WO2023120360A1 - Fishing net antifouling coating composition and fishing net, fishing net gear, or underwater structure having on surface thereof antifouling coating film formed using said composition - Google Patents

Fishing net antifouling coating composition and fishing net, fishing net gear, or underwater structure having on surface thereof antifouling coating film formed using said composition Download PDF

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Publication number
WO2023120360A1
WO2023120360A1 PCT/JP2022/046178 JP2022046178W WO2023120360A1 WO 2023120360 A1 WO2023120360 A1 WO 2023120360A1 JP 2022046178 W JP2022046178 W JP 2022046178W WO 2023120360 A1 WO2023120360 A1 WO 2023120360A1
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Prior art keywords
monomer
meth
acrylate
fishing net
antifouling
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PCT/JP2022/046178
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French (fr)
Japanese (ja)
Inventor
貴義 藤本
博一 竹縄
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日東化成株式会社
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Application filed by 日東化成株式会社 filed Critical 日東化成株式会社
Priority to KR1020247024304A priority Critical patent/KR20240123374A/en
Priority to JP2023569367A priority patent/JPWO2023120360A1/ja
Publication of WO2023120360A1 publication Critical patent/WO2023120360A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • 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
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
    • 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
    • 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
    • C09D5/1687—Use of special additives
    • 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
    • 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
    • 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 is intended to prevent aquatic fouling organisms from adhering to fishing nets for aquaculture or set nets, fishing net tools such as floats and ropes used in these, and underwater structures such as cooling water pipes in power plants over a long period of time. It relates to a fishing net antifouling coating composition for antifouling, and a fishing net, fishing net tool or underwater structure having an antifouling coating film formed using the composition on its surface.
  • fishing nets, fishing net tools, and underwater structures are installed in the sea for a long period of time, if they are used without being treated with antifouling paint for fishing nets, they may damage green algae such as sea lettuce and green laver, red algae such as gisu, and barnacles.
  • Various aquatic fouling organisms such as crustaceans such as crustaceans, coelenterates such as hydra worms, serpra, bryozoans, and mollusks adhere. As a result, the mesh of the fishing nets is blocked and the seawater flow becomes poor, and a large number of farmed fish die due to lack of oxygen, and infectious diseases occur, making it impossible to ship them.
  • an antifouling coating composition for fishing nets using an organic tin compound has been widely used in the past, but it has become unusable due to environmental considerations.
  • antifouling coating compositions for fishing nets to replace organic tin compounds
  • inorganic compounds and organic compounds are used as antifouling agents, which are blended with natural resin-based or synthetic resin-based spreading resins.
  • antifouling coating compositions for fishing nets have been used. However, these had problems such as poor physical properties of the coating film and a short antifouling period.
  • an antifouling paint composition for fishing nets in which a specific polyether-modified silicone oil is blended with a spreading resin as a drug elution control agent, has been proposed (Patent Documents 1 to 3).
  • the present invention has been made in view of the above circumstances, and maintains an appropriate amount of drug release from the initial stage of immersion in water, maintains an antifouling effect for a long period of time, and is excellent in antifouling against organisms attached to fishing nets.
  • An object of the present invention is to provide an antifouling coating composition for fishing nets that can continuously exhibit its performance for a long period of time.
  • an antifouling coating composition containing a copolymer (A), a silicone oil (B), and an antifouling agent (C), wherein the copolymer (A) has the general formula ( 1) and a copolymer of an ethylenically unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is the A fishing net antifouling paint containing a compound in which n in the general formula (1) is 2 or more, and wherein the silicone oil (B) is a modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5 to 9.
  • a composition is provided.
  • a fishing net, a fishing net tool, or an underwater structure having on its surface an antifouling coating film formed using the fishing net antifouling coating composition is also provided.
  • Fishing net antifouling paint composition contains copolymer A, silicone oil B and antifouling agent C.
  • Copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer (a) and the monomer Including monomeric units derived from mer (b).
  • the content of the monomer (a) with respect to the sum of the monomer (a) and the monomer (b) is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, and 5 to 60% by mass. More preferably, 5 to 40% by mass is particularly preferable.
  • Monomer (a) is represented by general formula (1).
  • R 1 represents hydrogen or a methyl group
  • R 2 represents hydrogen, a methyl group, or a phenyl group
  • R 3 may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group. It is an alkyl group having 1 to 8 carbon atoms or represents a phenyl group
  • n represents an integer of 1 to 10.
  • R 2 is preferably hydrogen or a methyl group.
  • the number of carbon atoms in the alkoxy group or alkyl group of R 3 is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and within the range between any two of the numerical values exemplified here good too.
  • R 3 is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, benzyl group, phenyl group, 2-methoxyethyl group, 4-methoxybutyl group, vinyl group or allyl group, preferably methyl group, ethyl group, isopropyl group or n-butyl group.
  • n represents an integer of 1 to 10
  • n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, any two of the numerical values exemplified here may be within the range.
  • the monomer (a) includes compounds in which n in general formula (1) is 2 or more. When a compound in which n is 2 or more is contained as the monomer (a), the long-term antifouling property is enhanced.
  • the monomer (a) may be composed only of a compound in which n is 2 or more, or may be a mixture of a compound in which n is 1 and a compound in which n is 2 or more.
  • the monomer (a) preferably consists of a monomer (a1) and a monomer (a2).
  • the content of monomer (a1) in monomer (a) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and particularly preferably 60 to 70% by mass.
  • the monomer (a1) tends to increase the strength of the coating film and reduce the long-term antifouling property compared to the monomer (a2). Therefore, if the content of the monomer (a1) is too small, the strength of the coating film tends to be low, and the surface condition of the coating film tends to deteriorate after a long period of time. On the other hand, if the content of the monomer (a1) is too high, the long-term antifouling performance may deteriorate.
  • Monomer (a1) is a compound in which n is 1 in general formula (1).
  • Examples of the monomer (a1) include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, t-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyl (meth)acrylate Oxycarbonylmethyl, phenoxycarbonylmethyl (meth)acrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, 4-methoxybutoxycarbonylmethyl (meth)acrylate, allyloxycarbonylmethyl (meth)acrylate, (meth)
  • the monomer (a2) is a compound of general formula (1) in which n is 2 or more.
  • n in formula (1) is preferably 2 to 6 from the viewpoint of long-term antifouling properties.
  • the monomer (a2) preferably contains both a compound in which n is 2 and a compound in which n is 3 or more.
  • the mass ratio (n(2)/n(2-10)) in terms of solid content is preferably 0.4 to 0.8, more preferably 0.5 to 0.7.
  • this value is, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, where It may be in a range between any two of the numerical values given.
  • Examples of the monomer (a2) include methyl (meth)acrylate di(oxycarbonylmethyl), ethyl (meth)acrylate di(oxycarbonylmethyl), isopropyl(meth)acrylate di(oxycarbonylmethyl), (meth)acrylate ) n-propyl di(oxycarbonylmethyl) acrylate, n-butyl di(oxycarbonylmethyl) acrylate (meth), t-butyl di(oxycarbonylmethyl) acrylate (meth), 2-ethylhexyl di(meth) acrylate ( oxycarbonylmethyl), cyclohexyl di(oxycarbonylmethyl) (meth)acrylate, benzyl di(oxycarbonylmethyl) (meth)acrylate, phenyl di(oxycarbonylmethyl) (meth)acrylate, 2-methoxy (meth)acrylate Ethyl di (oxycarbonylmethyl), 4-methoxybutyl di (oxycarbonylmethyl) (
  • monomer (b) is an ethylenically unsaturated monomer other than monomer (a).
  • the monomer (b) can be classified into a monomer (b1) and a monomer (b2). ) and the monomer (b2), preferably the monomer (b1).
  • the content of the monomer (b1) in the copolymer A is preferably 1-30% by mass, more preferably 2-25% by mass, still more preferably 3-20% by mass.
  • the coating film formed using the obtained coating composition has improved compatibility with the silicone oil that controls the elution of the drug, and as a result, there is an advantage that an appropriate amount of drug can be eluted.
  • the content of the monomer (b1) is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30% by mass, even within the range between any two of the numerical values illustrated here good.
  • the monomer (b1) is represented by general formula (2).
  • R 4 represents hydrogen or a methyl group
  • R 5 represents an alkyl group having 10 to 22 carbon atoms
  • R5 examples include decyl, isodecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and the like.
  • the carbon number of R 5 is preferably 12-18. Specifically, the carbon number of R 5 is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, and any one of the numerical values exemplified here is 2 It may be within a range between two.
  • Examples of the monomer (b1) include decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (lauryl) (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (myristyl (meth)acrylate). ), pentadecyl (meth)acrylate, hexadecyl (palmityl) (meth)acrylate, heptadecyl (margaryl) (meth)acrylate, octadecyl (stearyl) (meth)acrylate, nonadecyl (meth)acrylate, and the like.
  • the monomer (b1) can be used singly or in combination of two or more.
  • Examples of the monomer (b2) include ethylenically unsaturated monomers other than the monomer (a) and the monomer (b1), such as methyl (meth)acrylate and ethyl (meth)acrylate.
  • n-butyl (meth)acrylate isobutyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid esters such as 2-hydroxyethyl acid, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-ethoxy-diethylene glycol (meth)acrylate; vinyl chloride, vinylidene chloride , (meth)acrylonitrile, vinyl acetate, butyl vinyl ether,
  • (meth)acrylic acid esters are particularly preferable, and methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2 -hydroxybutyl, 2-ethoxy-diethylene glycol (meth)acrylate are more preferred.
  • the monomer (b2) can be used singly or in combination of two or more.
  • the weight average molecular weight (Mw) of copolymer A is preferably 10,000 to 500,000, more preferably 80,000 to 300,000. If the molecular weight is less than 10,000, the coating film of the antifouling paint will be brittle and easily peeled off or cracked. Specifically, this Mw is, for example, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000. It may be in the range between. Examples of methods for measuring Mw include gel permeation chromatography (GPC method).
  • the glass transition temperature (Tg) of the copolymer A is preferably about -50 to 50°C, more preferably about -35 to 35°C.
  • Tg glass transition temperature
  • the above Tg value refers to a value actually measured using a differential scanning calorimeter (eg, DSC1 manufactured by METTLER TOLEDO) with reference to the measurement method of JIS K 7121.
  • Copolymer A is a random copolymer, alternating copolymer, periodic copolymer, or block copolymer of monomer (a) and monomer (b).
  • Copolymer A can be obtained, for example, by polymerizing monomer (a) and monomer (b) in the presence of a polymerization initiator.
  • polymerization initiator examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile ), dimethyl-2,2′-azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (N-butyl-2-methylpropionamide and other azo compounds; benzoylper oxide, di-tert-butylperoxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetra
  • polymerization initiators can be used alone or in combination of two or more.
  • -methylbutyronitrile 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 - Ethylhexanoate is preferred.
  • the molecular weight of the copolymer A can be adjusted.
  • a chain transfer agent is used to adjust the molecular weight of the resulting polymer.
  • Chain transfer agents include, for example, mercaptans such as n-dodecylmercaptan, thioglycolic acid esters such as octyl thioglycolate, ⁇ -methylstyrene dimer, and terpinolene.
  • polymerization methods include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization.
  • solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that the copolymer A can be obtained easily and accurately.
  • an organic solvent may be used as necessary.
  • the organic solvent is not particularly limited, but for example, aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether.
  • ester solvents such as 2-acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. mentioned. Among them, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferred. 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 polymerization initiator, etc., and is usually 50 to 160°C, preferably 60 to 150°C.
  • the polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the content of copolymer A in the fishing net antifouling paint composition is not particularly limited, but is 3 to 50% by mass, preferably 5 to 30% by mass in terms of solid content.
  • Silicone oil B is a modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5-9.
  • modified silicone oil include polyether-modified polydimethylsiloxane, polyether-modified polyalkyl(methyl)siloxane, polyester-modified polydimethylsiloxane, polyether long-chain alkylaralkyl-modified dimethylsilicone oil, amino-modified silicone oil, and various others.
  • Functional group-modified silicone oils and the like can be mentioned, and polyether-modified polydimethylsiloxane or polyether long-chain alkylaralkyl-modified dimethylsilicone oil is preferable.
  • these modified silicone oils may be used alone, or two or more of them may be used in combination.
  • the HLB value is preferably 1-5. Specifically, HLB values are, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0 and within the range between any two of the numerical values exemplified herein. may
  • the HLB value can be calculated by the Griffin method. In Griffin's method, the HLB value is defined as 20 ⁇ (sum of molecular weights of hydrophilic portions/total molecular weight).
  • the viscosity of silicone oil B is preferably 1000 poise or less, more preferably 100 poise or less, and even more preferably 10 poise or less, from the viewpoint of coating performance and coating film properties.
  • the content of silicone oil B is not particularly limited. ⁇ 50 parts by mass.
  • the antifouling coating composition for fishing nets may contain only silicone oil B, or may contain other silicone oils in addition to silicone oil B.
  • silicone oils include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, fluorosilicone oil, long-chain alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, and the like.
  • the antifouling agent C used in the present invention is not particularly limited as long as it is a compound having a killing or repelling effect on marine fouling organisms.
  • examples include the following organic compounds and inorganic compounds.
  • organic compounds include 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, zinc ethylene bisdithiocarbamate, bis(dimethyldithiocarbamate) zinc, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, pyridine. ⁇ Triphenylborane, n-octadecylamine ⁇ Triphenylborane, 3-(2-ethylhexyloxy)propylamine ⁇ Triphenylborane, 4-isopropyl-diphenylmethyl, 4-phenylpyridyl-diphenylborane, 2,4,6- trichloromaleimide, n-(2,6-
  • inorganic compounds include cuprous oxide, monovalent copper glass, divalent copper glass, copper thiocyanate, cupronickel, copper powder, etc. Cuprous oxide, monovalent copper glass and divalent Copper glass is particularly preferred, and may be used singly or in combination of two or more.
  • the solvent or water-insoluble antifouling agent preferably has an average particle size of 10 ⁇ m or less, particularly preferably 3 ⁇ m or less, from the viewpoint of dispersibility.
  • average particle diameters can be measured with a particle size distribution meter manufactured by Nikkiso Co., Ltd., model Microtrac MT3300EXII (measurement principle: laser diffraction/scattering method).
  • the content of the antifouling agent C in the coating composition of the present invention is not limited, it is usually 1 to 300 parts by mass, preferably 5 to 200 parts by mass, based on 100 parts by mass of the copolymer A. 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 physical properties of the coating film tend to deteriorate.
  • the coating composition used in the present invention includes other elution modifiers, dispersants, other spreading resins, anti-settling agents, anti-sagging agents, plasticizers, surfactants, antifoaming agents, dyes, Pigments, organic solvents, water, and the like can be arbitrarily contained in arbitrary blending ratios within a range that does not impair the object of the present invention.
  • ⁇ Other elution modifiers> (Ethylene/ ⁇ -olefin copolymer)
  • Examples of the ethylene/ ⁇ -olefin copolymer include general formula (3): (Wherein, R 6 represents a linear or branched alkyl group having 1 to 10 carbon atoms, and x, y and p are each the same or different and represent an integer of 1 or more). Examples include ⁇ -olefin copolymers.
  • the linear or branched alkyl group having 1 to 10 carbon atoms represented by R 6 particularly includes 1 carbon atom groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group.
  • An alkyl group of ⁇ 4 is preferred, and a methyl group is more preferred.
  • the ethylene/ ⁇ -olefin copolymer represented by the general formula (3) is a copolymer obtained by copolymerizing ethylene and an ⁇ -olefin.
  • the ethylene/ ⁇ -olefin copolymer may be a random copolymer, a block copolymer or a graft copolymer.
  • a commercially available product can be used as the ethylene/ ⁇ -olefin copolymer.
  • Commercially available products include, for example, Lucant HC-10, Lucant HC-20, Lucant HC-40, Lucant HC-100, Lucant HC-150, Lucant HC-600, Lucant HC-2000 (all registered trademarks, Mitsui Chemicals, Inc.
  • the number average molecular weight (Mn) of the ethylene/ ⁇ -olefin copolymer is preferably 10,000 or less, more preferably 1,000 to 3,000, from the viewpoint of coating performance and coating film properties.
  • the ethylene/ ⁇ -olefin copolymer preferably has a viscosity at 0° C. of 20,000 Pa ⁇ s or less, more preferably 500 Pa ⁇ s or less.
  • the content of the ethylene/ ⁇ -olefin copolymer is not particularly limited, but is 1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, in terms of solid content, with respect to 100 parts by mass of the silicone oil. More preferably, it is 50 to 300 parts by mass.
  • Polybutenes include polybutene, polyisobutene, and the like.
  • a commercial item can be used as polybutenes.
  • Examples of commercial products include Nisseki polybutene grade LV-7, Nisseki polybutene grade LV-50, Nisseki polybutene grade LV-100, Nisseki polybutene grade HV-35, Nisseki polybutene grade HV-50, and Nisseki polybutene.
  • polybutene is not particularly limited, it is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass in terms of solid content per 100 parts by mass of silicone oil. is.
  • paraffins examples include n-paraffin, liquid paraffin, chlorinated paraffin and the like.
  • the content of paraffins is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. is.
  • waxes for example, petroleum-based waxes such as microcrystalline wax and paraffin wax, Synthetic waxes such as polyethylene wax and polypropylene wax, plant waxes, animal waxes, and the like can be used.
  • the content of the wax is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. is.
  • petrolatums examples include white petrolatum and yellow petrolatum.
  • the content of petroleum jelly is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. is.
  • Dialkylsulfide compounds include di-tert-butyldesulfide, dipentyltetrasulfide, dipentylpentasulfide, dipentyldecasulfide, dioctyltetrasulfide, dioctylpentasulfide, dinonyltetrasulfide, dinonylpentasulfide, and di-tert-nonyltetrasulfide.
  • the content of the dialkyl sulfide compound is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. Department.
  • Dispersants include polyamide phosphoric acid-based dispersants, polyamide-based dispersants, unsaturated polycarboxylic acid-based dispersants, and polyethylene oxide-based dispersants. Examples thereof include Disparlon 6900-20X, Disparlon 4200 and Disparlon 1860 manufactured by Kusumoto Kasei Co., Ltd. These dispersants can be used alone or in combination of two or more.
  • the content of the dispersant is not particularly limited, but is 0.01 to 50 parts by mass, preferably 0.1 to 40 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the antifouling agent in terms of solid content. is 0.5 to 30 parts by mass.
  • a spreading resin other than the copolymer A can be contained in an arbitrary blending ratio that does not interfere with the effects of the present invention.
  • the spreading resin include vinyl resins, alkyd resins, urethane resins, polyester resins, synthetic rubbers, synthetic resins such as chlorinated polyethylene, and natural resins such as wood rosin, gum rosin, and modified rosin.
  • Plasticizers examples include phthalates, adipates, and tricresyl phosphate.
  • Water or Organic Solvent It is usually preferable to dissolve or disperse the composition of the present invention in water or an organic solvent. Thereby, it can be suitably used as a paint.
  • organic solvents examples include aromatic solvents such as xylene, toluene, Solvesso 100 and Solvesso 150 (both registered trademarks, manufactured by ExxonMobil); ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK). ; Ester solvents such as butyl acetate, isobutyl acetate and isopentyl acetate can be used.
  • aromatic solvents such as xylene, toluene, Solvesso 100 and Solvesso 150 (both registered trademarks, manufactured by ExxonMobil)
  • ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK).
  • Ester solvents such as butyl acetate, isobutyl acetate and isopentyl acetate can be used.
  • organic solvents with low toxicity, low odor, and low environmental load can also be used.
  • aromatic/alicyclic/aliphatic hydrocarbon mixed solvents propylene glycol monomethyl ether acetate, glycol ester solvents such as propylene glycol monoethyl ether acetate; ethylcyclohexane, dimethylcyclohexane, Likasolve (registered trademark) 900 (C9 aromatic hydrogenated), alicyclic hydrocarbon solvents such as Likasolve (registered trademark) 1000 (C10 aromatic hydrogenated); Shellsol D40 (registered trademark, manufactured by Shell Chemicals), Exsol D30, Exsol D40 Alicyclic and aliphatic hydrocarbon mixed solvents such as (registered trademark, manufactured by ExxonMobil); and aliphatic hydrocarbon mixed solvents such as Isopar G and Isopar H (both registered trademarks, manufactured by ExxonMobil) can.
  • These organic solvents can be used alone or in combination of
  • composition of the present invention can be used to form antifouling coating films for various fishing tools, underwater structures, and the like.
  • the composition of the present invention can be suitably used as an antifouling coating composition for fishing nets.
  • the antifouling coating composition for fishing nets of the present invention can be prepared by mixing the above components A to C and, if necessary, the above components.
  • the amount of each component to be added at the time of mixing may be appropriately adjusted so as to achieve the above blending amount and content.
  • a known method such as mixing using a stirring device may be adopted.
  • the method for forming a fishing net antifouling coating film of the present invention comprises applying the above fishing net antifouling coating composition to the surface of a coating film forming object. It is characterized by forming a coating film.
  • the antifouling coating film obtained by the forming method of the present invention can prevent attachment of aquatic fouling organisms by gradually releasing the antifouling agent from the surface.
  • coated film-forming objects examples include underwater objects placed in seawater.
  • An underwater object is not an object that moves at high speed like a ship, but an object that moves little or not at all in seawater.
  • objects placed in water examples include fishing tools and underwater structures.
  • fishing tools include fishing nets for aquaculture or stationary use, and fishing net tools such as floats and ropes used for the fishing nets.
  • Underwater structures include, for example, 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 fishing net antifouling coating composition to the surface (entirely or partially) of a coating film forming object.
  • Application methods include, for example, a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method, and the like. These may be used singly or in combination of two or more.
  • a dipping method as the coating method.
  • the drying temperature may be room temperature.
  • the drying time may be appropriately set according to the adhesion amount of the fishing net antifouling paint.
  • the adhesion amount of the fishing net antifouling paint may be appropriately set according to the type of the object to be coated and the like.
  • the amount of the dry coating film deposited is preferably 1 to 30 parts by weight, more preferably 4 to 15 parts by weight, per 100 parts by weight of the fishing net.
  • the coated article of the present invention has the antifouling coating film on its surface.
  • the coated article of the present invention may have the antifouling coating film on the entire surface or on a part of the surface.
  • % in each Production Example, Example and Comparative Example indicates % by mass.
  • the weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC.
  • the conditions for GPC are as follows.
  • HLC-8220GPC manufactured by Tosoh Corporation
  • the heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Coating component test method-heating residue".
  • Production Example 1-1 Production Example of Monomer (a1) ⁇ Production Example 1 (Production of Monomer a1-1)> In a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, methyl chloroacetate: 109 g (1.00 mol), acrylic acid: 72 g (1.00 mol), 4-methoxyphenol: 0.1 g, Ethyl acetate: 500 g was charged, and triethylamine: 101 g (1.00 mol) was added dropwise while stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours.
  • 2-methoxyethyl methacrylate trade name “Acryester MT” (Mitsubishi Chemical ( Co., Ltd.) 2-hydroxyethyl methacrylate: manufactured by Tokyo Kasei Co., Ltd.
  • xylene trade name “xylene” (manufactured by Mitsui Chemicals, Inc.) 1-butanol: manufactured by Tokyo Kasei Co., Ltd. Butyl acetate: manufactured by Tokyo Kasei Co., Ltd.
  • DAF-1 di-tert-nonyl pentasulfide (manufactured by DIC Corporation) Cuprous oxide: trade name “NC-301” (manufactured by Nisshin Chemco Co., Ltd.) Copper pyrithione: trade name “Copper Omadine Powder”: bis(2-sulfidepyridine-1-orato) copper (manufactured by Lonza Japan Co., Ltd.)
  • TOC-3204F Zinc bis(dimethyldithiocarbamoyl)ethylenebisdithiocarbamate (manufactured by Nutrition & Bioscience Co., Ltd.) 3-(2-ethylhexyloxy)propylamine/triphenylborane: trade name “OPA” (manufactured by Nitto Kasei Co., Ltd.) n-octadecylamine/triphenylborane: trade name “ODA” (manufactured by Beni
  • Example 1 Anti-fouling effect confirmation test for animal fouling organisms
  • Examples H-1 to H-17, I-1 to I-14, J-1 to J-14, Comparative Examples CH-1 to CH-3, CI-1 to CI-3 described in Tables 4 to 6 , CJ-1 to CJ-3 were dip-coated on polyethylene fishing nets (400 denier, 50 nets, 8 nodes, 15 cm long and 8 cm wide) and dried at room temperature for 2 days.
  • a fishing net coated with the obtained antifouling coating composition was fixed to a SUS frame of 40 ⁇ 75 cm and immersed in water to a depth of about 2 m from the sea. observable.

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Abstract

The present invention addresses the problem of providing a fishing net antifouling coating composition capable of maintaining a suitable chemical release amount from the initial phase of immersion in water, sustaining an antifouling effect over an extended period of time, and persistently exhibiting exceptional antifouling performance against organisms adhering to fishing nets over an extended period of time.　Provided according to the present invention is a fishing net antifouling coating composition containing a copolymer (A), a silicone oil (B), and an antifouling agent (C), wherein the copolymer (A) is a copolymer of a monomer (a) represented by general formula (1) and an ethylenically unsaturated monomer (b) other than the monomer (a), the monomer (a) includes a compound for which n in general formula (1) is greater than or equal to 2, and the silicone oil (B) is a modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5-9.

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 coating composition, fishing net, fishing net tool or underwater structure having on its surface an antifouling coating film formed using the composition
　本発明は、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長期にわたって防止するための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に関する。 The present invention is intended to prevent aquatic fouling organisms from adhering to fishing nets for aquaculture or set nets, fishing net tools such as floats and ropes used in these, and underwater structures such as cooling water pipes in power plants over a long period of time. It relates to a fishing net antifouling coating composition for antifouling, and a fishing net, fishing net tool or underwater structure having an antifouling coating film formed using the composition on its 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 being treated with antifouling paint for fishing nets, they may damage green algae such as sea lettuce and green laver, red algae such as gisu, and barnacles. Various aquatic fouling organisms such as crustaceans such as crustaceans, coelenterates such as hydra worms, serpra, bryozoans, and mollusks adhere. As a result, the mesh of the fishing nets is blocked and the seawater flow becomes poor, and a large number of farmed fish die due to lack of oxygen, and infectious diseases occur, making it impossible to ship them.
　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。 In order to prevent the adhesion of these aquatic fouling organisms, an antifouling coating composition for fishing nets using an organic tin compound has been widely used in the past, but it has become unusable 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。それらの問題を解決すべく、展着樹脂に薬剤の溶出コントロール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１～３）。 Therefore, various researches and proposals have been made as antifouling coating compositions for fishing nets to replace organic tin compounds, and inorganic compounds and organic compounds are used as antifouling agents, which are blended with natural resin-based or synthetic resin-based spreading resins. antifouling coating compositions for fishing nets have been used. However, these had problems such as poor physical properties of the coating film and a short antifouling period. In order to solve these problems, an antifouling paint composition for fishing nets, in which a specific polyether-modified silicone oil is blended with a spreading resin as a drug elution control agent, has been proposed (Patent Documents 1 to 3).
　しかし、上記発明はいずれも、漁網浸漬初期に薬剤を過剰に放出してしまい、塗料の防汚性能を十分に発揮できず、結果長期の防汚効果を発揮することができなかった。 However, in all of the above inventions, the chemical was excessively released at the initial stage of immersion in the fishing net, and the antifouling performance of the paint could not be fully demonstrated, resulting in a long-term antifouling effect.
特開２００１－１９８４８JP 2001-19848 特開２００２－２６５８４９JP 2002-265849 特開２００９－２０３３４１JP 2009-203341
　本発明は、上記事情に鑑みてなされたものであり、水中浸漬初期から、適度な薬剤放出量を維持し、防汚効果が長期間持続し、漁網への付着生物に対して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 maintains an appropriate amount of drug release from the initial stage of immersion in water, maintains an antifouling effect for a long period of time, and is excellent in antifouling against organisms attached to fishing nets. An object of the present invention is to provide an antifouling coating composition for fishing nets that can continuously exhibit its performance for a long period of time.
　本発明によれば、共重合体（Ａ）、シリコーンオイル（Ｂ）、および防汚薬剤（Ｃ）を含有する防汚塗料組成物であって、前記共重合体（Ａ）は、一般式（１）で表される単量体（ａ）と、前記単量体（ａ）以外のエチレン性不飽和単量体（ｂ）の共重合体であり、前記単量体（ａ）は、前記一般式（１）中のｎが２以上である化合物を含み、前記シリコーンオイル（Ｂ）は、親水親油バランス（ＨＬＢ値）が０．５～９の変性シリコーンオイルである、漁網防汚塗料組成物が提供される。 According to the present invention, there is provided an antifouling coating composition containing a copolymer (A), a silicone oil (B), and an antifouling agent (C), wherein the copolymer (A) has the general formula ( 1) and a copolymer of an ethylenically unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is the A fishing net antifouling paint containing a compound in which n in the general formula (1) is 2 or more, and wherein the silicone oil (B) is a modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5 to 9. A composition is 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、共重合体Ａ、シリコーンオイルＢ、および防汚薬剤Ｃを含む漁網防汚塗料組成物が、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 problems, the present inventors found that a fishing net antifouling coating composition containing a copolymer A, a silicone oil B, and an antifouling agent C can solve the above problems. The present invention has been completed.
　また、本発明によれば、上記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、漁網用具又は水中構造物も提供される。 Further, according to the present invention, a fishing net, a fishing net tool, or an underwater structure having on its surface an antifouling coating film formed using the fishing net antifouling coating composition is also provided.
以下、本発明について詳細を説明する。 The present invention will be described in detail below.
１．漁網防汚塗料組成物
　本発明の漁網防汚塗料組成物は、共重合体Ａ、シリコーンオイルＢおよび防汚薬剤Ｃを含有する。 1. Fishing net antifouling paint composition The fishing net antifouling paint composition of the present invention contains copolymer A, silicone oil B and antifouling agent C.
１－１．共重合体Ａ
　共重合体Ａは、単量体（ａ）と、単量体（ａ）以外のエチレン性不飽和単量体単量体（ｂ）の共重合体であり、単量体（ａ）及び単量体（ｂ）に由来する単量体単位を含む。単量体（ａ）と単量体（ｂ）の合計に対する単量体（ａ）の含有量は、５～９０質量％が好ましく、５～７０質量％が更に好ましく、５～６０質量％が更に好ましく、５～４０質量％が特に好ましい。具体的には例えば、５、８、１０、１５、２０、２５、３０、３５、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０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。この場合に、長期防汚性が特に良好となる。 1-1. Copolymer A
Copolymer A is a copolymer of a monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer (a) and the monomer Including monomeric units derived from mer (b). The content of the monomer (a) with respect to the sum of the monomer (a) and the monomer (b) is preferably 5 to 90% by mass, more preferably 5 to 70% by mass, and 5 to 60% by mass. More preferably, 5 to 40% by mass is particularly preferable. Specifically, for example, 5, 8, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90% by mass, where It may be in a range between any two of the numerical values given. In this case, the long-term antifouling property is particularly good.
１－１－１．単量体（ａ）
　単量体（ａ）は、一般式（１）で表される。
　
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ１は水素又はメチル基を示し、Ｒ２は、水素、メチル基、フェニル基を示し、Ｒ３は、炭素数１～８のアルコキシ基又はフェニル基で置換されていてもよい炭素数１～８のアルキル基であるか、又はフェニル基を示し、ｎは、１～１０の整数を示す。） 1-1-1. monomer (a)
Monomer (a) is represented by general formula (1).

Figure JPOXMLDOC01-appb-C000003
 (In the formula, R 1 represents hydrogen or a methyl group, R 2 represents hydrogen, a methyl group, or a phenyl group, and R 3 may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group. It is an alkyl group having 1 to 8 carbon atoms or represents a phenyl group, and n represents an integer of 1 to 10.)
　Ｒ２は、好ましくは、水素、又はメチル基である。 R 2 is preferably hydrogen or a methyl group.
　Ｒ３のアルコキシ基又はアルキル基の炭素数は、例えば、１、２、３、４、５、６、７、８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。Ｒ３は、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、ｔ－ブチル基、２－エチルヘキシル基、シクロヘキシル基、ベンジル基、フェニル基、２－メトキシエチル基、４－メトキシブチル基、ビニル基、又はアリル基であり、好ましくは、メチル基、エチル基、イソプロピル基、又はｎ－ブチル基である。 The number of carbon atoms in the alkoxy group or alkyl group of R 3 is, for example, 1, 2, 3, 4, 5, 6, 7, or 8, and within the range between any two of the numerical values exemplified here good too. R 3 is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, benzyl group, phenyl group, 2-methoxyethyl group, 4-methoxybutyl group, vinyl group or allyl group, preferably methyl group, ethyl group, isopropyl group or n-butyl group.
　ｎは、１～１０の整数を示し、ｎは、例えば、１、２、３、４、５、６、７、８、９、１０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。 n represents an integer of 1 to 10, n is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, any two of the numerical values exemplified here may be within the range.
　単量体（ａ）は、一般式（１）中のｎが２以上である化合物を含む。単量体（ａ）としてｎが２以上である化合物が含まれると、長期防汚性が高くなる。単量体（ａ）は、ｎが２以上である化合物のみで構成されていてもよく、ｎが１である化合物とｎが２以上である化合物の混合物であってもよい。 The monomer (a) includes compounds in which n in general formula (1) is 2 or more. When a compound in which n is 2 or more is contained as the monomer (a), the long-term antifouling property is enhanced. The monomer (a) may be composed only of a compound in which n is 2 or more, or may be a mixture of a compound in which n is 1 and a compound in which n is 2 or more.
　単量体（ａ）は、好ましくは、単量体（ａ１）と単量体（ａ２）で構成される。単量体（ａ）中の単量体（ａ１）の含有量は、５０～８０質量％が好ましく、５５～７５質量％が更に好ましく、６０～７０質量％が特に好ましい。単量体（ａ１）は、単量体（ａ２）に比べて、塗膜強度を高め、長期防汚性を低下させる傾向にある。このため、単量体（ａ１）の含有量が少なすぎると、塗膜強度が低くなる傾向があり、長期間経過後に塗膜表面状態が悪くなりやすくなる場合がある。一方、単量体（ａ１）の含有量が多すぎると、長期防汚性能が低下してしまう場合がある。 The monomer (a) preferably consists of a monomer (a1) and a monomer (a2). The content of monomer (a1) in monomer (a) is preferably 50 to 80% by mass, more preferably 55 to 75% by mass, and particularly preferably 60 to 70% by mass. The monomer (a1) tends to increase the strength of the coating film and reduce the long-term antifouling property compared to the monomer (a2). Therefore, if the content of the monomer (a1) is too small, the strength of the coating film tends to be low, and the surface condition of the coating film tends to deteriorate after a long period of time. On the other hand, if the content of the monomer (a1) is too high, the long-term antifouling performance may deteriorate.
＜単量体（ａ１）＞
　単量体（ａ１）は、一般式（１）のｎが１である化合物である。
　単量体（ａ１）としては、例えば、（メタ）アクリル酸メトキシカルボニルメチル、（メタ）アクリル酸エトキシカルボニルメチル、（メタ）アクリル酸イソプロポキシカルボニルメチル、（メタ）アクリル酸ｎ－プロポキシカルボニルメチル、（メタ）アクリル酸ｎ－ブトキシカルボニルメチル、（メタ）アクリル酸ｔ－ブトキシカルボニルメチル、（メタ）アクリル酸２－エチルヘキシルオキシカルボニルメチル、（メタ）アクリル酸シクロヘキシルオキシカルボニルメチル、（メタ）アクリル酸ベンジルオキシカルボニルメチル、（メタ）アクリル酸フェノキシカルボニルメチル、（メタ）アクリル酸２－メトキシエトキシカルボニルメチル、（メタ）アクリル酸４－メトキシブトキシカルボニルメチル、（メタ）アクリル酸アリロキシカルボニルメチル、（メタ）アクリル酸ビニロキシカルボニルメチル、（メタ）アクリル酸１－（メトキシカルボニル）エチル、（メタ）アクリル酸１－（エトキシカルボニル）エチル、（メタ）アクリル酸１－（ｎ－プロポキシカルボニル）エチル、（メタ）アクリル酸１－（イソプロポキシカルボニル）エチル、（メタ）アクリル酸１－（ｎ－ブトキシカルボニル）エチル、（メタ）アクリル酸１－（ｔ－ブトキシカルボニル）エチル、（メタ）アクリル酸α－（メトキシカルボニル）ベンジル、（メタ）アクリル酸α－（エトキシカルボニル）ベンジルが挙げられ、好ましくは、（メタ）アクリル酸メトキシカルボニルメチル、（メタ）アクリル酸エトキシカルボニルメチル、（メタ）アクリル酸イソプロポキシカルボニルメチル、（メタ）アクリル酸ｎ－プロポキシカルボニルメチル、（メタ）アクリル酸ｎ－ブトキシカルボニルメチル、（メタ）アクリル酸１－（メトキシカルボニル）エチル、（メタ）アクリル酸１－（エトキシカルボニル）エチルが挙げられる。 <Monomer (a1)>
Monomer (a1) is a compound in which n is 1 in general formula (1).
Examples of the monomer (a1) include methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate, isopropoxycarbonylmethyl (meth)acrylate, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, t-butoxycarbonylmethyl (meth)acrylate, 2-ethylhexyloxycarbonylmethyl (meth)acrylate, cyclohexyloxycarbonylmethyl (meth)acrylate, benzyl (meth)acrylate Oxycarbonylmethyl, phenoxycarbonylmethyl (meth)acrylate, 2-methoxyethoxycarbonylmethyl (meth)acrylate, 4-methoxybutoxycarbonylmethyl (meth)acrylate, allyloxycarbonylmethyl (meth)acrylate, (meth)acrylate Vinyloxycarbonylmethyl acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, 1-(ethoxycarbonyl)ethyl (meth)acrylate, 1-(n-propoxycarbonyl)ethyl (meth)acrylate, (meth) ) 1-(isopropoxycarbonyl) ethyl acrylate, 1-(n-butoxycarbonyl) ethyl (meth) acrylate, 1-(t-butoxycarbonyl) ethyl (meth) acrylate, (meth) acrylate α-( methoxycarbonyl)benzyl and α-(ethoxycarbonyl)benzyl (meth)acrylate, preferably methoxycarbonylmethyl (meth)acrylate, ethoxycarbonylmethyl (meth)acrylate and isopropoxycarbonyl (meth)acrylate. methyl, n-propoxycarbonylmethyl (meth)acrylate, n-butoxycarbonylmethyl (meth)acrylate, 1-(methoxycarbonyl)ethyl (meth)acrylate, 1-(ethoxycarbonyl)ethyl (meth)acrylate mentioned.
＜単量体（ａ２）＞
　単量体（ａ２）は、一般式（１）のｎが２以上である化合物である。一般式（１）のｎは、長期防汚性の観点から２～６が好ましい。 <Monomer (a2)>
The monomer (a2) is a compound of general formula (1) in which n is 2 or more. n in formula (1) is preferably 2 to 6 from the viewpoint of long-term antifouling properties.
　単量体（ａ２）としては、ｎが２である化合物と、ｎが３以上である化合物の両方を含むことが好ましい。具体的には例えば、固形分換算で、質量比（ｎ（２）／ｎ（２～１０））が０．４～０．８が好ましく、０．５～０．７が更に好ましい。この場合、安定した塗膜溶解が持続する傾向が見られている。この値は、具体的には例えば、０．４０、０．４５、０．５０、０．５５、０．６０、０．６５、０．７０、０．７５、０．８０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 monomer (a2) preferably contains both a compound in which n is 2 and a compound in which n is 3 or more. Specifically, for example, the mass ratio (n(2)/n(2-10)) in terms of solid content is preferably 0.4 to 0.8, more preferably 0.5 to 0.7. In this case, there is a tendency for stable coating film dissolution to continue. Specifically, this value is, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, where It may be in a range between any two of the numerical values given.
　単量体（ａ２）としては、例えば、（メタ）アクリル酸メチルジ（オキシカルボニルメチル）、（メタ）アクリル酸エチルジ（オキシカルボニルメチル）、（メタ）アクリル酸イソプロピルジ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－プロピルジ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－ブチルジ（オキシカルボニルメチル）、（メタ）アクリル酸ｔ－ブチルジ（オキシカルボニルメチル）、（メタ）アクリル酸２－エチルヘキシルジ（オキシカルボニルメチル）、（メタ）アクリル酸シクロヘキシルジ（オキシカルボニルメチル）、（メタ）アクリル酸ベンジルジ（オキシカルボニルメチル）、（メタ）アクリル酸フェニルジ（オキシカルボニルメチル）、（メタ）アクリル酸２－メトキシエチルジ（オキシカルボニルメチル）、（メタ）アクリル酸４－メトキシブチルジ（オキシカルボニルメチル）、（メタ）アクリル酸アリルジ（オキシカルボニルメチル）、（メタ）アクリル酸ビニルジ（オキシカルボニルメチル）、（メタ）アクリル酸メチルジ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸エチルジ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸ｎ－プロピルジ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸イソプロピルジ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸ｎ－ブチルジ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸ｔ－ブチルジ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸メチルジ〔α－（オキシカルボニル）ベンジル〕、（メタ）アクリル酸エチルジ〔α－（オキシカルボニル）ベンジル〕が挙げられ、好ましくは、（メタ）アクリル酸メチルジ（オキシカルボニルメチル）、（メタ）アクリル酸エチルジ（オキシカルボニルメチル）、（メタ）アクリル酸イソプロピルジ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－プロピルジ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－ブチルジ（オキシカルボニルメチル）、（メタ）アクリル酸メチルジ〔１－（オキシポリカルボニルエチル）〕、（メタ）アクリル酸エチルジ〔１－（オキシポリカルボニルエチル）〕、（メタ）アクリル酸メチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸エチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸イソプロピルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－プロピルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－ブチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ｔ－ブチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸２－エチルヘキシルポリ（オキシカルボニルメチル）、（メタ）アクリル酸シクロヘキシルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ベンジルポリオキシカルボニルメチル）、（メタ）アクリル酸フェニルポリ（オキシカルボニルメチル）、（メタ）アクリル酸２－メトキシエチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸４－メトキシブチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸アリルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ビニルポリ（オキシカルボニルメチル）、（メタ）アクリル酸メチルポリ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸エチルポリ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸ｎ－プロピルポリ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸イソプロピルポリ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸ｎ－ブチルポリ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸ｔ－ブチルポリ〔１－（オキシポリカルボニル）エチル〕、（メタ）アクリル酸メチルポリ〔α－（オキシカルボニル）ベンジル〕、（メタ）アクリル酸エチルポリ〔α－（オキシカルボニル）ベンジル〕が挙げられ、好ましくは、（メタ）アクリル酸メチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸エチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸イソプロピルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－プロピルポリ（オキシカルボニルメチル）、（メタ）アクリル酸ｎ－ブチルポリ（オキシカルボニルメチル）、（メタ）アクリル酸メチルポリ〔１－（オキシポリカルボニルエチル）〕、（メタ）アクリル酸エチルポリ〔１－（オキシポリカルボニルエチル）〕等が挙げられる。 Examples of the monomer (a2) include methyl (meth)acrylate di(oxycarbonylmethyl), ethyl (meth)acrylate di(oxycarbonylmethyl), isopropyl(meth)acrylate di(oxycarbonylmethyl), (meth)acrylate ) n-propyl di(oxycarbonylmethyl) acrylate, n-butyl di(oxycarbonylmethyl) acrylate (meth), t-butyl di(oxycarbonylmethyl) acrylate (meth), 2-ethylhexyl di(meth) acrylate ( oxycarbonylmethyl), cyclohexyl di(oxycarbonylmethyl) (meth)acrylate, benzyl di(oxycarbonylmethyl) (meth)acrylate, phenyl di(oxycarbonylmethyl) (meth)acrylate, 2-methoxy (meth)acrylate Ethyl di (oxycarbonylmethyl), 4-methoxybutyl di (oxycarbonylmethyl) (meth) acrylate, allyl di (oxycarbonylmethyl) (meth) acrylate, vinyl di (oxycarbonylmethyl) (meth) acrylate, (meth) ) Methyl di[1-(oxypolycarbonyl)ethyl] acrylate, (meth)ethyl acrylate di[1-(oxypolycarbonyl)ethyl], (meth)acrylate n-propyl di[1-(oxypolycarbonyl)ethyl] , (meth) isopropyl di[1-(oxypolycarbonyl)ethyl] acrylate, n-butyl di[1-(oxypolycarbonyl)ethyl] (meth)acrylate, t-butyl di(meth)acrylate [1-( oxypolycarbonyl)ethyl], methyl (meth)acrylate di[α-(oxycarbonyl)benzyl], ethyl (meth)acrylate di[α-(oxycarbonyl)benzyl], preferably (meth)acrylic acid Methyldi(oxycarbonylmethyl), Ethyl(oxycarbonylmethyl)(meth)acrylate, Isopropyl(oxycarbonylmethyl)(meth)acrylate, n-propyl(oxycarbonylmethyl)(meth)acrylate, (meth)acryl acid n-butyl di(oxycarbonylmethyl), methyl (meth)acrylate di[1-(oxypolycarbonylethyl)], ethyl(meth)acrylate di[1-(oxypolycarbonylethyl)], methyl(meth)acrylate poly (oxycarbonylmethyl), ethyl (meth)acrylate poly(oxycarbonylmethyl), isopropyl(meth)acrylate poly(oxycarbonylmethyl), n-propyl acrylate poly(oxycarbonylmethyl) (meth)acrylate, (meth)acrylic Acid n-butyl poly(oxycarbonylmethyl), t-butyl acrylate poly(oxycarbonylmethyl) (meth)acrylate, 2-ethylhexyl (meth)acrylate poly(oxycarbonylmethyl), cyclohexyl acrylate poly(oxycarbonylmethyl) (meth)acrylate ), benzyl (meth)acrylate polyoxycarbonylmethyl), phenyl (meth)acrylate poly(oxycarbonylmethyl), (meth)acrylate 2-methoxyethyl poly(oxycarbonylmethyl), (meth)acrylate 4- methoxybutyl poly(oxycarbonylmethyl), allyl (meth)acrylate poly(oxycarbonylmethyl), vinyl (meth)acrylate poly(oxycarbonylmethyl), methyl (meth)acrylate poly[1-(oxypolycarbonyl)ethyl], (Meth) ethyl acrylate poly[1-(oxypolycarbonyl)ethyl], (meth)acrylic acid n-propylpoly[1-(oxypolycarbonyl)ethyl], (meth)acrylate poly[1-(oxypolycarbonyl) carbonyl) ethyl], (meth) n-butyl acrylate poly [1-(oxypolycarbonyl) ethyl], (meth) t-butyl acrylate poly [1-(oxypolycarbonyl) ethyl], (meth) acrylate poly methyl acrylate [ α-(oxycarbonyl) benzyl], ethyl (meth) acrylate poly [α-(oxycarbonyl) benzyl], preferably methyl (meth) acrylate poly (oxycarbonylmethyl), ethyl (meth) acrylate poly ( oxycarbonylmethyl), isopropyl (meth)acrylate poly(oxycarbonylmethyl), n-propyl acrylate poly(oxycarbonylmethyl) (meth)acrylate, n-butyl acrylate poly(oxycarbonylmethyl) (meth)acrylate, (meth) methyl acrylate poly[1-(oxypolycarbonylethyl)], ethyl (meth)acrylate poly[1-(oxypolycarbonylethyl)] and the like.
１－１－２．単量体（ｂ）
　単量体（ｂ）は、単量体（ａ）以外のエチレン性不飽和単量体である。単量体（ｂ）は、単量体（ｂ１）と単量体（ｂ２）に分類することができ、共重合体Ａの重合に用いる単量体（ｂ）には、単量体（ｂ１）と単量体（ｂ２）の一方又は両方が含まれ、単量体（ｂ１）が含まれることが好ましい。 1-1-2. monomer (b)
Monomer (b) is an ethylenically unsaturated monomer other than monomer (a). The monomer (b) can be classified into a monomer (b1) and a monomer (b2). ) and the monomer (b2), preferably the monomer (b1).
　単量体（ｂ１）の含有量は、共重合体Ａ中、１～３０質量％が好ましく、より好ましくは２～２５質量％、更に好ましくは３～２０質量％である。前記範囲内にある場合、得られる塗料組成物を用いて形成した塗膜が、薬剤の溶出をコントロールしているシリコーンオイルとの相溶性が向上し、結果適切量の薬剤溶出を可能とする利点を有する。前記単量体（ｂ１）の含有量は、具体的には例えば、１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２、２３、２４、２５、２６、２７、２８、２９、３０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 content of the monomer (b1) in the copolymer A is preferably 1-30% by mass, more preferably 2-25% by mass, still more preferably 3-20% by mass. When within the above range, the coating film formed using the obtained coating composition has improved compatibility with the silicone oil that controls the elution of the drug, and as a result, there is an advantage that an appropriate amount of drug can be eluted. have Specifically, the content of the monomer (b1) is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30% by mass, even within the range between any two of the numerical values illustrated here good.
＜単量体（ｂ１）＞
　単量体（ｂ１）は、一般式（２）で表される。 <Monomer (b1)>
The monomer (b1) is represented by general formula (2).
Figure JPOXMLDOC01-appb-C000004
 （式中、Ｒ４は水素又はメチル基、Ｒ５は炭素数１０～２２のアルキル基を示す）
Figure JPOXMLDOC01-appb-C000004
 (Wherein, R 4 represents hydrogen or a methyl group, and R 5 represents an alkyl group having 10 to 22 carbon atoms)
　Ｒ５は、例えば、デシル、イソデシル、ドデシル、トリデシル、テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデシル、オクタデシル、ノナデシルなどが挙げられる。Ｒ５の炭素数は、１２～１８が好ましい。Ｒ５の炭素数は、具体的には例えば、１０、１１、１２、１３、１４、１５、１６、１７、１８、１９、２０、２１、２２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。 Examples of R5 include decyl, isodecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and the like. The carbon number of R 5 is preferably 12-18. Specifically, the carbon number of R 5 is, for example, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, and any one of the numerical values exemplified here is 2 It may be within a range between two.
　単量体（ｂ１）としては、例えば、（メタ）アクリル酸デシル、（メタ）アクリル酸イソデシル、（メタ）アクリル酸ドデシル（ラウリル）、（メタ）アクリル酸トリデシル、（メタ）アクリル酸テトラデシル（ミリスチル）、（メタ）アクリル酸ペンタデシル、（メタ）アクリル酸ヘキサデシル（パルミチル）、（メタ）アクリル酸ヘプタデシル（マルガリル）、（メタ）アクリル酸オクタデシル（ステアリル）、（メタ）アクリル酸ノナデシル等が挙げられる。単量体（ｂ１）は単独又は二種以上で使用できる。 Examples of the monomer (b1) include decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (lauryl) (meth)acrylate, tridecyl (meth)acrylate, and tetradecyl (myristyl (meth)acrylate). ), pentadecyl (meth)acrylate, hexadecyl (palmityl) (meth)acrylate, heptadecyl (margaryl) (meth)acrylate, octadecyl (stearyl) (meth)acrylate, nonadecyl (meth)acrylate, and the like. The monomer (b1) can be used singly or in combination of two or more.
＜単量体（ｂ２）＞
　単量体（ｂ２）としては、単量体（ａ）および単量体（ｂ１）以外のエチレン性不飽和単量体が挙げられ、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ｎ－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）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル、（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、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸２－エトキシ－ジエチレングリコール等の（メタ）アクリル酸エステル；塩化ビニル、塩化ビニリデン、（メタ）アクリロニトリル、酢酸ビニル、ブチルビニルエーテル、ラウリルビニルエーテル、Ｎ－ビニルピロリドン等のビニル化合物；スチレン、ビニルトルエン、α－メチルスチレン等の芳香族化合物等が挙げられる。この中でも特に、（メタ）アクリル酸エステルが好ましく、（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ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸イソペンチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－メトキシエチル、（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、（メタ）アクリル酸２－ヒドロキシブチル、（メタ）アクリル酸２－エトキシ－ジエチレングリコールがより好ましい。単量体（ｂ２）は、単独又は二種以上で使用できる。 <Monomer (b2)>
Examples of the monomer (b2) include ethylenically unsaturated monomers other than the monomer (a) and the monomer (b1), such as methyl (meth)acrylate and ethyl (meth)acrylate. , n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, (meth)acrylic acid (Meth)acrylic acid esters such as 2-hydroxyethyl acid, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-ethoxy-diethylene glycol (meth)acrylate; vinyl chloride, vinylidene chloride , (meth)acrylonitrile, vinyl acetate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone; and aromatic compounds such as styrene, vinyltoluene, and α-methylstyrene. Among these, (meth)acrylic acid esters are particularly preferable, and methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, Hexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 2 -hydroxybutyl, 2-ethoxy-diethylene glycol (meth)acrylate are more preferred. The monomer (b2) can be used singly or in combination of two or more.
１－１－３．共重合体Ａの物性・製造方法
　共重合体Ａの重量平均分子量（Ｍｗ）は１００００～５０００００であることが望ましく、８００００～３０００００であることが更に望ましい。分子量が１００００未満であれば、防汚塗料の塗膜が脆弱となり、剥離やクラックを起こし易く、また、５０００００を超えると、重合体溶液の粘度が上昇し、取扱いが困難となるからである。このＭｗは、具体的には例えば、１００００、２００００、３００００、４００００、５００００、６００００、７００００、８００００、９００００、１０００００、２０００００、３０００００、４０００００、５０００００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。
　Ｍｗの測定方法としては、例えばゲル浸透クロマトグラフィー（ＧＰＣ法）が挙げられる。 1-1-3. Physical properties and production method of copolymer A The weight average molecular weight (Mw) of copolymer A is preferably 10,000 to 500,000, more preferably 80,000 to 300,000. If the molecular weight is less than 10,000, the coating film of the antifouling paint will be brittle and easily peeled off or cracked. Specifically, this Mw is, for example, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, 400000, 500000. It may be in the range between.
Examples of methods for measuring Mw include gel permeation chromatography (GPC method).
　前記共重合体Ａのガラス転移温度（Ｔｇ）は、－５０～５０℃程度が好ましく、－３５～３５℃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 copolymer A is preferably about -50 to 50°C, more preferably about -35 to 35°C. When the Tg is within the above range, the coating film becomes too tacky after being applied to the fishing net, which does not hinder the coating work. There is no problem that the antifouling effect is lost. The above Tg value refers to a value actually measured using a differential scanning calorimeter (eg, DSC1 manufactured by METTLER TOLEDO) with reference to the measurement method of JIS K 7121.
　共重合体Ａは、単量体（ａ）と単量体（ｂ）とのランダム共重合体、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。 Copolymer A is a random copolymer, alternating copolymer, periodic copolymer, or block copolymer of monomer (a) and monomer (b). may
　共重合体Ａは、例えば、重合開始剤の存在下、単量体（ａ）と単量体（ｂ）を重合させることにより得ることができる。 Copolymer A can be obtained, for example, by polymerizing monomer (a) and monomer (b) in the presence of a polymerization initiator.
　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、２，２'－アゾビス（２－メチルブチロニトリル）、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル－２，２'－アゾビスイソブチレート、ジメチル２，２'－アゾビスイソブチレート、２，２'－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド等のアゾ化合物；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、ｔ－ヘキシルパーオキシ－２－エチルヘキサノエート、ジ－ｔ－ヘキシルパーオキサイド、ｔ－ブチルパーオキシ－２－エチルヘキシルモノカルボネート、ジ－ｔ－ブチルパーオキサイド、１，１，３，３－テトラメチルブチルパーオキシネオデカノエート、ｔ－アミルパーオキシネオデカノエート、ｔ－ヘキシルパーオキシピバレート、ｔ－アミルパーオキシピバレート、１，１，３，３－テトラメチルブチルパーオキシ－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、２，２'－アゾビス（２－メチルブチロニトリル）、２，２'－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル２，２'－アゾビスイソブチレート及び１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエートが好ましい。重合開始剤の使用量を適宜設定することにより、共重合体Ａの分子量を調整することができる。また、得られるポリマーの分子量の調整のために、連鎖移動剤を使用することができる。連鎖移動剤としては、例えば、ｎ－ドデシルメルカプタン等のメルカプタン類；チオグリコール酸オクチル等のチオグリコール酸エステル類；α－メチルスチレンダイマー、ターピノーレンが挙げられる。 Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile ), dimethyl-2,2′-azobisisobutyrate, dimethyl 2,2′-azobisisobutyrate, 2,2′-azobis (N-butyl-2-methylpropionamide and other azo compounds; benzoylper oxide, di-tert-butylperoxide, tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate , di-t-hexyl peroxide, t-butyl peroxy-2-ethylhexyl monocarbonate, di-t-butyl peroxide, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, t- Peroxides such as amyl peroxyneodecanoate, t-hexyl peroxypivalate, t-amyl peroxypivalate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, etc. These polymerization initiators can be used alone or in combination of two or more. -methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 - Ethylhexanoate is preferred.By appropriately setting the amount of the polymerization initiator used, the molecular weight of the copolymer A can be adjusted.In addition, a chain transfer agent is used to adjust the molecular weight of the resulting polymer. Chain transfer agents include, for example, mercaptans such as n-dodecylmercaptan, thioglycolic acid esters such as octyl thioglycolate, α-methylstyrene dimer, and terpinolene.
　重合方法としては、例えば、溶液重合、塊状重合、乳化重合、懸濁重合、非水分散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、共重合体Ａを得ることができる点で、溶液重合、又は非水分散重合が好ましい。 Examples of polymerization methods include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and non-aqueous dispersion polymerization. Among these, solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that the copolymer A can be obtained easily and accurately.
　前記重合反応においては、必要に応じて有機溶媒を用いてもよい。有機溶剤としては、特に限定されないが、例えば、キシレン、トルエン等の芳香族炭化水素系溶剤；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、プロピレングリコール１－モノメチルエーテル２－アセタート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、プロピレングリコールモノメチルエーテ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。
　その中でも、酢酸ブチル、酢酸イソブチル、ブチルアルコール、プロピレングリコールモノメチルエーテル、プロピレングリコール１－モノメチルエーテル２－アセタート、トルエン、キシレンが好ましい。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, an organic solvent may be used as necessary. The organic solvent is not particularly limited, but for example, aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents; ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether. ester solvents such as 2-acetate; alcohol solvents such as isopropyl alcohol, butyl alcohol and propylene glycol monomethyl ether; ether solvents such as dioxane, diethyl ether and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. mentioned.
Among them, butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferred. 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５０～１６０℃であり、好ましくは６０～１５０℃である。 The reaction temperature in the polymerization reaction may be appropriately set according to the type of polymerization initiator, etc., and is usually 50 to 160°C, preferably 60 to 150°C.
　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 polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen gas or argon gas.
　漁網防汚塗料組成物中の共重合体Ａの含有量は、特に限定されないが、固形分換算で３～５０質量％、好ましくは５～３０質量％である。 The content of copolymer A in the fishing net antifouling paint composition is not particularly limited, but is 3 to 50% by mass, preferably 5 to 30% by mass in terms of solid content.
１－２．シリコーンオイルＢ
　シリコーンオイルＢは、親水親油バランス（ＨＬＢ値）が０．５～９の変性シリコーンオイルである。前記変性シリコーンオイルとしては、例えば、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、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、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、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。本発明では、これらの変性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。 1-2. Silicone oil B
Silicone oil B is a modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5-9. Examples of the modified silicone oil include polyether-modified polydimethylsiloxane, polyether-modified polyalkyl(methyl)siloxane, polyester-modified polydimethylsiloxane, polyether long-chain alkylaralkyl-modified dimethylsilicone oil, amino-modified silicone oil, and various others. Functional group-modified silicone oils and the like can be mentioned, and polyether-modified polydimethylsiloxane or polyether long-chain alkylaralkyl-modified dimethylsilicone oil is preferable. In the present invention, these modified silicone oils may be used alone, or two or more of them may be used in combination.
　ＨＬＢ値は、好ましくは、１～５である。ＨＬＢ値は、具体的には例えば、０．５、１．０、１．５、２．０、２．５、３．０、３．５、４．０、４．５、５．０、５．５、６．０、６．５、７．０、７．５、８．０、８．５、９．０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。ＨＬＢ値は、グリフィン法により算出することができる。グリフィン法では、ＨＬＢ値＝２０×（親水部の分子量の総和／全体の分子量）で定義される。 The HLB value is preferably 1-5. Specifically, HLB values are, for example, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0 and within the range between any two of the numerical values exemplified herein. may The HLB value can be calculated by the Griffin method. In Griffin's method, the HLB value is defined as 20×(sum of molecular weights of hydrophilic portions/total molecular weight).
　シリコーンオイルＢ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く、１０ポイズ以下がさらに好ましい。 The viscosity of silicone oil B is preferably 1000 poise or less, more preferably 100 poise or less, and even more preferably 10 poise or less, from the viewpoint of coating performance and coating film properties.
　シリコーンオイルＢの含有量は、特に限定されないが、固形分換算で、共重合体Ａ１００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 silicone oil B is not particularly limited. ~50 parts by mass.
　漁網防汚塗料組成物には、シリコーンオイルＢのみが含まれていてもよく、シリコーンオイルＢに加えて、その他のシリコーンオイルも含まれていてもよい。その他のシリコーンオイルとしては、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、フロロシリコーンオイル、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等が挙げられる。 The antifouling coating composition for fishing nets may contain only silicone oil B, or may contain other silicone oils in addition to silicone oil B. Other silicone oils include polydimethylsiloxane, polymethylphenylsiloxane, methylphenylsiloxane-dimethylsiloxane copolymer, fluorosilicone oil, long-chain alkyl-modified polydimethylsiloxane, aralkyl-modified polydimethylsiloxane, and the like.
１－３．防汚薬剤Ｃ
　本発明に使用される防汚薬剤Ｃ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。
　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。 1-3. Antifouling agent C
The antifouling agent C used in the present invention is not particularly limited as long as it is a compound having a killing or repelling effect on marine fouling organisms. Examples include the following organic compounds and inorganic compounds.
Examples of organic compounds include 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide zinc, zinc ethylene bisdithiocarbamate, bis(dimethyldithiocarbamate) zinc, bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate, pyridine.・Triphenylborane, n-octadecylamine ・Triphenylborane, 3-(2-ethylhexyloxy)propylamine ・Triphenylborane, 4-isopropyl-diphenylmethyl, 4-phenylpyridyl-diphenylborane, 2,4,6- trichloromaleimide, n-(2,6-diethylphenyl)2,3-dichloromaleimide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, chloromethyl-n-octyl disulfide, 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 phthalonitrile, N-dichlorofluoromethylthio-N',N'-dimethyl-Np-tolylsulfamide, N-dichloromethylthio-N',N'-dimethyl-N-phenylsulfamide, 2-(4 -thiazolyl)benzimidazole, and the like.
　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、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、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, 3-(2-ethylhexyloxy)propylamine/triphenylborane, tetraethylthiuram disulfide, 2-mercaptopyridine N-oxide copper, 2-mercaptopyridine N-oxide Zinc and bisdimethyldithiocarbamoyl zinc ethylene bisdithiocarbamate are particularly preferred, and may be used singly or in combination of two or more.
　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 inorganic compounds include cuprous oxide, monovalent copper glass, divalent copper glass, copper thiocyanate, cupronickel, copper powder, etc. Cuprous oxide, monovalent copper glass and divalent Copper glass is particularly preferred, and may be used singly or in combination of two or more.
　上記防汚薬剤Ｃ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 above antifouling agents C, the solvent or water-insoluble antifouling agent preferably has an average particle size of 10 μm or less, particularly preferably 3 μm or less, from the viewpoint of dispersibility. These average particle diameters can be measured with a particle size distribution meter manufactured by Nikkiso Co., Ltd., model Microtrac MT3300EXII (measurement principle: laser diffraction/scattering method).
　本発明の塗料組成物における防汚薬剤Ｃの含有量は限定的ではないが、共重合体Ａ１００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。 Although the content of the antifouling agent C in the coating composition of the present invention is not limited, it is usually 1 to 300 parts by mass, preferably 5 to 200 parts by mass, based on 100 parts by mass of the copolymer A. 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 physical properties of the coating film tend to deteriorate.
１－４．その他の添加成分
　本発明に用いられる塗料組成物は、他の溶出調整剤、分散剤、他の展着樹脂、沈降防止剤、タレ止め剤、可塑剤、界面活性剤、消泡剤、染料、顔料、有機溶剤及び水等を、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。 1-4. Other additive components The coating composition used in the present invention includes other elution modifiers, dispersants, other spreading resins, anti-settling agents, anti-sagging agents, plasticizers, surfactants, antifoaming agents, dyes, Pigments, organic solvents, water, and the like can be arbitrarily contained in arbitrary blending ratios within a range that does not impair the object of the present invention.
＜他の溶出調整剤＞
（エチレン・α－オレフィン共重合体）
　エチレン・α－オレフィン共重合体としては、例えば、一般式（３）：
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ６は炭素数１～１０の直鎖もしくは分枝鎖状のアルキル基を示し、ｘ、ｙおよびｐはそれぞれ同一又は異なって１以上の整数を示す）で表されるエチレン・α－オレフィン共重合体が挙げられる。 <Other elution modifiers>
(Ethylene/α-olefin copolymer)
Examples of the ethylene/α-olefin copolymer include general formula (3):
Figure JPOXMLDOC01-appb-C000005
 (Wherein, R 6 represents a linear or branched alkyl group having 1 to 10 carbon atoms, and x, y and p are each the same or different and represent an integer of 1 or more). Examples include α-olefin copolymers.
　Ｒ６で表される炭素数１～１０の直鎖もしくは分枝鎖状のアルキル基としては、特に、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基等の炭素原子数１～４のアルキル基が好ましく、メチル基がより好ましい。 The linear or branched alkyl group having 1 to 10 carbon atoms represented by R 6 particularly includes 1 carbon atom groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group and isobutyl group. An alkyl group of ∼4 is preferred, and a methyl group is more preferred.
　一般式（３）で表されるエチレン・α－オレフィン共重合体は、エチレンとα－オレフィンとを共重合させることにより得られる共重合体である。前記エチレン・α－オレフィン共重合体は、ランダム共重合体、ブロック共重合体又はグラフト共重合体のいずれであってもよい。
　前記エチレン・α－オレフィン共重合体としては市販品を用いることができる。市販品としては、例えば、ルーカントＨＣ－１０、ルーカントＨＣ－２０、ルーカントＨＣ－４０、ルーカントＨＣ－１００、ルーカントＨＣ－１５０、ルーカントＨＣ－６００、ルーカントＨＣ－２０００（いずれも登録商標、三井化学株式会社製）等が挙げられる。これらのエチレン・α－オレフィン共重合体は、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。
　前記エチレン・α－オレフィン共重合体の数平均分子量（Ｍｎ）は、塗工性能および塗膜物性の観点から、１０，０００以下が好ましく、１，０００～３，０００がより好ましい。前記エチレン・α－オレフィン共重合体は、０℃における粘度が２０，０００Ｐａ・ｓ以下のものが好ましく、５００Ｐａ・ｓ以下のものがより好ましい。
　エチレン・α－オレフィン共重合体の含有量は、特に限定されないが、シリコーンオイル１００質量部に対して、固形分換算で、１～１０００質量部であり、好ましくは１～５００質量部であり、さらに好ましくは５０～３００質量部である。 The ethylene/α-olefin copolymer represented by the general formula (3) is a copolymer obtained by copolymerizing ethylene and an α-olefin. The ethylene/α-olefin copolymer may be a random copolymer, a block copolymer or a graft copolymer.
A commercially available product can be used as the ethylene/α-olefin copolymer. Commercially available products include, for example, Lucant HC-10, Lucant HC-20, Lucant HC-40, Lucant HC-100, Lucant HC-150, Lucant HC-600, Lucant HC-2000 (all registered trademarks, Mitsui Chemicals, Inc. manufactured by the company). These ethylene/α-olefin copolymers may be used alone or in combination of two or more.
The number average molecular weight (Mn) of the ethylene/α-olefin copolymer is preferably 10,000 or less, more preferably 1,000 to 3,000, from the viewpoint of coating performance and coating film properties. The ethylene/α-olefin copolymer preferably has a viscosity at 0° C. of 20,000 Pa·s or less, more preferably 500 Pa·s or less.
The content of the ethylene/α-olefin copolymer is not particularly limited, but is 1 to 1,000 parts by mass, preferably 1 to 500 parts by mass, in terms of solid content, with respect to 100 parts by mass of the silicone oil. More preferably, it is 50 to 300 parts by mass.
（ポリブテン類）
　ポリブテン類としては、ポリブテン、ポリイソブテン等が挙げられる。ポリブテン類としては、市販品を用いることができる。市販品としては、例えば、日石ポリブテングレードＬＶ－７、日石ポリブテングレードＬＶ－５０、日石ポリブテングレードＬＶ－１００、日石ポリブテングレードＨＶ－３５、日石ポリブテングレードＨＶ－５０、日石ポリブテングレードＨＶ－１００、日石ポリブテングレードＨＶ－３００、日石ポリブテングレードＨＶ－１９００、日石ポリブテングレードＳＶ－７０００（いずれもＥＮＥＯＳ株式会社製）；ポリブテン０Ｎ、ポリブテン５Ｎ、ポリブテン０ＳＨ（いずれも日油株式会社製）等が挙げられる。
　ポリブテンの含有量は、特に限定されないが、固形分換算で、シリコーンオイル１００質量部に対して１～１０００質量部であり、好ましくは１～５００質量部であり、さらに好ましくは５０～３００質量部である。 (Polybutenes)
Polybutenes include polybutene, polyisobutene, and the like. A commercial item can be used as polybutenes. Examples of commercial products include Nisseki polybutene grade LV-7, Nisseki polybutene grade LV-50, Nisseki polybutene grade LV-100, Nisseki polybutene grade HV-35, Nisseki polybutene grade HV-50, and Nisseki polybutene. Grade HV-100, Nisseki polybutene grade HV-300, Nisseki polybutene grade HV-1900, Nisseki polybutene grade SV-7000 (both manufactured by ENEOS Corporation); Polybutene 0N, polybutene 5N, polybutene 0SH (both NOF Co., Ltd.) and the like.
Although the content of polybutene is not particularly limited, it is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass in terms of solid content per 100 parts by mass of silicone oil. is.
（パラフィン類）
　パラフィン類としては、例えば、ｎ－パラフィン、流動パラフィン、塩素化パラフィン等が挙げられる。
　パラフィン類の含有量は、特に限定されないが、固形分換算でシリコーンオイル１００質量部に対して１～１０００質量部であり、好ましくは１～５００質量部であり、さらに好ましくは５０～３００質量部である。 (Paraffins)
Examples of paraffins include n-paraffin, liquid paraffin, chlorinated paraffin and the like.
The content of paraffins is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. is.
（ワックス類）
　ワックス類として、例えば、
　マイクロクリスタリンワックス、パラフィンワックス等の石油系ワックス、
　ポリエチレンワックス、ポリプロピレンワックス等の合成ワックス、植物系ワックス、動物系ワックス等が挙げられる。
　ワックス類の含有量は、特に限定されないが、固形分換算でシリコーンオイル１００質量部に対して１～１０００質量部であり、好ましくは１～５００質量部であり、さらに好ましくは５０～３００質量部である。 (Waxes)
As waxes, for example,
petroleum-based waxes such as microcrystalline wax and paraffin wax,
Synthetic waxes such as polyethylene wax and polypropylene wax, plant waxes, animal waxes, and the like can be used.
The content of the wax is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. is.
（ワセリン類）
　ワセリン類としては、例えば、白色ワセリン、黄色ワセリン等が挙げられる。
　ワセリン類の含有量は、特に限定されないが、固形分換算でシリコーンオイル１００質量部に対して１～１０００質量部であり、好ましくは１～５００質量部であり、さらに好ましくは５０～３００質量部である。 (Vaseline)
Examples of petrolatums include white petrolatum and yellow petrolatum.
The content of petroleum jelly is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. is.
（ジアルキルスルフィド化合物）
　ジアルキルスルフィド化合物としては、ジ－ｔｅｒｔ－ブチルデカスルフィド、ジペンチルテトラスルフィド、ジペンチルペンタスルフィド、ジペンチルデカスルフィド、ジオクチルテトラスルフィド、ジオクチルペンタスルフィド、ジノニルテトラスルフィド、ジノニルペンタスルフィド、ジ－ｔｅｒｔ－ノニルテトラスルフィド、ジ－ｔｅｒｔ－ノニルペンタスルフィド、ジデシルテトラスルフィド、ジドデシルテトラスルフィド、ジオクタデシルテトラスルフィド、ジノナデシルテトラスルフィド等が挙げられる。 (Dialkyl sulfide compound)
Dialkylsulfide compounds include di-tert-butyldesulfide, dipentyltetrasulfide, dipentylpentasulfide, dipentyldecasulfide, dioctyltetrasulfide, dioctylpentasulfide, dinonyltetrasulfide, dinonylpentasulfide, and di-tert-nonyltetrasulfide. sulfide, di-tert-nonylpentasulfide, didecyltetrasulfide, didodecyltetrasulfide, dioctadecyltetrasulfide, dinonadecyltetrasulfide and the like.
　ジアルキルスルフィド化合物の含有量は、特に限定されないが、固形分換算でシリコーンオイル１００質量部に対して１～１０００質量部であり、好ましくは１～５００質量部であり、さらに好ましくは５０～３００質量部である。 The content of the dialkyl sulfide compound is not particularly limited, but is 1 to 1000 parts by mass, preferably 1 to 500 parts by mass, more preferably 50 to 300 parts by mass based on 100 parts by mass of silicone oil in terms of solid content. Department.
＜分散剤＞
　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。 <Dispersant>
Examples of dispersants include polyamide phosphoric acid-based dispersants, polyamide-based dispersants, unsaturated polycarboxylic acid-based dispersants, and polyethylene oxide-based dispersants. Examples thereof include Disparlon 6900-20X, Disparlon 4200 and Disparlon 1860 manufactured by Kusumoto Kasei Co., Ltd. These dispersants can be used alone or in combination of two or more.
　分散剤の含有量は、特に限定されないが、固形分換算で、防汚薬剤１００質量部に対して０．０１～５０質量部であり、好ましくは０．１～４０質量部であり、さらに好ましくは０．５～３０質量部である。 The content of the dispersant is not particularly limited, but is 0.01 to 50 parts by mass, preferably 0.1 to 40 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the antifouling agent in terms of solid content. is 0.5 to 30 parts by mass.
＜他の展着樹脂＞
　共重合体Ａ以外の他の展着樹脂を本発明の効果を妨げない任意の配合割合で含有させることができる。
　前記展着樹脂としては、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>
A spreading resin other than the copolymer A can be contained in an arbitrary blending ratio that does not interfere with the effects of the present invention.
Examples of the spreading resin include vinyl resins, alkyd resins, urethane resins, polyester resins, synthetic rubbers, synthetic resins such as chlorinated polyethylene, and natural resins such as wood rosin, gum rosin, and modified rosin.
＜可塑剤＞
　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利用可能である。 <Plasticizer>
Examples of plasticizers that can be used include phthalates, adipates, and tricresyl phosphate.
１－５．水又は有機溶剤
　本発明の組成物は、通常、水又は有機溶剤に溶解又は分散させておくことが好ましい。これにより、塗料として好適に用いることができる。 1-5. Water or Organic Solvent It is usually preferable to dissolve or disperse the composition of the present invention in water or an organic solvent. Thereby, it can be suitably used as a paint.
　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 organic solvents include aromatic solvents such as xylene, toluene, Solvesso 100 and Solvesso 150 (both registered trademarks, manufactured by ExxonMobil); ketone solvents such as isobutyl methyl ketone (MIBK) and diisobutyl ketone (DIBK). ; Ester 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 with low toxicity, low odor, and low environmental load can also be used. ) and other aromatic/alicyclic/aliphatic hydrocarbon mixed solvents; propylene glycol monomethyl ether acetate, glycol ester solvents such as propylene glycol monoethyl ether acetate; ethylcyclohexane, dimethylcyclohexane, Likasolve (registered trademark) 900 (C9 aromatic hydrogenated), alicyclic hydrocarbon solvents such as Likasolve (registered trademark) 1000 (C10 aromatic hydrogenated); Shellsol D40 (registered trademark, manufactured by Shell Chemicals), Exsol D30, Exsol D40 Alicyclic and aliphatic hydrocarbon mixed solvents such as (registered trademark, manufactured by ExxonMobil); and aliphatic hydrocarbon mixed solvents such as Isopar G and Isopar H (both registered trademarks, manufactured by ExxonMobil) can.
These organic solvents can be used alone or in combination of two or more.
１－６．漁網防汚塗料組成物の用途及び製造方法
　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。 1-6. Use and Production Method of Fishing Net Antifouling Coating Composition The composition of the present invention can be used to form antifouling coating films 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～Ｃ成分、ならびに必要に応じて上記各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 antifouling coating composition for fishing nets of the present invention can be prepared by mixing the above components A to C and, if necessary, the above components. The amount of each component to be added at the time of mixing may be appropriately adjusted so as to achieve the above blending amount and content. There are no particular restrictions on the order in which the components are mixed. As for the 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、表面から徐々に防汚薬剤が放出されることにより、水棲汚損生物の付着防止を図ることができる。 2. Method for Forming Fishing Net Antifouling Coating Film, Antifouling Coating Film, and Coated Object The method for forming a fishing net antifouling coating film of the present invention comprises applying the above fishing net antifouling coating composition to the surface of a coating film forming object. It is characterized by forming a coating film. The antifouling coating film obtained by the forming method of the present invention can prevent attachment of aquatic fouling organisms by gradually releasing the antifouling agent from the surface.
　被塗膜形成物としては、海水中に載置される水中載置物が挙げられる。水中載置物は、船舶のように高速で移動するものではなく、海水中でほとんど又は全く移動しない載置物である。水中載置物としては、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、ロープ等の漁網用具等が挙げられる。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 coated film-forming objects include underwater objects placed in seawater. An underwater object is not an object that moves at high speed like a ship, but an object that moves little or not at all in seawater. Examples of objects placed in water include fishing tools and underwater structures. Examples of fishing tools include fishing nets for aquaculture or stationary use, and fishing net tools such as floats and ropes used for the fishing nets. Underwater structures include, for example, 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 fishing net antifouling coating composition to the surface (entirely or partially) of a coating film forming object.
　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。
　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。 Application methods include, for example, a brush coating method, a spray method, a dipping method, a flow coating method, a spin coating method, and the like. These may be used singly 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 employ a dipping method as the coating method.
After application, dry. The drying temperature may be room temperature. The drying time may be appropriately set according to the adhesion amount of the fishing net antifouling paint.
　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 adhesion amount of the fishing net antifouling paint may be appropriately set according to the type of the object to be coated and the like. For example, when the object to be coated with a film is a fishing net, the amount of the dry coating film deposited is preferably 1 to 30 parts by weight, more preferably 4 to 15 parts by weight, per 100 parts by weight 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 article of the present invention has the antifouling coating film on its surface. The coated article of the present invention may have the antifouling coating film on the entire surface or on a part of the surface.
　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。
　各製造例、実施例及び比較例中の％は質量％を示す。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。 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.
% in each Production Example, Example and Comparative Example indicates % by mass. The weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC. The conditions for GPC are as follows.
装置・・・　東ソー株式会社製　ＨＬＣ－８２２０ＧＰＣ
カラム・・・　ＴＳＫｇｅｌ　ＳｕｐｅｒＨＺＭ－Ｍ　　２本
流量・・・　０．３５　ｍＬ／ｍｉｎ
検出器・・・　ＲＩ
カラム恒温槽温度・・・　４０℃
溶離液・・・　ＴＨＦ
　加熱残分は、ＪＩＳ　Ｋ　５６０１－１－２：１９９９（ＩＳＯ　３２５１：１９９３）「塗料成分試験方法－加熱残分」に準拠して測定した値である。 Apparatus: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSKgel SuperHZM-M 2 Flow rate: 0.35 mL/min
Detector... RI
Column constant temperature bath temperature: 40°C
Eluent... THF
The heating residue is a value measured in accordance with JIS K 5601-1-2:1999 (ISO 3251:1993) "Coating component test method-heating residue".
１．製造例
１－１．単量体（ａ１）の製造例
＜製造例１（単量体a１－１の製造）＞
　温度計、冷却器、攪拌装置及び滴下ロートを備えた四ツ口フラスコに、クロロ酢酸メチル：１０９ｇ（１．００ｍｏｌ）、アクリル酸：７２ｇ（１．００ｍｏｌ）、４－メトキシフェノール：０．１ｇ、酢酸エチル：５００ｇを仕込み、攪拌しながらトリエチルアミン：１０１ｇ（１．００ｍｏｌ）を４０℃以下に保ちながら滴下した。滴下終了後、７０～８０℃で６時間攪拌した。反応終了後、市水、塩酸水、重曹水の順に有機層を洗浄後、減圧濃縮により溶媒を留去することで単量体ａ１－１：１２９．７ｇを得た。 1. Production Example 1-1. Production Example of Monomer (a1) <Production Example 1 (Production of Monomer a1-1)>
In a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, methyl chloroacetate: 109 g (1.00 mol), acrylic acid: 72 g (1.00 mol), 4-methoxyphenol: 0.1 g, Ethyl acetate: 500 g was charged, and triethylamine: 101 g (1.00 mol) was added dropwise while stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid aqueous solution and sodium bicarbonate aqueous solution in that order, and the solvent was distilled off by vacuum concentration to obtain 129.7 g of monomer a1-1.
＜製造例２～３（単量体ａ１－２～ａ１－３の製造）＞
　表１に示す原料を用いて、製造例１と同様の操作で反応を行うことにより単量体ａ１－２～ａ１－３を得た。製造例１～３の反応条件、収量を表１に示す。 <Production Examples 2-3 (production of monomers a1-2 to a1-3)>
Monomers a1-2 to a1-3 were obtained by carrying out reactions in the same manner as in Production Example 1 using the raw materials shown in Table 1. Table 1 shows the reaction conditions and yields of Production Examples 1 to 3.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
１－２．単量体（ａ２）の製造例
＜製造例４（単量体a２－１の製造）＞
（第１反応）
　温度計、冷却器、攪拌装置を備えた四ツ口フラスコに、モノクロロ酢酸ナトリウム：２１５ｇ（１．８５ｍｏｌ）、クロロ酢酸メチル：２０１ｇ（１．８５ｍｏｌ）、Ｎ－メチル－２－ピロリドン：３００ｇを仕込み、７０～８０℃で６時間攪拌した。反応終了後、反応液にトルエン：５００ｍｌを仕込み、市水、塩酸水、重曹水の順に有機層を洗浄後、減圧濃縮により溶媒を留去することでクロロ酢酸メトキシカルボニルメチル：２６２ｇを得た。 1-2. Production Example of Monomer (a2) <Production Example 4 (Production of Monomer a2-1)>
(First reaction)
A four-necked flask equipped with a thermometer, a condenser, and a stirrer was charged with 215 g (1.85 mol) of sodium monochloroacetate, 201 g (1.85 mol) of methyl chloroacetate, and 300 g of N-methyl-2-pyrrolidone. , and stirred at 70-80° C. for 6 hours. After completion of the reaction, 500 ml of toluene was added to the reaction solution, and the organic layer was washed in this order with city water, hydrochloric acid, and sodium bicarbonate.
（第２反応）
　次いで、温度計、冷却器、攪拌装置及び滴下ロートを備えた四ツ口フラスコに、第１反応の生成物であるクロロ酢酸メトキシカルボニルメチル：２００ｇ（１．２０ｍｏｌ）、アクリル酸：８７ｇ（１．２０ｍｏｌ）、４－メトキシフェノール：０．１ｇ、酢酸エチル：５００ｇを仕込み、攪拌しながらトリエチルアミン：１２２ｇ（１．２０ｍｏｌ）を４０℃以下に保ちながら滴下した。滴下終了後、７０～８０℃で６時間攪拌した。反応終了後、市水、塩酸水、重曹水の順に有機層を洗浄後、減圧濃縮により溶媒を留去することで単量体ａ２－１：２３０．６ｇを得た。 (Second reaction)
Next, 200 g (1.20 mol) of methoxycarbonylmethyl chloroacetate, which is the product of the first reaction, and 87 g (1.20 mol) of acrylic acid were added to a four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel. 20 mol), 4-methoxyphenol: 0.1 g, and ethyl acetate: 500 g were charged, and triethylamine: 122 g (1.20 mol) was added dropwise while stirring while maintaining the temperature at 40°C or lower. After the dropwise addition was completed, the mixture was stirred at 70 to 80°C for 6 hours. After completion of the reaction, the organic layer was washed with city water, hydrochloric acid water, and sodium bicarbonate water in that order, and the solvent was distilled off by vacuum concentration to obtain 230.6 g of monomer a2-1.
＜製造例５～１８（単量体ａ２－２～ａ２－１５の製造）＞
　表２に示す原料を用いて、製造例４と同様の操作で反応を行うことにより、表２に示す単量体ａ２－２～ａ２－１５を得た。製造例４～１８の反応条件、収量を表２に示す。 <Production Examples 5 to 18 (production of monomers a2-2 to a2-15)>
Monomers a2-2 to a2-15 shown in Table 2 were obtained by performing reactions in the same manner as in Production Example 4 using the raw materials shown in Table 2. Table 2 shows the reaction conditions and yields of Production Examples 4 to 18.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　表１～表２中の原料の詳細は、以下の通りである。
ＣＡＭｅ：クロロ酢酸メチル
ＣＡＥｔ：クロロ酢酸エチル
ＡＡ：アクリル酸
ＭＡＡ：メタクリル酸
ＴＥＡ：トリエチルアミン
ＭＥＨＱ：４－メトキシフェノール
ＣＡＮａ：モノクロロ酢酸ナトリウム
ＮＭＰ：Ｎ－メチル－２－ピロリドン The details of the raw materials in Tables 1 and 2 are as follows.
CAMe: methyl chloroacetate CAEt: ethyl chloroacetate AA: acrylic acid MAA: methacrylic acid TEA: triethylamine MEHQ: 4-methoxyphenol CANa: sodium monochloroacetate NMP: N-methyl-2-pyrrolidone
１－３．共重合体溶液の製造例
＜製造例Ｐ１（共重合体溶液Ａ－１の製造）＞
　温度計、冷却器、攪拌装置及び滴下ロートを備えた四ツ口フラスコに、溶剤として、キシレン：１５０ｇを仕込み、窒素ガスを導入し、攪拌しながら９５℃を保持した。そこへ、表３に示す配合量（ｇ）の単量体（ａ１）、単量体（ａ２）、単量体（ｂ１）及び単量体（ｂ２）と、重合開始剤として、ｔ－ブチルパーオキシ－２－エチルヘキサノエート：０．０５ｇ（初期添加）の混合液を９５℃で保持しながら３時間かけて滴下した。その後、９５℃で１時間攪拌を行った後、１，１，３，３－テトラメチルブチルパーオキシ－２－エチルヘキサノエート：０．２ｇを１時間毎に５回添加し、さらに同温度で２時間攪拌を行った後、室温に冷却し、共重合体溶液Ａ－１を得た。Ａ－１の加熱残分、Ｍｗを表３に示す。 1-3. Production Example of Copolymer Solution <Production Example P1 (Production of Copolymer Solution A-1)>
A four-necked flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel was charged with 150 g of xylene as a solvent, nitrogen gas was introduced, and the temperature was maintained at 95° C. while stirring. There, a monomer (a1), a monomer (a2), a monomer (b1) and a monomer (b2) in the amount (g) shown in Table 3, and a polymerization initiator, t-butyl A mixture of 0.05 g (initial addition) of peroxy-2-ethylhexanoate was added dropwise over 3 hours while maintaining the temperature at 95°C. Then, after stirring at 95 ° C. for 1 hour, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate: 0.2 g was added 5 times every hour, and the temperature was the same. After stirring for 2 hours at , the mixture was cooled to room temperature to obtain a copolymer solution A-1. Table 3 shows the heating residue and Mw of A-1.
＜製造例Ｐ２～Ｐ１７（共重合体溶液Ａ－２～Ａ－１５、共重合体溶液Ｒ－１～Ｒ－２の製造）＞
　表３に示す単量体、及び溶剤を用いた以外は、製造例Ｐ１と同様の操作で重合反応を行うことにより共重合体溶液Ａ－２～Ａ－１５、共重合体溶液Ｒ－１～Ｒ－２を得た。各重合体の加熱残分、Ｍｗを表３に示す。表中の原料の配合量の数値の単位は、ｇである。 <Production Examples P2 to P17 (production of copolymer solutions A-2 to A-15 and copolymer solutions R-1 to R-2)>
Copolymer solutions A-2 to A-15 and copolymer solutions R-1 to R-2 was obtained. Table 3 shows the heating residue and Mw of each polymer. The unit of numerical values for the amounts of raw materials in the table is g.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表３中の各成分の詳細は、以下の通りである。
アクリル酸ステアリル：東京化成（株）製
メタクリル酸ステアリル：東京化成（株）製
メタクリル酸ラウリル：東京化成（株）製
メタクリル酸トリデシル：東京化成（株）製
メタクリル酸メチル：東京化成（株）製
アクリル酸ｎ－ブチル：東京化成（株）製
メタクリル酸イソブチル：東京化成（株）製
メタクリル酸シクロヘキシル：東京化成（株）製
メタクリル酸２－メトキシエチル：商品名「アクリエステルＭＴ」（三菱ケミカル（株）製）
メタクリル酸２－ヒドロキシエチル：東京化成（株）製
キシレン：商品名「キシレン」（三井化学（株）製）
１－ブタノール：東京化成（株）製
酢酸ブチル：東京化成（株）製 Details of each component in Table 3 are as follows.
Stearyl acrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Stearyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Lauryl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Tridecyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. Methyl methacrylate: manufactured by Tokyo Chemical Industry Co., Ltd. n-butyl acrylate: Tokyo Kasei Co., Ltd. isobutyl methacrylate: Tokyo Kasei Co., Ltd. cyclohexyl methacrylate: Tokyo Kasei Co., Ltd. 2-methoxyethyl methacrylate: trade name “Acryester MT” (Mitsubishi Chemical ( Co., Ltd.)
2-hydroxyethyl methacrylate: manufactured by Tokyo Kasei Co., Ltd. xylene: trade name “xylene” (manufactured by Mitsui Chemicals, Inc.)
1-butanol: manufactured by Tokyo Kasei Co., Ltd. Butyl acetate: manufactured by Tokyo Kasei Co., Ltd.
２．漁網防汚塗料組成物の製造
＜実施例Ｈ－１～Ｈ－１７、Ｉ－１～Ｉ－１４、Ｊ－１～Ｊ－１４、比較例ＣＨ－１～ＣＨ－３、ＣＩ－１～ＣＩ－３、ＣＪ－１～ＣＪ－３＞
　表４～表６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漁網防汚塗料組成物を製造した。実施例Ｈ－１～Ｈ－１７及び比較例ＣＨ－１～ＣＨ－３では、防汚薬剤として亜酸化銅及び銅ピリチオンを使用した。実施例Ｉ－１～Ｉ－１４及び比較例ＣＩ－１～ＣＩ－３では、防汚薬剤としてＴＯＣ－３２０４Ｆを使用した。実施例Ｊ－１～Ｊ－１４及び比較例ＣＪ－１～ＣＪ－３では、防汚薬剤として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等を使用した。 2. Production of fishing net antifouling paint composition <Examples H-1 to H-17, I-1 to I-14, J-1 to J-14, Comparative Examples CH-1 to CH-3, CI-1 to CI -3, CJ-1 to CJ-3>
The components shown in Tables 4 to 6 were blended in proportions (parts by mass) shown in the same tables, and mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce an antifouling coating composition for fishing nets. In Examples H-1 to H-17 and Comparative Examples CH-1 to CH-3, cuprous oxide and copper pyrithione were used as antifouling agents. In Examples I-1 to I-14 and Comparative Examples CI-1 to CI-3, TOC-3204F was used as the antifouling agent. In Examples J-1 to J-14 and Comparative Examples CJ-1 to CJ-3, 3-(2-ethylhexyloxy)propylamine/triphenylborane or the like was used as the antifouling agent.
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４～表６中の各成分の詳細は、以下の通りである。
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）、ＨＬＢ値＝４、２５℃での動粘度が１８０ｍｍ２／ｓ、比重が１．００
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）、ＨＬＢ値＝１、２５℃での動粘度が７０ｍｍ２／ｓ、比重が０．９６
　商品名「ＫＦ－９６－１００ｃｓ」：ポリジメチルシロキサン（信越化学工業（株）製）、ＨＬＢ値＝０、２５℃での動粘度が１００ｍｍ２／ｓ、比重が０．９６５
　商品名「ポリブテン０Ｎ」：可塑剤（日油（株）製）
　商品名「ルーカントＨＣ－４０」：エチレン・α－オレフィン共重合体（三井化学（株）製）
　黄色ワセリン：商品名「ワセリン（黄色）」ナカライテスク（株）製
　商品名「ＤＡＦ－１」：ジ－ｔｅｒｔ－ノニルペンタスルフィド（ＤＩＣ（株）製）
　亜酸化銅：商品名「ＮＣ－３０１」（日新ケムコ（株）製）
　銅ピリチオン：商品名「Ｃｏｐｐｅｒ　Ｏｍａｄｉｎｅ　Ｐｏｗｄｅｒ」：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）　
　ＴＯＣ－３２０４Ｆ：ビス(ジメチルジチオカルバモイル)エチレンビスジチオカルバミン酸亜鉛（ニュートリション＆バイオサイエンス（株）製）
　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：商品名「ＯＰＡ」（日東化成（株）製）
　ｎ－オクタデシルアミン・トリフェニルボラン：商品名「ＯＤＡ」（ベニートヤマ（株）製）
　テトラエチルチウラムジスルフィド：商品名「ノクセラーＴＥＴ－Ｇ」（大内新興化学工業（株）製）
　
　商品名「ディスパロン６９００－２０Ｘ」：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）
　商品名「ディスパロン１８６０」：長鎖ポリアミノアマイドと高分子ポリエステル酸との塩（楠本化成（株）製）
　商品名「ディスパロンＦＡ－６２」：アクリル系重合物とシリコーンとの混合物（楠本化成（株）製）） Details of each component in Tables 4 to 6 are as follows.
Product name “KF-6020”: polyether-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.), HLB value = 4, kinematic viscosity at 25 ° C. is 180 mm 2 /s, specific gravity is 1.00
Product name “X-22-2516”: Polyether long-chain alkylaralkyl-modified dimethyl silicone oil (manufactured by Shin-Etsu Chemical Co., Ltd.), HLB value = 1, kinematic viscosity at 25°C is 70 mm 2 /s, and specific gravity is 0. .96
Product name “KF-96-100cs”: polydimethylsiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), HLB value = 0, kinematic viscosity at 25 ° C. is 100 mm / s, specific gravity is 0.965
Product name “Polybutene 0N”: plasticizer (manufactured by NOF Corporation)
Product name “Lucant HC-40”: Ethylene/α-olefin copolymer (manufactured by Mitsui Chemicals, Inc.)
Yellow petrolatum: trade name “Vaseline (yellow)” manufactured by Nacalai Tesque Co., Ltd. trade name “DAF-1”: di-tert-nonyl pentasulfide (manufactured by DIC Corporation)
Cuprous oxide: trade name “NC-301” (manufactured by Nisshin Chemco Co., Ltd.)
Copper pyrithione: trade name “Copper Omadine Powder”: bis(2-sulfidepyridine-1-orato) copper (manufactured by Lonza Japan Co., Ltd.)
TOC-3204F: Zinc bis(dimethyldithiocarbamoyl)ethylenebisdithiocarbamate (manufactured by Nutrition & Bioscience Co., Ltd.)
3-(2-ethylhexyloxy)propylamine/triphenylborane: trade name “OPA” (manufactured by Nitto Kasei Co., Ltd.)
n-octadecylamine/triphenylborane: trade name “ODA” (manufactured by Benitoyama Co., Ltd.)
Tetraethylthiuram disulfide: trade name “Noccellar TET-G” (manufactured by Ouchi Shinko Chemical Industry Co., Ltd.)

Product name “Disparlon 6900-20X”: Polyamide wax (manufactured by Kusumoto Kasei Co., Ltd.)
Product name “Disparon 4200-20”: Polyethylene oxide wax (manufactured by Kusumoto Kasei Co., Ltd.)
Trade name “Disparlon 1860”: a salt of long-chain polyaminoamide and polymeric polyester acid (manufactured by Kusumoto Kasei Co., Ltd.)
Product name “Disparon FA-62”: a mixture of acrylic polymer and silicone (manufactured by Kusumoto Kasei Co., Ltd.))
３．漁網防汚塗料組成物の評価
　得られた防汚塗料組成物について、次の試験を行った。 3. Evaluation of Fishing Net Antifouling Paint Composition The obtained antifouling paint composition was subjected to the following tests.
＜試験例１（動物性汚損生物への防汚効果確認試験）→
　表４～表６記載の実施例Ｈ－１～Ｈ－１７、Ｉ－１～Ｉ－１４、Ｊ－１～Ｊ－１４、比較例ＣＨ－１～ＣＨ－３、ＣＩ－１～ＣＩ－３、ＣＪ－１～ＣＪ－３の各防汚塗料組成物を、ポリエチレン製の漁網（４００デニール、５０本、８節、縦１５ｃｍ・横８ｃｍ）に、浸漬塗布し２日間室温で乾燥した。得られた防汚塗料組成物が塗布された漁網を４０×７５ｃｍのＳＵＳの枠に固定し、海中から水深約２ｍに垂下浸漬し、その防汚性能を表７～表９記載の期間にわたって定期的に観測した。なお、実施例Ｈ－１～Ｈ－１７及びＪ－１～Ｊ－１４、比較例ＣＨ－１～ＣＨ－３、ＣＪ－１～ＣＪ－３の防汚塗料組成物を塗布した漁網に関しては、和歌山県串本沖の筏にて防汚効果確認試験を行い、実施例Ｉ－１～Ｉ－１４及び比較例ＣＩ－１～ＣＩ－３の防汚塗料組成物を塗布した漁網に関しては、北海道根室沖の定置網にて防汚効果確認試験を行った。結果を表７～表９に示す。表中の数字は、水棲汚損生物の付着面積（％）を表す。 <Test Example 1 (Anti-fouling effect confirmation test for animal fouling organisms) →
Examples H-1 to H-17, I-1 to I-14, J-1 to J-14, Comparative Examples CH-1 to CH-3, CI-1 to CI-3 described in Tables 4 to 6 , CJ-1 to CJ-3 were dip-coated on polyethylene fishing nets (400 denier, 50 nets, 8 nodes, 15 cm long and 8 cm wide) and dried at room temperature for 2 days. A fishing net coated with the obtained antifouling coating composition was fixed to a SUS frame of 40×75 cm and immersed in water to a depth of about 2 m from the sea. observable. Regarding the fishing nets coated with the antifouling coating compositions of Examples H-1 to H-17 and J-1 to J-14, Comparative Examples CH-1 to CH-3, and CJ-1 to CJ-3, An antifouling effect confirmation test was performed on a raft off the coast of Kushimoto, Wakayama Prefecture, and the fishing nets coated with the antifouling coating compositions of Examples I-1 to I-14 and Comparative Examples CI-1 to CI-3 were tested off the coast of Nemuro, Hokkaido. An antifouling effect confirmation test was conducted using a fixed net. The results are shown in Tables 7-9. The numbers in the table represent the adhesion area (%) of aquatic fouling organisms.
　表７～表９に示すように、全ての実施例では、全ての比較例より水棲汚損生物が付着しにくかった。また、実施例の中でも、単量体（ａ）の割合が８０質量％である共重合体Ａ－１０を用いた実施例（実施例Ｈ－１０及びＪ－１０）、及び単量体（ｂ１）を含有していない共重合体Ａ－１１～Ａ－１２を用いた実施例（実施例Ｈ－１１～Ｈ－１２、Ｉ－１１～Ｉ－１２、Ｊ－１１～Ｊ－１２）は、その他の実施例に比べて防汚性能が若干劣っていた。 As shown in Tables 7 to 9, in all Examples, aquatic fouling organisms were less likely to adhere than in all Comparative Examples. Also, among the examples, examples using the copolymer A-10 in which the proportion of the monomer (a) is 80% by mass (Examples H-10 and J-10), and the monomer (b1 ) using copolymers A-11 to A-12 (Examples H-11 to H-12, I-11 to I-12, J-11 to J-12) The antifouling performance was slightly inferior to that of other examples.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014

Claims (4)

  1. 　共重合体（Ａ）、シリコーンオイル（Ｂ）、および防汚薬剤（Ｃ）を含有する防汚塗料組成物であって、
    　前記共重合体（Ａ）は、一般式（１）で表される単量体（ａ）と、前記単量体（ａ）以外のエチレン性不飽和単量体（ｂ）の共重合体であり、
    　前記単量体（ａ）は、前記一般式（１）中のｎが２以上である化合物を含み、
    　前記シリコーンオイル（Ｂ）は、親水親油バランス（ＨＬＢ値）が０．５～９の変性シリコーンオイルである、漁網防汚塗料組成物。
    一般式（１）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１は水素又はメチル基を示し、Ｒ２は、水素、メチル基、フェニル基を示し、Ｒ３は、炭素数１～８のアルコキシ基又はフェニル基で置換されていてもよい炭素数１～８のアルキル基であるか、又はフェニル基を示し、ｎは、１～１０の整数を示す。）     An antifouling paint composition containing a copolymer (A), a silicone oil (B), and an antifouling agent (C),
    The copolymer (A) is a copolymer of a monomer (a) represented by the general formula (1) and an ethylenically unsaturated monomer (b) other than the monomer (a). can be,
    The monomer (a) includes a compound in which n in the general formula (1) is 2 or more,
    The silicone oil (B) is a modified silicone oil having a hydrophilic-lipophilic balance (HLB value) of 0.5-9.
    General formula (1):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 represents hydrogen or a methyl group, R 2 represents hydrogen, a methyl group, or a phenyl group, and R 3 may be substituted with an alkoxy group having 1 to 8 carbon atoms or a phenyl group. It is an alkyl group having 1 to 8 carbon atoms or represents a phenyl group, and n represents an integer of 1 to 10.)
  2. 　前記単量体（ｂ）は、単量体（ｂ１）を含み、
    　前記単量体（ｂ１）は、一般式（２）で表される単量体である、請求項１記載の漁網防汚塗料組成物。
    　一般式（２）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ４は水素又はメチル基、Ｒ５は炭素数１０～２２のアルキル基を示す）     The monomer (b) comprises a monomer (b1),
    The fishing net antifouling coating composition according to claim 1, wherein the monomer (b1) is a monomer represented by the general formula (2).
    General formula (2):
    Figure JPOXMLDOC01-appb-C000002
     (Wherein, R 4 represents hydrogen or a methyl group, and R 5 represents an alkyl group having 10 to 22 carbon atoms)
  3. 　更に、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、ワックス類、ワセリン類、ジアルキルスルフィド化合物から選ばれる１種又は２種以上を含む、請求項１記載の漁網防汚塗料組成物。 The antifouling coating composition for fishing nets according to claim 1, further comprising one or more selected from ethylene/α-olefin copolymers, polybutenes, paraffins, waxes, petroleum jelly, and dialkyl sulfide compounds.
  4. 請求項１～請求項３の何れか１つ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 on its surface an antifouling coating film formed using the fishing net antifouling coating composition according to any one of claims 1 to 3.
PCT/JP2022/046178 2021-12-21 2022-12-15 Fishing net antifouling coating composition and fishing net, fishing net gear, or underwater structure having on surface thereof antifouling coating film formed using said composition WO2023120360A1 (en)

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Citations (7)

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Publication number Priority date Publication date Assignee Title
JPH09176577A (en) * 1995-12-26 1997-07-08 Chugoku Marine Paints Ltd Underwater antifouling composition and antifouling treatment of hull, fishing net and underwater structure using the same
JP2002265849A (en) * 2001-03-14 2002-09-18 Nippon Paint Marine Kk Coating composition
JP2003119420A (en) * 2001-10-12 2003-04-23 Chugoku Marine Paints Ltd Antifouling coating material composition and coated article
JP2003119419A (en) * 2001-10-12 2003-04-23 Dainippon Ink & Chem Inc Antifouling coating material composition and coated article
JP2009203341A (en) * 2008-02-27 2009-09-10 Nitto Kasei Co Ltd Antifouling paint composition
WO2020045211A1 (en) * 2018-08-29 2020-03-05 日東化成株式会社 Anti-fouling coating material composition
JP2022129226A (en) * 2021-02-24 2022-09-05 日東化成株式会社 Anti-fouling coating composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4902037B2 (en) 1999-07-08 2012-03-21 中国塗料株式会社 Antifouling agent composition, antifouling treatment substrate, and antifouling treatment method for substrate

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Publication number Priority date Publication date Assignee Title
JPH09176577A (en) * 1995-12-26 1997-07-08 Chugoku Marine Paints Ltd Underwater antifouling composition and antifouling treatment of hull, fishing net and underwater structure using the same
JP2002265849A (en) * 2001-03-14 2002-09-18 Nippon Paint Marine Kk Coating composition
JP2003119420A (en) * 2001-10-12 2003-04-23 Chugoku Marine Paints Ltd Antifouling coating material composition and coated article
JP2003119419A (en) * 2001-10-12 2003-04-23 Dainippon Ink & Chem Inc Antifouling coating material composition and coated article
JP2009203341A (en) * 2008-02-27 2009-09-10 Nitto Kasei Co Ltd Antifouling paint composition
WO2020045211A1 (en) * 2018-08-29 2020-03-05 日東化成株式会社 Anti-fouling coating material composition
JP2022129226A (en) * 2021-02-24 2022-09-05 日東化成株式会社 Anti-fouling coating composition

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