WO2020189415A1 - Composition de matériau de revêtement antisalissure - Google Patents

Composition de matériau de revêtement antisalissure Download PDF

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Publication number
WO2020189415A1
WO2020189415A1 PCT/JP2020/010309 JP2020010309W WO2020189415A1 WO 2020189415 A1 WO2020189415 A1 WO 2020189415A1 JP 2020010309 W JP2020010309 W JP 2020010309W WO 2020189415 A1 WO2020189415 A1 WO 2020189415A1
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Prior art keywords
monomer
copolymer
antifouling
meth
group
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PCT/JP2020/010309
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English (en)
Japanese (ja)
Inventor
崇 松木
英典 和久
慧 小林
拓也 安井
基道 伊藤
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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 CN202080017847.4A priority Critical patent/CN113498426A/zh
Priority to KR1020217032800A priority patent/KR20210141989A/ko
Priority to SG11202107353YA priority patent/SG11202107353YA/en
Publication of WO2020189415A1 publication Critical patent/WO2020189415A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • 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 coating composition.
  • the antifouling coating film made of the antifouling paint had an insufficient elution rate in a relatively early period after immersion in seawater, and there was room for improvement. Further, if a hydrophilic component is added in order to improve the elution rate in the initial stage after immersion in seawater, there is a problem that the physical properties of the coating film are impaired.
  • the present invention has been made in view of such circumstances, and an antifouling coating composition capable of forming a coating film having good coating film physical properties and a good elution rate in the initial stage after immersion in seawater. It is to provide.
  • an antifouling coating composition containing a copolymer A and an antifouling agent B, wherein the copolymer A is a monomer (a), a monomer (b), and It is a copolymer with an ethylenically unsaturated monomer (c) other than the monomers (a) and (b), and the monomer (a) is represented by the general formula (1) and is simply described.
  • the polymer (b) contains an oxygen atom at a site other than the (meth) acrylic group, and the content of the monomer (a) is based on the total mass of the monomers (a) to (c).
  • the mass ratio ((a) / (b)) of the content of the monomer (a) to the content of the monomer (b) is 0.40 to 2 by mass%.
  • the antifouling agent B is at least 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole and 4,5-dichloro-2-n-octyl-3-isothiazolone.
  • an antifouling coating composition is provided.
  • the antifouling paint composition of the present invention contains a copolymer A and an antifouling agent B.
  • Copolymer A is a copolymer with a monomer (a), an oxygen atom-containing monomer (b), and an ethylenically unsaturated monomer (c) other than the monomers (a) and (b). Is. Copolymer A contains monomeric units derived from the monomers (a), (b) and (c).
  • the monomer (a) is a triorganosilyl monomeric acid metallylate monomer and is represented by the general formula (1).
  • R 1 represents a methyl group
  • R 2 to R 4 represent the same or different branched alkyl group or phenyl group having 3 to 8 carbon atoms, respectively).
  • the branched alkyl group of R 2 ⁇ R 4 having 3 to 8 carbon atoms for example, isopropyl, isobutyl, s- butyl, t- butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methyl Pentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, texyl group, cyclohexyl group, 1,1-dimethylpentyl group, 1-methylhexyl group, 1,1-dimethylhexyl group, 1-methyl Examples thereof include heptyl group, 2-methylbutyl group, 2-ethylbutyl group, 2,2-dimethylpropyl group, cyclohexylmethyl group, 2-ethylhexyl group, 2-propylpentyl group and 3-methylpentyl group.
  • R2 to R4 are an isopropyl group, an s-butyl group, a t-butyl group, a phenyl group, and a 2-ethylhexyl group. Particularly preferred are an isopropyl group and a 2-ethylhexyl group.
  • Examples of the monomer (a) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tris-butylsilyl methacrylate, triisopentylsilyl methacrylate, triphenylsilyl methacrylate, diisopropylphenylsilyl methacrylate, and methacrylic acid.
  • Diisopropylisobutylsilyl acid acid diisopropyls-butylsilyl methacrylate, diisopropylisopentylsilyl methacrylate, isopropyldiisobutylsilylacrylate, isopropyldis-butylsilyl methacrylate, t-butyldiisoputylsilylmethacrylate, t-butyldiisomethacrylate Pentylsilyl, t-butyldiphenylsilyl methacrylate, diisopropyltexylsilyl methacrylate, diisopropylcyclohexylsilyl methacrylate, tricyclohexylsilyl methacrylate, tri-1,1-dimethylpentylsilyl methacrylate, tri 2,2-dimethylpropyl methacrylate
  • Examples thereof include silyl, tricyclohexylmethyls
  • triisopropylsilyl methacrylate tris-butylsilyl methacrylate, t-butyldiphenylsilyl methacrylate, tri2-ethylhexylsilyl methacrylate and the like can be mentioned.
  • These monomers (a) can be used alone or in combination of two or more.
  • the monomer (b) is an oxygen atom-containing monomer containing an oxygen atom at a site other than the (meth) acrylic group, and is a monomer having an oxygen atom-containing group other than the (meth) acrylic group.
  • the oxygen atom-containing group include an alkoxy group, a hydroxyl group, and an ether group.
  • Examples of the monomer (b) include 2-methoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 2-ethoxyethyl (meth) acrylate. , (Meth) propylene glycol monomethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other oxygen atom-containing ethylenically unsaturated monomers.
  • the monomer (c) is an ethylenically unsaturated monomer other than the monomers (a) and (b), and is, for example, an acrylic acid silyl ester, a (meth) acrylic acid ester, a vinyl compound, an aromatic compound, and the like. Examples thereof include dialkyl ester compounds of dibasic acid.
  • the (meth) acrylic acid ester means an acrylic acid ester or a metaacrylic acid ester.
  • (meth) acrylic acid ester examples include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth). ) Acrylic acid esters such as 21-ethylhexyl acrylate, lauryl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, etc. Kind and the like.
  • vinyl compound examples include vinyl compounds having a functional group such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, and vinyl acetate.
  • aromatic compounds examples include styrene, vinyltoluene, ⁇ -methylstyrene and the like.
  • dialkyl ester compound of dibasic acid examples include dimethyl maleate, dibutyl maleate, dimethyl fumarate and the like.
  • these monomers (c) can be used alone or in combination of two or more.
  • (meth) acrylic acid ester is preferable from the viewpoint of physical properties of the coating film, and methyl methacrylate, butyl (meth) acrylate, and (meth) acrylic acid are particularly preferable from the viewpoint of crack resistance. More preferably, isobutyl acid acid, t-butyl (meth) acrylate, 21-ethylhexyl (meth) acrylate and the like.
  • the monomer (a) in the copolymer A is 10 to 40% by mass, preferably 15 to 40%, and even more preferably 20 to 40% by mass.
  • the content of the monomer (a) is, for example, 10, 15, 20, 25, 30, 35, 40% by mass, and is within the range between any two of the numerical values exemplified here. There may be.
  • the mass ratio ((a) / (b)) of the content of the monomer (a) to the content of the monomer (b) in the copolymer A is 0.40 to 2.00. It is preferably 0.45 to 2.00, and more preferably 0.50 to 1.60. Specifically, the mass ratio is, for example, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, 0.80, 0.85.
  • the coating film solubility is particularly good.
  • the weight average molecular weight (Mw) of the copolymer A is 5000 to 300,000. This is because if the molecular weight is less than 5,000, the coating film of the antifouling paint becomes fragile and easily peels or cracks, and if it exceeds 300,000, the viscosity of the polymer solution increases, making handling difficult.
  • this Mw is, for example, 5000, 10000, 20000, 30000, 40,000, 50000, 60000, 70000, 80000, 90000, 100000, 200,000, 300,000, and is between any two of the numerical values exemplified here. It may be within the range.
  • Examples of the method for measuring Mw include gel permeation chromatography (GPC method).
  • the copolymer A is any of a monomer (a), a random copolymer of the monomer (b) and the monomer (c), an alternating copolymer, a periodic copolymer, or a block copolymer. It may be a copolymer of.
  • the copolymer A can be obtained, for example, by polymerizing the monomer (a), the monomer (b) and the monomer (c) in the presence of a polymerization initiator.
  • polymerization initiator examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2,4-dimethylvaleronitrile).
  • the polymerization initiators can be used alone or in combination of two or more.
  • the polymerization initiators include, in particular, 2,2'-azobisisobutyronitrile and 2,2'-azobis (2). -Methylbutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate and 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate is preferable.
  • the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • polymerization method examples include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, non-aqueous dispersion polymerization and the like.
  • solution polymerization or non-aqueous dispersion polymerization is particularly preferable in that copolymer A can be obtained easily and accurately.
  • an organic solvent may be used if necessary.
  • the organic solvent is not particularly limited, but for example, an aromatic hydrocarbon solvent such as xylene and toluene; an aliphatic hydrocarbon solvent; an ester solvent such as ethyl acetate, butyl acetate, isobutyl acetate and methoxypropyl acetate; isopropyl.
  • Alcohol-based solvents such as 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 can be mentioned.
  • butyl acetate, isobutyl acetate, butyl alcohol, propylene glycol monomethyl ether, propylene glycol 1-monomethyl ether 2-acetate, toluene and xylene are preferable.
  • These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the polymerization reaction may be appropriately set according to the type of the polymerization initiator and the like, and is usually 50 to 160 ° C, preferably 60 to 150 ° C.
  • the polymerization reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen gas or argon gas.
  • the antifouling agent B is at least one of 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole and 4,5-dichloro-2-n-octyl-3-isothiazolone.
  • Examples of commercially available products of 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole include Econea 028 (manufactured by Janssen PMP).
  • Examples of commercially available products of 4,5-dichloro-2-n-octyl-3-isothiazolone include SEA-NINE 211N (manufactured by Dow Chemical Co., Ltd.).
  • the content of the antifouling agent B in the composition of the present invention is not particularly limited, but is usually 0.1 to 10.0% by mass, preferably 0.5 to 7.0% by mass in terms of solid content. Yes, particularly preferably 4.0 to 6.0% by mass.
  • the content of the antifouling agent B is, for example, 0.1, 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, 9.5, 10.0 mass% It may be within the range between any two of the numerical values exemplified here.
  • the resin for antifouling paint of the present invention includes resin components other than copolymer A, elution adjusters, plasticizers, antifouling agents other than antifouling agent B, pigments, and dyes, if necessary.
  • Antifoaming agent, dehydrating agent, rocking agent, organic solvent and the like can be added to obtain an antifouling paint.
  • the polymer P is a polymer obtained by polymerizing the monomer (d).
  • the monomer (d) is any ethylenically unsaturated monomer other than the monomer (a) (that is, the monomer (b) or the monomer (c)).
  • the monomer (d) used for the polymerization of the polymer P may have the same composition as the monomer (b) or the monomer (c) used for the polymerization of the copolymer A, or may have a different composition. Good.
  • the monomer (d) can be used alone or in combination of two or more, and in particular, from the viewpoint of compatibility with the copolymer A, methyl (meth) acrylate and ethyl (meth) acrylate.
  • 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 is usually 0 in terms of solid content (polymer P / copolymer A). It is .1 to 9.0, preferably 0.1 to 4.0.
  • Examples of the elution adjuster include monocarboxylic acids such as rosin, rosin derivatives, naphthenic acid, cycloalkenylcarboxylic acid, bicycloalkenylcarboxylic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, and metal salts thereof.
  • Examples thereof include the salt thereof or the alicyclic hydrocarbon resin. These can be used alone or in combination of two or more.
  • Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
  • Examples of the commercially available alicyclic hydrocarbon resin include Quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like.
  • rosin, rosin derivative, naphthenic acid, versatic acid, trimethylisobutenylcyclohexenecarboxylic acid, or metal salts thereof are preferable, and rosin and rosin derivative are more preferable.
  • plasticizer examples include phosphoric acid esthetics, phthalates, adipates, sebacic acid esters, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonyl pentasulfide, and vaseline.
  • plasticizer examples include polybutene, tristrimellitic acid (2-ethylhexyl), silicone oil, and chlorinated paraffin. These can be used alone or in combination of two or more.
  • Examples of the antifouling agent include inorganic agents and organic agents.
  • Examples of the inorganic drug include cuprous oxide, copper thiocyanate (generic name: copper rodan), copper powder and the like. Of these, copper cuprous oxide and copper rodane are particularly preferable, and copper cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, ricitin, mineral oil, etc., has long-term stability during storage. Is more preferable.
  • organic agents examples include 2-mercaptopyridine-N-copper oxidone (generic name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (generic name: zinc pyrithione), and zinc ethylenebisdithiocarbamate (generic name: dineb).
  • Examples of the dehydrating agent include silicates such as calcium sulfate, sodium sulfate, magnesium sulfate, synthetic zeolite-based adsorbents, orthoesters, tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. Can be mentioned. These can be used alone or in combination of two or more.
  • a mixed solution containing the copolymer A, the antifouling agent B, other additives and the like is mixed and dispersed using a disperser.
  • the mixed solution is preferably one in which various materials such as the copolymer A and the antifouling agent B are dissolved or dispersed in a solvent.
  • the disperser for example, one that can be used as a fine pulverizer can be preferably used.
  • a commercially available homomixer, sand mill, bead mill, dispar or the like can be used.
  • the mixed solution may be mixed and dispersed by using a container provided with a stirrer to which glass beads or the like for mixing and dispersing are added.
  • an antifouling coating film is formed on the surface of the coating film to be formed using the above antifouling coating composition.
  • the antifouling coating film is gradually dissolved from the surface and the surface of the coating film is constantly updated, so that adhesion of aquatic polluted organisms can be prevented.
  • the coating film-forming product include ships (particularly the bottom of ships), fishing gear, underwater structures, and the like.
  • the thickness of the antifouling coating film may be appropriately set according to the type of the coating film to be formed, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film to be formed is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700 ⁇ m, preferably 100 to 600 ⁇ m.
  • % In each production example, example and comparative example indicates mass%.
  • the weight average molecular weight (Mw) is a value (polystyrene conversion value) obtained by GPC.
  • the conditions of GPC are as follows.
  • ⁇ Production Example 1 (Production of Copolymer Solution A-1)> 230 g (initial solvent) of xylene was charged into a four-necked flask equipped with a thermometer, a cooler, a stirrer and a dropping funnel, nitrogen gas was introduced, and the temperature was maintained at 100 ° C. while stirring. There, 200 g of triisopropylsilyl methacrylate, 125 g of 2-methoxyethyl methacrylate, 25 g of 2-methoxyethyl acrylate, 100 g of methyl methacrylate, 25 g of ethyl acrylate, 25 g of n-butyl acrylate, and t-butylperoxy-2.
  • a mixed solution of 5.0 g (initial addition) of ethylhexanoate was added dropwise over 3 hours while maintaining at 100 ° C. Then, after stirring at 100 ° C. for 1 hour, 1.0 g (post-addition) of t-butylperoxy-2-ethylhexanoate was added 3 times every 1 hour, and further stirred at the same temperature for 2 hours. After that, 270 g (diluting solvent) of xylene was added and the mixture was cooled to room temperature to obtain a copolymer solution A-1 containing a copolymer containing triisopropylsilyl methacrylate. Table 1 shows the viscosity, heating residue, Mw and glass transition temperature of A-1.
  • a coating composition was produced by blending the components shown in Tables 2 to 3 in the proportions (mass%) shown in the table and mixing and dispersing them with glass beads having a diameter of 1.5 to 2.5 mm.
  • antifouling agent B Details of antifouling agent B, other antifouling agents, and other additives in the table are as follows.
  • ⁇ Anti-fouling agent B> Econea 028: 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole, trade name "Econea 028" (manufactured by Janssen PMP)
  • SEA-NINE 211N 4,5-dichloro-2-n-octyl-3-isothiazolone, trade name "SEA-NINE 211N", active ingredient 30% xylene solution (manufactured by Dow Chemical)
  • Copper oxide Product name "NC-301", average particle size 3 ⁇ m (manufactured by Nissin Kemco Co., Ltd.) Copper Pirition: Product name "Copper Omagin” (manufactured by LONZA Co., Ltd.)
  • Zinc pyrithione Product name "Zinc pyrithione” (manufactured by LONZA Co., Ltd.)
  • Zineb (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Medetomidine: Product name "Selektope” (manufactured by Aitec)
  • Gum rosin solution Chinese gum rosin (WW) solid content 50% xylene solution
  • rosin zinc salt solution Use the one produced in Production Example 4
  • Hydrogenated rosin solution Trade name "Hyper CH” (manufactured by Arakawa Chemical Industry Co., Ltd.) Solid content 50% xylene solution.
  • Hydrogenated rosin zinc salt solution The one produced in Production Example 5 is used.
  • Chlorinated paraffin Trade name "Toyoparax A40S” (manufactured by Tosoh Corporation)
  • Epoxy soybean oil Product name "Sun Sizar E-2000H” (manufactured by New Japan Chemical Co., Ltd.)
  • Bis phthalate (2-ethylhexyl) Reagent (Fujifilm Wako Pure Chemical Industries, Ltd.)
  • Talc Product name "Talc MS” (manufactured by Japan Talc Co., Ltd.)
  • Zinc oxide Product name "Zinc oxide 2 types” (manufactured by Shodo Chemical Industry Co., Ltd.)
  • Bengala Product name "Bengala Kingyoku” (manufactured by Morishita Benji Kogyo Co., Ltd.)
  • Titanium oxide Product name "FR-41” (manufactured by Furukawa Co., Ltd.) Tetraethoxysilane: Special grade reagent (manufactured by Kishida Chemical
  • Example 1 Wet & Dry Cycle Test
  • An antifouling coating composition was applied to a glass plate using a 400 ⁇ m applicator to obtain a test plate.
  • This test plate was subjected to a test in which a 12-hour 40 ° C. freshwater immersion test and a 12-hour aerial exposure were repeated for 6 months, and then the physical properties of the test plate were visually evaluated. Those without peeling were marked with ⁇ , and those with peeling were marked with x.
  • Example 2 (Rotary test)> A rotating drum with a diameter of 515 mm and a height of 440 mm was installed in the center of the water tank so that it could be rotated by a motor. In addition, a cooling device for keeping the temperature of seawater constant and an automatic pH controller for keeping the pH of seawater constant were installed. A test plate was prepared according to the following method. First, a rust preventive paint (epoxy vinyl A / C) is applied onto a titanium plate (71 x 100 x 0.5 mm) so that the thickness after drying is about 100 ⁇ m, and the rust preventive coating film is formed by drying. did.
  • a rust preventive paint epoxy vinyl A / C
  • the coating compositions obtained in Examples and Comparative Examples were applied onto the rust-preventive coating film so that the thickness after drying was about 400 ⁇ m.
  • the obtained coating film was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 400 ⁇ m.
  • the prepared test plate was fixed to the rotating drum of the rotating device of the above device so as to come into contact with seawater, and the rotating drum was rotated at a speed of 20 knots. During that time, the temperature of the seawater was maintained at 10 to 15 ° C. and the pH was maintained at 8.0 to 8.2, and the seawater was replaced every week.
  • the initial film thickness of each test plate and the residual film thickness after every 6 months were measured with a laser focus displacement meter, and the dissolved coating film thickness was calculated from the difference to determine the dissolved coating film amount.
  • the coating film dissolution amount was expressed as the coating film dissolution amount ( ⁇ m / month) per month.
  • the coating film formed by using the composition containing the copolymer A and the antifouling agent B has good coating film physical properties and the elution rate at the initial stage after immersion in seawater. It turned out to be good.

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Abstract

L'invention fournit une composition de matériau de revêtement antisalissure qui permet de former un film de revêtement présentant des propriétés de film de revêtement satisfaisantes, et une vitesse de dissolution également satisfaisante en phase initiale après immersion dans une eau de mer.　Plus précisément, l'invention fournit une composition de matériau de revêtement antisalissure qui comprend un copolymère (A) et un agent chimique antisalissure (B). Ledit copolymère (A) consiste en un copolymère d'un monomère (a), d'un monomère (b) et d'un monomère éthyléniquement insaturé (c) autre que lesdits monomères (a) et (b). Ledit monomère (a) est représenté par la formule générale (1). Ledit monomère (b) comprend un atome d'oxygène en une position autre que celle d'un groupe (méth)acrylique. La teneur en monomère (a) est comprise entre 10 et 40% en masse pour la masse totale desdits monomères (a) à (c). Le rapport massique （（ａ）／（ｂ）） entre la teneur en monomère (a) et la teneur en monomère (b), est compris entre ０,４０ et ２,００. Ledit agent chimique antisalissure (B) consiste en un ２－（ｐ－chlorophényl）－３－cyanoー４－bromoー５－trifluorométhylpyrrole et/ou un ４，５－dichloro－２－ｎ－octyle－３－isothiazolone.
PCT/JP2020/010309 2019-03-15 2020-03-10 Composition de matériau de revêtement antisalissure WO2020189415A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN202080017847.4A CN113498426A (zh) 2019-03-15 2020-03-10 防污涂料组合物
KR1020217032800A KR20210141989A (ko) 2019-03-15 2020-03-10 방오 도료 조성물
SG11202107353YA SG11202107353YA (en) 2019-03-15 2020-03-10 Antifouling coating composition

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Application Number Priority Date Filing Date Title
JP2019048089A JP7287648B2 (ja) 2019-03-15 2019-03-15 防汚塗料組成物
JP2019-048089 2019-03-15

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SG11202107353YA (en) 2021-09-29

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