WO2012165628A1 - Copolymère à teneur en métal, procédé de fabrication de celui-ci, composition de peinture antisalissures, peinture antisalissures et article ayant un revêtement de celle-ci - Google Patents

Copolymère à teneur en métal, procédé de fabrication de celui-ci, composition de peinture antisalissures, peinture antisalissures et article ayant un revêtement de celle-ci Download PDF

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WO2012165628A1
WO2012165628A1 PCT/JP2012/064313 JP2012064313W WO2012165628A1 WO 2012165628 A1 WO2012165628 A1 WO 2012165628A1 JP 2012064313 W JP2012064313 W JP 2012064313W WO 2012165628 A1 WO2012165628 A1 WO 2012165628A1
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Prior art keywords
acid
meth
general formula
metal
antifouling
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PCT/JP2012/064313
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English (en)
Japanese (ja)
Inventor
亘晃 金澤
岩本　暁生
浩二 寺田
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三菱レイヨン株式会社
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Priority to CN201280026999.6A priority Critical patent/CN103582657B/zh
Priority to JP2012526772A priority patent/JP5949549B2/ja
Priority to KR1020137032792A priority patent/KR101668909B1/ko
Publication of WO2012165628A1 publication Critical patent/WO2012165628A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

Definitions

  • the present invention relates to a coating composition having antifouling properties and a copolymer suitable for preparing the same. More specifically, the present invention relates to an antifouling coating composition and an antifouling paint capable of forming a coating film that prevents adhesion of marine organisms and seaweeds to underwater structures, fishing nets, and ship bottoms.
  • the coating film formed from the antifouling paint exhibits an antifouling effect when the antifouling agent contained therein elutes into the sea.
  • a coating film formed from a disintegrating antifouling paint using a rosin compound is immersed in the sea for a long period of time, the eluted components gradually decrease and non-eluting components increase. Becomes uneven, and as a result, the effect of preventing the attachment of organisms such as marine organisms is significantly reduced.
  • the coating film formed from the hydrolyzable antifouling paint gradually dissolves and renews the surface of the coating (self-polishing), and the antifouling component is always exposed on the coating film surface. Long-term antifouling effect is demonstrated.
  • Patent Document 1 a resin having at least one group containing zinc, copper, or tellurium atoms at the end of at least one side chain, and the resin is soluble.
  • a hydrolyzable antifouling paint composition comprising a metal-containing resin composition comprising an organic solvent is disclosed.
  • Patent Document 2 proposes a hydrolyzable antifouling paint composition containing a copolymer comprising a polymerizable monomer unit containing a metal atom as a constituent and an antifouling agent. .
  • the antifouling paint using the metal atom-containing copolymer described in Patent Document 1 and Patent Document 2 has a decrease in antifouling property in a stationary state due to a decrease in hydrolyzability or generation of cracks. There is a problem that it is difficult to obtain an antifouling effect in a stationary state for a long time.
  • the object of the present invention is to solve these problems, maintain an excellent antifouling performance even in a stationary state over a long period of time, and prevent the formation of coating film defects and antifouling paints. Is to provide. Moreover, it is providing the metal atom containing copolymer used for this antifouling-paint composition and antifouling-paint.
  • M represents a divalent metal
  • R 1 represents a hydrocarbon having 2 or 3 carbon atoms
  • n is an integer from 1 to 20.
  • M represents a divalent metal
  • R 2 to R 5 represent hydrocarbons.
  • m is 0 or 1.
  • M represents a divalent metal
  • R 1 and R 6 each independently represent a hydrocarbon having 2 or 3 carbon atoms.
  • n is an integer from 1 to 20
  • p is an integer from 0 to 20.
  • M represents a divalent metal
  • R 1 represents a hydrocarbon having 2 or 3 carbon atoms
  • R 4 and R 5 represent a hydrocarbon.
  • n is an integer from 1 to 20.
  • M represents a divalent metal
  • R 1 represents a hydrocarbon having 2 or 3 carbon atoms
  • R 7 represents an organic acid residue.
  • n is an integer from 1 to 20.
  • Polymerizable monomer (a6) represented by general formula (6), polymerizable monomer (a7) represented by general formula (7), and polymerizable monomer represented by general formula (8) A monovalent comprising a divalent metal-containing polymerizable monomer (a) containing at least one polymerizable monomer selected from the group (a8) and a divalent metal-free polymerizable monomer (b).
  • M represents a divalent metal
  • R 8 and R 9 each independently represent H or CH 3
  • R 1 and R 6 represent a hydrocarbon having 2 or 3 carbon atoms.
  • n is an integer from 1 to 20
  • p is an integer from 0 to 20.
  • M is a divalent metal
  • R 8 and R 9 are each independently H or CH 3
  • R 1 is a hydrocarbon having 2 or 3 carbon atoms
  • R 4 and R 5 are carbonized. Indicates hydrogen.
  • n is an integer from 1 to 20.
  • M represents a divalent metal
  • R 8 represents H or CH 3
  • R 1 represents a hydrocarbon having 2 or 3 carbon atoms
  • R 7 represents an organic acid residue.
  • n is an integer from 1 to 20.
  • a divalent metal-containing polymerizable monomer (a) containing a polymerizable monomer (a9) represented by the general formula (9), and a divalent metal-free polymerizable monomer (b) The method for producing a metal-containing copolymer according to [1], wherein a monomer mixture containing is copolymerized.
  • M represents a divalent metal
  • R 8 and R 9 each independently represent H or CH 3
  • R 2 to R 5 represent hydrocarbons.
  • m is 0 or 1.
  • M represents a divalent metal
  • R 8 represents H or CH 3
  • R 2 and R 3 represent hydrocarbons
  • R 7 represents an organic acid residue.
  • An antifouling paint composition comprising the metal-containing copolymer according to [1] or [2].
  • An antifouling paint comprising the antifouling paint composition.
  • the metal-containing copolymer of the present invention provides an antifouling paint composition and an antifouling paint that are free from coating film defects such as cracks and can maintain excellent performance over a long period of time even in a stationary state. be able to.
  • (meth) acryl means acryl or methacryl.
  • the metal-containing copolymer of the present invention is a divalent metal-containing copolymer having one or more structures selected from the structure represented by the general formula (1) and the structure represented by the general formula (2).
  • the antifouling paint containing the antifouling paint composition using the metal-containing copolymer having such a configuration can impart high hydrolyzability to the resulting coating film. Furthermore, this coating film is also excellent in crack resistance, and can exhibit an excellent antifouling effect over a long period of time. From the viewpoint of imparting long-term antifouling properties and crack resistance to the resulting coating film, the metal-containing copolymer preferably has a structure represented by the general formula (1).
  • the structure represented by the general formula (1) is selected from the group consisting of the structure represented by the general formula (3), the structure represented by the general formula (4), and the structure represented by the general formula (5). It is preferable that
  • the divalent metal contained in the structural formula can be appropriately selected as necessary, but from the viewpoint of solubility of the metal-containing copolymer in water, from the group of zinc, copper, magnesium and calcium. One or more selected are preferable, and zinc and copper are particularly preferable from the viewpoint of water resistance of the coating film.
  • the content of the structure represented by the general formula (1) or the general formula (2) in the metal-containing copolymer is preferably 1% by mass or more, and particularly preferably 2% by mass or more. If it is 1 mass% or more, the hydrolyzability of the obtained coating film will become favorable, and also crack resistance will become favorable, and the outstanding antifouling effect can be exhibited over a long period of time.
  • the copolymer containing the divalent metal of the present invention can be obtained, for example, by the following method (1) or (2).
  • “Production method 2” in which transesterification is performed using a metal ester of an acid.
  • the polymerizable monomers (a6), (a7), and (a8) are particularly preferable because long-term antifouling properties and crack resistance can be imparted to the coating film.
  • Polymerizable monomer (a6) Specific examples of the polymerizable monomer (a6) represented by the general formula (6) include the following. Di (3-acryloyloxypropionic acid) zinc, di (3-acryloyloxypropionic acid) copper, di (3-acryloyloxypropionic acid) magnesium, di (3-methacryloyloxy-2-methylpropionic acid) zinc, di (3 -Methacryloyloxy 2-methylpropionic acid) copper, di (3-methacryloyloxy-2-methylpropionic acid) magnesium, (meth) acrylic acid 3-acryloyloxypropionic acid zinc, (meth) acrylic acid 3-acryloyloxypropionic acid copper (Meth) acrylic acid 3-acryloyloxypropionate magnesium, (meth) acrylic acid 3-methacryloyloxy 2-methylpropionate zinc, (meth) acrylic acid 3-methacryloyloxy-2-methylpropionate copper, and (meth) )acrylic 3-methacryloyloxy-2-
  • polymerizable monomer (a7) Specific examples of the polymerizable monomer (a7) represented by the general formula (7) include the following. 2- (meth) acryloyloxyethyl succinic acid, zinc 3-acryloyloxypropionate, 2- (meth) acryloyloxyethyl 3-succinic acid, copper acryloyloxypropionate, 2- (meth) acryloyloxyethyl 3-acryloyloxy succinate Magnesium propionate, succinic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate zinc, succinic acid 2- (meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate copper, succinic acid 2- (Meth) acryloyloxyethyl 3-methacryloyloxy 2-methylpropionate magnesium, 2- (meth) acryloyloxyethyl 3-acryloyloxypropionate
  • polymerizable monomer (a8) Specific examples of the polymerizable monomer (a8) represented by the general formula (8) include the following. 3- (meth) acryloyloxypropionic acid (versaic acid) zinc, 3- (meth) acryloyloxypropionic acid (octylic acid) zinc, 3- (meth) acryloyloxypropionic acid (stearic acid) zinc, 3- (meth) Zinc acryloyloxypropionate (abithienoic acid), 3- (meth) acryloyloxypropionic acid (versaic acid) copper, 3- (meth) acryloyloxypropionic acid (octylic acid) copper, 3- (meth) acryloyloxypropionic acid ( Stearic acid) copper, 3- (meth) acryloyloxypropionic acid (abitienoic acid) copper, 3- (meth) acryloyloxypropionic acid (versaic acid) magnesium, 3- (meth)
  • polymerizable monomer (a9) Specific examples of the polymerizable monomer (a9) represented by the general formula (9) include the following. Di (succinic acid 2- (meth) acryloyloxyethyl) zinc, di (2- (meth) acryloyloxyethyl) succinic acid copper, di (2- (meth) acryloyloxyethyl) succinic acid magnesium, di (phthalic acid 2 -(Meth) acryloyloxyethyl) zinc, di (2- (meth) acryloyloxyethyl) phthalate, di (2- (meth) acryloyloxyethyl) magnesium phthalate, di (hexahydrophthalic acid 2- (meth) ) Acryloyloxyethyl) zinc, di (hexahydrophthalic acid 2- (meth) acryloyloxyethyl) copper, di (hexahydrophthalic acid 2- (meth) acrylo
  • polymerizable monomer (a10) Specific examples of the polymerizable monomer (a10) represented by the general formula (10) include the following. 2- (meth) acryloyloxyethyl (versaic acid) zinc succinate, 2- (meth) acryloyloxyethyl (octylate) zinc succinate, 2- (meth) acryloyloxyethyl (stearic acid) zinc succinate, succinic acid 2- (meth) acryloyloxyethyl (abithienic acid) zinc, succinic acid 2- (meth) acryloyloxyethyl (versaic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (octylic acid) copper, succinic acid 2- (Meth) acryloyloxyethyl (stearic acid) copper, succinic acid 2- (meth) acryloyloxyethyl (abithienic acid) copper, succinic acid
  • the polymerizable monomers (a6), (a7) and (a9) can be produced, for example, by a method of reacting an inorganic metal compound and a carboxyl group-containing polymerizable monomer.
  • the polymerizable monomers (a8) and (a10) include, for example, an inorganic metal compound, a carboxyl group-containing polymerizable monomer and a carboxyl group-containing non-polymerizable compound (hereinafter referred to as “carboxyl group-containing”). It may be referred to as a “compound”).
  • “polymerizable monomer” means a compound having a polymerizable unsaturated double bond
  • non-polymerizable compound means a compound having no polymerizable unsaturated double bond.
  • the reaction temperature may be a temperature at which the carboxyl group-containing polymerizable monomer is not polymerized, and is preferably 120 ° C. or lower.
  • a reaction method a method in which an inorganic metal compound and a carboxyl group-containing compound are reacted in an organic solvent containing an alcohol compound is preferable. By this method, the compatibility between the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b) is improved, and the polymerization for obtaining the metal-containing copolymer is easy. It becomes.
  • the alcohol compound contained in the organic solvent include ethanol, isopropanol, butanol, and propylene glycol monomethyl ether.
  • inorganic metal compounds include metal oxides such as magnesium oxide, copper oxide, and zinc oxide; metal hydroxides such as magnesium hydroxide, copper hydroxide, and zinc hydroxide; metal chlorides such as magnesium chloride, copper chloride, and zinc chloride. Thing etc. are mentioned.
  • the carboxyl group-containing polymerizable monomer is a metal-containing compound selected from the group of metal-containing polymerizable monomers represented by the general formulas (6), (7), (8), (9) and (10). What is necessary is just to select so that 1 or more types of polymerizable monomers may be produced
  • 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, and ⁇ -CEA are preferable.
  • Examples of the carboxyl group-containing non-polymerizable compound include the following. Acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexylic acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, Stearol acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, ⁇ -naphthoic acid, ⁇ -naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline Carboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, purvinic acid, naphthenic acid, abietic acid,
  • the ratio of the metal atom and the carboxyl group-containing polymerizable monomer in the inorganic metal compound is such that the metal atom is 0.3 mol or more and 2.5 mol or less with respect to 1 mol of the carboxyl group-containing polymerizable monomer. Is preferred. If the metal atom is 0.3 mol or more, the amount of the metal and unreacted carboxyl groups is reduced, and the water resistance of the coating film tends to be good. If the metal atom is 2.5 mol or less, the amount of the polymerizable monomer in the raw material mixture for the reaction is increased, so that the amount of the metal-containing polymerizable monomer generated is increased. It becomes easy for the coating film to be continuously dissolved over a long period of time.
  • the ratio of the metal atom in the inorganic metal compound to the carboxyl group-containing compound is preferably such that the metal atom is 0.6 mol or less with respect to 1 mol of the carboxyl group-containing compound.
  • the metal atom is 0.6 mol or less, the carboxyl group and the unreacted metal atom are reduced, and the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b)
  • the transparency of the mixture tends to be good.
  • the divalent metal-free polymerizable monomer (b) is a polymerizable monomer that does not contain a divalent metal, and is particularly a monomer having a polymerizable unsaturated double bond. It is not limited, For example, the following are mentioned.
  • Acid ester monomer water such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Group-containing (meth) acrylic acid ester monomers; hydroxyl-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, ethylene oxide, propylene oxide, Adducts with ⁇ -butyrolactone or ⁇ -caprolactone; carboxyl group-containing monomers such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, sorbic acid; carboxylic acids such as itaconic anhydride and maleic anhydride Anhydride group-containing monomers; dicarboxylic acid monoesters such as monoalkyl itaconate and monoalkyl maleate; hydroxyl group-containing (meth) acrylic such as 2-
  • a known solution polymerization method can be used as a method for polymerizing the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b).
  • the chain transfer agent is preferably a chain transfer agent other than mercaptan, and preferably styrene dimer.
  • the solvent known organic solvents can be used, and examples thereof include the following. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like. The solvent may be used alone or in combination of two or more.
  • the polymerization temperature is not particularly limited and is, for example, about 60 to 180 ° C.
  • the polymerization time is not particularly limited and is, for example, about 2 to 14 hours.
  • the ratio of the charged amount of the divalent metal-containing polymerizable monomer (a) and the divalent metal-free polymerizable monomer (b) as the polymerization raw material is not particularly limited, and is 5:95 to 70: It is about 30 (mass%).
  • Production method 2 is a method of reacting a metal compound and a monobasic organic acid as necessary with respect to the acid group-containing copolymer (c), or the acid group-containing copolymer (c). And a transesterification method using a metal ester of a monobasic organic acid.
  • Examples of the method for producing the acid group-containing copolymer (c) include a method of copolymerizing an acid group-containing polymerizable monomer with another polymerizable monomer, and a method of polymerizing a hydroxyl group-containing polymerizable monomer with another polymerization. Examples thereof include a method of introducing an acid group by reacting an acid anhydride or the like with a hydroxyl group after copolymerization with a functional monomer.
  • the acid group-containing polymerizable monomer may be selected so as to obtain a divalent metal-containing copolymer having a structure represented by the general formula (1) or (2), and examples thereof include the following. . 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, (meth) Acrylic acid, ⁇ -CEA (manufactured by Daicel Corporation / Cytec), and the like.
  • 2-carboxyethyl acrylate, 2-carboxypropyl methacrylate, and ⁇ -CEA are preferable.
  • hydroxyl group-containing polymerizable monomer examples include the following. Hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; and Of hydroxyl group-containing (meth) acrylic acid ester monomers such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate with ethylene oxide, propylene oxide, ⁇ -butyrolactone or ⁇ -caprolactone Things.
  • Examples of the acid anhydride to be reacted with the hydroxyl group include the following.
  • Dibasic acid anhydrides such as phthalic anhydride, hexahydrophthalic acid, tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and succinic acid.
  • a known solution polymerization method can be used as a method for producing the acid group-containing copolymer (c), for example.
  • a known solution polymerization method can be used as the solvent for polymerization.
  • known organic solvents can be used, and examples thereof include the following. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like.
  • the solvent may be used alone or in combination of two or more.
  • the polymerization temperature is not particularly limited and is, for example, about 60 to 180 ° C.
  • the polymerization time is not particularly limited and is, for example, about 2 to 14 hours.
  • Examples of the metal compound to be reacted with the acid group-containing copolymer (c) include metal oxides such as magnesium oxide, copper oxide and zinc oxide; metal hydroxides such as magnesium hydroxide, copper hydroxide and zinc hydroxide; Examples thereof include metal chlorides such as magnesium, copper chloride, and zinc chloride.
  • a monobasic organic acid can be used as necessary.
  • the monobasic organic acid include the following compounds. Acetic acid, monochloroacetic acid, monofluoroacetic acid, propionic acid, caproic acid, caprylic acid, 2-ethylhexylic acid, capric acid, versatic acid, isostearic acid, palmitic acid, cresotic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, Stearol acid, ricinoleic acid, ricinoelaidic acid, brassic acid, erucic acid, ⁇ -naphthoic acid, ⁇ -naphthoic acid, benzoic acid, 2,4,5-trichlorophenoxyacetic acid, 2,4-dichlorophenoxyacetic acid, quinoline Carboxylic acid, nitrobenzoic acid, nitronaphthalene carboxylic acid, purvinic acid, naphthenic
  • the transesterification method in “Production Method 2” is a method using an acid group-containing copolymer (c) and a metal ester of a monobasic organic acid.
  • a metal ester of a monobasic organic acid a compound composed of the above-mentioned monobasic organic acid and a metal such as magnesium, copper, or zinc can be used, and examples thereof include the following. Copper acetate, zinc acetate, magnesium acetate, copper propionate, zinc propionate, magnesium propionate and the like.
  • Examples of the solvent used for transesterification include the following organic solvents. Xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, n-butanol and the like.
  • the solvent may be used alone or in combination of two or more.
  • reaction temperature is not specifically limited, It is preferable to carry out below the decomposition temperature of metal ester.
  • the divalent metal-containing polymerizable monomer in order that the metal content in the metal-containing copolymer is 2% by mass or more and 20% by mass or less) It is preferable to set the use amount of a) or the acid group-containing copolymer (c).
  • the metal content in the metal-containing copolymer is 2% by mass or more, the hydrolyzability of the coating film becomes good and the antifouling performance becomes good.
  • the crack resistance and water resistance of a coating film become favorable.
  • the metal content is particularly preferably 4% by mass or more and 15% by mass or less.
  • the content of the carboxyl group-containing polymerizable monomer unit selected so that at least one structure represented by the general formula (1) or the general formula (2) is generated is , Preferably 1% by mass or more, particularly preferably 2% by mass or more. If it is 1 mass% or more, the hydrolyzability of the obtained coating film will become favorable, and also crack resistance will become favorable, and the outstanding antifouling effect can be exhibited over a long period of time.
  • the content of the carboxyl group-containing polymerizable monomer unit is an amount calculated from the following formula.
  • the antifouling paint composition of the present invention is an antifouling paint composition containing the metal-containing copolymer and a solvent used in the production of the copolymer.
  • the composition for antifouling paints of the present invention can retain excellent antifouling performance in the formed coating film by containing the metal-containing copolymer.
  • the antifouling coating composition of the present invention can further improve antifouling performance by blending an antifouling agent.
  • the antifouling paint of the present invention can be prepared by blending the antifouling paint composition of the present invention with an antifouling agent, a solvent for dilution, and an additive such as a pigment.
  • an antifouling agent e.g., an antifouling agent for dilution
  • an additive such as a pigment.
  • the proportion of the metal-containing copolymer in the antifouling paint is usually 15% by mass (in terms of solid content) or more as the resin component. Is preferred. If the blending amount is 15% by mass or more, the solubility of the metal-containing copolymer in the antifouling paint is good, and the antifouling property and crack resistance of the coating film are good.
  • the antifouling agent can be appropriately selected and used according to the required performance, and examples thereof include the following. Copper antifouling agents such as cuprous oxide, thiocyanic copper and copper powder; metal compounds such as lead, zinc and nickel; amine derivatives such as diphenylamine; nitrile compounds, benzothiazole compounds, maleimide compounds and pyridine compounds. These can be used alone or in combination.
  • a silicone compound such as dimethylpolysiloxane and silicone oil, a fluorine-containing compound such as fluorocarbon, and the like are blended for the purpose of imparting lubricity to the coating surface and preventing the adhesion of organisms. can do.
  • extender pigments, color pigments, plasticizers, various paint additives, other resins, and the like can be blended in the antifouling paint of the present invention as necessary.
  • Examples of the solvent for dilution used in the antifouling paint of the present invention include organic solvents such as xylene, propylene glycol methyl ether, toluene, methyl isobutyl ketone, n-butyl acetate, and n-butanol.
  • the organic solvent may be used alone or in combination of two or more.
  • Article with coating film examples include ships, various fishing nets, power plant conduits, oil fences, bridges, buoys, and submarines.
  • Formation of the coating film using the antifouling paint of the present invention is performed, for example, by the following method (1) or (2).
  • An antifouling paint is applied directly to the surface of a base material such as an underwater structure such as a ship, various fishing nets, a port facility, an oil fence, a bridge, and a submarine base.
  • a primer such as wash primer, chlorinated rubber, epoxy, etc. to the base material, and an intermediate coating, etc., and brush coating, spray coating, roller coating, submersion on the resulting coating film Apply antifouling paint by means such as painting.
  • the amount applied is generally an amount that results in a dry coating thickness of 50 to 400 ⁇ m.
  • the coating film is generally dried at room temperature, but may be dried by heating.
  • Coating film wear degree test A coating film having a thickness of about 300 ⁇ m was formed on a hard vinyl chloride plate having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm, and the obtained test piece was attached to a rotating drum installed in seawater. Then, the film was rotated at a peripheral speed of 7.7 m / s (15 knots), and the consumed film thickness was measured after 3 months, 6 months, and 12 months.
  • a coating with a thickness of about 300 ⁇ m was formed on a sandblasted steel plate that had been coated with a rust-preventive paint in advance, and the resulting specimen was immersed in Hiroshima Bay for 12 months. After 6 months, And the adhesion area (%) of the attached organism after 12 months was examined. The determination was made according to the following criteria.
  • C The adhesion area of the attached organism after 12 months is 40% or more and less than 80%.
  • D The adhesion area of attached organisms after 12 months is 80% or more and 100% or less.
  • a coating film having a thickness of about 300 ⁇ m is formed on a sandblasted steel plate to which a rust preventive paint has been applied in advance, and the obtained test piece is sterilized and filtered at 20 ° C. for 6 months and 12 months. After soaking, it was dried at 20 ° C. for 1 week. And the coating-film surface was observed. Evaluation was performed according to the following criteria. A: Cracks and peeling are not observed at all. B: Slight cracks are observed. C: Cracks and peeling are partially observed. D: Cracks and peeling are observed on the entire surface.
  • a transparent metal-containing polymerizable monomer (a) mixture M1 was added to obtain a transparent metal-containing polymerizable monomer (a) mixture M1.
  • the solid content of the mixture M1 was 51.4% by mass.
  • the metal content of the mixture M1 was 9.6% by mass.
  • the metal content of the mixture was calculated from the following calculation formula.
  • Example 1 The following five types of materials were mixed to prepare an antifouling paint. An appropriate amount of xylene was added, and the viscosity was adjusted to 80 to 90 KU with a stoma viscometer (25 ° C.). -Varnish C1: 40 parts, -Cuprous oxide: 50 parts, -Iron oxide: 1.5 parts, ⁇ Powdered silica: 3 parts Dispalon 4200-20 (manufactured by Enomoto Kasei Co., Ltd., anti-settling agent): 1 part.
  • the obtained antifouling paint was applied onto a predetermined substrate so that the dry film thickness was about 300 ⁇ m, and dried at room temperature for 1 week.
  • the obtained coating film was subjected to a wear degree test, an antifouling test, and a crack resistance test. Table 7 shows the evaluation results.
  • Examples 2 to 4, 6 to 14, and 16 to 28 An antifouling paint was prepared in the same manner as in Example 1 except that the types of materials were changed to the conditions shown in Tables 7 to 9, and coated on a substrate to obtain a coating film. The evaluation results are shown in Tables 7 to 9.
  • Example 5 The following six materials were mixed to prepare an antifouling paint. An appropriate amount of xylene was added, and the viscosity was adjusted to 80 to 90 KU with a stoma viscometer (25 ° C.). ⁇ Varnish C4: 40 parts, ⁇ Rodan copper: 40 parts, 2-pyridinethiol-1-oxide zinc salt: 3 parts -Titanium oxide: 10 parts, ⁇ Powdered silica: 3 parts Disparon 4200-20: 1 part.
  • the obtained antifouling paint was applied on the substrate in the same manner as in Example 1 to obtain a coating film.
  • Table 7 shows the evaluation results.
  • Example 15 An antifouling paint was prepared in the same manner as in Example 5 except that the type of material was changed to the conditions shown in Table 7, and was applied onto a substrate to obtain a coating film. Table 8 shows the evaluation results.
  • Example 1 A paint was prepared in the same manner as in Example 1 except that the material type was changed to the conditions shown in Tables 7 to 9, and coated on a substrate to obtain a coating film.
  • the evaluation results are shown in Tables 7 to 9.
  • Comparative Examples 1 to 6 since the structure of the present invention is not contained in the metal-containing copolymer, the degree of coating film consumption is insufficient, or crack peeling is rank D, which is sufficient as a result. Antifouling property was not obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention a pour but de proposer ce qui suit : une composition de peinture antisalissures et une peinture antisalissures qui ne produisent pas de défauts de revêtement et conservent une excellente performance antisalissures pendant une longue période de durée même lorsqu'elle est stationnaire ; et un copolymère à teneuir en atome de métal utilisé dans ladite composition de peinture antisalissures et une peinture antisalissures. A cet effet, l'invention concerne un copolymère à teneur en métal qui a au moins une structure choisie parmi des structures représentées par la formule générale (1) et des structures représentées par la formule générale (2). Dans la formule (1), M représente un métal divalent, R1 représente un groupe hydrocarboné en C2 ou C3 et n représente un nombre entier de 1 à 20. Dans la formule (2), M représente un métal divalent, R2 à R5 représentent des goupes hydrocarbonés et m représente 0 ou 1. Egalement, l'invention concerne une composition de peinture antisalissures contenant le copolymère à teneur en métal précédemment mentionné. Formule générale (1) : -COO-(R1-COO)n-M- Formule générale (2) : -COO-(R2-OCO-R3-COO)m-M-OCO-R4-COO-R5-OCO-
PCT/JP2012/064313 2011-06-01 2012-06-01 Copolymère à teneur en métal, procédé de fabrication de celui-ci, composition de peinture antisalissures, peinture antisalissures et article ayant un revêtement de celle-ci WO2012165628A1 (fr)

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CN201280026999.6A CN103582657B (zh) 2011-06-01 2012-06-01 含金属的共聚物、其制造方法、防污涂料用组合物、防污涂料及具有该防污涂料的涂膜的物品
JP2012526772A JP5949549B2 (ja) 2011-06-01 2012-06-01 金属含有共重合体、その製造方法、防汚塗料用組成物、防汚塗料およびその塗膜を有する物品
KR1020137032792A KR101668909B1 (ko) 2011-06-01 2012-06-01 금속 함유 공중합체, 그의 제조 방법, 방오 도료용 조성물, 방오 도료 및 그의 도막을 갖는 물품

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JP2011123308 2011-06-01
JP2011-123308 2011-06-01
JP2011-209375 2011-09-26
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PCT/JP2012/064313 WO2012165628A1 (fr) 2011-06-01 2012-06-01 Copolymère à teneur en métal, procédé de fabrication de celui-ci, composition de peinture antisalissures, peinture antisalissures et article ayant un revêtement de celle-ci

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CN109311284B (zh) * 2016-07-01 2021-07-13 中国涂料株式会社 层叠防污涂膜、防污基材和船舶
KR102231192B1 (ko) 2016-07-05 2021-03-24 미쯔비시 케미컬 주식회사 중합체 함유 조성물 및 방오 도료 조성물
CN110607109B (zh) * 2019-09-16 2021-08-03 浙江鱼童新材料股份有限公司 一种环保型防腐涂料及其制备方法

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JP2002105127A (ja) * 2000-10-02 2002-04-10 Nippon Shokubai Co Ltd 金属塩をもつビニルモノマーを含む反応生成物およびこれを用いたポリマー
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WO2007026692A1 (fr) * 2005-09-01 2007-03-08 Chugoku Marine Paints, Ltd. Composition de revêtement antitache, film de revêtement antitache, substrat ayant un film de revêtement, substrat antitache, procédé de formation d'un film de revêtement sur la surface du substrat et procédé d’imperméabilisation aux taches du substrat
JP2011016958A (ja) * 2009-07-10 2011-01-27 Mitsubishi Rayon Co Ltd 防汚塗料用金属含有共重合体の製造方法および防汚塗料組成物

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KR101668909B1 (ko) 2016-10-24
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CN103582657A (zh) 2014-02-12
JPWO2012165628A1 (ja) 2015-02-23
KR20140009558A (ko) 2014-01-22
JP5949549B2 (ja) 2016-07-06
CN103608366A (zh) 2014-02-26
JPWO2012165618A1 (ja) 2015-02-23
WO2012165618A1 (fr) 2012-12-06

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