WO2023145634A1 - 防汚塗料組成物 - Google Patents

防汚塗料組成物 Download PDF

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Publication number
WO2023145634A1
WO2023145634A1 PCT/JP2023/001651 JP2023001651W WO2023145634A1 WO 2023145634 A1 WO2023145634 A1 WO 2023145634A1 JP 2023001651 W JP2023001651 W JP 2023001651W WO 2023145634 A1 WO2023145634 A1 WO 2023145634A1
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Prior art keywords
monomer
meth
acrylate
group
copolymer
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PCT/JP2023/001651
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English (en)
French (fr)
Japanese (ja)
Inventor
永都 岡
同 北村
英典 和久
崇 松木
拓也 安井
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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 KR1020247027039A priority Critical patent/KR20240134194A/ko
Priority to JP2023576866A priority patent/JPWO2023145634A1/ja
Priority to CN202380018474.6A priority patent/CN118591599A/zh
Publication of WO2023145634A1 publication Critical patent/WO2023145634A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to an antifouling paint composition.
  • Aquatic fouling organisms such as barnacles, serpra, mussels, mussels, sea squirts, green laver, sea lettuce, and slimes may be found on ships (especially on the bottom of ships), fishing nets, fishing tools such as fishing net accessories, and underwater structures such as power plant water pipes.
  • problems such as the deterioration of the functions of the ships and the like and the deterioration of the appearance due to the adhesion.
  • an antifouling coating composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is slowly released from the antifouling coating film, thereby providing long-term antifouling.
  • Techniques for exhibiting performance are known (Patent Documents 1 to 4).
  • the antifouling coating film composed of a polymer containing a (meth)acrylic acid alkoxycarbonylmethyl ester group described in Patent Documents 1 to 4 has remarkably low coating film solubility, and therefore exhibits antifouling properties over a long period of time. It was difficult to demonstrate.
  • a technique has been proposed in which the coating film dissolves over a long period of time to exhibit antifouling performance (Patent Document 5).
  • the antifouling coating film made of the antifouling coating composition described in Patent Document 5 has improved coating film solubility, etc., but there is still room for improvement in terms of coating film physical properties such as cracks and peeling.
  • the present invention has been made in view of such circumstances, and provides an antifouling coating composition capable of maintaining excellent coating film surface conditions and antifouling performance over a long period of time.
  • an antifouling coating composition containing a copolymer A and an antifouling agent, wherein the copolymer A comprises a monomer (a) and A copolymer of an ethylenically unsaturated monomer (b), wherein the monomer (a) is composed of a monomer (a1) and a monomer (a2), and the monomer (a1) is represented by the general formula (1), the monomer (a2) is represented by the general formula (2), and the content of the monomer (a1) in the monomer (a) is
  • An antifouling coating composition is provided that is 50 to 80% by weight.
  • the antifouling paint composition of the present invention contains the copolymer A and an antifouling agent, and may contain the copolymer B and other additives.
  • Copolymer A is a copolymer containing monomer (a), and the content of monomer (a) is preferably 5 to 95% by mass, more preferably 10 to 85% by mass. Specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95% by mass, where It may be within a range between any two of the exemplified numerical values, in which case the coating film solubility is particularly good.
  • monomer (a) is composed of monomer (a1) and monomer (a2).
  • the content of monomer (a1) in monomer (a) is 50 to 80% by mass, preferably 55 to 75% by mass, more preferably 60 to 70% by mass.
  • the monomer (a1) has the property of increasing the coating film strength and lowering the coating film solubility as compared with the monomer (a2). Therefore, if the content of the monomer (a1) is too small, the strength of the coating film becomes too low, and the surface condition of the coating film tends to deteriorate after a long period of time.
  • the content of the monomer (a1) is, for example, 50, 55, 60, 65, 70, 75, 80% by mass, and may be within a range between any two of the numerical values exemplified here. .
  • the monomer (a1) 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 represents a hydrocarbon group having 5 to 12 carbon atoms or a hetero group having 2 to 12 carbon atoms. indicates a hydrocarbon group containing atoms.
  • R 2 is preferably hydrogen or a methyl group.
  • the number of carbon atoms in the hydrocarbon group of R 3 is, for example, 5, 6, 7, 8, 9, 10, 11, or 12, and may be within a range between any two of the numerical values exemplified here.
  • Hydrocarbon groups for R 3 are, for example, pentyl, isopentyl, hexyl, isohexyl, cyclohexyl, octyl, 2-ethylhexyl, nonyl, isononyl, neononyl, decyl, isodecyl and dodecyl groups.
  • phenyl, tolyl, benzyl, naphthyl or biphenyl preferably normalhexyl, cyclohexyl, 2-ethylhexyl, phenyl, tolyl and benzyl.
  • the number of carbon atoms in the hydrocarbon group containing a heteroatom for R 3 is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12, and any of the numerical values exemplified here are 2 It may be within a range between two.
  • the heteroatom is preferably an oxygen atom, a nitrogen atom, or a sulfur atom, more preferably an oxygen atom.
  • a hydrocarbon group containing a heteroatom for R 3 is, for example, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-methoxyethoxyethyl group, a 2-phenoxyethyl group, a furfuryl group or a tetrahydrofurfuryl group, Preferred are 2-methoxyethyl group, 2-phenoxyethyl group and tetrahydrofurfuryl group.
  • Examples of the monomer (a1) include (meth) n-hexyl acrylate (oxycarbonylmethyl), (meth)cyclohexyl acrylate (oxycarbonylmethyl), (meth) 2-ethylhexyl acrylate (oxycarbonylmethyl), (meth) phenyl (oxycarbonylmethyl) acrylate, benzyl (oxycarbonylmethyl) (meth)acrylate, (meth) 2-methoxyethyl (oxycarbonylmethyl) acrylate, (meth) 2-ethoxyethyl acrylate (oxycarbonylmethyl), (meth) 2-methoxyethoxyethyl (oxycarbonylmethyl) acrylate, (meth) 2-phenoxyethyl acrylate (oxycarbonylmethyl), (meth)acrylate tetrahydrofurfuryl(oxycarbonylmethyl)acrylate, is mentioned.
  • the monomer (a2) is represented by general formula (2).
  • R 4 represents hydrogen or a methyl group
  • R 5 represents hydrogen, a methyl group, or a phenyl group
  • R 6 represents a hydrocarbon group having 5 to 12 carbon atoms or a heteroatom having 2 to 12 carbon atoms.
  • n is an integer of 2-10.
  • R5 and R6 are the same as for R2 and R3 .
  • n represents an integer of 2 to 10, preferably 2 to 6 from the viewpoint of long-term antifouling properties. n is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, and may be in the range between any two of the numerical values exemplified here.
  • the monomer (a2) preferably includes both a compound in which n is 2 and a compound in which n is 3 or more. In this case, there is a tendency for stable coating film dissolution to continue.
  • Examples of the monomer (a2) include (meth) n-hexyl di(oxycarbonylmethyl)acrylate, (meth)cyclohexyl di(oxycarbonylmethyl)acrylate, (meth) 2-ethylhexyl di(oxycarbonylmethyl) acrylate, (meth) phenyl di(oxycarbonylmethyl)acrylate, benzyl di(oxycarbonylmethyl) (meth)acrylate, (meth) 2-methoxyethyl di(oxycarbonylmethyl) acrylate, (meth) 2-ethoxyethyl di(oxycarbonylmethyl) acrylate, (meth) 2-methoxyethoxyethyl di(oxycarbonylmethyl) acrylate, (meth) 2-phenoxyethyl di(oxycarbonylmethyl) acrylate, (meth)acrylate tetrahydrofurfuryl di(oxycarbonylmethyl)acrylate,
  • (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester.
  • 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 monomer (b2), or both.
  • the monomer (b1) is represented by general formula (3).
  • R 7 is hydrogen or a methyl group
  • R 8 to R 10 are the same or different and each represent a branched alkyl group having 3 to 8 carbon atoms or a phenyl group.
  • Branched alkyl groups include, for example, isopropyl group, isopropenyl group, isobutyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-dimethyl propyl group, 1,1-dimethylbutyl group, thexyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methylheptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpent
  • R 8 to R 10 are preferably the same or different and are preferably isopropyl, isopropenyl, s-butyl, t-butyl, phenyl, and 2-ethylhexyl, particularly preferably isopropyl and 2-ethylhexyl groups.
  • Examples of the monomer (b1) include triisopropylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, triisopentylsilyl (meth)acrylate, meth (Meth)triphenylsilyl acrylate, diisopropylphenylsilyl (meth)acrylate, diisopropylisobutylsilyl (meth)acrylate, diisopropyl s-butylsilyl (meth)acrylate, diisopropylisopentylsilyl (meth)acrylate, (meth)acrylate Isopropyldiisobutylsilyl acrylate, isopropyldi-s-butylsilyl (meth)acrylate, t-butyldiisobutylsilyl (meth)acrylate, t-butyldi
  • These monomers (b1) can be used alone or in combination of two or more.
  • the monomer (b2) is obtained by removing the monomer (b1) from the monomer (b).
  • the monomer (b2) is a monomer not represented by any of general formulas (1) to (3).
  • the monomer (b2) include (meth)acrylic acid esters, vinyl compounds, aromatic compounds, and dialkyl ester compounds of dibasic acids, which are not represented by the general formulas (1) to (3).
  • (meth)acrylic acid ester means acrylic acid ester or methacrylic acid ester.
  • Examples of (meth)acrylic acid esters not represented by general formulas (1) to (3) include methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and isobutyl (meth)acrylate.
  • t-butyl (meth)acrylate 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, (meth)acrylic Acid 4-methoxybutyl, benzyl (meth) acrylate, phenyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, propylene glycol monomethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( 2-hydroxypropyl meth)acrylate, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, methacryl Acid 2-[2-(2-hydroxyethoxy)e
  • vinyl compounds include vinyl compounds having functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyrate, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone. be done.
  • aromatic compounds examples include styrene, vinyltoluene, ⁇ -methylstyrene, and the like.
  • dialkyl ester compounds of dibasic acids examples include dimethyl maleate, dibutyl maleate, and dimethyl fumarate.
  • these monomers (b) can be used singly or in combination of two or more.
  • the monomer (b) preferably contains a (meth)acrylic acid ester of the monomer (b1) or the monomer (b2).
  • the monomer (b) preferably contains a (meth)acrylic acid ester of the monomer (b2), such as methyl (meth)acrylate, butyl (meth)acrylate, (meth) ) isobutyl acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2- (meth)acrylate More preferably, it contains hydroxyethyl, glycidyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like.
  • a (meth)acrylic acid ester of the monomer (b2) such as methyl (meth)acrylate, butyl (meth)acrylate, (meth) ) isobutyl acrylate, t-butyl (meth)
  • the monomer (b) preferably contains the monomer (b1), triisopropylsilyl (meth)acrylate, t-butyldiphenylsilyl (meth)acrylate, (meth) ) more preferably tri-2-ethylhexylsilyl acrylate and the like.
  • the weight average molecular weight (Mw) of Copolymer A is preferably 5,000 to 300,000. If the molecular weight is less than 5,000, the coating film of the antifouling paint will be brittle and easily peeled off or cracked. Specifically, this Mw is, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000. may be within the range.
  • Examples of methods for measuring Mw include gel permeation chromatography (GPC method).
  • 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, and the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • 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, xylene, ethylbenzene, aromatic hydrocarbon solvents such as toluene; aliphatic hydrocarbon solvents; ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene Glycol 1-monomethyl ether 2-acetate, 3-methoxy-3-methylbutyl acetate, diethylene glycol monoethyl ether acetate, butyl propionate, ethyl 2-methylpropionate, 2-methylpropyl 2-methylpropionate, 3-ethoxypropionic acid Ester solvents such as ethyl; isopropyl alcohol, butyl alcohol, propylene glycol monomethyl ether, diacetone alcohol, 2-butoxyethanol, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene
  • 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.
  • Copolymer B is a copolymer of monomer (b1) and monomer (b2), and contains monomer units derived from monomer (b1) and monomer (b2).
  • the content of the monomer (b1) with respect to the sum of the monomers (b1) and (b2) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass.
  • the numerical values exemplified here It may be in the range between any two. In this case, the coating film solubility is particularly good.
  • the content of the copolymer B in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A is converted to solid content, and the mass ratio (copolymer B/copolymer A) is It is usually 0.05 to 0.9, preferably 0.05 to 0.7.
  • This mass ratio is, for example, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, where may be within a range between any two of the numerical values exemplified in .
  • Antifouling agents include, for example, inorganic agents and organic agents.
  • inorganic chemicals include cuprous oxide, copper thiocyanate (common name: rhodan copper), and copper powder.
  • cuprous oxide and rhodan copper are particularly preferable, and cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, lycithin, mineral oil, etc. is preferred for long-term storage stability. is more preferable.
  • organic agents include copper 2-mercaptopyridine-N-oxide (generic name: copper pyrithione), zinc 2-mercaptopyridine-N-oxide (generic name: zinc pyrithione), zinc ethylene bisdithiocarbamate (generic name: Zineb ), 4,5-dichloro-2-n-octyl-3-isothiazolone (generic name: Seanine 211), 3,4-dichlorophenyl-NN-dimethylurea (generic name: diuron), 2-methylthio-4- t-Butylamino-6-cyclopropylamino-s-triazine (generic name: Irgalol 1051), 2-(p-chlorophenyl)-3-cyano-4-bromo-5-trifluoromethylpyrrole (generic name: Econea28) , 4-[1-(2,3-dimethylphenyl)ethyl]-1H-imidazole (gen
  • organic agents can be adsorbed on activated carbon, encapsulated by coating, converted into organic salts, or diluted with various solvents to improve handling and effectiveness.
  • Organic agents that are appropriately adjusted by the technique can also be used.
  • These antifouling agents can be used singly or in combination of two or more.
  • the content of the antifouling agent in the composition of the present invention is not particularly limited, it is usually 0.1 to 60.0% by mass in terms of solid content.
  • the content of the antifouling agent is, for example, 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and may be within a range between any two of the numerical values exemplified here.
  • the antifouling paint composition of the present invention may optionally contain resin components other than copolymers A and B, elution modifiers, plasticizers, pigments, dyes, antifoaming agents, dehydrating agents,
  • An antifouling paint can be prepared by adding a thixotropic agent, an organic solvent, or the like.
  • Polymer P is a polymer obtained by polymerizing the monomer (b2).
  • the monomer (b2) can be used alone or in combination of two or more.
  • the polymerization method, initiator, solvent, temperature, other conditions, Mw measurement method, and the like can be applied to the method described above for copolymer A.
  • the content of the polymer P in the composition of the present invention is not particularly limited, but the content ratio with the copolymer A, in terms of solid content, the mass ratio (polymer P / copolymer A) is usually 0 0.05 to 0.7, preferably 0.05 to 0.6. This mass ratio is, for example, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7. It may be within a range between two.
  • Dissolution modifiers include, for example, monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof. salts or the above alicyclic hydrocarbon resins. These can be used singly or in combination of two or more.
  • the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
  • Examples of the alicyclic hydrocarbon resin include commercially available products such as Quinton 1500, 1525L, and 1700 (trade names, manufactured by Nippon Zeon Co., Ltd.). Among these, rosin, rosin derivatives, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferred.
  • plasticizer examples include phosphates, phthalates, cyclohexanecarboxylic acid esters, adipates, sebacates, polyesters, epoxidized soybean oil, alkyl vinyl ether polymers, and polyalkylene glycols. , t-nonylpentasulfide, vaseline, polybutene, tris(2-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, and the like. These can be used singly or in combination of two or more.
  • dehydrating agents include calcium sulfate, synthetic zeolite adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used singly or in combination of two or more.
  • the organic solvent is not particularly limited, but includes, for example, the solvents described as the organic solvent in the polymerization reaction of the copolymer A. Among them, butyl acetate, isobutyl acetate, methoxypropyl acetate, propylene glycol 1-monomethyl ether 2-acetate, 3-methoxy-3-methylbutyl acetate, butyl propionate, ethyl 2-methylpropionate, 2-methylpropyl 2-methylpropionate, ethyl 3-ethoxypropionate, butyl alcohol, propylene glycol monomethyl ether, Propylene glycol 1-monomethyl ether 2-acetate, 2-butoxyethanol, ethylene glycol propyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methyl isobutyl ketone, methyl amyl ketone, diisobutyl ket
  • the antifouling coating composition of the present invention can be prepared, for example, by mixing and dispersing a mixture containing a copolymer, an antifouling agent, other additives, etc. using a disperser. can be manufactured. It is preferable that the mixed liquid is prepared by dissolving or dispersing various materials such as a copolymer and an antifouling agent in a solvent.
  • the disperser for example, one that can be used as a fine pulverizer can be suitably used. For example, a commercially available homomixer, sand mill, bead mill, disper, etc. can be used.
  • the mixed liquid may be mixed and dispersed using a container equipped with a stirrer to which glass beads or the like for mixing and dispersing are added.
  • the antifouling coating composition is used to form an antifouling coating film on the surface of a coating film-forming object.
  • the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing adhesion of aquatic fouling organisms.
  • the object to be coated include ships (particularly ship bottoms), fishing tools, underwater structures, and the like.
  • the thickness of the antifouling coating film may be set as appropriate according to the type of object to be coated, sailing speed of the ship, seawater temperature, and the like. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating is usually 50-700 ⁇ m, preferably 100-600 ⁇ m.
  • % 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. 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".
  • Production Example 1-1 Production Example of Monomer (a1) ⁇ Production Example 1 (Production of Monomer a1-1)> A four-neck flask equipped with a thermometer, a condenser, a stirrer and a dropping funnel, normal hexyl chloroacetate: 178 g (1.00 mol), acrylic acid: 72 g (1.00 mol), 4-methoxyphenol: 0.1 g, Ethyl acetate: 500 g was charged as a solvent, 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 in order with city water, hydrochloric acid water, and sodium bicarbonate water, and the solvent was distilled off by vacuum concentration to obtain 175 g of monomer a1-1.
  • H hydrogen Me: methyl group
  • Hx normal hexyl group
  • Ch cyclohexyl group
  • 2EtHx 2-ethylhexyl group
  • Ph phenyl group
  • 2-MeOEt 2-methoxyethyl group
  • 2-PhOEt 2-phenoxyethyl group
  • THFMe tetrahydrofurfuryl group
  • AA acrylic acid MAA: methacrylic acid
  • NMP N-methyl-2-pyrrolidone
  • CANa sodium monochloroacetate
  • CPANa sodium 2-chloropropionate
  • CAMe methyl chloroacetate
  • CAHx normal hexyl chloroacetate
  • CACh cyclohexyl chloroacetate
  • CA2-EtHx 2-ethylhexyl chloroacetate
  • CAPh phenyl chloroacetate
  • CA2-MeOEt 2-methoxyethyl chloroacetate
  • CA2-PhOEt 2-phenoxyethyl chloroacetate
  • CATHFMe tetrahydrofurfuryl chloroacetate
  • MEHQ 4-methoxyphenol
  • TEA triethylamine
  • the unit of numerical values for the amounts of raw materials in the tables is g, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, which is a polymerization initiator, In each production example, an appropriate amount was added so as to obtain the Mw of each copolymer described in .
  • Production Example D1 (Production of gum rosin solution)> 300 g of Chinese gum rosin (WW) and 310 g of xylene are placed in a flask equipped with a thermometer, a reflux condenser, and a stirrer, and dehydrated under reduced pressure at 70-80° C. for 1 hour under reduced pressure to obtain xylene of gum rosin. A solution (brown clear liquid, 50% solids) was obtained. The heating residue of the resulting solution was 50.3%.
  • ⁇ Production Example D4 (Production of trimethylisobutenylcyclohexenecarboxylic acid solution)> 320 g of alloocimene, 175 g of methacrylic acid and 0.17 g of MEHQ were placed in a flask equipped with a thermometer, a reflux condenser and a stirrer, and heated and stirred at 35-45° C. for 24 hours. Thereafter, unreacted raw materials were distilled off under reduced pressure to obtain 73 g of trimethylisobutenylcyclohexenecarboxylic acid with brown viscosity. Xylene was added to this to prepare a trimethylisobutenylcyclohexenecarboxylic acid solution (solid content: 50%).
  • Examples 1 to 33 and Comparative Examples 1 to 3 production of coating composition
  • a coating composition was produced by blending the components shown in Tables 12 to 18 at the ratios (% by mass) shown in the same tables and mixing and dispersing the mixture with glass beads having a diameter of 1.5 to 2.5 mm.
  • Cuprous oxide trade name “NC-301” (manufactured by Nisshin Chemco Co., Ltd.)
  • Rhodan copper Cuprous thiocyanate (manufactured by Nippon Kagaku Sangyo Co., Ltd.)
  • Copper pyrithione trade name “Copper Omagin” (manufactured by LONZA Co., Ltd.)
  • Sea Nine trade name “Sea Nine 211”, 4,5-dichloro-2-octyl-4-isothiazolin-3-one (manufactured by R&H), 30% active ingredient in xylene solution
  • Zineb [ethylene bis(dithiocarbamate)] zinc (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
  • Diuron Product name “Diuron” (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Tolylfluanid trade name "Preventol A 5-S (manufacture
  • Bengara Product name "Bengara goldfish” (manufactured by Morishita Bengara Kogyo Co., Ltd.)
  • Talc Product name “Talc MS” (manufactured by Nippon Talc Co., Ltd.)
  • Zinc oxide Product name “Type 2 zinc oxide” (manufactured by Seido Chemical Industry Co., Ltd.)
  • Titanium oxide trade name “FR-41” (manufactured by Furukawa Co., Ltd.)
  • Disparlon A603-20X amide-based thixotropic agent: trade name "Disparlon A603-20X” (manufactured by Kusumoto Kasei Co., Ltd.) Tetraethoxysilane: trade name “Ethyl Silicate 28” (manufactured by Colcoat Co., Ltd.) Tricresyl phosphate: (manufactured by Daihachi Chemical Industry Co., Ltd.)
  • Example 1 (rotary test)> A rotating drum with a diameter of 515 mm and a height of 440 mm was attached to the center of the water tank, and it was made to rotate by a motor. In addition, a cooling device for keeping the seawater temperature constant and a pH automatic controller for keeping the seawater pH constant were installed.
  • a test plate was prepared according to the following method. First, on a titanium plate (71 ⁇ 100 ⁇ 0.5 mm), an antirust paint (epoxy vinyl A/C) is applied so that the thickness after drying is about 100 ⁇ m, and dried to form an antirust coating film. bottom. After that, the coating compositions obtained in Examples and Comparative Examples were applied so that the dry film thickness was about 300 ⁇ m, and dried at 40° C.
  • an antirust paint epoxy vinyl A/C
  • the prepared test plate was fixed to the rotating drum of the rotating device of the apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During this period, the temperature of the seawater was kept at 25°C and the pH at 8.0-8.2, and the seawater was replaced every two weeks. After 36 months from the start of the test on each test plate, the surface condition of the coating film was evaluated by observing the surface of each coating film with the naked eye and a microscope. The coating film surface condition was evaluated according to the following criteria. S: No abnormality A: Hair cracks observed in less than 10% of the total coating surface area.
  • B Hair cracks observed in 10% or more and less than 30% of the total coating surface area.
  • C Hair cracks observed in 30% or more and less than 50% of the total coating surface area.
  • D Hair cracks observed in 50% or more of the total coating surface area.
  • E Abnormalities in the paint film such as large cracks, blisters or peeling (only the surface of the paint film and part of the edge are peeled off), peeling (the entire paint film is peeled off and no test paint film remains). What can be done.
  • Example 2 immersion test> The coating compositions obtained in Examples and Comparative Examples were applied to both sides of a hard PVC board (100 ⁇ 200 ⁇ 2 mm) so that the thickness of the dry coating film would be about 300 ⁇ m.
  • the evaluation was carried out by visually observing the state of the coating film surface, and judged according to the following criteria. ⁇ : No attachment of fouling organisms such as shellfish and algae, and almost no slime. ⁇ : No fouling organisms such as shellfish and algae adhered, and slime was thinly adhered (to the extent that the coating film surface was visible), but could be removed by lightly wiping with a brush. ⁇ : No fouling organisms such as shellfish or algae adhered, but the slime adhered so thickly that the coating film surface was not visible, and could not be removed by wiping strongly with a brush. x: Level at which fouling organisms such as shellfish and algae adhere.

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EP4303276A4 (en) * 2021-03-02 2024-08-21 Nitto Kasei Co., Ltd. ANTIFOULING COATING MATERIAL COMPOSITION
JP7576722B1 (ja) * 2024-03-26 2024-10-31 中国塗料株式会社 水系防汚塗料組成物

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JP2005520912A (ja) * 2002-03-26 2005-07-14 ヨトゥン エイエス 皮膜形成性ポリマーと防汚塗料
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WO2022102492A1 (ja) * 2020-11-10 2022-05-19 日東化成株式会社 防汚塗料組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4303276A4 (en) * 2021-03-02 2024-08-21 Nitto Kasei Co., Ltd. ANTIFOULING COATING MATERIAL COMPOSITION
JP7576722B1 (ja) * 2024-03-26 2024-10-31 中国塗料株式会社 水系防汚塗料組成物

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