WO2021106868A1 - Antifouling coating composition for fishing net, and fishing net, fishing-net accessory, or underwater structure each having antifouling coating film formed on surface from said composition - Google Patents

Antifouling coating composition for fishing net, and fishing net, fishing-net accessory, or underwater structure each having antifouling coating film formed on surface from said composition Download PDF

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Publication number
WO2021106868A1
WO2021106868A1 PCT/JP2020/043665 JP2020043665W WO2021106868A1 WO 2021106868 A1 WO2021106868 A1 WO 2021106868A1 JP 2020043665 W JP2020043665 W JP 2020043665W WO 2021106868 A1 WO2021106868 A1 WO 2021106868A1
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meth
fishing
antifouling
fishing net
antifouling coating
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PCT/JP2020/043665
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French (fr)
Japanese (ja)
Inventor
博一 竹縄
貴義 藤本
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日東化成株式会社
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Priority to KR1020227021933A priority Critical patent/KR20220104815A/en
Publication of WO2021106868A1 publication Critical patent/WO2021106868A1/en

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    • 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
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01K—ANIMAL HUSBANDRY; AVICULTURE; APICULTURE; PISCICULTURE; FISHING; REARING OR BREEDING ANIMALS, NOT OTHERWISE PROVIDED FOR; NEW BREEDS OF ANIMALS
    • A01K75/00—Accessories for fishing nets; Details of fishing nets, e.g. structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D123/04—Homopolymers or copolymers of ethene
    • C09D123/08—Copolymers of ethene
    • C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09D123/0853—Vinylacetate
    • 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
    • C09D131/00—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 at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • 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
    • C09D133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/80—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in fisheries management
    • Y02A40/81—Aquaculture, e.g. of fish

Definitions

  • the present invention relates to a fishing net antifouling paint composition and a fishing net, a fishing net tool or an underwater structure having an antifouling coating film formed by using the composition on the surface.
  • antifouling paint compositions for fishing nets using organic tin compounds have been widely used in order to prevent the adhesion of these aquatic polluted organisms, but they can no longer be used due to environmental considerations.
  • antifouling paint compositions for fishing nets to replace organic tin compounds
  • inorganic compounds and organic compounds are used as antifouling agents and blended with natural resin-based or synthetic resin-based spreading resins.
  • Antifouling paint compositions for fishing nets have been used. However, these have problems such as poor physical characteristics of the coating film and a short antifouling period.
  • Patent Documents 1 to 4 In order to solve these problems, antifouling coating compositions for fishing nets in which a specific polyether-modified silicone oil is blended with a spreading resin as an elution adjusting agent for chemicals have been proposed (Patent Documents 1 to 4).
  • JP-A-3-20370 Japanese Patent Application Laid-Open No. 9-176577 JP 2001-19848 JP-A-2009-215527
  • the present invention has been made in view of the above circumstances, and is capable of maintaining an appropriate amount of chemicals released for a long period of time from the time of immersion in water and continuously exhibiting excellent antifouling performance for a long period of time.
  • An object of the present invention is to provide a coating composition.
  • a fishing net antifouling coating composition containing a (meth) acrylic acid ester polymer (A), an ethylene-vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D). Things are provided.
  • the present inventor has found that the above-mentioned composition can solve the above-mentioned problems, and has completed the present invention.
  • the fishing net antifouling paint composition of the present invention includes fishing nets for cultivation or fixed nets, fishing net tools such as floats and ropes used for these, and underwater structures such as cooling water conduits for power plants. It is a composition for preventing aquatic polluted organisms from adhering to objects.
  • the composition of the present invention contains a (meth) acrylic acid ester polymer (A), an ethylene-vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D).
  • A acrylic acid ester polymer
  • B ethylene-vinyl acetate copolymer
  • C silicone oil
  • D antifouling agent
  • the polymer (A) is a polymer formed by using a monomer containing a (meth) acrylic acid ester, and may be a copolymer of one kind of monomer, but a plurality of kinds of simple polymers. It is preferably a copolymer of a monomer.
  • the monomer for forming the polymer (A) may contain an ethylenically unsaturated monomer copolymerizable with the (meth) acrylic acid ester.
  • the ratio of the (meth) acrylic acid ester in the monomer for forming the polymer (A) is, for example, 60% by mass or more, and specifically, for example, 60, 65, 70, 75, 80, It is 85, 90, 95, 100% by mass, and may be in the range between any two of the numerical values exemplified here.
  • Examples of the (meth) acrylic acid ester forming the polymer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth).
  • T-butyl acrylate 21-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, ( 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) ) Glycidyl acrylate, (meth) fluoric acid acrylate, (meth) tetrahydroflufuryl acrylate, (meth) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate, benzyl (meth) acrylate, and (meth) acrylic Examples
  • Examples of the monomer other than the (meth) acrylic acid ester include olefins such as propylene, isobutylene, ⁇ -octene, ⁇ -dodecene and ⁇ -octadecene, acrylic acid, methacrylic acid, crotonic acid and maleic acid.
  • Unsaturated acids such as maleic anhydride and itaconic acid or salts thereof or mono or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylicamide, ethylene sulfonic acid, allyl sulfonic acid and metaallyl.
  • Olefin sulfonic acid such as sulfonic acid or a salt thereof, alkyl vinyl ethers, N-acrylamide methyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallylvinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) Polyoxyalkylene (meth) allyl ethers such as allyl ethers and polyoxypropylene (meth) allyl ethers, polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylates and polyoxypropylene (meth) acrylates, and polyoxyethylene.
  • Polyoxyalkylene (meth) allyl ethers such as allyl ethers and polyoxypropylene (meth) allyl ethers
  • polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylates and polyoxypropylene (
  • Polyoxyalkylene (meth) acrylamide such as (meth) acrylamide and polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene Examples thereof include vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, and polyoxypropylene vinylamine.
  • the glass transition temperature (Tg) of the polymer (A) is preferably about ⁇ 65 to 50 ° C., more preferably about ⁇ 50 to 35 ° C.
  • Tg is within the above range, the tack of the coating film after application to the fishing net becomes too large and there is no problem of hindering the application work, and the flexibility of the coating film is impaired to cause cracks and cracks. It does not cause problems such as occurrence and reduction of antifouling effect.
  • the Tg value refers to a value actually measured by referring to the measurement method of JIS K 7121 using a differential scanning calorimetry device (eg, METTLER TOLEDO, DSC1).
  • the mass average molecular weight (Mw) of the polymer (A) is about 10,000 to 7,000, preferably about 50,000 to 5,000,000. When Mw is about 50,000 to 5,000,000, it is preferable in terms of toughness of the coating film.
  • Examples of the method for measuring Mw include gel permeation chromatography (GPC). When Mw is measured by GPC, Mw is displayed as a value (polystyrene-equivalent value) obtained by creating a calibration curve using polystyrene as a standard substance and measuring it.
  • the polymer (A) is obtained by polymerizing the monomer, and is a copolymer of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. May be good.
  • polymerization method examples include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. Of these, solution polymerization and emulsion polymerization are particularly preferable in that the polymer (A) can be synthesized easily and accurately.
  • the polymerization of the polymer (A) is carried out, for example, in the presence of a polymerization initiator.
  • a polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, and dimethyl-2,2'-azobisisobutyrate.
  • Azo compounds such as benzoyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate and other peroxides, etc. Can be mentioned.
  • polymerization initiators can be used alone or in combination of two or more.
  • the polymerization initiator 2,2'-azobisisobutyronitrile and t-butylperoxy-2-ethylhexanoate are particularly preferable.
  • the molecular weight of the copolymer can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • water or an organic solvent may be used if necessary.
  • the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl.
  • Alcohol-based solvents such as alcohol and butyl alcohol; ether-based solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned.
  • aromatic hydrocarbon solvents are particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually about 70 to 140 ° C., preferably about 80 to 120 ° C.
  • the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
  • the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • any one conventionally used in emulsion polymerization can be used.
  • a water-soluble polymerization initiator such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl hydroperoxide; 2,2'-azobisisobutyronitrile, 2, Examples thereof include oil-soluble polymerization initiators such as 2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate, benzoyl peroxide, and di-tert-butyl peroxide.
  • a water-soluble polymerization initiator is preferable. It is also possible to use these polymerization initiators in combination with a reducing agent as a redox-based polymerization initiator.
  • the reaction temperature in emulsion polymerization may be appropriately set according to the type of polymerization initiator and the like, and is usually about 40 to 80 ° C, preferably about 55 to 70 ° C.
  • the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 10 hours, preferably about 6 to 9 hours.
  • the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • Surfactants in emulsion polymerization include anionic surfactants such as sulfate ester salts of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, aliphatic carboxylates, and sulfate ester salts of nonionic surfactants.
  • anionic surfactants such as sulfate ester salts of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, aliphatic carboxylates, and sulfate ester salts of nonionic surfactants.
  • One or two or more nonionic surfactants such as an alkyl ester type, an alkyl phenyl ether type, and an alkyl ether type of polyethylene glycol can be used.
  • a cationic surfactant or an amphoteric surfactant can also be used.
  • polymer (A) as commercially available products, for example, Vanstar X1290B11 (manufactured by Chubu Saiden Co., Ltd.), Polysol (R) AP-4650N (manufactured by Showa Denko KK), Polysol (R) AP-4780N. (Made by Showa Denko KK), etc.
  • the content of the polymer (A) is not particularly limited, but is used in the coating composition in terms of solid content in an amount of 1 to 50% by mass, preferably 3 to 30% by mass.
  • the copolymer (B) is a copolymer formed by using a monomer containing ethylene and vinyl acetate.
  • the monomer for forming the copolymer (B) may contain an ethylenically unsaturated monomer copolymerizable with ethylene and vinyl acetate in addition to ethylene and vinyl acetate.
  • the total ratio of ethylene and vinyl acetate in the monomer for forming the copolymer (B) is, for example, 60% by mass or more, and specifically, for example, 60, 65, 70, 75, 80. , 85, 90, 95, 100% by mass, and may be within the range between any two of the numerical values exemplified here.
  • Examples of the monomer other than ethylene and vinyl acetate include those described above as the monomer other than the (meth) acrylic acid ester.
  • the mass average molecular weight (Mw) of the copolymer (B) is about 10,000 to 7,000, preferably about 50,000 to 5,000,000. When Mw is about 50,000 to 5,000,000, it is preferable in terms of toughness of the coating film.
  • the copolymer (B) is obtained by polymerizing the monomer, and is a copolymer of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. You may.
  • the method described above for the polymer (A) can be applied to the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like.
  • copolymer (B) examples include Polysol (R) EVA P-3N (manufactured by Showa Denko Corporation), Novatec (TM) EVA LV-211A (manufactured by Japan Polyethylene Corporation), and the like. Can be mentioned.
  • the content of the copolymer (B) is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, based on the total mass of the polymer (A) and the copolymer (B). It is particularly preferably 50 to 80% by mass. When it is within the above range, a good antifouling effect can be maintained for a long period of time, and the physical characteristics of the coating film when immersed in seawater are remarkably improved. Good coating film physical properties can be maintained even for nets.
  • silicone oil (C) examples include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, polyether-modified polyalkyl (methyl) siloxane, and polyester-modified polydimethyl.
  • Examples thereof include siloxane, long-chain alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, polyether long-chain alkyl-aralkyl-modified dimethylsilicone oil, fluorosilicone oil, amino-modified silicone oil, and other modified silicone oils with various functional groups.
  • a polyether-modified silicone oil having a hydrophilic lipophilic balance (HLB value) of 0.5 to 9 is preferable, and specifically, a polyether-modified polydimethylsiloxane or a polyether long-chain alkylaralkyl-modified dimethyl having a hydrophilic lipophilic balance (HLB value) of 0.5 to 9 is preferable.
  • HLB value hydrophilic lipophilic balance
  • Silicone oil is preferred. More preferable are polyether-modified polydimethylsiloxane or polyether long-chain alkyl aralkyl-modified dimethylsilicone oil having a hydrophilic lipophilic balance (HLB value) in the range of 1 to 5. Sufficient antifouling performance can be obtained by using a silicone oil having an HLB value in the range of 0.5 to 9. In the present invention, these silicone oils may be used alone or in combination of two or more.
  • HLB value hydrophilic lipophilic balance
  • the viscosity of the silicone oil is preferably 1000 poise or less, more preferably 100 poise or less, from the viewpoint of coating performance and coating film physical characteristics.
  • the content of the silicone oil (C) is not particularly limited, but is preferably 1 to 150 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the copolymer (B) in terms of solid content. Is 5 to 100 parts by mass, more preferably 10 to 50 parts by mass.
  • the silicone oil (C) When the silicone oil (C) is used in an aqueous antifouling composition, it is emulsified with an emulsifier, a dispersant or the like. At that time, it is preferable that the silicone oil is dispersed as particles having an average particle diameter of 0.01 to 100 ⁇ m, preferably 0.1 to 50 ⁇ m, from the viewpoint of dispersibility and storage stability.
  • silicone oil and an emulsifier are charged, and then distilled water is added while stirring with a stirrer, and the mixture is stirred while appropriately setting so that emulsified particles in a target particle size range can be obtained. Just do.
  • emulsifier examples include nonionic surfactants and anionic surfactants.
  • nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene oxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene oxypropylene alkyl phenyl ether, polyoxyethylene distyryl phenyl ether, and polyoxy.
  • examples thereof include ethyleneoxypropylene distyrylphenyl ether and polyoxyethylene tristyrylphenyl ether, and two or more of them may be used in combination.
  • anionic surfactant examples include sulfate ester salt and phosphoric acid ester salt of nonionic surfactant, polyoxyethylene alkyl ether carboxylate, alkylbenzene sulfonate, alkylnaphthalene sulfonate and the like. Two or more types may be used in combination.
  • the antifouling agent (D) is not particularly limited as long as it is a compound having a killing or repellent action against marine polluted organisms.
  • the following organic compounds and inorganic compounds can be mentioned.
  • organic compound examples include 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, zincethylene bisdithiocarbamate, bis (dimethyldithiocarbamic acid) zinc, bisdimethyldithiocarbamoylzincethylene bisdithiocarbamate, and pyridine.
  • n-octadecylamine / triphenylborane, tetraethylthiuram disulfide, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc and bisdimethyldithiocarbamoylzincethylene bisdithiocarbamate are particularly preferable.
  • One type or two or more types may be used in combination.
  • the inorganic compound examples include cuprous oxide, monovalent copper glass, divalent copper glass, copper thiocyanate, cupronickel, copper powder and the like, and include cuprous oxide, monovalent copper glass and divalent copper. Copper glass is particularly preferable, and one type or two or more types may be used in combination.
  • antifouling agents (D) those having an average particle size of 10 ⁇ m or less are preferable, and those having an average particle size of 3 ⁇ m or less are particularly preferable, because of the problem of dispersibility.
  • These average particle sizes can be measured by a particle size distribution meter manufactured by Nikkiso Co., Ltd., and a model Microtrack MT3300EXII (measurement principle laser diffraction / scattering method).
  • the content of the antifouling agent (D) in the coating composition of the present invention is not limited, but is usually 1 to 300 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the copolymer (B). It is a part, preferably 5 to 200 parts by mass. If the amount of the antifouling agent used is less than 1 part by mass, the antifouling property is not sufficient, while if it exceeds 300 parts by mass, the coating performance and the physical characteristics of the coating film tend to deteriorate.
  • the coating composition used in the present invention includes other spreading resins, other elution modifiers, dyes, pigments, waxes, preservatives, plasticizers, dispersants, defoamers, film-forming aids, and anti-settling agents.
  • Anti-sagging agent, surfactant, solvent and the like can be arbitrarily contained in an arbitrary compounding ratio within a range that does not impair the object of the present invention.
  • Other spreading resins include vinyl resins, alkyd resins, urethane resins, polyester resins, synthetic rubbers, synthetic resins such as chlorinated polyethylene, wood rosin, gum rosin, other than the polymer (A) and copolymer (B). Examples include natural resins such as modified rosin.
  • elution regulators examples include ethylene / ⁇ -olefin copolymers, polybutenes, paraffins, petrolatums, dialkyl sulfide compounds and the like.
  • plasticizer examples include phthalates, adipates, tricresyl phosphate and the like.
  • dispersant examples include polyamide phosphoric acid-based dispersants, polyamide-based dispersants, unsaturated polycarboxylic acid-based dispersants, and polyethylene oxide-based dispersants. Examples thereof include Disparon 6900-20X, Disparon 4200, Disparon 1860, etc. manufactured by Kusumoto Kasei Co., Ltd. These dispersants can be used alone or in admixture of two or more.
  • Examples of the solvent include organic solvents and water.
  • Examples of the organic solvent include aromatic solvents such as xylene, toluene, Solbesso 100 and Solbesso 150 (all registered trademarks, manufactured by Exxon Mobile); ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK). ; Ester-based solvents such as butyl acetate, isobutyl acetate, and isopentyl acetate can be used.
  • aromatic solvents such as xylene, toluene, Solbesso 100 and Solbesso 150 (all registered trademarks, manufactured by Exxon Mobile)
  • ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK).
  • Ester-based solvents such as butyl acetate, isobutyl acetate, and isopentyl
  • organic solvents that are low in toxicity, low odor, and low environmental load can also be used.
  • Pegasol AN45, Pegasol AS100 (all registered trademarks, manufactured by Exxon Mobile), LAWS, and HAWS (all manufactured by Shell Chemicals) can be used.
  • other aromatic / alicyclic / aliphatic hydrocarbon mixed solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethylcyclohexane, dimethylcyclohexane, and lycasolve (registered trademark) 900 (C9).
  • Arocyclic hydrocarbon solvents such as Jamaicasolv (registered trademark) 1000 (C10 aromatic hydrocarbon); Shelsol D40 (registered trademark, manufactured by Shell Chemicals), Exol D30, Exol D40 (any of them). Also registered trademark, alicyclic / aliphatic hydrocarbon mixed solvent such as Exxon Mobile); Isopar G, Isopar H (both registered trademarks, manufactured by Exxon Mobile) and other aliphatic hydrocarbon mixed solvents can also be used. it can. These organic solvents can be used alone or in combination of two or more.
  • composition of the present invention can be used for forming an antifouling coating film for various fishing tools, underwater structures, and the like.
  • composition of the present invention can be suitably used as an antifouling coating composition for fishing nets.
  • the fishing net antifouling paint composition of the present invention can be prepared by mixing the above components (A) to (D) and, if necessary, the above additive components.
  • the amount of each component added at the time of mixing may be appropriately adjusted so as to be the above-mentioned blending amount and content.
  • the order in which each component is mixed is not particularly limited.
  • a mixing method a known method such as mixing using a stirring device may be adopted.
  • the fishing net antifouling coating film forming method of the present invention uses the above fishing net antifouling coating film composition to prevent stains on the surface of the coating film to be formed. It is characterized by forming a coating film.
  • the antifouling coating film obtained by the forming method of the present invention gradually dissolves from the surface and the surface of the coating film is constantly updated, so that adhesion of aquatic polluted organisms can be prevented. Further, by overcoating the above composition after dissolving the coating film, the antifouling effect can be continuously exhibited.
  • Examples of the coating film-forming product include fishing gear, underwater structures, and the like.
  • Examples of fishing nets include fishing nets for aquaculture or stationary fishing nets, floats used for the fishing nets, fishing net accessories such as ropes, and the like.
  • Examples of underwater structures include power plant water pipes, bridges, harbor facilities, and the like.
  • the fishing net antifouling coating film of the present invention can be formed by applying the above fishing net antifouling coating composition to the surface (whole or part) of the coating film to be formed.
  • the coating method examples include a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method, and the like. These may be performed alone or in combination of two or more.
  • a dipping method as the application method.
  • the drying temperature may be room temperature.
  • the drying time may be appropriately set according to the amount of the fishing net antifouling paint adhered.
  • the amount of the fishing net antifouling paint adhered may be appropriately set according to the type of the coating film to be formed and the like.
  • the amount of the dry coating film adhered is preferably 1 to 30 parts by mass, and more preferably 4 to 15 parts by mass with respect to 100 parts by mass of the fishing net.
  • the coated material of the present invention has the antifouling coating film on its surface.
  • the coated material of the present invention may have the antifouling coating film on the entire surface or a part thereof.
  • the weight average molecular weight (Mw) is a value (polystyrene-equivalent value) obtained by GPC.
  • the conditions for GPC are as follows. Equipment: HLC-8220GPC manufactured by Tosoh Corporation Guard column ⁇ ⁇ ⁇ TSKguardcolum SuperHZ-L (manufactured by Tosoh Corporation) Column ⁇ ⁇ ⁇ TSKgel SuperHZM-M (manufactured by Tosoh Corporation) 2 series connection Flow rate ⁇ ⁇ ⁇ 0.35 mL / min Detector ⁇ ⁇ ⁇ RI Column constant temperature bath temperature ⁇ ⁇ ⁇ 40 °C Developing solvent: THF (manufactured by Wako Pure Chemical Industries, Ltd .; special grade reagent) Standard sample: TSK standard polystyrene (manufactured by Tosoh Corporation)
  • the heating residue is a value obtained by JIS K5601-1-2 (heating at 125 ° C. for 1 hour).
  • Production Example ⁇ Production Example 1 (Production of Polymer Solution A-1)> 41 g of xylene, 17 g of methyl methacrylate, 21 g of butyl acrylate, 2 g of stearyl methacrylate, and 0.02 g of t-butylperoxy2-ethylhexanoate in a 300 ml flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel (initial). (Addition) was charged, and the mixture was stirred at 95 ⁇ 5 ° C. for 1 hour while introducing nitrogen gas.
  • ⁇ Production Example 2 (Production of Polymer Solution A-2)> 29.0 g of xylene, 60 g of isobutyl methacrylate, 19 g of butyl acrylate, and 0.02 g of t-butylperoxy2-ethylhexanoate in a 300 ml flask equipped with a thermometer, a cooler, a stirrer, and a dropping funnel (initial addition). Was charged, and the mixture was stirred at 95 ⁇ 5 ° C. for 1 hour while introducing nitrogen gas.
  • the antifouling paint composition for fishing nets of Examples and Comparative Examples was applied to polyethylene fishing nets (400 denier, 40 lines, 8 sections) and nylon fishing nets (210 denier, 48 lines, 10 sections) with a dry coating.
  • the fishing net was dipped and coated so that the amount of adhesion was 15 parts by mass with respect to 100 parts by mass of the fishing net, and dried.
  • the fishing net on which the coating film was formed was fixed to a frame of 40 x 60 cm SUS and immersed in the draft part in the raft of Owase, Mie Prefecture, which is a sea area where aquatic polluted organisms are strongly active, and the antifouling evaluation was carried out for 10 months and 12 months. Observed regularly over.
  • Adhesion area of aquatic organisms is 0%
  • Adhesion area of aquatic organisms is more than 0 and less than 10%
  • Adhesion area of aquatic organisms is 10 or more and less than 50%
  • Adhesion area of aquatic organisms is 50% or more

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Abstract

Provided is an antifouling coating composition for fishing nets which retains a moderate chemical release rate over a long period from initiation of immersion in water and can continuously exhibit excellent antifouling performance over a long period.　The present invention provides an antifouling coating composition for fishing nets which comprises a (meth)acrylic ester polymer (A), an ethylene/vinyl acetate copolymer (B), a silicone oil (C), and an antifouling chemical (D).

Description

漁網防汚塗料組成物、該組成物を用いて形成される防汚塗膜を表面に有する漁網、漁網用具又は水中構造物Fishing net antifouling paint composition, fishing nets, fishing net tools or underwater structures having an antifouling coating film formed using the composition on the surface.
　本発明は、漁網防汚塗料組成物、及び該組成物を用いて形成される防汚塗膜を表面に有する漁網、漁網用具又は水中構造物に関する。 The present invention relates to a fishing net antifouling paint composition and a fishing net, a fishing net tool or an underwater structure having an antifouling coating film formed by using the composition on the surface.
　漁網、漁網用具及び水中構造物などは、海中に長期間設置されるため、漁網用の防汚塗料での処理をせずに使用すると、アオサ、アオノリ等の緑藻類、イギス等の紅藻類、フジツボ等の甲殻動物、ヒドラ虫等の腔腸動物、セルプラ、コケムシ、軟体動物類などの種々の水棲汚損生物が付着する。これにより、漁網の網の目がふさがれて海水の流れが悪くなり、酸素欠乏で養殖魚が大量に死んだり、伝染病が発生して出荷できなくなったりし、大きな損害を受けることがある。 Since fishing nets, fishing net tools, and underwater structures are installed in the sea for a long period of time, if they are used without treatment with antifouling paint for fishing nets, green algae such as sea lettuce and green laver, red algae such as Igis, and hydra Crustaceans such as sea lettuce, coelenterates such as hydra, and various aquatic pollutants such as sea lettuce, sea lettuce, and soft animals adhere. As a result, the mesh of the fishing net is blocked and the flow of seawater is impaired, and a large number of farmed fish die due to lack of oxygen, or an infectious disease occurs and the fish cannot be shipped, which may cause great damage.
　これらの水棲汚損生物の付着を防止するために、従来は有機錫化合物を用いた漁網用防汚塗料組成物が広く使用されてきたが、環境に対する配慮などから使用できなくなった。 Conventionally, antifouling paint compositions for fishing nets using organic tin compounds have been widely used in order to prevent the adhesion of these aquatic polluted organisms, but they can no longer be used due to environmental considerations.
　そこで、有機錫化合物に替わる漁網用防汚塗料組成物として、種々の研究、提案がなされ、無機化合物や有機化合物を防汚薬剤として用い、これを天然樹脂系または合成樹脂系展着樹脂に配合した漁網用防汚塗料組成物が使用されてきた。しかし、これらは塗膜物性が悪く、防汚期間が短い等の問題があった。 Therefore, various studies and proposals have been made as antifouling paint compositions for fishing nets to replace organic tin compounds, and inorganic compounds and organic compounds are used as antifouling agents and blended with natural resin-based or synthetic resin-based spreading resins. Antifouling paint compositions for fishing nets have been used. However, these have problems such as poor physical characteristics of the coating film and a short antifouling period.
　それらの問題を解決すべく、展着樹脂に薬剤の溶出調整剤として特定のポリエーテル変性シリコーンオイルを配合した漁網用防汚塗料組成物が提案された（特許文献１～４）。 In order to solve these problems, antifouling coating compositions for fishing nets in which a specific polyether-modified silicone oil is blended with a spreading resin as an elution adjusting agent for chemicals have been proposed (Patent Documents 1 to 4).
　しかしながら、上記発明はいずれも、漁網浸漬初期においては良好な防汚効果を発揮するものの浸漬期間が長期に亘るにつれ薬剤の溶出が不安定となり、長期間に亘る良好な防汚効果を得ることは困難であった。 However, although all of the above inventions exhibit a good antifouling effect at the initial stage of fishing net immersion, the elution of the chemical becomes unstable as the immersion period becomes long, and a good antifouling effect over a long period of time can be obtained. It was difficult.
特開平３－２０３７０JP-A-3-20370 特開平９－１７６５７７Japanese Patent Application Laid-Open No. 9-176577 特開２００１－１９８４８JP 2001-19848 特開２００９－２１５５２７JP-A-2009-215527
　本発明は、上記事情に鑑みてなされたものであり、水中浸漬時から長期に亘り適度な薬剤放出量を維持し、優れた防汚性能を長期間継続的に発揮することができる漁網防汚塗料組成物を提供することを課題とする。 The present invention has been made in view of the above circumstances, and is capable of maintaining an appropriate amount of chemicals released for a long period of time from the time of immersion in water and continuously exhibiting excellent antifouling performance for a long period of time. An object of the present invention is to provide a coating composition.
　本発明によれば、（メタ）アクリル酸エステル重合体（Ａ）、エチレン酢酸ビニル共重合体（Ｂ）、シリコーンオイル（Ｃ）、及び、防汚薬剤（Ｄ）を含有する漁網防汚塗料組成物が提供される。 According to the present invention, a fishing net antifouling coating composition containing a (meth) acrylic acid ester polymer (A), an ethylene-vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D). Things are provided.
　本発明者は、上記課題を解決すべく鋭意研究を重ねた結果、上記組成物が、上記課題を解決できることを見出し、本発明を完成するに至った。 As a result of intensive research to solve the above-mentioned problems, the present inventor has found that the above-mentioned composition can solve the above-mentioned problems, and has completed the present invention.
　以下、本発明について詳細を説明する。 Hereinafter, the present invention will be described in detail.
１．漁網防汚塗料組成物
　本発明の漁網防汚塗料組成物は、養殖用又は定置網用の漁網およびこれらに使用される浮き子、ロープ等の漁網用具、ならびに発電所の冷却水導管等の水中構造物等に水棲汚損生物が付着することを防止するための組成物である。本発明の組成物は、（メタ）アクリル酸エステル重合体（Ａ）、エチレン酢酸ビニル共重合体（Ｂ）、シリコーンオイル（Ｃ）、及び、防汚薬剤（Ｄ）を含有する。以下、詳細に説明する。 1. 1. Fishing net antifouling paint composition The fishing net antifouling paint composition of the present invention includes fishing nets for cultivation or fixed nets, fishing net tools such as floats and ropes used for these, and underwater structures such as cooling water conduits for power plants. It is a composition for preventing aquatic polluted organisms from adhering to objects. The composition of the present invention contains a (meth) acrylic acid ester polymer (A), an ethylene-vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D). Hereinafter, a detailed description will be given.
＜（メタ）アクリル酸エステル重合体（Ａ）＞
　重合体（Ａ）は、（メタ）アクリル酸エステルを含む単量体を用いて形成される重合体であり、１種類の単量体の単独重合体であってもよいが、複数種類の単量体の共重合体であることが好ましい。重合体（Ａ）を形成するための単量体中は、（メタ）アクリル酸エステル以外に、（メタ）アクリル酸エステルと共重合可能なエチレン性不飽和単量体を含有してもよい。 <(Meta) acrylic acid ester polymer (A)>
The polymer (A) is a polymer formed by using a monomer containing a (meth) acrylic acid ester, and may be a copolymer of one kind of monomer, but a plurality of kinds of simple polymers. It is preferably a copolymer of a monomer. In addition to the (meth) acrylic acid ester, the monomer for forming the polymer (A) may contain an ethylenically unsaturated monomer copolymerizable with the (meth) acrylic acid ester.
　重合体（Ａ）を形成するための単量体中の（メタ）アクリル酸エステルの割合は、例えば、６０質量％以上であり、具体的には例えば、６０、６５、７０、７５、８０、８５、９０、９５、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The ratio of the (meth) acrylic acid ester in the monomer for forming the polymer (A) is, for example, 60% by mass or more, and specifically, for example, 60, 65, 70, 75, 80, It is 85, 90, 95, 100% by mass, and may be in the range between any two of the numerical values exemplified here.
　重合体（Ａ）を形成する（メタ）アクリル酸エステルとしては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２一エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－メトキシプロピル、（メタ）アクリル酸４－メトキシブチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸プロピレングリコールモノメチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸グリシジル、（メタ）アクリル酸フルフリル、（メタ）アクリル酸テトラヒドロフルフリル、（メタ）アクリル酸ジメチルアミノエチル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸ベンジル、及び（メタ）アクリル酸フェニル等が挙げられる。 Examples of the (meth) acrylic acid ester forming the polymer (A) include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth). T-butyl acrylate, 21-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, ( 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) ) Glycidyl acrylate, (meth) fluoric acid acrylate, (meth) tetrahydroflufuryl acrylate, (meth) dimethylaminoethyl acrylate, (meth) diethylaminoethyl acrylate, benzyl (meth) acrylate, and (meth) acrylic Examples include phenyl acid acid.
　この中でも特に、重合性の点から（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸２一エチルヘキシル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸２－メトキシエチル、（メタ）アクリル酸２－メトキシプロピル、（メタ）アクリル酸４－メトキシブチル、（メタ）アクリル酸２－エトキシエチル、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル等が好ましい。 Among these, in particular, from the viewpoint of polymerizable properties, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, (meth) acrylic 21-ethylhexyl acid, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, ( 2-ethoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like are preferable.
　（メタ）アクリル酸エステル以外の単量体としては、例えば、例えば、プロピレン、イソブチレン、α－オクテン、α－ドデセン、α－オクタデセン等のオレフィン類、アクリル酸、メタクリル酸、クロトン酸、マレイン酸、無水マレイン酸、イタコン酸等の不飽和酸類あるいはその塩あるいはモノ又はジアルキルエステル等、アクリロニトリル、メタクリロニトリル等のニトリル類、アクリルアミド、メタクリルアミド等のアミド類、エチレンスルホン酸、アリルスルホン酸、メタアリルスルホン酸等のオレフィンスルホン酸あるいはその塩、アルキルビニルエーテル類、Ｎ－アクリルアミドメチルトリメチルアンモニウムクロライド、アリルトリメチルアンモニウムクロライド、ジメチルアリルビニルケトン、Ｎ－ビニルピロリドン、塩化ビニル、塩化ビニリデン、ポリオキシエチレン（メタ）アリルエーテル、ポリオキシプロピレン（メタ）アリルエーテルなどのポリオキシアルキレン（メタ）アリルエーテル、ポリオキシエチレン（メタ）アクリレート、ポリオキシプロピレン（メタ）アクリレート等のポリオキシアルキレン（メタ）アクリレート、ポリオキシエチレン（メタ）アクリルアミド、ポリオキシプロピレン（メタ）アクリルアミド等のポリオキシアルキレン（メタ）アクリルアミド、ポリオキシエチレン（１－（メタ）アクリルアミド－１，１－ジメチルプロピル）エステル、ポリオキシエチレンビニルエーテル、ポリオキシプロピレンビニルエーテル、ポリオキシエチレンアリルアミン、ポリオキシプロピレンアリルアミン、ポリオキシエチレンビニルアミン、ポリオキシプロピレンビニルアミン等が挙げられる。 Examples of the monomer other than the (meth) acrylic acid ester include olefins such as propylene, isobutylene, α-octene, α-dodecene and α-octadecene, acrylic acid, methacrylic acid, crotonic acid and maleic acid. Unsaturated acids such as maleic anhydride and itaconic acid or salts thereof or mono or dialkyl esters, nitriles such as acrylonitrile and methacrylonitrile, amides such as acrylamide and methacrylicamide, ethylene sulfonic acid, allyl sulfonic acid and metaallyl. Olefin sulfonic acid such as sulfonic acid or a salt thereof, alkyl vinyl ethers, N-acrylamide methyltrimethylammonium chloride, allyltrimethylammonium chloride, dimethylallylvinyl ketone, N-vinylpyrrolidone, vinyl chloride, vinylidene chloride, polyoxyethylene (meth) Polyoxyalkylene (meth) allyl ethers such as allyl ethers and polyoxypropylene (meth) allyl ethers, polyoxyalkylene (meth) acrylates such as polyoxyethylene (meth) acrylates and polyoxypropylene (meth) acrylates, and polyoxyethylene. Polyoxyalkylene (meth) acrylamide such as (meth) acrylamide and polyoxypropylene (meth) acrylamide, polyoxyethylene (1- (meth) acrylamide-1,1-dimethylpropyl) ester, polyoxyethylene vinyl ether, polyoxypropylene Examples thereof include vinyl ether, polyoxyethylene allylamine, polyoxypropylene allylamine, polyoxyethylene vinylamine, and polyoxypropylene vinylamine.
　前記重合体（Ａ）のガラス転移温度（Ｔｇ）は、－６５～５０℃程度が好ましく、－５０～３５℃程度がより好ましい。Ｔｇが前記範囲内の場合、漁網へ塗布した後の塗膜のタックが大きくなりすぎて塗布作業に支障をきたす問題も生じず、また、塗膜の柔軟性が損なわれてクラックや割れなどを生じたり、防汚効果を落としたりという問題を生じない。前記のＴｇの値は、示差走査熱量測定装置（例：ＭＥＴＴＬＥＲ　ＴＯＬＥＤＯ社製、ＤＳＣ１）を用いて、ＪＩＳ　Ｋ　７１２１の測定法を参照し、実測した値をいう。 The glass transition temperature (Tg) of the polymer (A) is preferably about −65 to 50 ° C., more preferably about −50 to 35 ° C. When Tg is within the above range, the tack of the coating film after application to the fishing net becomes too large and there is no problem of hindering the application work, and the flexibility of the coating film is impaired to cause cracks and cracks. It does not cause problems such as occurrence and reduction of antifouling effect. The Tg value refers to a value actually measured by referring to the measurement method of JIS K 7121 using a differential scanning calorimetry device (eg, METTLER TOLEDO, DSC1).
　前記重合体（Ａ）の質量平均分子量（Ｍｗ）は、１００００～７００００００程度であり、好ましくは５００００～５００００００程度である。Ｍｗが５００００～５００００００程度の場合、塗膜の強靭性という点で好ましい。Ｍｗの測定方法としては、例えば、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）が挙げられる。ＧＰＣによってＭｗを測定する場合、Ｍｗは、ポリスチレンを標準物質として検量線を作成して測定することにより求めた値（ポリスチレン換算値）として表示される。 The mass average molecular weight (Mw) of the polymer (A) is about 10,000 to 7,000, preferably about 50,000 to 5,000,000. When Mw is about 50,000 to 5,000,000, it is preferable in terms of toughness of the coating film. Examples of the method for measuring Mw include gel permeation chromatography (GPC). When Mw is measured by GPC, Mw is displayed as a value (polystyrene-equivalent value) obtained by creating a calibration curve using polystyrene as a standard substance and measuring it.
　前記重合体（Ａ）は、前記単量体を重合させることにより得られ、ランダム共重合体、交互共重合体、周期的共重合体、又はブロック共重合体のいずれの共重合体であってもよい。 The polymer (A) is obtained by polymerizing the monomer, and is a copolymer of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. May be good.
　重合方法としては、例えば、溶液重合、乳化重合、塊状重合、懸濁重合等が挙げられる。この中でも特に、簡便に、且つ、精度良く、前記重合体（Ａ）を合成できる点で、溶液重合、乳化重合が好ましい。 Examples of the polymerization method include solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization and the like. Of these, solution polymerization and emulsion polymerization are particularly preferable in that the polymer (A) can be synthesized easily and accurately.
　溶液重合の場合、前記重合体（Ａ）の重合は、例えば、重合開始剤の存在下で行われる。
　前記重合開始剤としては、例えば、２，２'－アゾビスイソブチロニトリル（ＡＩＢＮ）、２，２'－アゾビス－２－メチルブチロニトリル、ジメチル－２，２'－アゾビスイソブチレート等のアゾ化合物；ベンゾイルパーオキサイド、ジ－ｔｅｒｔ－ブチルパーオキサイド、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシイソプロピルカーボネート、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等の過酸化物等が挙げられる。これら重合開始剤は、単独又は２種以上を組み合わせて使用できる。前記重合開始剤としては、特に、２，２'－アゾビスイソブチロニトリル及びｔ－ブチルパーオキシ－２－エチルヘキサノエートが好ましい。前記重合開始剤の使用量を適宜設定することにより、前記共重合体の分子量を調整することができる。 In the case of solution polymerization, the polymerization of the polymer (A) is carried out, for example, in the presence of a polymerization initiator.
Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis-2-methylbutyronitrile, and dimethyl-2,2'-azobisisobutyrate. Azo compounds such as benzoyl peroxide, di-tert-butyl peroxide, tert-butylperoxybenzoate, tert-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexanoate and other peroxides, etc. Can be mentioned. These polymerization initiators can be used alone or in combination of two or more. As the polymerization initiator, 2,2'-azobisisobutyronitrile and t-butylperoxy-2-ethylhexanoate are particularly preferable. The molecular weight of the copolymer can be adjusted by appropriately setting the amount of the polymerization initiator used.
　前記重合反応においては、必要に応じて水又は有機溶媒を用いてもよい。有機溶剤としては、例えば、キシレン、トルエン等の芳香族炭化水素系溶剤；ヘキサン、ヘプタン等の脂肪族炭化水素系溶剤；酢酸エチル、酢酸ブチル、酢酸イソブチル、酢酸メトキシプロピル等のエステル系溶剤；イソプロピルアルコール、ブチルアルコール等のアルコール系溶剤；ジオキサン、ジエチルエーテル、ジブチルエーテル等のエーテル系溶剤；メチルエチルケトン、メチルイソブチルケトン等のケトン系溶剤等が挙げられる。この中でも特に、芳香族炭化水素系溶剤が好ましく、キシレンがより好ましい。これら溶媒については、単独あるいは２種以上を組み合わせて使用できる。 In the polymerization reaction, water or an organic solvent may be used if necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl. Alcohol-based solvents such as alcohol and butyl alcohol; ether-based solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone can be mentioned. Of these, aromatic hydrocarbon solvents are particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.
　重合反応における反応温度は、重合開始剤の種類等に応じて適宜設定すればよく、通常７０～１４０℃程度、好ましくは８０～１２０℃程度である。重合反応における反応時間は、反応温度等に応じて適宜設定すればよく、通常４～８時間程度である。
　重合反応は、窒素ガス、アルゴンガス等の不活性ガス雰囲気下で行われることが好ましい。 The reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually about 70 to 140 ° C., preferably about 80 to 120 ° C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
　また、乳化重合の場合、重合開始剤としては、従来、乳化重合において使用されているものであれば使用できる。重合開始剤として、例えば、過硫酸カリウム、過硫酸アンモニウム、過硫酸ナトリウム、過酸化水素、ｔｅｒｔ－ブチルハイドロパーオキサイド等の水溶性重合開始剤；２，２'－アゾビスイソブチロニトリル、２，２'－アゾビス－２－メチルブチロニトリル、ジメチル－２，２'－アゾビスイソブチレート等、過酸化ベンゾイル、ジ－ｔｅｒｔ－ブチルパーオキサイド等の油溶性重合開始剤が挙げられる。特に、水溶性重合開始剤が好ましい。また、これらの重合開始剤を還元剤と組み合わせてレドックス系重合開始剤として使用することも可能である。 Further, in the case of emulsion polymerization, as the polymerization initiator, any one conventionally used in emulsion polymerization can be used. As the polymerization initiator, for example, a water-soluble polymerization initiator such as potassium persulfate, ammonium persulfate, sodium persulfate, hydrogen peroxide, tert-butyl hydroperoxide; 2,2'-azobisisobutyronitrile, 2, Examples thereof include oil-soluble polymerization initiators such as 2'-azobis-2-methylbutyronitrile, dimethyl-2,2'-azobisisobutyrate, benzoyl peroxide, and di-tert-butyl peroxide. In particular, a water-soluble polymerization initiator is preferable. It is also possible to use these polymerization initiators in combination with a reducing agent as a redox-based polymerization initiator.
　乳化重合における反応温度は、重合開始剤の種類等に応じて適宜設定すればよく、通常４０～８０℃程度、好ましくは５５～７０℃程度である。重合反応における反応時間は、反応温度等に応じて適宜設定すればよく、通常４～１０時間、好ましくは６～９時間程度である。
　重合反応は、窒素ガス、アルゴンガス等の不活性ガス雰囲気下で行われることが好ましい。 The reaction temperature in emulsion polymerization may be appropriately set according to the type of polymerization initiator and the like, and is usually about 40 to 80 ° C, preferably about 55 to 70 ° C. The reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 10 hours, preferably about 6 to 9 hours.
The polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
　乳化重合における界面活性剤としては、高級アルコールの硫酸エステル塩、アルキルベンゼンスルホン酸塩、脂肪族スルホン酸塩、脂肪族カルボン酸塩、非イオン性界面活性剤の硫酸エステル塩等のアニオン性界面活性剤；ポリエチレングリコールのアルキルエステル型、アルキルフェニルエーテル型、アルキルエーテル型等のノニオン性界面活性剤を一種又は二種以上で使用できる。また、カチオン性界面活性剤や両性界面活性剤を使用することもできる。 Surfactants in emulsion polymerization include anionic surfactants such as sulfate ester salts of higher alcohols, alkylbenzene sulfonates, aliphatic sulfonates, aliphatic carboxylates, and sulfate ester salts of nonionic surfactants. One or two or more nonionic surfactants such as an alkyl ester type, an alkyl phenyl ether type, and an alkyl ether type of polyethylene glycol can be used. In addition, a cationic surfactant or an amphoteric surfactant can also be used.
　前記重合体（Ａ）としては、市販品として、例えば、バンスター　Ｘ１２９０Ｂ１１　（中部サイデン（株）製）、ポリゾール（Ｒ）　ＡＰ－４６５０Ｎ（昭和電工（株）製）、ポリゾール（Ｒ）　ＡＰ－４７８０Ｎ（昭和電工（株）製）などが挙げられる。 As the polymer (A), as commercially available products, for example, Vanstar X1290B11 (manufactured by Chubu Saiden Co., Ltd.), Polysol (R) AP-4650N (manufactured by Showa Denko KK), Polysol (R) AP-4780N. (Made by Showa Denko KK), etc.
　前記重合体（Ａ）の含有量は、特に限定されないが、固形分換算で塗料組成物中に１～５０質量％使用され、好ましくは３～３０質量％である。 The content of the polymer (A) is not particularly limited, but is used in the coating composition in terms of solid content in an amount of 1 to 50% by mass, preferably 3 to 30% by mass.
＜エチレン酢酸ビニル共重合体（Ｂ）＞
　共重合体（Ｂ）は、エチレンと酢酸ビニルを含む単量体を用いて形成される共重合体である。共重合体（Ｂ）を形成するための単量体は、エチレン、酢酸ビニル以外に、これらと共重合可能なエチレン性不飽和単量体を含有してもよい。 <Ethylene Vinyl Acetate Copolymer (B)>
The copolymer (B) is a copolymer formed by using a monomer containing ethylene and vinyl acetate. The monomer for forming the copolymer (B) may contain an ethylenically unsaturated monomer copolymerizable with ethylene and vinyl acetate in addition to ethylene and vinyl acetate.
　共重合体（Ｂ）を形成するための単量体中のエチレンと酢酸ビニルの合計の割合は、例えば、６０質量％以上であり、具体的には例えば、６０、６５、７０、７５、８０、８５、９０、９５、１００質量％であり、ここで例示した数値の何れか２つの間の範囲内であってもよい。 The total ratio of ethylene and vinyl acetate in the monomer for forming the copolymer (B) is, for example, 60% by mass or more, and specifically, for example, 60, 65, 70, 75, 80. , 85, 90, 95, 100% by mass, and may be within the range between any two of the numerical values exemplified here.
　エチレンと酢酸ビニル以外の単量体としては、例えば、（メタ）アクリル酸エステル以外の単量体として上述したものが挙げられる。 Examples of the monomer other than ethylene and vinyl acetate include those described above as the monomer other than the (meth) acrylic acid ester.
　前記共重合体（Ｂ）の質量平均分子量（Ｍｗ）は、１００００～７００００００程度であり、好ましくは５００００～５００００００程度である。Ｍｗが５００００～５００００００程度の場合、塗膜の強靭性という点で好ましい。 The mass average molecular weight (Mw) of the copolymer (B) is about 10,000 to 7,000, preferably about 50,000 to 5,000,000. When Mw is about 50,000 to 5,000,000, it is preferable in terms of toughness of the coating film.
　前記共重合体（Ｂ）は、前記単量体を重合させることにより得られ、ランダム共重合体、交互共重合体、周期的共重合体、又はブロック共重合体のいずれの共重合体であってもよい。 The copolymer (B) is obtained by polymerizing the monomer, and is a copolymer of a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer. You may.
　重合方法、開始剤、溶媒、温度、その他の条件、Ｍｗの測定方法等は、重合体（Ａ）で既記の手法が適用できる。 The method described above for the polymer (A) can be applied to the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like.
　前記共重合体（Ｂ）としては、市販品として、例えば、ポリゾール（Ｒ）　ＥＶＡ　Ｐ－３Ｎ（昭和電工（株）製）、ノバテック（ＴＭ）ＥＶＡ　ＬＶ－２１１Ａ（日本ポリエチレン（株）製）などが挙げられる。 Examples of the copolymer (B) include Polysol (R) EVA P-3N (manufactured by Showa Denko Corporation), Novatec (TM) EVA LV-211A (manufactured by Japan Polyethylene Corporation), and the like. Can be mentioned.
　共重合体（Ｂ）の含有量は、重合体（Ａ）と共重合体（Ｂ）の合計質量に対して、２０～９０質量％であることが好ましく、３０～９０質量％が更に好ましく、５０～８０質量％であることが特に好ましい。前記範囲内にある場合、長期に亘り良好な防汚効果を維持でき、更に、海水への浸漬時における塗膜物性が著しく向上し、特にナイロン網のような比較的塗膜形成が難しい素材の網に対しても良好な塗膜物性を維持することができる。 The content of the copolymer (B) is preferably 20 to 90% by mass, more preferably 30 to 90% by mass, based on the total mass of the polymer (A) and the copolymer (B). It is particularly preferably 50 to 80% by mass. When it is within the above range, a good antifouling effect can be maintained for a long period of time, and the physical characteristics of the coating film when immersed in seawater are remarkably improved. Good coating film physical properties can be maintained even for nets.
　＜シリコーンオイル（Ｃ）＞
　シリコーンオイル（Ｃ）としては、例えば、ポリジメチルシロキサン、ポリメチルフェニルシロキサン、メチルフェニルシロキサン－ジメチルシロキサン共重合体、ポリエーテル変性ポリジメチルシロキサン、ポリエーテル変性ポリアルキル（メチル）シロキサン、ポリエステル変性ポリジメチルシロキサン、長鎖アルキル変性ポリジメチルシロキサン、アラルキル変性ポリジメチルシロキサン、ポリエーテル長鎖アルキルアラルキル変性ジメチルシリコーンオイル、フロロシリコーンオイル、アミノ変性シリコーンオイル、その他各種官能基による変性シリコーンオイル等が挙げられる。特に、親水親油バランス（ＨＬＢ値）が０．５～９のポリエーテル変性シリコーンオイルが好ましく、具体的には０．５～９のポリエーテル変性ポリジメチルシロキサン又はポリエーテル長鎖アルキルアラルキル変性ジメチルシリコーンオイルが望ましい。さらに好ましいものとして、親水親油バランス（ＨＬＢ値）が１～５の範囲にあるポリエーテル変性ポリジメチルシロキサン又はポリエーテル長鎖アルキルアラルキル変性ジメチルシリコーンオイルが挙げられる。ＨＬＢ値が０．５～９の範囲内のシリコーンオイルを使用することで、十分な防汚性能を得ることができる。
　本発明では、これらのシリコーンオイルを単独で用いてもよいし、２種以上を組み合わせて用いてもよい。 <Silicone oil (C)>
Examples of the silicone oil (C) include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, polyether-modified polydimethylsiloxane, polyether-modified polyalkyl (methyl) siloxane, and polyester-modified polydimethyl. Examples thereof include siloxane, long-chain alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, polyether long-chain alkyl-aralkyl-modified dimethylsilicone oil, fluorosilicone oil, amino-modified silicone oil, and other modified silicone oils with various functional groups. In particular, a polyether-modified silicone oil having a hydrophilic lipophilic balance (HLB value) of 0.5 to 9 is preferable, and specifically, a polyether-modified polydimethylsiloxane or a polyether long-chain alkylaralkyl-modified dimethyl having a hydrophilic lipophilic balance (HLB value) of 0.5 to 9 is preferable. Silicone oil is preferred. More preferable are polyether-modified polydimethylsiloxane or polyether long-chain alkyl aralkyl-modified dimethylsilicone oil having a hydrophilic lipophilic balance (HLB value) in the range of 1 to 5. Sufficient antifouling performance can be obtained by using a silicone oil having an HLB value in the range of 0.5 to 9.
In the present invention, these silicone oils may be used alone or in combination of two or more.
　シリコーンオイルの粘度は、塗工性能および塗膜物性の観点から、１０００ポイズ以下が好ましく、１００ポイズ以下がより好ましい。 The viscosity of the silicone oil is preferably 1000 poise or less, more preferably 100 poise or less, from the viewpoint of coating performance and coating film physical characteristics.
　シリコーンオイル（Ｃ）の含有量は、特に限定されないが、固形分換算で、重合体（Ａ）及び共重合体（Ｂ）の合計量１００質量部に対して１～１５０質量部であり、好ましくは５～１００質量部であり、さらに好ましくは、１０～５０質量部である。 The content of the silicone oil (C) is not particularly limited, but is preferably 1 to 150 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the copolymer (B) in terms of solid content. Is 5 to 100 parts by mass, more preferably 10 to 50 parts by mass.
　シリコーンオイル（Ｃ）を水性防汚組成物中において用いる場合、乳化剤や分散剤等によりエマルション化したものを用いる。その際、シリコーンオイルが、平均粒子径０．０１～１００μｍ、好ましくは０．１～５０μｍの粒子として分散していることが分散性や貯蔵安定性の観点から好ましい。 When the silicone oil (C) is used in an aqueous antifouling composition, it is emulsified with an emulsifier, a dispersant or the like. At that time, it is preferable that the silicone oil is dispersed as particles having an average particle diameter of 0.01 to 100 μm, preferably 0.1 to 50 μm, from the viewpoint of dispersibility and storage stability.
　前記エマルション化の方法としては、例えば、シリコーンオイルと乳化剤とを仕込み、その後、攪拌機で攪拌しながら、蒸留水を添加し、目的の粒子径範囲の乳化粒子が得られるように適宜設定しながら撹拌を行えばよい。 As the method of emulsification, for example, silicone oil and an emulsifier are charged, and then distilled water is added while stirring with a stirrer, and the mixture is stirred while appropriately setting so that emulsified particles in a target particle size range can be obtained. Just do.
　前記乳化剤としては、例えば、ノニオン性界面活性剤、アニオン性界面活性剤が挙げられる。 Examples of the emulsifier include nonionic surfactants and anionic surfactants.
　ノニオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンオキシプロピレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンオキシプロピレンアルキルフェニルエーテル、ポリオキシエチレンジスチリルフェニルエーテル、ポリオキシエチレンオキシプロピレンジスチリルフェニルエーテル、ポリオキシエチレントリスチリルフェニルエーテル等が挙げられ、２種以上を組み合わせて用いてもよい。 Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene oxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene oxypropylene alkyl phenyl ether, polyoxyethylene distyryl phenyl ether, and polyoxy. Examples thereof include ethyleneoxypropylene distyrylphenyl ether and polyoxyethylene tristyrylphenyl ether, and two or more of them may be used in combination.
　アニオン性界面活性剤としては、例えば、非イオン界面活性剤の硫酸エステル塩、リン酸エステル塩や、ポリオキシエチレンアルキルエーテルカルボン酸塩、アルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸塩等が挙げられ、２種以上を組み合わせて用いてもよい。 Examples of the anionic surfactant include sulfate ester salt and phosphoric acid ester salt of nonionic surfactant, polyoxyethylene alkyl ether carboxylate, alkylbenzene sulfonate, alkylnaphthalene sulfonate and the like. Two or more types may be used in combination.
　＜防汚薬剤（Ｄ）＞
　防汚薬剤（Ｄ）としては、海棲汚損生物に対して殺傷又は忌避作用を有する化合物であればよく、特に限定されない。例えば、以下の有機化合物及び無機化合物が挙げられる。 <Anti-fouling agent (D)>
The antifouling agent (D) is not particularly limited as long as it is a compound having a killing or repellent action against marine polluted organisms. For example, the following organic compounds and inorganic compounds can be mentioned.
　有機化合物としては、例えば、２－メルカプトピリジンＮ―オキシド銅、２－メルカプトピリジンＮ―オキシド亜鉛、ジンクエチレンビスジチオカーバメート、ビス（ジメチルジチオカルバミン酸）亜鉛、ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート、ピリジン・トリフェニルボラン、ｎ－オクタデシルアミン・トリフェニルボラン、３－（２－エチルヘキシルオキシ）プロピルアミン・トリフェニルボラン、４－イソプロピル－ジフェニルメチル、４－フェニルピリジル－ジフェニルボラン、２，４，６－トリクロロマレイミド、ｎ－（２，６ジエチルフェニル）２，３ジクロロマレイミド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、クロロメチル－ｎ－オクチルジスルフィド、４，５－ジクロロ－２－ｎ－オクチルー３－イソチアゾロン、３，４－ジクロロフェニル－Ｎ－Ｎ－ジメチルウレア、２－メチルチオ－４－ｔ－ブチルアミノ－６－シクロプロピルアミノ－ｓ－トリアジン、２，４，５，６－テトラクロロイソフタロニトリル、Ｎ－ジクロロフルオロメチルチオ－Ｎ'，Ｎ'－ジメチル－Ｎ－ｐ－トリルスルファミド、Ｎ－ジクロロメチルチオ－Ｎ'，Ｎ'－ジメチル－Ｎ－フェニルスルファミド、２－（４－チアゾリル）ベンズイミダゾール、等が挙げられる。 Examples of the organic compound include 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, zincethylene bisdithiocarbamate, bis (dimethyldithiocarbamic acid) zinc, bisdimethyldithiocarbamoylzincethylene bisdithiocarbamate, and pyridine. -Triphenylboran, n-octadecylamine-triphenylboran, 3- (2-ethylhexyloxy) propylamine triphenylboran, 4-isopropyl-diphenylmethyl, 4-phenylpyridyl-diphenylboran, 2,4,6- Trichloromaleimide, n- (2,6 diethylphenyl) 2,3 dichloromaleimide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, chloromethyl-n-octyldisulfide, 4,5-dichloro-2-n- Octyl-3-isothiazolone, 3,4-dichlorophenyl-NN-dimethylurea, 2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine, 2,4,5,6-tetrachloroiso Phtalonitrile, N-dichlorofluoromethylthio-N', N'-dimethyl-Np-tolyl sulfamide, N-dichloromethylthio-N', N'-dimethyl-N-phenylsulfamide, 2- (4) -Thiazolyl) benzimidazole, etc. can be mentioned.
　上記有機化合物のうち、ｎ－オクタデシルアミン・トリフェニルボラン、テトラエチルチウラムジスルフィド、２－メルカプトピリジンＮ―オキシド銅、２－メルカプトピリジンＮ－オキシド亜鉛及びビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメートが特に好ましく、１種または２種以上併用してもよい。 Among the above organic compounds, n-octadecylamine / triphenylborane, tetraethylthiuram disulfide, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc and bisdimethyldithiocarbamoylzincethylene bisdithiocarbamate are particularly preferable. One type or two or more types may be used in combination.
　無機化合物としては、例えば、亜酸化銅、１価の銅ガラス、２価の銅ガラス、チオシアン酸銅、キュプロニッケル、銅粉等が挙げられ、亜酸化銅、１価の銅ガラス及び２価の銅ガラスが特に好ましく、１種または２種以上併用してもよい。 Examples of the inorganic compound include cuprous oxide, monovalent copper glass, divalent copper glass, copper thiocyanate, cupronickel, copper powder and the like, and include cuprous oxide, monovalent copper glass and divalent copper. Copper glass is particularly preferable, and one type or two or more types may be used in combination.
　上記防汚薬剤（Ｄ）のうち、溶剤又は水に不溶の防汚薬剤については、分散性の問題から平均粒径１０μｍ以下のものが好ましく、特に３μｍ以下のものが好ましい。これらの平均粒径は、日機装（株）社製粒度分布計、機種マイクロトラックＭＴ３３００ＥＸII（測定原理レーザー回析・散乱法）により測定することができる。 Among the antifouling agents (D), those having an average particle size of 10 μm or less are preferable, and those having an average particle size of 3 μm or less are particularly preferable, because of the problem of dispersibility. These average particle sizes can be measured by a particle size distribution meter manufactured by Nikkiso Co., Ltd., and a model Microtrack MT3300EXII (measurement principle laser diffraction / scattering method).
　本発明の塗料組成物における防汚薬剤（Ｄ）の含有量は限定的ではないが、重合体（Ａ）及び共重合体（Ｂ）の合計量１００質量部に対して、通常１～３００質量部であり、好ましくは５～２００質量部である。防汚薬剤の使用量が１質量部未満では防汚性が充分でなく、一方、３００質量部超では塗工性能、塗膜物性が劣化する傾向がある。 The content of the antifouling agent (D) in the coating composition of the present invention is not limited, but is usually 1 to 300 parts by mass with respect to 100 parts by mass of the total amount of the polymer (A) and the copolymer (B). It is a part, preferably 5 to 200 parts by mass. If the amount of the antifouling agent used is less than 1 part by mass, the antifouling property is not sufficient, while if it exceeds 300 parts by mass, the coating performance and the physical characteristics of the coating film tend to deteriorate.
＜その他の添加成分＞
　本発明に用いられる塗料組成物は、他の展着樹脂、他の溶出調整剤、染料、顔料、ワックス類、防腐剤、可塑剤、分散剤、消泡剤、造膜助剤、沈降防止剤、タレ止め剤、界面活性剤、溶剤等を、本発明の目的を損なわない範囲内で任意に、任意の配合割合で含有することができる。 <Other additive ingredients>
The coating composition used in the present invention includes other spreading resins, other elution modifiers, dyes, pigments, waxes, preservatives, plasticizers, dispersants, defoamers, film-forming aids, and anti-settling agents. , Anti-sagging agent, surfactant, solvent and the like can be arbitrarily contained in an arbitrary compounding ratio within a range that does not impair the object of the present invention.
　他の展着樹脂としては、重合体（Ａ）および共重合体（Ｂ）以外の、ビニル樹脂、アルキッド樹脂、ウレタン樹脂、ポリエステル樹脂、合成ゴム、塩素化ポリエチレン等の合成樹脂、ウッドロジン、ガムロジン、変性ロジン等の天然樹脂が挙げられる。 Other spreading resins include vinyl resins, alkyd resins, urethane resins, polyester resins, synthetic rubbers, synthetic resins such as chlorinated polyethylene, wood rosin, gum rosin, other than the polymer (A) and copolymer (B). Examples include natural resins such as modified rosin.
　他の溶出調整剤としては、例えば、エチレン・α－オレフィン共重合体、ポリブテン類、パラフィン類、ワセリン類、ジアルキルスルフィド化合物等が挙げられる。 Examples of other elution regulators include ethylene / α-olefin copolymers, polybutenes, paraffins, petrolatums, dialkyl sulfide compounds and the like.
　可塑剤としては、例えば、フタル酸エステル、アジピン酸エステル、トリクレジルフォスフェート等が挙げられる。 Examples of the plasticizer include phthalates, adipates, tricresyl phosphate and the like.
　分散剤としては、例えば、ポリアマイド燐酸系分散剤、ポリアマイド系分散剤、不飽和ポリカルボン酸系分散剤、酸化ポリエチレン系分散剤等が挙げられる。例として、楠本化成（株）製、ディスパロン６９００－２０Ｘ、ディスパロン４２００、ディスパロン１８６０等が挙げられる。これら分散剤は、単独で又は２種以上を混合して用いることができる。 Examples of the dispersant include polyamide phosphoric acid-based dispersants, polyamide-based dispersants, unsaturated polycarboxylic acid-based dispersants, and polyethylene oxide-based dispersants. Examples thereof include Disparon 6900-20X, Disparon 4200, Disparon 1860, etc. manufactured by Kusumoto Kasei Co., Ltd. These dispersants can be used alone or in admixture of two or more.
　溶剤としては、有機溶剤や水が挙げられる。有機溶剤としては、例えば、キシレン、トルエン、ソルベッソ１００、ソルベッソ１５０（いずれも登録商標、エクソンモービル製）等の芳香族系溶剤；イソブチルメチルケトン（ＭＩＢＫ）、ジイソブチルケトン（ＤＩＢＫ）等のケトン系溶剤；酢酸ブチル、酢酸イソブチル、酢酸イソペンチル等のエステル系溶剤が使用できる。 Examples of the solvent include organic solvents and water. Examples of the organic solvent include aromatic solvents such as xylene, toluene, Solbesso 100 and Solbesso 150 (all registered trademarks, manufactured by Exxon Mobile); ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK). ; Ester-based solvents such as butyl acetate, isobutyl acetate, and isopentyl acetate can be used.
　また、低毒・低臭・低環境負荷を考慮した有機溶剤も使用することができ、例えば、ペガソールＡＮ４５、ペガソールＡＳ１００（いずれも登録商標、エクソンモービル製）、ＬＡＷＳ、ＨＡＷＳ（いずれもシェルケミカルズ製）等の芳香族・脂環式・脂肪族炭化水素混合溶剤；プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のグリコール系エステル溶剤；エチルシクロヘキサン、ジメチルシクロヘキサン、リカソルブ（登録商標）９００（Ｃ９芳香族水添体）、リカソルブ（登録商標）１０００（Ｃ１０芳香族水添体）等の脂環式炭化水素系溶剤；シェルゾールＤ４０（登録商標、シェルケミカルズ製）、エクソールＤ３０、エクソールＤ４０（いずれも登録商標、エクソンモービル製）等の脂環式・脂肪族炭化水素混合溶剤；アイソパーＧ、アイソパーＨ（いずれも登録商標、エクソンモービル製）等の脂肪族炭化水素混合溶剤なども使用することができる。
　これら有機溶剤は、単独で又は２種以上を混合して用いることができる。 In addition, organic solvents that are low in toxicity, low odor, and low environmental load can also be used. For example, Pegasol AN45, Pegasol AS100 (all registered trademarks, manufactured by Exxon Mobile), LAWS, and HAWS (all manufactured by Shell Chemicals) can be used. ) And other aromatic / alicyclic / aliphatic hydrocarbon mixed solvents; glycol-based ester solvents such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethylcyclohexane, dimethylcyclohexane, and lycasolve (registered trademark) 900 (C9). Arocyclic hydrocarbon solvents such as Ricasolv (registered trademark) 1000 (C10 aromatic hydrocarbon); Shelsol D40 (registered trademark, manufactured by Shell Chemicals), Exol D30, Exol D40 (any of them). Also registered trademark, alicyclic / aliphatic hydrocarbon mixed solvent such as Exxon Mobile); Isopar G, Isopar H (both registered trademarks, manufactured by Exxon Mobile) and other aliphatic hydrocarbon mixed solvents can also be used. it can.
These organic solvents can be used alone or in combination of two or more.
　本発明の組成物は、種々の漁業具、水中構造物等の防汚塗膜の形成に使用できる。特に、本発明の組成物は、漁網用防汚塗料組成物として好適に使用できる。 The composition of the present invention can be used for forming an antifouling coating film for various fishing tools, underwater structures, and the like. In particular, the composition of the present invention can be suitably used as an antifouling coating composition for fishing nets.
　本発明の漁網防汚塗料組成物は、上記（Ａ）～（Ｄ）成分、ならびに必要に応じて上記の添加成分を混合することにより調製できる。混合する際の各成分の添加量については、上記配合量および含有量となるよう適宜調整すればよい。各成分を混合する順序については特に制限されない。混合方法については、撹拌装置を用いて混合する等、公知の方法を採用すればよい。 The fishing net antifouling paint composition of the present invention can be prepared by mixing the above components (A) to (D) and, if necessary, the above additive components. The amount of each component added at the time of mixing may be appropriately adjusted so as to be the above-mentioned blending amount and content. The order in which each component is mixed is not particularly limited. As a mixing method, a known method such as mixing using a stirring device may be adopted.
２．漁網防汚塗膜の形成方法、防汚塗膜、および塗装物
　本発明の漁網防汚塗膜の形成方法は、上記漁網防汚塗料組成物を用いて被塗膜形成物の表面に防汚塗膜を形成することを特徴とする。本発明の形成方法により得られる防汚塗膜は、表面から徐々に溶解し塗膜表面が常に更新されることにより、水棲汚損生物の付着防止を図ることができる。また、塗膜を溶解させた後、上記組成物を上塗りすることにより、継続的に防汚効果を発揮することができる。 2. Fishing net antifouling coating film forming method, antifouling coating film, and coating material The fishing net antifouling coating film forming method of the present invention uses the above fishing net antifouling coating film composition to prevent stains on the surface of the coating film to be formed. It is characterized by forming a coating film. The antifouling coating film obtained by the forming method of the present invention gradually dissolves from the surface and the surface of the coating film is constantly updated, so that adhesion of aquatic polluted organisms can be prevented. Further, by overcoating the above composition after dissolving the coating film, the antifouling effect can be continuously exhibited.
　被塗膜形成物としては、例えば、漁業具、水中構造物等が挙げられる。漁業具としては、例えば、養殖用又は定置用の漁網、該漁網に使用される浮き子、ロープ等の漁網付属具等が挙げられる。水中構造物としては、例えば、発電所導水管、橋梁、港湾設備等が挙げられる。 Examples of the coating film-forming product include fishing gear, underwater structures, and the like. Examples of fishing nets include fishing nets for aquaculture or stationary fishing nets, floats used for the fishing nets, fishing net accessories such as ropes, and the like. Examples of underwater structures include power plant water pipes, bridges, harbor facilities, and the like.
　本発明の漁網防汚塗膜は、上記漁網防汚塗料組成物を被塗膜形成物の表面（全体又は一部）に塗布することにより形成できる。 The fishing net antifouling coating film of the present invention can be formed by applying the above fishing net antifouling coating composition to the surface (whole or part) of the coating film to be formed.
　塗布方法としては、例えば、ハケ塗り法、スプレー法、ディッピング法、フローコート法、スピンコート法等が挙げられる。これらは、１種又は２種以上を併用して行ってもよい。例えば、本発明の漁網防汚塗料組成物を漁網に塗布する場合、塗布方法としてはディッピング法を採用することが好ましい。 Examples of the coating method include a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method, and the like. These may be performed alone or in combination of two or more. For example, when the fishing net antifouling coating composition of the present invention is applied to a fishing net, it is preferable to adopt a dipping method as the application method.
　塗布後、乾燥させる。乾燥温度は、室温でよい。乾燥時間は、漁網防汚塗料の付着量に応じて適宜設定すればよい。 After application, dry. The drying temperature may be room temperature. The drying time may be appropriately set according to the amount of the fishing net antifouling paint adhered.
　前記漁網防汚塗料の付着量は、被塗膜形成物の種類等に応じて適宜設定すればよい。例えば、被塗膜形成物が漁網の場合、乾燥塗膜の付着量が漁網１００質量部に対し、好ましくは１～３０質量部、さらに好ましくは４～１５質量部である。 The amount of the fishing net antifouling paint adhered may be appropriately set according to the type of the coating film to be formed and the like. For example, when the coating film-forming product is a fishing net, the amount of the dry coating film adhered is preferably 1 to 30 parts by mass, and more preferably 4 to 15 parts by mass with respect to 100 parts by mass of the fishing net.
　本発明の塗装物は、前記防汚塗膜を表面に有する。本発明の塗装物は、前記防汚塗膜を表面の全体に有していてもよく、一部に有していてもよい。 The coated material of the present invention has the antifouling coating film on its surface. The coated material of the present invention may have the antifouling coating film on the entire surface or a part thereof.
　以下に、実施例等を示し、本発明の特徴とするところをより一層明確にする。ただし、本発明は実施例等に限定されるものではない。 Examples and the like are shown below to further clarify the features of the present invention. However, the present invention is not limited to the examples and the like.
１．分析方法
＜分子量分析方法＞
　重量平均分子量（Ｍｗ）は、ＧＰＣにより求めた値（ポリスチレン換算値）である。ＧＰＣの条件は下記の通りである。
装置・・・　東ソー株式会社製　ＨＬＣ－８２２０ＧＰＣ
ガードカラム・・・ＴＳＫｇｕａｒｄｃｏｌｕｍｎ　ＳｕｐｅｒＨＺ－Ｌ（東ソー株式会社製）
カラム・・・　ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ（東ソー株式会社製）２本直列接続
　流量・・・　０．３５　ｍＬ／ｍｉｎ
検出器・・・　ＲＩ
　カラム恒温槽温度・・・　４０℃
展開溶媒・・・　ＴＨＦ（和光純薬工業社製；試薬特級）
標準サンプル・・・ＴＳＫ標準ポリスチレン（東ソー株式会社製） 1. 1. Analytical method <Molecular weight analysis method>
The weight average molecular weight (Mw) is a value (polystyrene-equivalent value) obtained by GPC. The conditions for GPC are as follows.
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Guard column ・ ・ ・ TSKguardcolum SuperHZ-L (manufactured by Tosoh Corporation)
Column ・ ・ ・ TSKgel SuperHZM-M (manufactured by Tosoh Corporation) 2 series connection Flow rate ・ ・ ・ 0.35 mL / min
Detector ・ ・ ・ RI
Column constant temperature bath temperature ・ ・ ・ 40 ℃
Developing solvent: THF (manufactured by Wako Pure Chemical Industries, Ltd .; special grade reagent)
Standard sample: TSK standard polystyrene (manufactured by Tosoh Corporation)
＜加熱残分分析方法＞
加熱残分は、ＪＩＳ　Ｋ５６０１－１－２（１２５℃、１時間加熱）により求めた値である。 <Heat residue analysis method>
The heating residue is a value obtained by JIS K5601-1-2 (heating at 125 ° C. for 1 hour).
２．製造例
＜製造例１（重合体溶液Ａ－１の製造）＞
　温度計、冷却器、撹拌装置及び滴下ロートを備えた３００ｍｌフラスコに、キシレン４１ｇ、メチルメタクリレート１７ｇ、ブチルアクリレート２１ｇ、ステアリルメタクリレート２ｇ、及びｔ－ブチルパーオキシ２－エチルヘキサノエート０．０２ｇ（初期添加）を仕込み、窒素ガスを導入しながら、９５±５℃で１時間攪拌した。その後、同温度にて、キシレン４０ｇ、メチルメタクリレート１７ｇ、ブチルアクリレート２１ｇ、ステアリルメタクリレート２ｇ、ｔ－ブチルパーオキシ２－エチルヘキサノエート０．０２ｇを滴下ロートより３０分間かけて滴下した。その後同温度にて１時間攪拌の後、ｔ－ブチルパーオキシ２－エチルヘキサノエート合計０．４ｇ（後添加分）を１時間毎に３回に分けて添加して重合反応を完結した後、キシレン４０ｇを添加し溶解させることにより、重合体溶液Ａ－１を得た。重合体溶液Ａ－１のＭｗは１２８０００、加熱残分は３９．８％であった。 2. Production Example <Production Example 1 (Production of Polymer Solution A-1)>
41 g of xylene, 17 g of methyl methacrylate, 21 g of butyl acrylate, 2 g of stearyl methacrylate, and 0.02 g of t-butylperoxy2-ethylhexanoate in a 300 ml flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel (initial). (Addition) was charged, and the mixture was stirred at 95 ± 5 ° C. for 1 hour while introducing nitrogen gas. Then, at the same temperature, 40 g of xylene, 17 g of methyl methacrylate, 21 g of butyl acrylate, 2 g of stearyl methacrylate, and 0.02 g of t-butylperoxy2-ethylhexanoate were added dropwise from the dropping funnel over 30 minutes. Then, after stirring at the same temperature for 1 hour, a total of 0.4 g (post-added portion) of t-butylperoxy2-ethylhexanoate was added every hour in 3 portions to complete the polymerization reaction. , 40 g of xylene was added and dissolved to obtain a polymer solution A-1. The Mw of the polymer solution A-1 was 128,000, and the heating residue was 39.8%.
＜製造例２（重合体溶液Ａ－２の製造）＞
　温度計、冷却器、撹拌装置及び滴下ロートを備えた３００ｍｌフラスコに、キシレン２９．０ｇ、イソブチルメタクリレート６０ｇ、ブチルアクリレート１９ｇ、及びｔ－ブチルパーオキシ２－エチルヘキサノエート０．０２ｇ（初期添加）を仕込み、窒素ガスを導入しながら、９５±５℃で１時間攪拌した。その後、同温度にて、ｔ－ブチルパーオキシ２－エチルヘキサノエート０．０２ｇを添加して、滴下ロートより２０分間かけてキシレン２０．２ｇを滴下して、４０分間攪拌した。その後、同温度にて、ｔ－ブチルパーオキシ２－エチルヘキサノエート０．０４ｇを添加して、滴下ロートより２０分間かけてキシレン２０．２ｇを滴下して、４０分間攪拌した。その後、同温度にて、ｔ－ブチルパーオキシ２－エチルヘキサノエート０．２１ｇを添加して、滴下ロートより２０分間かけてキシレン３０．６ｇを滴下して、４０分間攪拌した。その後、同温度にて、ｔ－ブチルパーオキシ２－エチルヘキサノエート０．１６ｇを添加して、６０分攪拌した。重合反応を完結した後、キシレン２１ｇを添加し溶解させることにより、重合体溶液Ａ－２を得た。重合体溶液Ａ－２のＭｗは２５９０００、加熱残分は３９．８％であった。 <Production Example 2 (Production of Polymer Solution A-2)>
29.0 g of xylene, 60 g of isobutyl methacrylate, 19 g of butyl acrylate, and 0.02 g of t-butylperoxy2-ethylhexanoate in a 300 ml flask equipped with a thermometer, a cooler, a stirrer, and a dropping funnel (initial addition). Was charged, and the mixture was stirred at 95 ± 5 ° C. for 1 hour while introducing nitrogen gas. Then, at the same temperature, 0.02 g of t-butylperoxy2-ethylhexanoate was added, 20.2 g of xylene was added dropwise from the dropping funnel over 20 minutes, and the mixture was stirred for 40 minutes. Then, at the same temperature, 0.04 g of t-butylperoxy2-ethylhexanoate was added, 20.2 g of xylene was added dropwise from the dropping funnel over 20 minutes, and the mixture was stirred for 40 minutes. Then, at the same temperature, 0.21 g of t-butylperoxy2-ethylhexanoate was added, 30.6 g of xylene was added dropwise from the dropping funnel over 20 minutes, and the mixture was stirred for 40 minutes. Then, at the same temperature, 0.16 g of t-butylperoxy2-ethylhexanoate was added, and the mixture was stirred for 60 minutes. After the polymerization reaction was completed, 21 g of xylene was added and dissolved to obtain a polymer solution A-2. The Mw of the polymer solution A-2 was 259,000, and the heating residue was 39.8%.
３．漁網防汚塗料組成物の製造
　表１～表１１に示す成分を同表に示す割合（質量部）で配合し、直径１．５～２．５ｍｍのガラスビーズと混合分散することにより、実施例・比較例の漁網防汚塗料組成物を製造した。
　なお表１～表７には水系防汚塗料、表８～表１１には油性防汚塗料を示す。 3. 3. Production of Fishing Net Antifouling Paint Composition Examples by blending the components shown in Tables 1 to 11 at the ratio (parts by mass) shown in the same table and mixing and dispersing with glass beads having a diameter of 1.5 to 2.5 mm. -A comparative example of a fishing net antifouling paint composition was produced.
Tables 1 to 7 show water-based antifouling paints, and Tables 8 to 11 show oil-based antifouling paints.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
表１～表１１中の各成分の詳細は、以下の通りである。 Details of each component in Tables 1 to 11 are as follows.
（（メタ）アクリル酸エステル重合体（Ａ））
　商品名「バンスター　Ｘ１２９０Ｂ１１」：アクリル酸エステル・メタクリル酸エステル共重合体エマルション（中部サイデン（株）製）
　商品名「ポリゾール（Ｒ）　ＡＰ－４６５０Ｎ」：アクリル酸エステル共重合体エマルション（昭和電工（株）製）
　商品名「ポリゾール（Ｒ）　ＡＰ－４７８０Ｎ」：アクリル酸エステル共重合体エマルション（昭和電工（株）製） ((Meta) acrylic acid ester polymer (A))
Product name "Vanstar X1290B11": Acrylic acid ester / methacrylate copolymer emulsion (manufactured by Chubu Saiden Co., Ltd.)
Product name "Polysol (R) AP-4650N": Acrylic acid ester copolymer emulsion (manufactured by Showa Denko KK)
Product name "Polysol (R) AP-4780N": Acrylic acid ester copolymer emulsion (manufactured by Showa Denko KK)
（エチレン酢酸ビニル共重合体（Ｂ））
　商品名「ポリゾール（Ｒ）　ＥＶＡ　Ｐ－３Ｎ」：エチレン－酢酸ビニル樹脂エマルジョン（昭和電工（株）製）
　商品名「ノバテック（ＴＭ）ＥＶＡ　ＬＶ－２１１Ａ」：エチレン・酢酸ビニル共重合樹脂（日本ポリエチレン（株）製） (Ethylene Vinyl Acetate Copolymer (B))
Product name "Polysol (R) EVA P-3N": Ethylene-vinyl acetate resin emulsion (manufactured by Showa Denko KK)
Product name "Novatec (TM) EVA LV-211A": Ethylene-vinyl acetate copolymer resin (manufactured by Japan Polyethylene Corporation)
（他の展着樹脂）
　商品名「ポリゾール（Ｒ）　Ｓ－６５」：酢酸ビニル樹脂エマルジョン（昭和電工（株）製） (Other spreading resin)
Product name "Polysol (R) S-65": Vinyl acetate resin emulsion (manufactured by Showa Denko KK)
（シリコーンオイル（Ｃ））
　商品名「ＫＦ－６０２０」：ポリエーテル変性ジメチルシリコーンオイル（信越化学工業（株）製）
　商品名「Ｘ－２２－２５１６」：ポリエーテル長鎖アルキルアラルキル変性ジメチルシリコーンオイル（信越化学工業（株）製） (Silicone oil (C))
Product name "KF-6020": Polyester-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
Product name "X-22-2516": Polyester long-chain alkyl aralkyl-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.)
（防汚薬剤（Ｄ））
　商品名「ＮＣ－３０１」：亜酸化銅（日進ケムコ（株）製）
　商品名「Ｃｏｐｐｅｒ　Ｏｍａｄｉｎｅ　Ｐｏｗｄｅｒ」：銅ピリチオン「ビス（２―スルフィドピリジン－１―オラト）銅」（ロンザ・ジャパン（株）製）
　商品名「ＴＯＣ－３２０４Ｆ」：ビスジメチルジチオカルバモイルジンクエチレンビスジチオカーバメート（ロームアンドハース製）
　商品名「ＯＰＡ」：３－（２－エチルヘキシルオキシ）プロピルアミン・トリフェニルボラン（日東化成（株）製）
　商品名「ＯＤＡ」：ｎ－オクタデシルアミン・トリフェニルボラン
　商品名「ノクセラーＴＥＴ－Ｇ」：テトラエチルチウラムジスルフィド（大内新興化学工業（株）製） (Anti-fouling agent (D))
Product name "NC-301": Copper oxide (manufactured by Nissin Chemco Co., Ltd.)
Product name "Copper Omade Powder": Copper pyrithione "Bis (2-sulfidepyridin-1-olato) copper" (manufactured by Lonza Japan Co., Ltd.)
Product name "TOC-3204F": Bisdimethyldithiocarbamoylzinc ethylenebisdithiocarbamate (manufactured by Rohm and Hearth)
Product name "OPA": 3- (2-ethylhexyloxy) propylamine / triphenylborane (manufactured by Nitto Kasei Co., Ltd.)
Product name "ODA": n-octadecylamine / triphenylborane Product name "Noxeller TET-G": Tetraethylthiuram disulfide (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
（顔料）
　商品名「タルクＭＳ」：タルク［含水珪酸マグネシウム］（日本タルク（株）製）
　商品名「ＡＦブラック　Ｅ－２Ｂ」：水系顔料分散体（大日精化（株）製）
　商品名「カーボンブラック＃４４」：黒色顔料（三菱ケミカル（株）製） (Pigment)
Product name "Talc MS": Talc [hydrous magnesium silicate] (manufactured by Nippon Talc Co., Ltd.)
Product name "AF Black E-2B": Water-based pigment dispersion (manufactured by Dainichiseika Co., Ltd.)
Product name "Carbon Black # 44": Black pigment (manufactured by Mitsubishi Chemical Corporation)
（ワックス類）
　商品名「ＥＭＵＳＴＡＲ－０００１」：マイクロクリスタリンワックスエマルション（日本精蝋（株）製） (Waxes)
Product name "EMUSTAR-0001": Microcrystalline wax emulsion (manufactured by Nippon Seiro Co., Ltd.)
（防腐剤）
　商品名「デルトップ１００Ｎ」：防腐剤（大阪ガスケミカル（株）製） (Preservative)
Product name "Dell Top 100N": Preservative (manufactured by Osaka Gas Chemical Co., Ltd.)
（可塑剤）
　商品名「エマウエット３０Ｅ」：ポリブテンエマルション（日油（株）製）
　商品名「ポリブテン０Ｎ」：可塑剤（日本油脂製）
　商品名「ルーカントＨＣ－４０」：可塑剤（三井化学株式会社）
　商品名「ＤＡＦ－１」：可塑剤（ＤＩＣ株式会社） (Plasticizer)
Product name "Emmawet 30E": Polybutene emulsion (manufactured by NOF CORPORATION)
Product name "Polybutene 0N": Plasticizer (manufactured by NOF)
Product name "Lucant HC-40": Plasticizer (Mitsui Chemicals, Inc.)
Product name "DAF-1": Plasticizer (DIC Corporation)
（分散剤）
　商品名「ＯＰＴＩＧＥＬ　ＷＭ」：レオロジー添加剤（ビック・ケミージャパン（株）製）
　商品名「ディスパロン６３０－２０Ｘ」：ポリアマイド系ワックス（楠本化成（株）製）
　商品名「ディスパロン４２００－２０」：酸化ポリエチレン系ワックス（楠本化成（株）製） (Dispersant)
Product name "OPTIGEL WM": Rheology additive (manufactured by BIC Chemie Japan Co., Ltd.)
Product name "Disparon 630-20X": Polyamide wax (manufactured by Kusumoto Kasei Co., Ltd.)
Product name "Disparon 4200-20": Polyethylene oxide wax (manufactured by Kusumoto Kasei Co., Ltd.)
（消泡剤）
　商品名「アンチフロスＳ１１０」：消泡剤（第一工業製薬（株）製）
　商品名「ディスパロンＦＡ－６２」：シリコン系消泡剤（楠本化成（株）製） (Defoamer)
Product name "Anti-floss S110": Antifoaming agent (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Product name "Disparon FA-62": Silicone defoamer (manufactured by Kusumoto Kasei Co., Ltd.)
（造膜助剤）
　商品名「テキサノール」：造膜助剤（ＥＡＳＴＭＡＮ　ＣＨＥＭＩＣＡＬ製） (Film formation aid)
Product name "Texanol": Membrane-forming aid (manufactured by EASTMAN CHEMICAL)
４．漁網防汚塗料組成物の評価
　得られた漁網防汚塗料組成物について、以下の方法で防汚効果確認試験を行った。その結果を表１２～表１８に示す。 4. Evaluation of Fishing Net Antifouling Paint Composition The obtained fishing net antifouling paint composition was subjected to an antifouling effect confirmation test by the following method. The results are shown in Tables 12 to 18.
　表１２～表１８に示すように、全ての実施例では、全ての比較例よりも良好な結果が得られた。 As shown in Tables 12 to 18, better results were obtained in all the examples than in all the comparative examples.
＜防汚効果確認試験＞
　実施例及び比較例の漁網防汚塗料組成物を、ポリエチレン製の漁網（４００デニール、４０本、８節）および、ナイロン製の漁網（２１０デニール、４８本、１０節）に、乾燥塗膜の付着量が漁網１００質量部に対し、１５質量部になるように浸漬塗布し乾燥させた。塗膜を形成した漁網を４０×６０ｃｍＳＵＳの枠に固定し、水棲汚損生物の活性の強い海域である三重県尾鷲の筏にて喫水部に浸漬し、その防汚評価を１０ヶ月及び１２ヶ月間にわたって定期的に観察した。 <Anti-fouling effect confirmation test>
The antifouling paint composition for fishing nets of Examples and Comparative Examples was applied to polyethylene fishing nets (400 denier, 40 lines, 8 sections) and nylon fishing nets (210 denier, 48 lines, 10 sections) with a dry coating. The fishing net was dipped and coated so that the amount of adhesion was 15 parts by mass with respect to 100 parts by mass of the fishing net, and dried. The fishing net on which the coating film was formed was fixed to a frame of 40 x 60 cm SUS and immersed in the draft part in the raft of Owase, Mie Prefecture, which is a sea area where aquatic polluted organisms are strongly active, and the antifouling evaluation was carried out for 10 months and 12 months. Observed regularly over.
評価は以下の方法で行った。なお、水棲生物の付着面積（％）は、試験期間（２、４、６、８、１０又は１２ヶ月）後に上から漁網の写真を撮影し、漁網における水棲生物の占有面積を目視で評価した。
◎：水棲生物の付着面積が０％
○：水棲生物の付着面積が０超１０％未満
△：水棲生物の付着面積が１０以上５０％未満
×：水棲生物の付着面積が５０％以上 The evaluation was performed by the following method. For the attached area (%) of aquatic organisms, a photograph of the fishing net was taken from above after the test period (2, 4, 6, 8, 10 or 12 months), and the occupied area of the aquatic organisms in the fishing net was visually evaluated. ..
⊚: Adhesion area of aquatic organisms is 0%
◯: Adhesion area of aquatic organisms is more than 0 and less than 10% Δ: Adhesion area of aquatic organisms is 10 or more and less than 50% ×: Adhesion area of aquatic organisms is 50% or more
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018

Claims (2)

  1. （メタ）アクリル酸エステル重合体（Ａ）、エチレン酢酸ビニル共重合体（Ｂ）、シリコーンオイル（Ｃ）、及び、防汚薬剤（Ｄ）を含有する、漁網防汚塗料組成物。 A fishing net antifouling coating composition containing an (meth) acrylic acid ester polymer (A), an ethylene-vinyl acetate copolymer (B), a silicone oil (C), and an antifouling agent (D).
  2. 　請求項１に記載の漁網防汚塗料組成物を用いて形成される防汚塗膜を表面に有する、漁網、漁網用具及び水中構築物。
          A fishing net, a fishing net tool, and an underwater structure having an antifouling coating film formed by using the fishing net antifouling paint composition according to claim 1 on the surface.
PCT/JP2020/043665 2019-11-29 2020-11-24 Antifouling coating composition for fishing net, and fishing net, fishing-net accessory, or underwater structure each having antifouling coating film formed on surface from said composition WO2021106868A1 (en)

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JPH05170983A (en) * 1991-12-24 1993-07-09 Mitsui Eng & Shipbuild Co Ltd Antifouling resin composition
JPH1161002A (en) * 1997-08-27 1999-03-05 Chugoku Marine Paints Ltd Non-tin antifouling paint composition, antifouling coating film, antifouling method and ship coated with this antifouling coating film
JPH11323206A (en) * 1998-05-18 1999-11-26 Nitto Kasei Co Ltd Antifouling agent for fishing net
JP2002265849A (en) * 2001-03-14 2002-09-18 Nippon Paint Marine Kk Coating composition
JP2006052284A (en) * 2004-08-11 2006-02-23 Kansai Paint Co Ltd Method for producing aqueous dispersion of resin containing triorganosilyl
JP2016222629A (en) * 2015-06-03 2016-12-28 日本曹達株式会社 Antimicrobial agent
JP2018141103A (en) * 2017-02-28 2018-09-13 中国塗料株式会社 Antifouling coating composition, its coating film, base material with antifouling coating film, fishing net, base material antifouling method, and method for producing base material with antifouling coating film

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