WO2020209208A1 - Composition de revêtement antisalissure - Google Patents

Composition de revêtement antisalissure Download PDF

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Publication number
WO2020209208A1
WO2020209208A1 PCT/JP2020/015399 JP2020015399W WO2020209208A1 WO 2020209208 A1 WO2020209208 A1 WO 2020209208A1 JP 2020015399 W JP2020015399 W JP 2020015399W WO 2020209208 A1 WO2020209208 A1 WO 2020209208A1
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acrylate
meth
copolymer
monomer
group
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PCT/JP2020/015399
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English (en)
Japanese (ja)
Inventor
慧 小林
崇 松木
英典 和久
拓也 安井
基道 伊藤
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日東化成株式会社
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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
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an antifouling coating composition.
  • Aquatic pollutants such as Fujitsubo, Serupura, Murasakiigai, Fusakokemushi, Hoya, Green laver, Sea lettuce, Slime, etc. Adhesion causes problems such as impairing the functions of those ships and impairing their appearance.
  • an antifouling paint composition is applied to a ship or the like to form an antifouling coating film, and an antifouling agent is gradually released from the antifouling coating film to prevent fouling over a long period of time.
  • Patent Document 1 A technique for exerting performance is known (Patent Document 1).
  • Patent Document 1 Even if the technology of Patent Document 1 is adopted, the coating film portion that is constantly submerged in seawater maintains long-term antifouling performance, but in the draft portion, which is the boundary between water and water, sunshine or the like There was a problem that the antifouling property was not fully exhibited because it was affected by various factors such as being easily affected by.
  • the present invention has been made in view of such circumstances, and the coating film dissolution continues for a long period of time even after being exposed to sunlight for a long period of time, and it is also good in a draft part where aquatic polluted organisms are likely to adhere. It is an object of the present invention to provide a composition for forming an antifouling coating film having high environmental safety, which can exhibit excellent antifouling performance.
  • an antifouling coating composition containing a resin component R and fired kaolin, wherein the resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group.
  • the copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a), and the monomer ( In a), an antifouling coating composition represented by the general formula (1) is provided.
  • (meth) acrylic means acrylic or methacrylic.
  • the antifouling paint composition of the present invention contains a resin component R and calcined kaolin.
  • Resin component R The resin component R is a copolymer A or an organopolysiloxane B having a cross-linking reactive functional group.
  • Copolymer A is a copolymer of the monomer (a) and an ethylenically unsaturated monomer (b) other than the monomer (a).
  • Copolymer A contains monomeric units derived from the monomers (a) and (b).
  • the monomer (a) is a triorganosilyl monomer (meth) acrylate and is represented by the general formula (1).
  • R 1 represents a hydrogen atom or 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 (meth) acrylate, triisobutylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, and triisopentylsilyl (meth) acrylate.
  • Preferred examples thereof include triisopropylsilyl (meth) acrylate, tris-butylsilyl (meth) acrylate, t-butyldiphenylsilyl (meth) acrylate, and tri2-ethylhexylsilyl (meth) acrylate.
  • These monomers (a) can be used alone or in combination of two or more.
  • the monomer (b) is an ethylenically unsaturated monomer other than the monomer (a), and is, for example, a (meth) acrylic acid ester, a vinyl compound, an aromatic compound, a dialkyl ester compound of a dibasic acid, or the like. Can be mentioned.
  • Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and (meth).
  • vinyl compound examples include vinyl compounds having a functional group 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 compound 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 (b) can be used alone or in combination of two or more.
  • (meth) acrylic acid ester is preferable from the viewpoint of coating material properties, and methyl methacrylate, butyl (meth) acrylic acid, and (meth) acrylic acid are particularly preferable from the viewpoint of crack resistance.
  • the monomer (a) in the copolymer A is preferably 5 to 75% by mass, more preferably 30 to 60% by mass.
  • the content of the monomer (a) is, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75% by mass. , It may be within the range between any two of the numerical values exemplified here.
  • 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 a copolymer of a random copolymer of a monomer (a) and a monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. You may.
  • the copolymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) 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.
  • Organopolysiloxane B is an organopolysiloxane having a cross-linking reactive functional group.
  • the crosslinkable functional group is preferably provided on a silicon atom in the molecular chain.
  • cross-linking reactive functional group examples include an alkoxy group such as a hydroxyl group, a methoxy group, an ethoxy group and a propoxy group; and an aralkyloxy group such as a benzyloxy group.
  • organic group examples include organic groups generally possessed by organopolysiloxane, and specifically, alkyl groups such as methyl group, ethyl group and propyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; vinyl group. , Alkenyl group such as allyl group; aralkyl group such as benzyl group; aryl group such as phenyl group and naphthyl group; alkyl halide group such as 3,3,3-trifluoropropyl group and the like.
  • Organopolysiloxane B forms an organopolysiloxane rubber by a condensation reaction in the presence of a catalyst and in the presence of moisture (which may be moisture in the air).
  • the cross-linking reactive functional group in the organopolysiloxane B forms a silicone rubber by condensation reaction with the cross-linking reactive functional group of another organopolysiloxane B or the hydrolyzable group in the cross-linking agent. , Becomes a film.
  • the reaction temperature in such a condensation reaction is usually 80 ° C. or lower, preferably 50 ° C. or lower.
  • the weight average molecular weight of the organopolysiloxane B is preferably 400 to 1,000,000, more preferably 2000 to 150,000, and even more preferably 4000 to 80,000. Two or more kinds having different weight average molecular weights can be used in combination. Specifically, the weight average molecular weight is, for example, 400, 2000, 4000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 100000, 150,000, 500000, 1000000, and the numerical values exemplified here are used. It may be within the range between any two.
  • organopolysiloxane B Commercially available products of organopolysiloxane B include RF-5000, RF-10000 (above, manufactured by Shin-Etsu Chemical Co., Ltd.), XIAMETER OHG-4010 Polymer, XIAMETER OHG-4012 Polymer (above, manufactured by Dow Corning), XC96- 723, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, YR3204 (above, Momentive Performance Materials), BLUESIL FLD 48V3500 (above, Elchem), POLYMER FD 6 (Wacker Chemie), DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S42, DMS-S45, DMS-S51, PDS-0332, PDS-9931, FMS-9922 (Gelest) Made) and the
  • Calcined Kaolin Calcined kaolin was dehydroxylated from naturally occurring hydrous kaolin (kaolinite, a hydrous aluminosilicate with a theoretical composition [Al 2 Si 2 O 5 (OH) 4 ]) that is naturally produced by thermal methods. Kaolin transformed into a form. Firing changes the kaolin structure from crystalline to amorphous, among other properties. The calcination is carried out by heat-treating the coarse or fine hydrous kaolin, for example at a temperature in the range of 500 ° C. to 1200 ° C., for example, at a temperature in the range of 800 ° C. to 1200 ° C., by any known method. To.
  • Examples of the commercially available calcined kaolin include Translink 445 (manufactured by BASF), Satintone W, Satintone 5, and Satintone 5HB (manufactured by BASF Corporation).
  • the whiteness of the calcined kaolin is preferably 75% or more, and more preferably 80% or more. Whiteness is measured by the measuring method defined by ISO2469.
  • the average particle size of the calcined kaolin is preferably 0.1 to 5.0 ⁇ m, more preferably 0.4 to 2.0 ⁇ m.
  • the average particle size is determined by, for example, a known method of sedimentation of particulate matter in a fully dispersed state in an aqueous medium using a Sedigraf® 5100 particle size analyzer manufactured by Micromeritics (Atlanta, Ga). Measured at.
  • the average particle size is, for example, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1. 0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 3.0, 4.0, It is 5.0 and may be in the range between any two of the numerical values exemplified here.
  • the content of calcined kaolin in the composition of the present invention is not particularly limited, but is usually 1 to 40% by mass, preferably 5 to 20% by mass in terms of solid content.
  • the content of calcined kaolin is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 , 20, 25, 30, 35, 40% by mass, and may be within the range between any two of the numerical values exemplified here.
  • Antifouling agents examples include inorganic agents and organic agents.
  • the inorganic drug examples include cuprous oxide, copper thiocyanate (generic name: copper rodan), copper powder and the like.
  • 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-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (generic name: zinc pyrithione), and zinc ethylenebisdithiocarbamate (generic name: dineb).
  • the content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 60% by mass, preferably 1 to 50% by mass in terms of solid content.
  • the content of the antifouling agent is, for example, 0.1, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60% by mass, and here. It may be in the range between any two of the illustrated values.
  • additives may be added to the antifouling paint resin of the present invention, if necessary.
  • the other additives include a resin component other than the copolymer A, an elution adjuster, a plasticizer, a pigment, a dye, a defoaming agent, a dehydrating agent, and shaking. Examples include agents and organic solvents.
  • the resin component R is organopolysiloxane B
  • other additives include plasticizers, pigments, dyes, defoamers, fillers, dehydrators, shakers, crosslinkers, condensation catalysts, and bleed oils. , Organic solvent and the like.
  • the polymer P is a polymer obtained by polymerizing the monomer (b).
  • the monomer (b) is any ethylenically unsaturated monomer other than the monomer (a).
  • the monomer (b) used for the polymerization of the polymer P may have the same composition as or different from the monomer (b) used for the polymerization of the copolymer A.
  • the monomer (b) 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 and the mass ratio (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 Zeon Corporation).
  • 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.
  • dehydrating agent examples include calcium sulfate, synthetic zeolite-based adsorbents, orthoesters, silicates such as tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides, and carbodiimidazoles. These can be used alone or in combination of two or more.
  • Examples of the filler include an inorganic filler and / or an organic filler.
  • Examples of the inorganic filler include calcium carbonate, precipitated barium sulfate, barite powder, titanium oxide, silica soil, aluminum hydroxide, fine granular alumina, magnesium oxide, magnesium carbonate, talc, zeolite, bentonite, silica powder, and phthalocyanine blue. , Carbon black and the like.
  • Examples of the organic filler include synthetic resin powders such as polypropylene, polyvinyl chloride, polystyrene, and acrylic silicone.
  • Examples of the rocking agent include fatty acid amide, polyethylene oxide, silica, fumed silica and the like. These can be used alone or in combination of two or more.
  • cross-linking agent examples include acetoxy having an acetoxy group such as diacetoxymethylsilane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane, and diacetoxymethylphenylsilane.
  • acetoxy having an acetoxy group such as diacetoxymethylsilane, diacetoxydimethylsilane, diacetoxymethylvinylsilane, methyltriacetoxysilane, triacetoxyvinylsilane, tetraacetoxysilane, ethyltriacetoxysilane, and diacetoxymethylphenylsilane.
  • Silanes having ketooxime groups such as silane, methyltri (butanoxime) silane, vinyltri (butanoxime) silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, methyltriisopropenoxysilane, triisopropenoxysilane, tetraprope
  • Examples thereof include silanes having an alkenoxy group such as noxysilane, phenyltrialkenoxysilane, isopropylpropenoxysilane, butyltripropenoxysilane, and vinyltripropenoxysilane, and one of these may be used alone or in combination of two or more. Can be used in combination.
  • condensation catalyst examples include an organic tin compound such as dibutyltin diacetate and an organic titanium compound such as tetraisopropyl titanate, and one of these can be used alone or in combination of two or more.
  • bleed oil examples include silicone oil, a graft copolymer composed of an acrylic polymer and dimethylpolysiloxane, perfluoropolyether oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and poly.
  • oxyethylene castor oil and polyoxyethylene cured castor oil examples of these compounds can be used alone or in combination of two or more.
  • the bleed oil has excellent compatibility with the organopolysiloxane rubber formed by the condensation reaction of the organopolysiloxane B. Therefore, according to the composition of the present invention, it is possible to suitably form a coating film having excellent coating film performance in which peeling and the like are unlikely to occur.
  • organic solvent examples include xylene, toluene, hexane, heptane, octane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, methanol, ethanol, propanol, isopropyl alcohol, isoamyl alcohol, n-butanol, 1 -Methoxy-2-propanol, glycol-based ester, aromatic hydrocarbon, aliphatic hydrocarbon, white spirit, alicyclic hydrocarbon-based solvent, naphthenic hydrocarbon, mineral spirit, aliphatic solvent naphtha, low boiling point aromatic Examples include naphtha, isoparaffin, normal paraffin and the like. These organic solvents can be used alone or in combination of two or more.
  • the antifouling coating composition of the present invention is produced by mixing and dispersing, for example, a mixed solution containing resin component R, calcined kaolin, other additives, etc. using a disperser. It can. It is also possible to produce by adding calcined kaolin after mixing and dispersing a mixed solution containing the resin component R, an antifouling agent, other additives and the like using a disperser.
  • the mixed solution is preferably one in which various materials such as resin component R and calcined kaolin are dissolved or dispersed in a solvent.
  • the solvent the same solvent as the above organic solvent can be used.
  • 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, disper, paint shaker 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.
  • the antifouling coating composition of the present invention may be composed of one liquid or a plurality of liquids (for example, two liquids).
  • the resin component R is an organopolysiloxane B
  • a plurality of liquids are formed, and at least one of the condensation catalyst and the cross-linking agent is mixed in a liquid different from the organopolysiloxane B and then mixed immediately before use as a paint. Is preferable. This improves storage stability.
  • 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.
  • Naphthezol 160 Naphthenic solvent manufactured by JXTG Energy Co., Ltd.
  • Examples and Comparative Examples Manufacturing of Paint Composition
  • a coating composition was produced by blending the components shown in Tables 2 to 5 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.
  • the antifouling coating composition of Examples and Comparative Examples shown in Table 5 had a two-component structure consisting of a liquid a having a component a and a liquid b having a component b.
  • Copper oxide Product name "NC-301” (manufactured by Nissin Chemco Co., Ltd.) Copper thiocyanate (I): Product name “Copper thiocyanate (I)” (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) Copper Pirition: Product name "Copper Omagin” (manufactured by LONZA Co., Ltd.) Zinc pyrithione: Product name “Zinc pyrithione” (manufactured by LONZA Co., Ltd.) Zineb: Product name “Zineb” (manufactured by SIGMA-ALDRICH) SeaNine211: 4,5-dichloro-2-n-octyl-3-isothiazolone (manufactured by R & H, 30% xylene solution of active ingredient) Medetomidine: Product name "Selektope” (manufactured by Aitec) Econea 028
  • DMS-S35 Trade name "DMS-S35", manufactured by Gelest, polydimethylsiloxane having both terminal silanol groups, Mw 49000 DMS-S32: Trade name “DMS-S32", manufactured by Gelest, polydimethylsiloxane having both terminal silanol groups, Mw 36000 YR3204: Trade name "YR3204", manufactured by Momentive, polymethylphenylsiloxane (90% solution) having both terminal silanol groups.
  • Polyether-modified silicone oil Trade name "KF-6020" Side-chain polyethylene oxide and polypropylene oxide-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Polyether / long-chain alkyl / aralkyl-modified silicone oil Trade name "X-22-2516" Side-chain polyethylene oxide, polypropylene oxide, long-chain alkyl, aralkyl-modified polysiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Polyoxyethylene (30) lanolin Product name "NIKKOL TW-30" (manufactured by Nikko Chemicals Co., Ltd.)
  • Methylphenyl silicone oil Product name "KF-50” (manufactured by Shin-Etsu Chemical Co., Ltd.)
  • Dibutyltin dilaurate Di-n-butyltin dilaurate, trade name "Neostan U-100" (manufactured by Nitto Kasei)
  • TES40 WN Partially hydrolyzed condensate of tetraethoxysilane
  • Example 1 to 23 and Comparative Examples 1 to 6 the coating composition was applied to both sides of a hard vinyl chloride plate (100 ⁇ 200 ⁇ 2 mm) as a dry coating film so as to have a thickness of about 200 ⁇ m.
  • the obtained coating film was dried at room temperature (25 ° C.) for 3 days to prepare a test plate having a dry coating film having a thickness of about 200 ⁇ m.
  • Examples 24 to 26 and Comparative Example 7 an epoxy-based primer HEMPADUR QUATTRO XO 17870 (manufactured by HEMPEL) was applied on a hard vinyl chloride plate (110 ⁇ 60 ⁇ 2 mm) with a dry film thickness of about 100 ⁇ m, and then further silicon-based. Tiecoat HEMPASIL NEXUS X-TEND 27500 (manufactured by HEMPEL) was applied in a dry film thickness of about 100 ⁇ m. A mixture of solutions a and b of the antifouling coating composition obtained in Examples and Comparative Examples was applied thereto with a dry film thickness of about 200 ⁇ m, and dried at room temperature for 3 days to prepare a test plate. ..
  • This test plate was exposed to solar radiation outdoors at an angle of 45 ° from the ground facing south, and the state of the coating film after 3 months and 6 months was evaluated. The evaluation was performed by the following method. ⁇ : There is no abnormality at all. X: Cracks are seen in the coating film. ⁇ Immersion test after weather resistance test> After performing the above weather resistance test for 6 months, the test plate was immersed 1.5 m below the sea level in Owase City, Mie Prefecture to stain the test plate with deposits after 6 months, 12 months, and 18 months. Observed after 24 months. The evaluation was performed by visually observing the state of the coating film surface, and judged according to the following criteria.
  • ⁇ There is no adhesion of polluted organisms such as shellfish and algae, and there is almost no slime.
  • ⁇ A level at which there is no attachment of polluted organisms such as shellfish and algae, and slime is thinly attached (to the extent that the coating film surface can be seen), but it can be lightly wiped off with a brush.
  • ⁇ There is no adhesion of polluted organisms such as shellfish and algae, but the slime is so thick that the coating film surface cannot be seen, and it cannot be removed even if it is wiped strongly with a brush.
  • ⁇ Level at which polluted organisms such as shellfish and algae are attached.

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Abstract

L'invention concerne une composition destinée à la formation d'un film de revêtement antisalissure hautement respectueux de l'environnement, apte à préserver de la dissolution le film de revêtement sur une période prolongée même après une exposition de longue durée à la lumière du soleil et présentant de bonnes performances antisalissure même sur les zones immergées où des organismes aquatiques salissants viennent souvent se fixer.　La présente invention concerne une composition de revêtement antisalissure comprenant un composant à base de résine R et du kaolin calciné, le composant à base de résine R étant un copolymère A ou un organopolysiloxane B comportant un groupe fonctionnel réticulable. Le copolymère A est un copolymère d'un monomère (a) avec un monomère à insaturation éthylénique (b) autre que le monomère (a) ; et le monomère (a) est représenté par la formule générale (1).
PCT/JP2020/015399 2019-04-09 2020-04-03 Composition de revêtement antisalissure WO2020209208A1 (fr)

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JP2019-074149 2019-04-09
JP2019074149A JP2022088688A (ja) 2019-04-09 2019-04-09 防汚塗料組成物

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WO2020209208A1 true WO2020209208A1 (fr) 2020-10-15

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Citations (12)

* Cited by examiner, † Cited by third party
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JPH02166178A (ja) * 1988-12-17 1990-06-26 Nitto Kagaku Kk 自動車の塗膜用汚れ防止剤
JPH0718216A (ja) * 1993-06-30 1995-01-20 Nippon Oil & Fats Co Ltd 塗料組成物
JPH09208888A (ja) * 1996-02-07 1997-08-12 Toshiba Silicone Co Ltd 塗膜用保護撥水性組成物
JP2001226440A (ja) * 2000-02-17 2001-08-21 Nippon Paint Co Ltd 共重合体及び塗料組成物
WO2009093348A1 (fr) * 2008-01-25 2009-07-30 Nitto Kasei Co., Ltd. Composition de revêtement antidépôt, revêtement antidépôt fabriqué avec cette composition, matière dont la surface est recouverte du revêtement, procédé de traitement antidépôt comprenant la formation du revêtement et kit de formation du revêtement antidépôt
WO2014010702A1 (fr) * 2012-07-12 2014-01-16 日立化成ポリマー株式会社 Résine polyester pour des matières de revêtement antisalissure, son procédé de fabrication, composition de matière de revêtement antisalissure, film de revêtement antisalissure et base antisalissure
WO2016009947A1 (fr) * 2014-07-14 2016-01-21 中国塗料株式会社 Composition de peinture antisalissure
JP2016065118A (ja) * 2014-09-24 2016-04-28 新日鐵住金株式会社 Ｓｎイオンを利用した弱溶剤形高耐食性塗料組成物
CN105647292A (zh) * 2016-02-02 2016-06-08 芜湖县双宝建材有限公司 一种船用耐腐蚀涂料
CN107352861A (zh) * 2017-06-06 2017-11-17 浙江加州国际纳米技术研究院台州分院 一种海工混凝土防护用地聚合物涂层材料的使用方法
WO2018003135A1 (fr) * 2016-07-01 2018-01-04 中国塗料株式会社 Composition de matériau de revêtement antisalissure, film de revêtement antisalissure, substrat doté d'un film de revêtement antisalissure et procédé de production associé, et procédé antisalissure
CN108948991A (zh) * 2018-05-19 2018-12-07 巢湖市翔宇渔具有限公司 一种缓释长效的渔网防污涂料

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02166178A (ja) * 1988-12-17 1990-06-26 Nitto Kagaku Kk 自動車の塗膜用汚れ防止剤
JPH0718216A (ja) * 1993-06-30 1995-01-20 Nippon Oil & Fats Co Ltd 塗料組成物
JPH09208888A (ja) * 1996-02-07 1997-08-12 Toshiba Silicone Co Ltd 塗膜用保護撥水性組成物
JP2001226440A (ja) * 2000-02-17 2001-08-21 Nippon Paint Co Ltd 共重合体及び塗料組成物
WO2009093348A1 (fr) * 2008-01-25 2009-07-30 Nitto Kasei Co., Ltd. Composition de revêtement antidépôt, revêtement antidépôt fabriqué avec cette composition, matière dont la surface est recouverte du revêtement, procédé de traitement antidépôt comprenant la formation du revêtement et kit de formation du revêtement antidépôt
WO2014010702A1 (fr) * 2012-07-12 2014-01-16 日立化成ポリマー株式会社 Résine polyester pour des matières de revêtement antisalissure, son procédé de fabrication, composition de matière de revêtement antisalissure, film de revêtement antisalissure et base antisalissure
WO2016009947A1 (fr) * 2014-07-14 2016-01-21 中国塗料株式会社 Composition de peinture antisalissure
JP2016065118A (ja) * 2014-09-24 2016-04-28 新日鐵住金株式会社 Ｓｎイオンを利用した弱溶剤形高耐食性塗料組成物
CN105647292A (zh) * 2016-02-02 2016-06-08 芜湖县双宝建材有限公司 一种船用耐腐蚀涂料
WO2018003135A1 (fr) * 2016-07-01 2018-01-04 中国塗料株式会社 Composition de matériau de revêtement antisalissure, film de revêtement antisalissure, substrat doté d'un film de revêtement antisalissure et procédé de production associé, et procédé antisalissure
CN107352861A (zh) * 2017-06-06 2017-11-17 浙江加州国际纳米技术研究院台州分院 一种海工混凝土防护用地聚合物涂层材料的使用方法
CN108948991A (zh) * 2018-05-19 2018-12-07 巢湖市翔宇渔具有限公司 一种缓释长效的渔网防污涂料

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