by following General formula (1) is mentioned, for example.
    [79] Formula 1
    [80]
    [81] In Formula 1, R 1 is selected from the group consisting of CH 2 = C (CH 3 )-, CH 2 = CH-, HOOC-CH = CH-, and HOOC-CH = C (CH 3 )-, and -COOH Represents an unsaturated bond-containing organic group which may form a metal salt or ester,
    [82] M represents a metal atom,
    [83] L represents an organic acid residue represented by -OCOR 2 (R 2 represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group, or the same unsaturated bond-containing organic group as said R 1 ),
    [84] n represents the number of valence-1 of the metal M).
    [85] In the general formula (1), M is preferably magnesium, zinc or copper, and particularly preferably zinc. As the organic acid residue L, monochloroacetic acid, monofluoroacetic acid, propionic acid, octylic acid, verticic acid, isostearic acid, palmitic acid, cresotic acid, α-naphthoic acid, β- Monovalent acids such as naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinolinecarboxylic acid, nitrobenzoic acid, nitronaphthalenecarboxylic acid, pulvic acid The thing derived from an organic acid is mentioned, Among these, a fatty-acid type is preferable.
    [86] Examples of the compound represented by the formula (1) include monochloromagnesium acetate (meth) acrylate, monochloro zinc acetate (meth) acrylate, monochloroacetate (meth) acrylate, and monofluoromagnesium acetate (meth). Acrylate, zinc monofluoroacetate (meth) acrylate, copper monofluoroacetate (meth) acrylate, magnesium propionate (meth) acrylate, zinc propionate (meth) acrylate, copper propionate (meth) acrylate, jade Magnesium titanate (meth) acrylate, octylic acid zinc (meth) acrylate, octylic acid copper (meth) acrylate, magnesium versatate (meth) acrylate, versatate zinc (meth) acrylate, copper versatic acid (meth) Acrylate, magnesium isostearate (meth) acrylate, zinc isostearate (meth) acrylate, iso Copper stearate (meth) acrylate, magnesium palmitate (meth) acrylate, zinc palmitate (meth) acrylate, copper palmitate (meth) acrylate, cresotin magnesium (meth) acrylate, creso Zinc tin (meth) acrylate, cresotin copper (meth) acrylate, α-naphtho magnesium (meth) acrylate, α-naphtho acid zinc (meth) acrylate, α-naphtho acid (meth) acrylate , β-naphtho magnesium (meth) acrylate, β-naphtho zinc (meth) acrylate, β-naphthoic acid (meth) acrylate, magnesium benzoate (meth) acrylate, zinc benzoate (meth) acrylate, Copper benzoate (meth) acrylate, 2,4,5-trichlorophenoxy acetate (meth) acrylate, 2,4,5-trichlorophenoxy zinc (meth) acrylate, 2,4,5- Trichlorophenoxy Acetic Acid (Meth) acrylate, 2,4-dichlorophenoxy acetate (meth) acrylate, 2,4-dichlorophenoxy acetate (meth) acrylate, 2,4-dichlorophenoxy acetate (meth) acrylate , Quinoline carboxylic acid magnesium (meth) acrylate, quinoline carboxylic acid zinc (meth) acrylate, quinoline carboxylic acid copper (meth) acrylate, nitrobenzoic acid magnesium (meth) acrylate, nitrobenzoic acid zinc (meth) acrylic acid Nitrate, copper nitro benzoate (meth) acrylate, nitronaphthalene carboxylic acid magnesium (meth) acrylate, nitronaphthalene carboxylic acid zinc (meth) acrylate, nitronaphthalene carboxylic acid copper (meth) acrylate, magnesium phosphate (Meth) acrylate, zinc phosphate (meth) acrylate, copper phosphate (meth) acrylate, etc. are mentioned.
    [87] As described above, the compound represented by Chemical Formula 1 may be obtained by reacting a compound having an inorganic metal compound with a carboxyl group such as (meth) acrylic acid in the presence of an alcohol-based organic solvent and water, or may be obtained by another production method. .
    [88] The polymerizable unsaturated monomer (a1) containing such a metal may be used individually by 1 type, and may be used in combination of 2 or more types. In this invention, it is especially preferable to use together a metal di (meth) acrylate (a11) and the metal containing monomer (a12) represented by the said Formula (1) as a polymerizable unsaturated monomer (a1) containing a metal.
    [89] Synthesis of the radical, but not containing metallic unsaturated monomers (a2)
    [90] As a radically polymerizable unsaturated monomer (a2) which does not contain the metal copolymerized with said (a1), for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate , 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (2-ethylhexaoxy) ethyl (meth) acrylate, 1-methyl-2-methoxyethyl (meth) acrylic Latex, 3-methoxybutyl (meth) acrylate, 3-methyl-3-methoxybutyl (meth) acrylate, m-methoxyphenyl (meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenylethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenylethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth ) Acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhex (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylic (Meth) acrylic acid ester monomers, such as a rate and glycidyl (meth) acrylate;
    [91] 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl ( Hydroxyl group-containing monomers such as meth) acrylate;
    [92] 2-hydroxyethyl (meth) acrylate and adducts, such as ethylene oxide, propylene oxide, (gamma) -butyrolactone or (epsilon) -caprolactone;
    [93] Dimers or trimers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
    [94] Monomers having a plurality of hydroxyl groups such as glycerol (meth) acrylate; Primary and secondary amino group-containing vinyl monomers such as butylaminoethyl (meth) acrylate and (meth) acrylamide;
    [95] Dimethylaminoethyl (meth) acrylate, Diethylaminoethyl (meth) acrylate, Dimethylaminopropyl (meth) acrylate, Dimethylaminobutyl (meth) acrylate, Dibutylaminoethyl (meth) acrylate, Dimethylaminoethyl Tertiary amino group-containing vinyl monomers such as (meth) acrylamide and dimethylaminopropyl (meth) acrylamide;
    [96] Heterocyclic basic monomers such as vinylpyrrolidone, vinylpyridine and vinylcarbazole;
    [97] You may use vinyl-type monomers, such as styrene, vinyltoluene, (alpha) -methylstyrene, (meth) acrylonitrile, vinyl acetate, and a vinyl propionate.
    [98] In such a radically polymerizable unsaturated monomer (a2) which does not contain a metal, the monomer (a21) which is (meth) acrylic acid or (meth) acrylic acid ester represented by following General formula (2) is preferable.
    [99] Formula 2
    [100]
    [101] (Wherein, R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group, a cycloalkyl group, an aryl group.).
    [102] Moreover, it is also preferable that the radically polymerizable unsaturated monomer (a2) which does not contain a metal used by this invention is a monomer (a22) represented by following General formula (3).
    [103] Formula 3
    [104]
    [105] (Wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkylene group, a cycloalkylene group, an arylene group, and R 7 represents a hydroxyl group, an alkoxyl group, a cycloalkoxyl group or an aryloxyl group.).
    [106] As a monomer (a22) represented by the said General formula (3), for example, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2- (2) -Ethylhexaoxy) ethyl (meth) acrylate, 1-methyl-2-methoxyethylacrylate, 3-methoxybutylacrylate, 3-methyl-3-methoxybutylacrylate, m-methoxyphenyl ( Meth) acrylate, p-methoxyphenyl (meth) acrylate, o-methoxyphenylethyl (meth) acrylate, m-methoxyphenylethyl (meth) acrylate, p-methoxyphenylethyl (meth) acrylic The rate etc. can be mentioned, One or more types of these can be selected suitably, and can be used. As such a monomer (a22), 2-methoxy ethyl acrylate, 3-methoxy butyl acrylate, etc. are more preferable.
    [107] The polymerizable unsaturated monomer (a2) which does not contain such a metal may be used individually by 1 type, and may be used in combination of 2 or more types. In this invention, it is especially preferable to use together the monomer (a21) shown by the said General formula (2) and the monomer (a22) shown by the said Formula (3) as a polymerizable unsaturated monomer (a2) which does not contain a metal.
    [108] · Metal-containing copolymer (A)
    [109] The metal-containing copolymer (A) used in the present invention is obtained by copolymerizing the polymerizable unsaturated monomer (a1) containing the metal described above with a radical polymerizable unsaturated monomer (a2) containing no metal.
    [110] The metal-containing copolymer (A) is not particularly limited, but is a radically polymerizable unsaturated resin containing 2 to 50% by weight, preferably 5 to 40% by weight of a component unit derived from (a1). It is preferable that it is a copolymer containing 50 to 98 weight%, preferably 60 to 90 weight% of the component unit derived from monomer (a2).
    [111] In addition, the metal-containing copolymer (A) used in the present invention contains 0.1 to 49.9% by weight, preferably 1 to 40% by weight of the component unit derived from the metal di (meth) acrylate (a11), A component derived from a radically polymerizable unsaturated monomer (a2) containing 0.1 to 49.9% by weight, preferably 1 to 40% by weight, of a component unit (a12) derived from the metal-containing monomer represented by 1 It is also preferable that it is a copolymer containing 50-98 weight% of units, Preferably 60-90 weight%.
    [112] Further, the metal-containing copolymer (A) used in the present invention contains 0.1 to 49.9% by weight, preferably 1 to 40% by weight of the component unit derived from the metal di (meth) acrylate (a11). A component unit (a12) derived from the metal-containing monomer represented by 1 is contained in an amount of 0.1 to 49.9% by weight, preferably 1 to 40% by weight, and a component unit derived from the monomer (a21) represented by the formula (2) 0.1-97.9 weight%, It is preferable that it is a copolymer containing 0.1-97.9 weight%, Preferably 1-90 weight% of the component unit derived from the monomer (a22) represented by the said Formula (3).
    [113] For example, when using the polymeric compound obtained by making an inorganic metal compound and (meth) acrylic acid react in presence of an alcoholic organic solvent and water as a polymerizable unsaturated monomer (a1) containing a metal, it is this reaction product (a1). ), A mixture of an organic solvent and water, and a radically polymerizable unsaturated monomer (a2) containing no metal, with respect to a total of 100 parts by weight of the mixture and (a2), (a2) is 16 to 97 parts by weight, preferably 40 It is also preferable that it is provided to copolymerization by the weight ratio which becomes -90 weight part, More preferably, it is 60-80 weight part.
    [114] The metal-containing copolymer (A) used in the present invention can be preferably obtained by copolymerizing each copolymerizing component in the above ratio. By copolymerizing in such a ratio, the metal-containing copolymer (A) obtained has an appropriate degree of water resistance and a good hydrolysis property over a long time when forming a coating film, and is excellent in the balance of the crack resistance and hydrolysis resistance of a coating film.
    [115] Although the copolymerization method which manufactures a metal containing copolymer (A) is not specifically limited, For example, the polymerizable unsaturated monomer (a1) containing a metal and the radically polymerizable unsaturated monomer (a2) containing no metal are mixed. Thus, the metal-containing copolymer (A) can be produced by reacting for about 5 to 14 hours at a reaction temperature of about 60 to 180 ° C in the presence of a radical initiator. In this copolymerization reaction, it is also preferable to use a chain transfer agent. As a chain transfer agent, it is preferable to use chain transfer agents other than mercaptan from a compatible viewpoint with the polymerizable unsaturated monomer (a1) containing a metal, For example, a styrene dimer etc. can be used.
    [116] As a copolymerization method, although solution polymerization method, suspension polymerization method, emulsion polymerization method, etc. can be employ | adopted, the solution polymerization method using a general organic solvent has good productivity, and is preferable.
    [117] As an organic solvent, Aromatic hydrocarbons, such as xylene and toluene;
    [118] Aliphatic hydrocarbons such as hexane and heptane;
    [119] Esters such as ethyl acetate and butyl acetate;
    [120] Alcohols such as isopropyl alcohol and butyl alcohol;
    [121] Ethers such as dioxane and diethyl ether;
    [122] Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Etc. can be mentioned.
    [123] As for the metal-containing copolymer (A) used by this invention, it is preferable that the weight average molecular weights (Mw) calculated | required by GPC (gel permeation chromatography) are 1000-20000 normally, Preferably it is about 3000-10000. If the weight average molecular weight is 20000 or less, the viscosity of the copolymer solution does not become too high and gelling of the resin by metal crosslinking in the copolymer resin can be prevented, and if it is 1000 or more, crack resistance when forming a coating film It is preferable because it has sex.
    [124] Although the ratio of the metal-containing copolymer (A) in the antifouling coating composition of the present invention is not particularly limited, for example, the amount of 15 to 30% by weight, preferably about 15 to 25% by weight in the antifouling coating composition. You can do
    [125] (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one
    [126] In the present invention, 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B) is a metal-containing copolymer (A) described above and (C) metal pyrithione compound described later Together, the antifouling coating composition of the present invention is constituted. The coating film made of such an antifouling coating composition has a small environmental load, and exhibits excellent antifouling property and excellent adhesion to a deteriorated coating film surface.
    [127] This component (B) is contained in the quantity of 0.1-40 weight part normally in 100 weight part of antifouling paint compositions of this invention, It is preferable that it is contained in the quantity of 0.5-20 weight part preferably. When the component (B) is contained in the antifouling coating composition of this invention in such quantity, it exists in the tendency for the antifouling property of the coating film obtained to be excellent and to be excellent in adhesiveness. In addition, the component (B) is preferably contained in an amount of 0.5 to 100 parts by weight, preferably 1 to 50 parts by weight with respect to 100 parts by weight of the metal-containing copolymer (A) in view of coating film properties.
    [128] (C) metal pyrithione compounds
    [129] As a metal pyrithione compound (C) used by this invention, the compound represented by following formula (4) is mentioned.
    [130]
    [131] In formula (4), R 8 to R 11 each independently represent hydrogen, an alkyl group, an alkoxy group or a halogenated alkyl group.
    [132] M represents metals such as copper, sodium, magnesium, calcium, barium, lead, iron and aluminum, and zinc is preferred in view of the persistence of the coating film consumption degree.
    [133] n represents the valence of the metal M.
    [134] Such a metal pyrithione compound is used 1 type or in combination of 2 or more types.
    [135] In the present invention, the metal pyrithione compound (C) is usually present in an amount of 1 to 90 parts by weight, preferably 5 to 55 parts by weight, based on 100 parts by weight of the metal-containing copolymer (A) (solid content). It is preferable that it is contained in the antifouling coating composition. When a metal pyrithione compound (C) is contained in such quantity in the antifouling coating composition of this invention, there exists a tendency for the antifouling coating film excellent in antifouling property to be obtained.
    [136] In addition, the metal pyrithione compound (C) is preferably contained in an amount of 0.2 to 40 parts by weight, preferably 1 to 20 parts by weight in 100 parts by weight of the antifouling coating composition of the present invention. When a metal pyrithione compound (C) is contained in such quantity in the antifouling coating composition of this invention, there exists a tendency for the antifouling property of the coating film obtained to be excellent.
    [137] The metal pyrithione compound (C) has a low load on the environment unlike copper oxide and the like, and the metal pyrithione compound (C) and 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one The antifouling coating composition obtained by using (B) in combination is excellent in impregnating property of a coating material, and the coating film is excellent in long-term antifouling property retention performance and the uniform consumption performance of the coating film over a long term, and it is continuous for a long time, such as an external ship line. It can be suitably applied to the application to be used, and it is hard to cause cracks and peeling on the coating film, and can form a coating film having excellent adhesion compared to the case of using pyridine-triphenylborane, etc. It is suitable as an antifouling paint or as an antifouling paint for fishing gear and fishing nets.
    [138] Random ingredient
    [139] The antifouling coating composition of the present invention includes the aforementioned metal-containing copolymer (A), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B) and a metal pyrithione compound (C). Pigments such as zinc oxide (zinc) (D), plasticizers such as chlorinated paraffin, sieving pigments such as talc, inorganic dehydrating agents, antifouling agents other than the above (A) to (C), and especially organic antifouling The various components normally mix | blended with antifouling paints, such as an agent (F), a plasticizer, an anti-sagging, anti-settling agent, the coating film forming component other than the said copolymer (A), and a solvent, may be included.
    [140] <Colored pigment>
    [141] As the pigment, various conventionally known organic and inorganic pigments can be used.
    [142] Examples of the organic pigments include carbon black, phthalocyanine blue, and blue wire.
    [143] Examples of the inorganic pigments include those that are neutral and non-reactive such as titanium bag, bengal (red iron oxide), baryta powder, chalk, iron oxide powder and the like; Basic and reactive with acidic substances in paints such as zinc oxide (ZnO, zinc oxide), white lead, red lead, zinc powder, lead suboxide powder (active pigments) ); Etc. can be mentioned. Moreover, various coloring agents, such as dye, may also be included.
    [144] Particularly, zinc oxide (D) is preferably used, and when zinc oxide (D) is blended, the zinc oxide is 100 parts by weight of the metal-containing copolymer (A) in view of the persistence and adhesion of the resulting coating film. It is preferable that it is contained in the quantity of 5-100 weight part normally, and also in the amount of 0.1-40 weight% in antifouling coating composition.
    [145] Constitutional Pigments (E)
    [146] The extender pigment (E) has a small refractive index and is transparent and uncovered when mixed with oil or varnish. As the extender pigment, for example, calcium carbonate, which is also used as talc, silica, mica, clay, and sedimentation inhibitor , Kaolin, alumina white, white carbon which is also used as a flatting agent, aluminum hydroxide, magnesium carbonate, barium carbonate, barium sulfate, bentonite which is also used as an antisettling agent, and the like. Talc, silica, mica, clay, calcium carbonate and kaolin are preferred.
    [147] These extender pigments (E) may be used alone or in combination of two or more. In addition, the degree of consumption can be adjusted according to the type of extender pigment.
    [148] The extender pigment is usually 0 to 50% by weight, preferably 0 to 30% by weight in the antifouling coating composition in consideration of cost reduction, increase effect, transparency and thickness level of the obtained coating film. It may be included.
    [149] <Inorganic dehydrating agent (stabilizer)>
    [150] The inorganic dehydrating agent (stabilizer) can further improve the storage stability of the antifouling coating composition. Examples of the inorganic dehydrating agent include anhydrous gypsum (CaSO 4 ), a synthetic zeolite-based adsorbent (trade name: Molecular Sieve, etc.), methyl orthoformate, methyl ortho acetate, and the like. Ortho esters, orthoboric acid esters, silicates, isocyanates (trade name: Additive TI), and the like, and anhydrous gypsum and Molecular Sieve are preferably used. These inorganic dehydrating agents can be used 1 type or in combination of 2 or more types.
    [151] <Other Organic Antifouling Agents>
    [152] Antifouling agents include other antifouling agents in addition to the metal-containing copolymer (A), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B) and metal pyrithione compound (C). In particular, the organic antifouling agent (F) or the like may be contained.
    [153] As the organic antifouling agent (F), tetramethylthiuram disulfide, carbamate-based poisons (eg, zinc dimethyldithiocarbamate, manganese-2-ethylenebisdithiocarbamate), 2,4,5,6-tetrachloroyi Sophthalonitrile, N, N-dimethyldichlorophenylurea, 2,4,6-trichlorophenylmaleimide, 2-methylthio-4-t-butylamino-6-cyclopropylamino S triazine, basic copper acetate Can be mentioned.
    [154] Such other organic antifouling agents (F) are usually 1 to 70% by weight, preferably in the antifouling coating composition as the total amount of antifouling agents (B) and (C), including (B) + (C) + (F). May be used in an amount of 5 to 50% by weight.
    [155] In the present invention, copper oxides of borane compounds and inorganic antifouling agents described in JP-A-54-1571, such as triphenylborane compounds such as pyridine-triphenylborane and tetraphenylborane compounds, etc. It is preferable that substantially no etc. are contained.
    [156] <Plasticizer (chlorinated paraffin)>
    [157] Examples of the plasticizer include TCP (tricresyl phosphate), paraffin chloride, polyvinyl ethyl ether, and the like. These plasticizers can be used 1 type or in combination of 2 or more types.
    [158] Although these plasticizers contribute to the improvement of the crack resistance of the coating film (also called "antifouling coating film" in this specification) of the obtained antifouling paint composition, chlorinated paraffin (chlorinated paraffin) is used preferably among these plasticizers.
    [159] The chlorinated paraffin (chlorinated paraffin) may be linear or branched, may be liquid at room temperature, or may be solid (powder), but the average carbon number is preferably 8 to 30, preferably 10 to 26. The number average molecular weight is usually 200 to 1200, preferably 300 to 1100, the viscosity is usually 1 or more (poise / 25 ° C), preferably 1.2 or more (poise / 25 ° C), and its specific gravity is 1.05. It is used preferably that it is -1.80 / 25 degreeC, Preferably it is 1.10-1.70 / 25 degreeC. When such carbon number chlorinated paraffin is used, the coating film with a small crack (crack) and peeling can be formed using the obtained antifouling coating composition. If the carbon number of the chlorinated paraffin is less than 8, the effect of inhibiting cracking may be insufficient. If the carbon number is more than 30, the consumable property (renewability) of the obtained coating film surface may be inferior, and the antifouling property may be inferior. In addition, the chlorination rate (chlorine content) of the chlorinated paraffin is usually 35 to 75%, preferably 35 to 65%. When the chlorinated paraffin of such a chlorination rate is used, the coating film with a small crack (crack) and peeling can be formed using the antifouling coating composition obtained. Examples of such chlorinated paraffins include "Toyoparax 150" manufactured by Tosoh Corporation, "Toyoparax A-70", and the like.
    [160] <Flow prevention / sedimentation inhibitor (concentrate)>
    [161] As a flow prevention and sedimentation inhibitor (thixotropic agent), you may mix | blend in arbitrary amounts except the impairing the storage stability of antifouling paint compositions, such as organic clay. Such flow preventing and antisettling agents include salts such as organic clay-based aluminum, calcium and zinc stearate salts, lecithin salts and alkyl sulfonates, polyethylene waxes, amide waxes, hydrogenated castor oil waxes, polyamide waxes and the like. The mixture, synthetic fine silica, a polyethylene oxide wax, etc. are mentioned, Preferably a polyamide wax, synthetic fine silica, a polyethylene oxide wax, an organoclay system can be used. As such a flow prevention and sedimentation inhibitor, those sold under the trade names of "Disparon A630-20X" in addition to "Disparlon 305" and "Disparon 4200-20" manufactured by Kusumoto Chemicals, Ltd. Can be mentioned.
    [162] <Other coating film forming components>
    [163] The antifouling coating composition of the present invention may contain a resin other than the metal-containing copolymer (A) as a coating film forming component within a range not contrary to the object of the present invention. As such "other coating film forming components", for example, acrylic resin, acrylic silicone resin, unsaturated polyester resin, fluorine resin, polybutene resin, silicone rubber, urethane resin (rubber), polyamide resin, vinyl chloride copolymer resin, Hardly water-insoluble or non-water-soluble resins (hereinafter, egg / bee) such as chlorinated rubber (resin), chlorinated olefin resin, styrene-butadiene copolymer resin, ethylene-vinyl acetate copolymer resin, vinyl chloride resin, alkyd resin, coumarone resin, petroleum resin Also called water-soluble resin).
    [164] More specifically as said vinyl chloride type copolymer resin, For example, a vinyl chloride vinyl acetate copolymer resin, a vinyl chloride vinyl acetate vinyl alcohol copolymer resin, a vinyl chloride vinyl i-butyl ether copolymer resin, a vinyl chloride vinyl propionate And chlorinated copolymer resins and ethylene-vinyl acetate copolymers.
    [165] In this invention, these resin or rubber can be used combining one type or two types or more. In this invention, the said egg / water-insoluble resin and the following water-soluble resin can be used in combination.
    [166] As water-soluble resin, rosin (for example, brand name "rosin WW"), a monocarboxylic acid, and its salt are mentioned. As monocarboxylic acid, a C9-C19 fatty acid and naphthenic acid are mentioned, for example. As a salt of a monocarboxylic acid, a copper salt, a zinc salt, a calcium salt, etc. are mentioned. Rosin includes gum rosin, wood rosin, tall oil rosin and the like, but any of them can be used in the present invention. These water-soluble resins can be used combining one type or two types or more.
    [167] <Solvent>
    [168] In the antifouling paint of the present invention, the above various components are dissolved or dispersed in a solvent. As a solvent used here, various solvents normally mix | blended with antifouling paints, such as an aliphatic type, aromatic type, a ketone type, ester type, and an ether type, are used. As said aromatic solvent, xylene, toluene is mentioned, for example. The ketone solvents include, for example, MIBK. Examples of the ether solvents include propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate (PMAC).
    [169] Preparation of antifouling paint composition
    [170] The antifouling coating composition of the present invention includes the aforementioned metal-containing copolymer (A), 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one (B), metal pyrithione compound (C) and It can manufacture by using a conventionally well-known method suitably using arbitrary components as needed. For example, a metal-containing copolymer (A), 4, 5- dichloro- 2-n-octyl-4- isothiazolin-3-one (B), a metal pyrithione compound (C), and it uses as needed Colored pigments, in particular zinc oxide (D), talc, silica, mica, clay, calcium carbonate, kaolin and other extender pigments (E), inorganic dehydrating agents (stabilizers), antifouling agents in particular organic antifouling agents (F), plasticizers, flow prevention -Precipitating agent, other coating film forming component, solvent (for example, xylene), etc. can be manufactured by adding, stirring, mixing, and disperse | distributing to a solvent at once or in arbitrary order in predetermined ratio.
    [171] Examples of the antifouling coating composition of the present invention include an underwater structure such as a water supply and drainage port of a thermal power plant and a nuclear power plant, a coastal road, a submarine tunnel, a port facility, a canal and a waterway, and a sludge diffusion prevention film of various marine civil works. When applied to the surface of various molded products such as ships, fishery materials (e.g. ropes, fishing nets, fishing gear, floats, buoys) according to the general method once to several times, the antifouling properties are excellent, The antifouling coating film or the underwater structure etc. which can be discharge | released gradually over and which have a moderate degree of flexibility and excellent crack resistance even if it is thickly coated are obtained.
    [172] That is, the antifouling coating film obtained by coating and curing the antifouling coating composition of the present invention on the surface of various molded products includes sea lettuce, barnacle, green laver, serpula, oyster, and moss. It is excellent in antifouling properties such as being able to prevent the attachment of aquatic organisms such as bugula for a long time.
    [173] In particular, the antifouling paint composition adheres well to the surface of these materials even when the material such as ships are FRP, steel, wood, aluminum alloy. In the case of steel boats and aluminum boats, the antifouling paint of the present invention is usually applied to the surface of the base material coated with a primer, anticorrosive paint and, if necessary, a binder paint. In addition, the antifouling coating composition may be overlaid on the surface of an existing antifouling coating film.
    [174] In addition, for example, when the antifouling paint composition is applied to the surface of the underwater structure, it is possible to prevent adhesion of marine organisms, to maintain the function of the structure for a long time, and to the fishing net to prevent the blockage of the fishing net, In addition, there is little concern about environmental pollution.
    [175] In addition, the antifouling coating composition of the present invention may be applied directly to a fishing net or may be applied to a surface of a ship or an underwater structure in which an undercoat such as a rust preventive agent or a primer is applied in advance. Furthermore, the antifouling coating composition of the present invention for repairing the surface of a ship, especially an FRP ship or an underwater structure, which has already been coated with a conventional antifouling paint or has been coated with the antifouling coating composition of the present invention. You can also laugh. Thus, although the thickness of the antifouling coating film formed in the surface of ships, underwater structures, etc. is not specifically limited, For example, it is about 30-150 micrometers / time.
    [176] The antifouling coating film of the present invention obtained as described above, or the coating film of the partial surface in contact with the water of a ship or an underwater structure, is formed of the antifouling coating composition as described above, is less concerned with environmental pollution, and has a wide range of organisms attached to marine and underwater structures. Excellent long-term antifouling properties.
    [177] According to the present invention, the load on the environment is small, the antifouling property is excellent, and the coating film is uniformly consumed at a constant speed over a long period of time, so that the uniform consumption of the coating film is excellent and the antifouling performance of the coating film can be maintained for a long time. It is excellent for use in outbound ships, hardly cracks or peels off, and has excellent adhesiveness compared to the coating film using pyridine-triphenylborane, etc., and is clear in color, less discoloration after confiscation and exposure, and white antifouling paint. It is possible to provide an antifouling coating composition, antifouling coating film, a ship coated with the antifouling coating film, an underwater structure, fishing gear or a fishing net, which can be manufactured and have a wide application field, and can form an antifouling coating film having excellent long-term antifouling properties with excellent performance. Can be.
    [178] When the antifouling coating composition of the present invention is applied and impregnated on the surface of a substrate of a coated object such as a vessel, offshore structure confiscation part, fishing gear, fishing net, and the like, the coating film is formed on the surface thereof, the fouling can be greatly reduced. The useful life can be improved remarkably, and in the antifouling paint composition in which the coloring pigment is compounded, a clear color coating film can be obtained.
    [179] In addition, the antifouling coating composition of the present invention can be dissolved in an organic solvent and is excellent in coating property to a fishing net.
    [180] Ships, underwater structures, fishing gear and fishing nets of the present invention are obtained using the antifouling coating composition of the present invention and have excellent antifouling performance over a long period of time.
    [181] Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples.
    [182] In addition, in a following example, a comparative example, etc., a part means a weight part.
    [183] Preparation Example 1
    [184] (Production of Metal-containing Monomer (a1-1))
    [185] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 85.4 parts of propylene glycol methyl ether (PGM) and 40.7 parts of zinc oxide, and the temperature was raised to 75 ° C while stirring. Subsequently, a mixture of 43.1 parts of methacrylic acid (MAA), 36.1 parts of acrylic acid (AA) and 5 parts of water was added dropwise at a constant velocity from the dropping funnel. After completion of the dropwise addition, the reaction solution became clear from the milky white state. After further stirring for 2 hours, 36 parts of propylene glycol methyl ether was added to obtain a transparent mixture solution (A) containing a metal-containing monomer (a1-1). Solid content (metal containing monomer (a1-1)) in the obtained mixture solution was 44.8 weight%.
    [186] Preparation Example 2
    [187] (Production of Metal-containing Monomer (a1-2))
    [188] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 24.3 parts of n-butanol (nBuOH), 61.1 parts of xylene, and 40.7 parts of zinc oxide, and the temperature was raised to 75 ° C while stirring. Subsequently, a mixture of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 5 parts of water was added dropwise at a constant velocity from the dropping funnel. After completion of the dropwise addition, the reaction solution became clear from the milky white state. After stirring for further 2 hours, 36 parts of xylene was added to obtain a transparent mixture solution (B) containing a metal-containing monomer (a1-2). Solid content (metal containing monomer (a1-2)) in the obtained mixture solution was 44.9 weight%.
    [189] Preparation Example 3
    [190] (Preparation of metal-containing monomer (a1-3))
    [191] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 85.4 parts of propylene glycol methyl ether and 46.8 parts of zinc oxide, and the temperature was raised to 75 ° C while stirring. Next, the mixture which consists of 46.1 parts of methacrylic acid, 36.1 parts of acrylic acid, and 5 parts of water was dripped at constant velocity from the dropping funnel. After completion of the dropwise addition, the reaction solution became translucent from the milky white state. After further stirring for 4 hours, 43.5 parts of propylene glycol methyl ether was added to obtain a slightly turbid mixture solution (C) containing a metal-containing monomer (a1-3). Solid content (metal containing monomer (a1-3)) in the obtained mixture solution was 44.9%.
    [192] Preparation Example 4
    [193] (Preparation of metal-containing monomer (a1-4))
    [194] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 70 parts of propylene glycol methyl ether, 15.4 parts of water, and 40.7 parts of zinc oxide, and heated to 75 ° C while stirring. Subsequently, a mixture of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 20.6 parts of water was added dropwise at a constant velocity from the dropping funnel. After completion of the dropwise addition, the reaction solution became clear from the milky white state. After stirring for further 2 hours, 20.4 parts of propylene glycol methyl ether was added to obtain a transparent mixture solution (D) containing a metal-containing monomer (a1-4). Solid content (metal containing monomer (a1-4)) in the obtained mixture solution was 44.2%.
    [195] Preparation Example 5
    [196] (Preparation of metal-containing monomer (a1-5))
    [197] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 85.4 parts of propylene glycol methyl ether and 20.2 parts of magnesium oxide, and the temperature was raised to 75 ° C while stirring. Subsequently, a mixture of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 5 parts of water was added dropwise at a constant velocity from the dropping funnel. After completion of the dropwise addition, the reaction solution became clear from the milky white state. After further stirring for 2 hours, 11 parts of propylene glycol methyl ether was added to obtain a transparent mixture solution (E) containing a metal-containing monomer (a1-5). Solid content (metal containing monomer (a1-5)) in the obtained mixture solution was 44.6%.
    [198] Preparation Example 6
    [199] (Preparation of metal-containing monomer (a1-6))
    [200] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 85.4 parts of propylene glycol methyl ether, 40.5 parts of zinc oxide, and 0.2 parts of cupric oxide, and heated to 75 ° C while stirring. Subsequently, a mixture of 43.1 parts of methacrylic acid, 36.1 parts of acrylic acid and 5 parts of water was added dropwise at constant velocity from the dropping funnel. After completion of dropping, the reaction solution turned green. After stirring for further 2 hours, 11 parts of propylene glycol methyl ether was added to obtain a transparent mixture solution (F) containing a metal-containing monomer (a1-6). Solid content (a1-6) in the obtained mixture solution was 44.9%.
    [201] Preparation Example 7
    [202] (Preparation of metal-containing copolymer (A-1))
    [203] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 57 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 1 part of methyl methacrylate, 66.2 parts of ethyl acrylate, 5.4 parts of 2-methoxyethyl acrylate, 52 parts of the mixture solution (A) obtained in Preparation Example 1, 10 parts of xylene, and a chain transfer agent (Nippon) 1 part of Nofmer MSD manufactured by Oil & Fats Co., Ltd., 2.5 parts AIBN (Azobisisobutyronitrile, Japan Hydrazine Company, Inc.), AMBN (Azobismethylbutyronitrile, Japan Hydrazine Company , Inc.) A 7-part clear mixture was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and stirred for an additional 1 hour and 30 minutes, followed by addition of 4.4 parts of xylene, followed by heating residue 45.6% and Gardner viscosity-Y. A resin composition containing no insoluble matter and a light yellow transparent metal-containing copolymer (A-1) was obtained.
    [204] Preparation Example 8
    [205] (Preparation of metal-containing copolymer (A-2))
    [206] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 60 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 10 parts of methyl methacrylate, 62.6 parts of ethyl acrylate, 5.4 parts of 2-methoxyethyl acrylate, 40 parts of the mixture solution (A) obtained in Preparation Example 1, 10 parts of xylene, and a chain transfer agent (Nippon) A transparent mixture consisting of 1 part of Novoma MSD) manufactured by Oil & Fats Co., Ltd., 2.5 parts of AIBN, and 5.5 parts of AMBN was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, followed by stirring for an additional 1 hour and 30 minutes, followed by addition of 8 parts of xylene, without insoluble matter having a heating residue of 46.1% and a Gardner viscosity of + V. A resin composition containing a pale yellow transparent metal-containing polymer (A-2) was obtained.
    [207] Preparation Example 9
    [208] (Preparation of metal-containing copolymer (A-3))
    [209] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 57 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 14.6 parts of methyl methacrylate, 52.6 parts of ethyl acrylate, 7.5 parts of n-butyl acrylate, 47.4 parts of the mixture solution (A) obtained in Preparation Example 1, 10 parts of xylene, and a chain transfer agent (Nippon Oil & A clear mixture of 1 part of Nova MSD) manufactured by Fats Co., Ltd., 2.5 parts of AIBN, and 8.5 parts of AMBN was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and after stirring for an additional 1 hour and 30 minutes, 6.9 parts of xylene was added, and there was no insoluble matter having a heating residue of 45.8% and a Gardner viscosity -Z2. A resin composition containing a pale yellow transparent metal-containing polymer (A-3) was obtained.
    [210] Preparation Example 10
    [211] (Preparation of metal-containing copolymer (A-4))
    [212] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 61 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 18 parts of methyl methacrylate, 61 parts of ethyl acrylate, and 37.8 parts of a mixture (A) obtained in Preparation Example 1, 10 parts of xylene, and a chain transfer agent (Nippon Oil & Fats Co., Ltd. A transparent mixture consisting of 1 part MSD), 2.5 parts AIBN, and 7 parts AMBN was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and after stirring for an additional 1 hour and 30 minutes, 8.2 parts of xylene was added, and there were no insoluble matters having a heating residue of 46.0% and a Gardner viscosity + T. A resin composition containing a pale yellow transparent metal-containing polymer (A-4) was obtained.
    [213] Preparation Example 11
    [214] (Preparation of metal-containing copolymer A-5)
    [215] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 57 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 5 parts of methyl methacrylate, 64.9 parts of ethyl acrylate, 5.4 parts of 2-methoxyethyl acrylate, 40 parts of the mixture solution (A) obtained in Production Example 1, and the mixture solution obtained in Production Example 5 ( E) 6 parts, 10 parts of xylene, 1 part of a chain transfer agent (Noffma MSD manufactured by Nippon Oil & Fats Co., Ltd.), 2.5 parts of AIBN, and 6 parts of AMBN were added dropwise at a constant rate for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and after stirring for an additional 1 hour and 30 minutes, 7.7 parts of xylene was added, and there were no insoluble matters having a heating residue of 46.2% and a Gardner viscosity of + U. A resin composition containing a pale yellow transparent metal-containing copolymer (A-5) was obtained.
    [216] Preparation Example 12
    [217] (Preparation of metal-containing copolymer (A-6))
    [218] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 57 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 1 part of methyl methacrylate, 66.2 parts of ethyl acrylate, 5.4 parts of 2-methoxyethyl acrylate, 52 parts of the mixture solution (F) obtained in Production Example 6, 10 parts of xylene, and a chain transfer agent (Nippon) A green phosphorus mixture consisting of 1 part of Nova MSD), 2.5 parts of AIBN, and 7 parts of AMBN manufactured by Oil & Fats Co., Ltd. was added dropwise at 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and stirred for an additional 1 hour and 30 minutes, followed by addition of 4.4 parts of xylene, without insoluble matter having a heating residue of 45.2% and a Gardner viscosity of + V. A resin composition containing a green metal-containing copolymer (A-6) was obtained.
    [219] Preparation Example 13
    [220] (Preparation of metal-containing copolymer (A-7))
    [221] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 15 parts of propylene glycol methyl ether and 61 parts of xylene and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 49.55 parts of methyl methacrylate, 50 parts of ethyl acrylate, and the mixture (A) obtained in Preparation Example 1 were added dropwise at a constant velocity for 4 hours to 1 part of AIBN, 2.5 parts of AIBN, and 2 parts of AMBN. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and after stirring for an additional 1 hour and 30 minutes, 38.45 parts of xylene was added, and there was no insoluble matter having 44.7% of heating residue and Gardner viscosity + B. A resin composition containing a transparent metal-containing copolymer (A-7) was obtained.
    [222] Preparation Example 14
    [223] (Preparation of metal-containing copolymer (A-8))
    [224] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 61 parts of xylene, and 4 parts of ethyl acrylate, and the temperature was raised to 100 ° C while stirring. Subsequently, from the dropping funnel, 18 parts of methyl methacrylate, 61 parts of ethyl acrylate, and 37.8 parts of a mixture solution (B) obtained in Preparation Example 2, 10 parts of xylene, and a chain transfer agent (Nippon Oil & Fats Co., Ltd. A transparent mixture consisting of 1 part MSD), 2.5 parts AIBN, and 7 parts AMBN was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and further stirred for 1 hour and 30 minutes, followed by addition of 8.2 parts of xylene, without insoluble matter having a heating residue of 46.2% and a Gardner viscosity of + Y. A resin composition containing a pale yellow transparent metal-containing polymer (A-8) was obtained.
    [225] Preparation Example 15
    [226] (Preparation of metal-containing copolymer (A-9))
    [227] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel, and a stirrer was charged with 15 parts of propylene glycol methyl ether, 57 parts of xylene, and 4 parts of ethyl acrylate and heated to 100 ° C while stirring. Subsequently, from the dropping funnel, 1 part of methyl methacrylate, 64.9 parts of ethyl acrylate, 5.4 parts of 2-methoxyethyl acrylate, 55 parts of the mixture solution (C) obtained in Preparation Example 3, 10 parts of xylene, and a chain transfer agent (Nippon) A transparent mixture consisting of 1 part of Novoma MSD) manufactured by Oil & Fats Co., Ltd., 2.5 parts of AIBN, and 7.5 parts of AMBN was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and further stirred for 1 hour and 30 minutes, followed by addition of 3.1 parts of xylene to slightly turbid pale yellow color having a heating residue of 46.3% and a Gardner viscosity of + W. A resin composition containing a metal-containing polymer (A-9) was obtained.
    [228] Preparation Example 16
    [229] (Preparation of metal-containing copolymer (A-10))
    [230] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 46.8 parts of propylene glycol methyl ether, 25.2 parts of xylene, and 4 parts of ethyl acrylate and heated to 90 ° C while stirring. Subsequently, 52 parts of mixed solution (D) obtained in the preparation example 4, 1 part of methyl methacrylates, 66.2 parts of ethyl acrylates, 5.4 parts of 2-methoxyethyl acrylates, and 10 parts of propylene glycol methyl ethers from a dropping funnel A transparent mixture of 1 part transfer agent (Noffma MSD manufactured by Nippon Oil & Fats Co., Ltd.), 2.5 parts AIBN, and 8 parts AMBN was added dropwise at constant speed for 6 hours. After completion of the dropwise addition, 0.5 part of t-butylperoctoate and 7 parts of xylene were added dropwise for 30 minutes, and then heated to 100 ° C., and further stirred for 1 hour, followed by addition of 4.4 parts of xylene, followed by heating residue 45.9% and having a Gardner viscosity of + V. A resin composition containing a slightly turbid pale yellow metal-containing polymer A-10 was obtained.
    [231] In Table 1, the filling amount (molar ratio) of the reaction material preparation of manufacture examples 1-6, the solvent amount in the mixture solution containing a reactant, content (weight%), and solid content of the water were described.
    [232] Table 2 also describes the filling amount (weight ratio), the viscosity (Gardner viscosity), the solid content (%) and the molecular weight (MW) of the resin when the metal-containing copolymer of Preparation Examples 7 to 16 were prepared.
    [233] In addition, the molecular weight of resin was measured by HLC-8120GPC using 2 TSK-gel (alpha) type separation columns ((alpha) -M) using DMF (dimethylformamide) which added 20 mM LiBr as an eluent. The weight average molecular weight was calculated | required as polystyrene conversion.
    [234]
    [235]
    [236] Production Examples 17-29
    [237] (Production of Metal-containing Copolymers (A-11) to (A-23))
    [238] A four-hole flask equipped with a cooler, a thermometer, a dropping funnel and a stirrer was charged with 30 parts by weight of PGM (propylene glycol methyl ether) and 40 parts by weight of xylene and heated to 100 ° C while stirring. Subsequently, the mixture of the monomer and polymerization initiator shown in Table 3 was dripped at constant speed from the dropping funnel for 3 hours. After completion of the dropwise addition, 1 part by weight of t-butylperoctoate and 10 parts by weight of xylene were added dropwise for 2 hours, and further stirred for 2 hours, followed by addition of 20 parts by weight of xylene to obtain a metal-containing copolymer having the characteristic values shown in Table 3 (A The solution containing -11)-(A-23) was obtained.
    [239]
    [240] Examples 1-65, Comparative Examples 1-44
    [241] Using the resin compositions containing the metal-containing copolymers (A-1) to (A-23) obtained in Production Examples 7 to 29, respectively, the antifouling coating compositions of the compound compositions shown in Tables 4 to 13 were prepared by a general method. It prepared.
    [242] The antifouling coating composition of the compound composition shown in Tables 4 to 12 is 20 micrometers thick, 150 micrometers thick, respectively. A test plate was prepared by coating and drying the sand blasted steel plate (length: 30 cm x width: 10 cm x thickness: 0.32 cm) coated to a thickness of 75 μm so as to have a dry film thickness of 100 μm. It was.
    [243] This test plate was immersed for 12 months in Hiroshima Bay in Hiroshima Bay, and the attachment area (%) of attached organisms was examined every month.
    [244] The results are shown together in Tables 4 to 12.
    [245] In addition, each substance shown in a compounding composition in Table 4-Table 12 represents the following goods, etc., respectively.
    [246] , Chlorinated paraffins:
    [247] "Toyo Parax 150" (average number of carbon: 14.5, chlorine content (quantity) 50%, viscosity: 12 poise / 25 degreeC, specific gravity: 1.25 / 25 degreeC, product made by Tosoh Corporation)
    [248] Zinc oxide: trade name "zinc white No. 3" (Kyushu Hakusui claim KK)
    [249] · Talc: trade name "TTK Talc" (Takehara Kagaku Kogyo KK claim)
    [250] , Red iron oxide: trade name "Wenger go getko (Bengara Gekko) BB" (Nippon Bengara Kogyo Co., Ltd claim.)
    [251] , Titanium white: trade name "R-5N titanium white" (Sakai Chemical Industry Co., Ltd. No.)
    [252] Lotan, Chemistry copper (copper rhodanide): Nippon Kagaku Sangyo Co., Ltd. The
    [253] , Zinc dimethyl dithiocarbamate:
    [254] `` Sanceler PZ '' (manufactured by Sanshin Chemical Industry Co., Ltd.)
    [255] - 2-methylthio -t- butyl-6-cyclopropylamino-triazine -S-:
    [256] Product name "irgarol (Irgarol) # 105" (product made in Ciba-Geigy company)
    [257] 2,4,5,6- tetrahydro-chloroisatin soap phthaloyl nitrile:
    [258] `` Marineside (Marincide C) '' (product made in San Nopco Limited)
    [259] · N, N- dimethyl dichlorophenyl urea: "DCMU" (Hodogaya Chemical Co., Ltd. No.)
    [260] · N- (dichloro-methylthio-fluorophenyl) phthalimide:
    [261] `` Preventol A-3 '' (made by Bayer Japan)
    [262] · N, N'- dimethyl -N'- phenyl- (dichloro methylthio with N- fluorophenyl) sulfamide:
    [263] `` Preventol A-4S '' (product made by Bayer Japan)
    [264] , Tetramethyl thiuram disulfide:
    [265] Sansella TT (manufactured by Sanshin Chemical Industry Co., Ltd.)
    [266] , 6-trichloro-phenyl maleimide:
    [267] `` IT-354 '' (manufactured by Ihara chemical Industry Co., Ltd.)
    [268] , 3,5, 6-tetrachloro-4- (methylsulfonyl) pyridine:
    [269] `` Densil S100 '' (manufactured by Avecia Co., Ltd.)
    [270] , 3-iodo-2-propynyl butyl carbamate:
    [271] `` TROYSAN POLYPHASE P100 '' (product made by TROY company)
    [272] Di-iodomethyl--p- tolyl sulfone:
    [273] `` Ami 48 '' (Abbott, Inc.)
    [274] Bis dimethyl dithio carbamoyl zinc ethylene bis dithiocarbamate:
    [275] `` TOC-3204 '' (manufactured by Tokyo Organic Chemical Industries, Ltd.)
    [276] , Zinc ethylene Beastie O carbamate:
    [277] `` Zineb '' (manufactured by Tokyo Organic Chemical Industries, Ltd.)
    [278] · Pyridine triphenylboron:
    [279] `` PK Boron '' (manufactured by Hokko Chemical Industry Co., Ltd.)
    [280] - 2-pyridine thiol-1-oxide zinc salt:
    [281] Product name "AF-Z" (manufactured by Yoshitomi Fine Chemical, Ltd.)
    [282] - 2-pyridine thiol-1-oxide copper salt:
    [283] "Copper pyrithione" (product made in Olin Ltd.)
    [284] , 4,5-dichloro -2-n- octyl-4-isothiazolin-3-one:
    [285] `` Sine-Nine 211 '' (product made by Rohm and Haas Company)
    [286] · Cuprous oxide:
    [287] 8 micrometers of average particle diameters, brand name "NC-801" (made by Nippon Chemical Industries Co., Ltd.)
    [288] , Oxidized polyethylene wax:
    [289] "Disparon 4200-20" (Dispal 4200-20X) (manufactured by Kusumoto Chemicals, Ltd.), 20% xylene paste.
    [290] · Aliphatic amide wax:
    [291] "Disparon A630-20X" (Dispal A630-20X) (manufactured by Kusumoto Chemicals, Ltd.), 20% xylene paste.
    [292] · Propylene glycol monomethyl ether:
    [293] `` Kuraray PGM '' (Kuraray PGM) (manufactured by Kuraray Co., Ltd .; solvent)
    [294] Evaluation criteria are as follows.
    [295] Evaluation standard
    [296] <Evaluation criteria of adhesion area of marine organisms (Political antifouling criteria)>
    [297] 5 points… … Attachment area of sea creatures is 0%.
    [298] 4 points… … Attachment area of marine organisms exceeds 0% and below 5%.
    [299] 3 points… … Attachment area of marine organisms exceeds 5% and below 10%.
    [300] 2 points… … Attachment area of marine organisms exceeds 10% and 25% or less.
    [301] 1 point… … Attachment area of marine organisms exceeds 25% and less than 50%.
    [302] 0 points… … Attachment area of marine organisms exceeds 50%.
    [303] <Adhesion with deteriorated antifouling coating film>
    [304] Adhesion with a deteriorated antifouling coating film is applied to each of the following antifouling coatings on a test plate, and immersed in seawater for 1 year. After each coating was formed to have a dry film thickness of 100 µm, it was immersed in seawater and evaluated six months later by the "JIS K-5400X Cut Tape Method". Here, the existing antifouling paints used for the test include "Chugoku AF", "Ravax AF", "Vinyl AF", "Marine Star 10 Kai", "AF Sea Flo Z-100 LEHS", "Sea Grandprix 500", "Sea Grand Prix 700" and "Sea Grand Prix 1000" (all manufactured by Chugoku Marine Paints, Ltd.).
    [305] <Measuring Film Consumption>
    [306] An iron substrate having a size of 170 mm (length) x 70 mm (width) x 4.5 mm (thickness) was prepared and bent in the longitudinal direction to R = 500 mm (bending radius), and the square of the substrate was turned into a rotating drum. A mounting screw hole was formed to make a sand blasted iron plate.
    [307] After applying several layers of shop primer, tar epoxy paint, and vinyl paint to the curved protruding surface of the sand blasted iron plate sequentially by spray coating, various test-providing paints were coated (dry film thickness of 200 mu m).
    [308] The test plate was mounted on a rotary drum of a rotary test raft installed in Hiroshima Ken Kureman, and rotated at a rotation speed of 15 knots. The test film was lifted from the sea every month to measure the film thickness to measure the film consumption rate.
    [309]
    [310]
    [311]
    [312]
    [313]
    [314]
    [315]
    [316]
    [317]
    权利要求:
    Claims (29)
    [1" claim-type="Currently amended] As an antifouling coating composition substantially free of cuprous oxide and organotin,
    (A) a metal-containing copolymer obtained by copolymerizing a polymerizable unsaturated monomer (a1) containing a metal with a radical polymerizable unsaturated monomer (a2) containing no metal,
    (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and
    (C) metal pyrithione compounds
    An antifouling paint composition comprising a.
    [2" claim-type="Currently amended] The antifouling coating composition according to claim 1, which is substantially free of a triphenylborane compound and a tetraphenylborane compound.
    [3" claim-type="Currently amended] (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one of Claim 1 or 2 with respect to 100 weight part of said (A) metal containing copolymers. An antifouling coating composition, characterized by containing in an amount of ˜100 parts by weight.
    [4" claim-type="Currently amended] The method according to claim 1 or 2, wherein (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is added to 100 parts by weight of the (A) metal-containing copolymer. An antifouling coating composition, characterized in that contained in an amount of ˜50 parts by weight.
    [5" claim-type="Currently amended] (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is 0.1-40 in any one of Claims 1-4 in 100 weight part of antifouling paint compositions. An antifouling coating composition, characterized by containing in an amount of parts by weight.
    [6" claim-type="Currently amended] (B) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one is 0.5-20 in any one of Claims 1-4 in 100 weight part of antifouling paint compositions. An antifouling coating composition, characterized by containing in an amount of parts by weight.
    [7" claim-type="Currently amended] The antifouling according to any one of claims 1 to 6, wherein (C) the metal pyrithione compound is contained in an amount of 1 to 90 parts by weight based on 100 parts by weight of the (A) metal-containing copolymer. Paint compositions.
    [8" claim-type="Currently amended] The antifouling according to any one of claims 1 to 6, wherein (C) the metal pyrithione compound is contained in an amount of 5 to 55 parts by weight based on 100 parts by weight of the (A) metal-containing copolymer. Paint compositions.
    [9" claim-type="Currently amended] The antifouling coating composition according to any one of claims 1 to 8, wherein (C) the metal pyrithione compound is contained in an amount of 0.2 to 40 parts by weight in 100 parts by weight of the antifouling coating composition.
    [10" claim-type="Currently amended] The antifouling coating composition according to any one of claims 1 to 8, wherein (C) the metal pyrithione compound is contained in an amount of 1 to 20 parts by weight in 100 parts by weight of the antifouling coating composition.
    [11" claim-type="Currently amended] (D) Zinc oxide is contained, The antifouling coating composition in any one of Claims 1-10 characterized by the above-mentioned.
    [12" claim-type="Currently amended] The antifouling coating composition according to claim 11, wherein (D) zinc oxide is contained in an amount of 5 to 100 parts by weight based on 100 parts by weight of the (A) metal-containing copolymer.
    [13" claim-type="Currently amended] The antifouling coating composition according to any one of claims 1 to 12, which contains (E) a extender pigment selected from the group consisting of talc, silica, mica, clay, calcium carbonate and kaolin.
    [14" claim-type="Currently amended] The organic antifouling agent according to any one of claims 1 to 13, wherein (F) 4,5-dichloro-2-n-octyl-4-isothiazolin-3-one and (C) ) Except for a metal pyrithione compound).
    [15" claim-type="Currently amended] 15. The polymerizable unsaturated monomer (a1) according to any one of claims 1 to 14, wherein the polymerizable unsaturated monomer (a1) is selected from the group consisting of metal (meth) acrylates, metal di (meth) acrylates and low polymers thereof. It is at least one type of monomer, The antifouling coating composition characterized by the above-mentioned.
    [16" claim-type="Currently amended] The polymerizable unsaturated monomer (a1) containing a metal is a polymeric compound as described in any one of Claims 1-14 obtained by making an inorganic metal compound and (meth) acrylic acid react in presence of an alcoholic organic solvent and water. Antifouling coating composition, characterized in that.
    [17" claim-type="Currently amended] The antifouling coating composition according to claim 16, wherein the inorganic metal compound is an oxide, hydroxide or chloride of a metal selected from the group consisting of zinc, copper and magnesium.
    [18" claim-type="Currently amended] 18. The polymerizable unsaturated monomer (a1) according to any one of claims 1 to 17, wherein the polymerizable unsaturated monomer (a1) comprises a metal di (meth) acrylate (a11) and a metal-containing monomer (a12) represented by the following formula (1). Antifouling coating composition, characterized in that;
    Formula 1

    In Formula 1, R 1 is selected from the group consisting of CH 2 = C (CH 3 )-, CH 2 = CH-, HOOC-CH = CH-, and HOOC-CH = C (CH 3 )-, and -COOH Represents an unsaturated bond-containing organic group which may form a metal salt or ester,
    M represents a metal atom,
    L represents an organic acid residue represented by -OCOR 2 (R 2 represents an alkyl group, a cycloalkyl group, an aromatic hydrocarbon group which may have a substituent, an aralkyl group),
    n represents the number of valence-1 of the metal M).
    [19" claim-type="Currently amended] The antifouling coating composition according to any one of claims 1 to 18, wherein the polymerizable unsaturated monomer (a1) containing a metal contains a metal selected from the group consisting of zinc, copper and magnesium.
    [20" claim-type="Currently amended] The radically polymerizable unsaturated monomer (a2) which does not contain a metal is selected from the group which consists of (meth) acrylic acid and (meth) acrylic acid ester represented by following General formula (2). An antifouling coating composition comprising one or more types of monomers (a21);
    Formula 2

    (Wherein, R 3 represents a hydrogen atom or a methyl group, R 4 represents an alkyl group, a cycloalkyl group, an aryl group.).
    [21" claim-type="Currently amended] The radically polymerizable unsaturated monomer (a2) which does not contain a metal is one or more types of monomers (a21) represented by following formula (2), and one type represented by following formula (3) in any one of Claims 1-19. An antifouling coating composition comprising the above monomers (a22);
    Formula 2

    (Wherein R 3 represents a hydrogen atom or a methyl group, and R 4 represents an alkyl group, a cycloalkyl group, or an aryl group.)
    Formula 3

    (Wherein R 5 represents a hydrogen atom or a methyl group, R 6 represents an alkylene group, a cycloalkylene group, an arylene group, and R 7 represents a hydroxyl group, an alkoxyl group, a cycloalkoxyl group or an aryloxyl group.).
    [22" claim-type="Currently amended] The metal-containing copolymer (A) according to any one of claims 1 to 21, which contains 2 to 50% by weight of a component unit derived from the polymerizable unsaturated monomer (a1) containing a metal and does not contain a metal. An antifouling coating composition comprising: 50 to 98% by weight of a component unit derived from a radical polymerizable unsaturated monomer (a2).
    [23" claim-type="Currently amended] 19. The method according to claim 18, wherein the metal-containing copolymer (A) is 0.1 to 49.9% by weight of the component unit derived from the metal di (meth) acrylate (a11), derived from the metal-containing monomer (a12) represented by Chemical Formula 1 above. An antifouling coating composition comprising 0.1 to 49.9% by weight of a component unit, and 50 to 98% by weight of a component unit derived from a radically polymerizable unsaturated monomer (a2) containing no metal.
    [24" claim-type="Currently amended] 22. The method according to claim 21, wherein the metal-containing copolymer (A) is 0.1 to 49.9% by weight of the component unit derived from the metal di (meth) acrylate (a11), derived from the metal-containing monomer (a12) represented by Formula 1 above. 0.1 to 49.9% by weight of the component unit, 0.1 to 99.9% by weight of the component unit derived from the monomer (a21) represented by the formula (2) and 0.1 to 4 to the component unit derived from the monomer (a22) represented by the formula (3) An antifouling coating composition comprising 97.9% by weight of a copolymer.
    [25" claim-type="Currently amended] The antifouling coating film formed from the antifouling coating composition of any one of Claims 1-24.
    [26" claim-type="Currently amended] A ship or an underwater structure, which is coated with a coating film formed from the antifouling coating composition according to any one of claims 1 to 24.
    [27" claim-type="Currently amended] The fishing gear or the fishing net is coat | covered with the coating film formed from the antifouling coating composition of any one of Claims 1-24.
    [28" claim-type="Currently amended] The antifouling method of a ship or an underwater structure characterized by covering the surface of a ship or an underwater structure with the coating film of the antifouling coating composition of any one of Claims 1-24.
    [29" claim-type="Currently amended] An antifouling method for fishing gear or fishing nets, wherein the surface of the fishing gear or fishing net is covered with a coating film of the antifouling coating composition according to any one of claims 1 to 24.
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    同族专利:
    公开号 | 公开日
    EP1457531A1|2004-09-15|
    DK1457531T3|2011-01-24|
    PT1457531E|2010-11-02|
    TWI225884B|2005-01-01|
    JPWO2004037932A1|2006-02-23|
    ES2352657T3|2011-02-22|
    HK1064696A1|2010-12-10|
    US20050065232A1|2005-03-24|
    EP1457531A4|2007-09-05|
    CN1606602A|2005-04-13|
    EP1457531B1|2010-10-13|
    DE60237991D1|2010-11-25|
    WO2004037932A1|2004-05-06|
    US8741983B2|2014-06-03|
    KR100592438B1|2006-06-26|
    CN1302077C|2007-02-28|
    NO20042602L|2005-05-23|
    AT484554T|2010-10-15|
    JP4979890B2|2012-07-18|
    TW200406473A|2004-05-01|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2002-10-23|Priority to JP2002308820
    2002-10-23|Priority to JPJP-P-2002-00308820
    2002-12-18|Application filed by 주고꾸 도료 가부시키가이샤
    2002-12-18|Priority to PCT/JP2002/013244
    2004-08-11|Publication of KR20040071245A
    2006-06-26|Application granted
    2006-06-26|Publication of KR100592438B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP2002308820|2002-10-23|
    JPJP-P-2002-00308820|2002-10-23|
    PCT/JP2002/013244|WO2004037932A1|2002-10-23|2002-12-18|Antifouling paint composition, antifouling paint films, and ships, underwater structures, fishing gear and fishing nets covered with the films|
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