WO2012026237A1 - Composition de revêtement anti-encrassement, copolymère pour composition de revêtement anti-encrassement et article recouvert d'un revêtement ayant une surface fournie avec un film de revêtement anti-encrassement formé en utilisant ladite composition - Google Patents

Composition de revêtement anti-encrassement, copolymère pour composition de revêtement anti-encrassement et article recouvert d'un revêtement ayant une surface fournie avec un film de revêtement anti-encrassement formé en utilisant ladite composition Download PDF

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WO2012026237A1
WO2012026237A1 PCT/JP2011/066155 JP2011066155W WO2012026237A1 WO 2012026237 A1 WO2012026237 A1 WO 2012026237A1 JP 2011066155 W JP2011066155 W JP 2011066155W WO 2012026237 A1 WO2012026237 A1 WO 2012026237A1
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Prior art keywords
coating film
copolymer
antifouling
monomer
acrylate
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PCT/JP2011/066155
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English (en)
Japanese (ja)
Inventor
貴義 藤本
英典 和久
拓也 安井
毛利　喜代美
同 北村
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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 CN201180040531.8A priority Critical patent/CN103080249B/zh
Priority to SG2013006036A priority patent/SG187606A1/en
Publication of WO2012026237A1 publication Critical patent/WO2012026237A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1668—Vinyl-type polymers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group

Definitions

  • the present invention relates to an antifouling coating composition, a copolymer for the antifouling coating composition, and a coated product having an antifouling coating film formed using the composition on the surface.
  • Aquatic fouling organisms such as barnacles, cell plastics, blue mussels, scallops, sea squirts, blue sea breams, blue sea breams, slime, etc., become submarine structures such as ships (especially ship bottoms), fishing nets, fishing net accessories, etc.
  • Adhering causes problems such as damage to the functions of the ship and the like, and the appearance. Since the ban on the use of organic tin-containing copolymers that have been used in the past, triorganosilyl group-containing copolymers with low toxicity and low environmental impact have been developed and used in antifouling paints.
  • the triorganosilyl group-containing copolymer is a copolymer obtained by copolymerizing a linear silyl ester-containing monomer with an alkyl group such as a tri-n-butylsilyl ester-containing copolymer.
  • the triorganosilyl group-containing copolymer when using a copolymer obtained by copolymerizing a triorganosilyl ester-containing monomer having a branched alkyl group, such as a triisopropylsilyl ester-containing copolymer, as the triorganosilyl group-containing copolymer, although it dissolves at a constant rate in seawater at an early stage, the dissolution rate of the coating film gradually increases and, after a long period of time, the dissolution rate of the coating film becomes too high, and the paint design is difficult. There's a problem. Moreover, the coating film which passed for a long time in seawater may cause coating film abnormalities, such as a crack.
  • a paint containing a triisopropylsilyl ester group-containing copolymer has a resin component that hydrolyzes during storage of the paint due to water contained in the raw materials to produce the paint or water generated during the paint production process.
  • a dehydrating agent or the like.
  • the present invention provides an antifouling coating composition excellent in long-term storage stability, and exhibits stable coating film solubility and antifouling performance without causing coating film abnormalities such as cracks in seawater for a long period of time. It is an object of the present invention to provide a copolymer having a specific structure for forming a highly environmentally safe antifouling coating film that can be maintained.
  • the t-butyldiphenylsilyl acrylate monomer (a) is 55 to 80% by mass, and the ethylenically unsaturated monomer (b) other than the monomer (a) is 20 to 45% by mass.
  • the monomer (b) is selected from the group consisting of methyl methacrylate, butyl (meth) acrylate, and 2-methoxyethyl (meth) acrylate.
  • An antifouling coating composition that is at least one monomer is provided.
  • the present inventors have a problem that the antifouling coating film formed using the antifouling coating material containing t-butyldiphenylsilyl methacrylate copolymer has a problem of coating abnormality such as poor adhesion to underwater structures and cracks.
  • the inventors have come up with a more flexible acrylate instead of methacrylate.
  • the antifouling coating film was formed using the antifouling paint containing tert-butyl diphenylsilyl acrylate copolymer, and the performance evaluation was performed. As a result, excellent results were obtained in the adhesion test and the flexibility test.
  • the t-butyldiphenylsilyl methacrylate copolymer has many The problem was solved. However, when the antifouling coating film formed using the antifouling paint containing the tert-butyldiphenylsilyl acrylate copolymer was studied in more detail, the antifouling coating film was found to be in a relatively short period of time. It has been found that there is a problem that the antifouling performance is lowered.
  • the hydrolysis rate of the t-butyldiphenylsilyl acrylate copolymer is not stable, suggesting that the antifouling performance decreases in a relatively short period of time.
  • the present inventor also examined how the performance of the antifouling coating film changed when the proportion of t-butyldiphenylsilyl acrylate in the copolymer was further increased.
  • the ratio of t-butyldiphenylsilyl acrylate is 55 to 80% by mass, excellent results can be obtained.
  • it exceeds 80% by mass the duration of the antifouling performance is shortened. It was.
  • the present inventor investigated this cause, and when the proportion of t-butyldiphenylsilyl acrylate in the copolymer exceeded 80% by mass, the dissolution rate of the coating film increased with the lapse of time. It was found that the cause was that the drug in the coating film disappeared early.
  • an antifouling coating film capable of maintaining antifouling performance for a long period of time can be formed by using an antifouling coating composition containing copolymer A obtained by copolymerization of Further, the antifouling paint composition of the present invention is particularly excellent in the storage stability of the paint as compared with conventional antifouling paint compositions containing a triisopropylsilyl ester-containing copolymer and the like.
  • the monomer (a) in the copolymer A has a slow hydrolysis rate from acidic to neutral, but has a high hydrolysis rate under alkaline conditions of weak alkalinity (pH 8-9) or higher. It is thought to be attributed to the property, and when water is mixed during the production or storage of the antifouling paint, it is difficult to be hydrolyzed and has excellent storage stability of the paint. On the other hand, in an alkaline condition of weak alkalinity (pH 8 to 9) or more, that is, in seawater, an appropriate hydrolysis rate is exhibited and an excellent antifouling effect can be exhibited for a long time.
  • an antifouling paint composition capable of forming an antifouling coating film which is excellent in storage stability and maintains a high antifouling performance over a long period of time.
  • the antifouling paint composition of the present invention comprises 55 to 80% by mass of a t-butyldiphenylsilyl acrylate monomer (a) and an ethylenically unsaturated monomer other than the monomer (a). And a copolymer A obtained by copolymerizing 20 to 45% by mass of the body (b).
  • Copolymer A is composed of 55 to 80% by mass of t-butyldiphenylsilyl acrylate monomer (a) and 20 to 45% by mass of ethylenically unsaturated monomer (b) other than monomer (a). Are obtained by copolymerization.
  • the monomer (a) is obtained by reacting a readily available diphenyldichlorosilane with a Grignard reagent or the like, filtering the reaction solution after completion of the reaction, and removing t-butyldiphenylchlorosilane obtained by removing the produced magnesium salt. It can be easily obtained by reacting with acrylic acid or the like under basic conditions and treating according to a conventional method.
  • the intermediate t-butyldiphenylchlorosilane and the monomer (a) can be used after being purified by distillation under reduced pressure if necessary, and the monomer (a) is used for ensuring storage stability.
  • General polymerization inhibitors such as hydroquinone, methoquinone and BHT can be contained.
  • the ethylenically unsaturated monomer (b) other than the monomer (a) is at least one selected from the group consisting of methyl methacrylate, butyl (meth) acrylate, and 2-methoxyethyl (meth) acrylate. Is a monomer.
  • the monomer (b) preferably contains methyl methacrylate, and the ratio of methyl methacrylate in the ethylenically unsaturated monomer is 15 to 90% by mass is preferable, and 30 to 90% by mass is more preferable. This ratio is, for example, 15, 20, 30, 40, 50, 60, 70, 80, 90 mass%, and may be within a range between any two of the numerical values exemplified here.
  • the monomer (b) preferably further contains 2-methoxyethyl (meth) acrylate, preferably 10 to 85% by mass, more preferably 10 to 60% by mass in the ethylenically unsaturated monomer. preferable.
  • the monomer (b) may contain only one of 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate or both. When both are included, the proportion of 2-methoxyethyl methacrylate is preferably 80 to 95 parts by mass, when the total of 2-methoxyethyl acrylate and 2-methoxyethyl methacrylate is 100 parts by mass. This ratio is 80, 85, 90, and 95% by mass, and may be within a range between any two of the numerical values exemplified here.
  • a preferred embodiment of the copolymer A contained in the composition of the present invention is 55 to 80% by mass of a t-butyldiphenylsilyl acrylate monomer (a), methyl methacrylate, butyl (meth) acrylate, ( It is a copolymer of 20 to 45% by mass of at least one monomer (b) selected from 2-methoxyethyl acrylate, and a more preferred embodiment is a t-butyldiphenylsilyl acrylate monomer ( a) 55 to 70% by mass of at least one monomer selected from methyl methacrylate, butyl (meth) acrylate and 2-methoxyethyl (meth) acrylate (b) 30 to 45% by mass It is a polymer.
  • the proportion of the monomer (a) in the copolymer is, for example, 55, 58, 60, 65, 70, 75, 80% by mass, and within the range between any two of the numerical values exempl
  • the weight average molecular weight (Mw) of the copolymer A is preferably 10,000 to 100,000, and particularly preferably 20,000 to 70,000.
  • Mw weight average molecular weight
  • the coating film does not become brittle, and the coating film is moderately dissolved, so that a desired antifouling effect can be effectively exhibited.
  • Examples of the method for measuring Mw include gel permeation chromatography (GPC).
  • Copolymer A is a random copolymer of monomer (a) and monomer (b), an alternating copolymer, a periodic copolymer, or a block copolymer. May be.
  • the copolymer A can be obtained, for example, by polymerizing the monomer (a) and the monomer (b) in the presence of a polymerization initiator.
  • the same polymerization initiators as those exemplified above can be used alone or in combination of two or more.
  • the polymerization initiator AIBN and t-butylperoxy 2-ethylhexanoate are particularly preferable.
  • the molecular weight of the copolymer A can be adjusted by appropriately setting the amount of the polymerization initiator used.
  • Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.
  • the solution polymerization is particularly preferable because the copolymer A can be obtained simply and accurately.
  • an organic solvent may be used as necessary.
  • the organic solvent include aromatic hydrocarbon solvents such as xylene and toluene; aliphatic hydrocarbon solvents such as hexane and heptane; ester solvents such as ethyl acetate, butyl acetate, isobutyl acetate, and methoxypropyl acetate; isopropyl
  • examples include alcohol solvents such as alcohol and butyl alcohol; ether solvents such as dioxane, diethyl ether, and dibutyl ether; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone.
  • an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents can be used alone or in combination of two or more.
  • the reaction temperature in the polymerization reaction may be appropriately set according to the kind of the polymerization initiator and the like, and is usually 70 to 140 ° C., preferably 80 to 120 ° C.
  • the reaction time in the polymerization reaction may be appropriately set according to the reaction temperature and the like, and is usually about 4 to 8 hours.
  • the polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen gas or argon gas.
  • the content of the copolymer A in the composition of the present invention is not particularly limited, but is usually 20 to 70% by mass, preferably 40 to 60% by mass in the solid content of the composition of the present invention.
  • the content of the copolymer A is 20% by mass to 70% by mass, an appropriate coating film dissolution rate and coating film physical properties in seawater can be obtained, and stable surface renewability can be maintained over a long period of time. An antifouling effect can be exhibited effectively. Moreover, the recoat performance which was excellent in the coating film can be exhibited.
  • an antifouling agent B In addition to the copolymer A, an antifouling agent B, an elution regulator C, a plasticizer D, another resin E, and the like can be blended in the antifouling coating composition in the present invention, if necessary. . Thereby, the more outstanding antifouling effect can be exhibited.
  • the antifouling agent B is not particularly limited as long as it is a substance having a killing or repelling action against a marine fouling organism.
  • medical agent are mentioned.
  • inorganic agents include cuprous oxide, copper thiocyanate (generic name: rhodan copper), cupronickel, copper powder, and the like. Of these, cuprous oxide and rhodan copper are particularly preferred.
  • organic agents examples include organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), and zinc ethylenebisdithiocarbamate.
  • organic copper compounds such as 2-mercaptopyridine-N-oxide copper (generic name: copper pyrithione), 2-mercaptopyridine-N-oxide zinc (generic name: zinc pyrithione), and zinc ethylenebisdithiocarbamate.
  • zinc pyrithione, copper pyrithione, pyridine / triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dineb, cineine 211 and irgarol 1051 are preferable, and copper pyrithione, zinc pyrithione, pyridine / triphenylborane and betoxazine are more preferable. preferable.
  • Antifouling agents B include cuprous oxide, rhodan copper, zinc pyrithione, copper pyrithione, pyridine / triphenylborane, 4-isopropylpyridyl-diphenylmethylborane, betoxazine, dinebu, cineine 211 and irgarol 1051, trifluanid, diclofluuride. Cuprous oxide, copper pyrithione, zinc pyrithione, pyridine triphenylborane and betoxazine are more preferred. These antifouling agents can be used alone or in combination of two or more.
  • the content of the antifouling agent B in the composition of the present invention is not particularly limited, but is usually 0.1 to 75% by mass, preferably 1 to 60% by mass in the solid content of the composition of the present invention.
  • the content of the antifouling agent B is less than 0.1% by mass, a sufficient antifouling effect may not be obtained.
  • the content of the antifouling agent B exceeds 75% by mass, the formed coating film is fragile, and further, the adhesion to the coating film formation is weak and the function as the antifouling coating film cannot be sufficiently performed. .
  • ⁇ Elution regulator C examples include rosin, rosin derivatives and their metal salts, monocarboxylic acids and salts thereof, or alicyclic hydrocarbon resins.
  • Examples of the rosin include tall oil rosin, gum rosin, and wood rosin.
  • Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin.
  • As the metal salt of rosin and the metal salt of rosin derivative a reaction product of a metal compound and rosin can be used.
  • Examples of the metal salt of rosin include gum rosin zinc (or copper) salt, wood rosin zinc (or copper) salt, Examples include tall oil rosin zinc (or copper) salt.
  • rosin zinc (or copper) salt hydrogenated rosin zinc (or copper) salt, disproportionated rosin zinc (or copper) salt, maleated rosin zinc (or copper) salt, formylated rosin zinc (or copper) salt, polymerization Examples include rosin zinc (or copper) salt.
  • Examples of the monocarboxylic acid include fatty acids having about 5 to 30 carbon atoms, synthetic fatty acids, and naphthenic acids.
  • Examples of the monocarboxylic acid salt include a copper salt, a zinc salt, a magnesium salt, and a calcium salt.
  • Examples of the alicyclic hydrocarbon resin include quinton 1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and the like as commercially available products.
  • the composition of the present invention is at least one selected from the group consisting of rosin, rosin derivatives, and metal salts thereof, as the elution modifier C, in that it can impart moderate elution promoting properties to the composition of the present invention.
  • the content of the elution regulator C in the composition of the present invention is usually 1 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the copolymer A.
  • the elution control agent C is less than 1 part by weight, the effect of preventing the adhesion of bioaffouling organisms, particularly the effect of preventing the adhesion of bioaffouling organisms during the outfitting period cannot be expected.
  • the content of the elution regulator C exceeds 80 parts by weight, defects such as cracks and peeling are likely to occur in the coating film, and there is a possibility that the effect of preventing the adhesion of bioaffouling soiling organisms may not be exhibited sufficiently.
  • the content of the elution regulator C is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, based on 100 parts by weight of the copolymer A. 70, 75, and 80 parts by weight, and may be within the range of any two numerical values exemplified here.
  • plasticizer D By including the plasticizer D in the antifouling coating composition of the present invention, the plasticity of the composition can be improved, and as a result, a tough coating film can be suitably formed.
  • plasticizer D examples include phosphate esters such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate, phthalates such as dibutyl phthalate and dioctyl phthalate, and adipine such as dibutyl adipate and dioctyl adipate.
  • phosphate esters such as tricresyl phosphate, trioctyl phosphate and triphenyl phosphate
  • phthalates such as dibutyl phthalate and dioctyl phthalate
  • adipine such as dibutyl adipate and dioctyl adipate.
  • Acid esters dibutyl sebacate, sebacic acid esters such as dioctyl sebacate, epoxidized soybean oil, epoxidized oil such as epoxidized linseed oil, alkyl vinyl ether polymers such as methyl vinyl ether polymer, ethyl vinyl ether polymer, Polyalkylene glycols such as polyethylene glycol and polypropylene glycol, t-nonyl pentasulfide, petrolatum, polybutene, trimellitic acid tris (2-ethylhexyl), silicone oil , Liquid paraffin, chlorinated paraffin and the like. These can be used alone or in combination of two or more.
  • the content of the plasticizer D in the composition of the present invention is usually 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the copolymer A.
  • ⁇ Other resin E> By including the other resin E in the antifouling paint composition of the present invention, the cost can be reduced without impairing the effects of the present invention, and a synergistic effect with the physical properties of the resin E can be obtained. it can.
  • other resins E include metal carboxylate-containing polymers, trialkylsilyl ester group-containing polymers, other (meth) acrylic resins, alkyd resins, polyester resins, chlorinated rubber resins, and vinyl resins.
  • the metal carboxylate-containing polymer has at least one general formula (1) in the molecule.
  • -COO-MY (1) [Wherein M is a metal selected from Cu, Zn, Ca and Mg. Y is an organic acid residue. ]
  • the polymer etc. which have the metal carboxylate group represented by these are mentioned.
  • M is Cu or Zn
  • Y is a residue of an organic acid selected from naphthenic acid, rosin (derivatives) and (meth) acrylic acid. Is particularly preferred.
  • trialkylsilyl ester group-containing polymer examples include triisopropylsilyl (meth) acrylate and tributylsilyl (meth) acrylate.
  • the other resin E in the composition of the present invention can be contained within a range in which an appropriate coating dissolution rate and coating film physical properties in seawater are not impaired, and the content thereof is 100 weight of the copolymer A.
  • the amount is 1 to 200 parts by weight, preferably 20 to 100 parts by weight per part.
  • pigments, dyes, antifoaming agents, anti-sagging agents, dispersants, anti-settling agents, dehydrating agents, organic solvents, and the like can be added to the antifouling coating composition of the present invention as necessary.
  • pigment examples include zinc oxide, bengara, talc, titanium oxide, silica, calcium carbonate, barium sulfate, calcium oxide, and magnesium oxide. These can be used alone or in combination of two or more.
  • dyes include various organic dyes that are soluble in organic solvents.
  • antifoaming agents examples include silicone resin-based antifoaming agents and acrylic resin-based antifoaming agents.
  • anti-sagging agent examples include fatty acid amide wax and polyethylene oxide.
  • dehydrating agent examples include anhydrous gypsum, synthetic zeolite adsorbent, orthoesters, silicates such as tetraethoxysilane, isocyanates, and the like. These can be used alone or in combination of two or more.
  • organic solvent examples include those usually blended in antifouling paints such as aliphatic solvents, aromatic solvents, ketone solvents, ester solvents, ether solvents and the like. These can be used alone or in combination of two or more.
  • the antifouling paint composition of the present invention can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer A or the like using a disperser.
  • the mixed solution is preferably a solution obtained by dissolving or dispersing various materials such as the copolymer A in a solvent.
  • a solvent the thing similar to the said organic solvent can be used.
  • the disperser for example, one that can be used as a fine pulverizer can be suitably used.
  • a commercially available homomixer, sand mill, bead mill or the like can be used.
  • the mixed solution may be mixed and dispersed using a container provided with a stirrer to which glass beads for mixing and dispersing are added.
  • Antifouling treatment method, antifouling coating film , and coated article forms an antifouling coating film on the surface of a coating film-forming article using the antifouling coating composition.
  • the antifouling coating film gradually dissolves from the surface and the coating film surface is constantly renewed, thereby preventing the adhesion of chickenpox fouling organisms.
  • the antifouling effect can be exhibited continuously by overcoating the said composition.
  • Examples of the coating film formation include ships (particularly ship bottom), fishing equipment, underwater structures, and the like.
  • Examples of the fishery tools include aquaculture or stationary fishing nets, fishing net accessories such as floats and ropes used in the fishing nets, and the like.
  • Examples of the underwater structure include a power plant conduit, a bridge, a port facility, and the like.
  • the antifouling coating film can be formed by applying the antifouling coating composition to the surface (entirely or partly) of the coating film forming article.
  • Examples of the application method include brush coating, spraying, dipping, flow coating, and spin coating. These may be used alone or in combination of two or more. After application, dry.
  • the drying temperature may be room temperature. What is necessary is just to set drying time suitably according to the thickness etc. of a coating film.
  • the antifouling coating film of the present invention formed using the antifouling coating composition exhibits an appropriate coating film dissolution rate and coating film properties in seawater, and can maintain a stable surface renewability over a long period of time.
  • the desired antifouling effect can be effectively exhibited.
  • it has the advantage that the outstanding recoat performance of a coating film can be exhibited.
  • the thickness of the antifouling coating film may be set as appropriate according to the type of coating film formation, the navigation speed of the ship, the seawater temperature, and the like. For example, when the coating film forming object is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 500 ⁇ m, preferably 100 to 400 ⁇ m.
  • the antifouling coating film of the present invention has an appropriate hardness. That is, the antifouling coating film of the present invention has a hardness that does not cause coating film abnormality such as cold flow.
  • the coated article of the present invention has the antifouling coating film on the surface.
  • the coated product of the present invention may have the antifouling coating film on the entire surface or a part thereof. Since the coated product of the present invention has a coating film excellent in long-term stable surface renewability and recoatability by improving an appropriate coating film dissolution rate and coating film properties in seawater, In particular, it can be suitably used as ship bottoms), fishing equipment, underwater structures and the like.
  • the antifouling coating film when the antifouling coating film is formed on the ship bottom surface of the ship, the antifouling coating film gradually dissolves from the surface, and the coating film surface is constantly renewed, thereby preventing adhesion of waterpox fouling organisms. it can. Moreover, the hydrolysis rate of the antifouling coating film is suitably suppressed. Therefore, the ship can maintain antifouling performance for a long period of time. For example, even in a stationary state such as during berthing or during outfitting, there is little adhesion and accumulation of Minamata fouling organisms, and the antifouling effect can be exhibited for a long period of time.
  • the antifouling coating on the surface basically does not crack or peel off. Therefore, it is not necessary to perform another operation such as forming a coating film after the coating film is completely removed. Therefore, an antifouling coating film can be suitably formed by directly overcoating the antifouling coating film composition. Thereby, it is possible to easily and continuously maintain the antifouling performance at low cost.
  • the viscosity is a measured value at 25 ° C., and is a value determined by a B-type viscometer.
  • the weight average molecular weight (Mw) is a value (polystyrene conversion value) determined by GPC.
  • the conditions of GPC are as follows. Equipment: HLC-8220GPC manufactured by Tosoh Corporation Column: TSKgel SuperHZM-M (Tosoh Corporation) 2 flow rate: 0.35 mL / min Detector ... RI Column thermostatic chamber temperature: 40 ° C Eluent: THF The heating residue is a value obtained by heating at 125 ° C. for 1 hour.
  • the unit of the compounding quantity of each component in Table 1 is g.
  • Production Example 7 (Production of copolymer solution A-7) In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a dropping funnel, 50 g of PGM (propylene glycol methyl ether) and 130 g of xylene were charged, and then stirred at 100 ⁇ 2 ° C. in a nitrogen atmosphere.
  • PGM propylene glycol methyl ether
  • Production Example 8 (Production of copolymer solution A-8) To a four-necked flask equipped with a thermometer, reflux condenser, stirrer, and dropping funnel, 325 g of xylene and 100 g of n-butanol were added and heated to 100-110 ° C., and then t-butyl acrylate in a nitrogen atmosphere A mixed solution of 275 g of diphenylsilyl, 10 g of acrylic acid, 75 g of ethyl acrylate, 90 g of cyclohexyl methacrylate, and 12 g of azobisisobutyronitrile (initial addition) was added dropwise over 4 hours. The mixture was kept at 110 ° C.
  • the dropping funnel is changed to a decanter, 74.9 g of copper propionate, 91.1 g of naphthenic acid, and 50 g of deionized water are added, heated to 100 ° C., and the propionic acid and water produced by the reaction are removed.
  • the reaction end point was determined by quantifying acetic acid in the distillate solvent.
  • the obtained varnish had a heating residue of 50.3%, a weight average molecular weight of 8,000, and a viscosity of 185 cps / 25 ° C.
  • Comparative production examples 1 to 4 Using the organic solvent, monomer, and polymerization initiator shown in Table 1, a polymerization reaction was carried out in the same manner as in Production Example 1 to obtain copolymer solutions C-1 to C-4.
  • Table 1 shows the viscosity, heating residue, and Mw of each copolymer solution obtained.
  • Examples 1 to 19 and Comparative Examples 1 to 4 Manufacture of coating compositions
  • the components shown in Table 2 were blended in the proportions (mass%) shown in Table 2, and were mixed and dispersed with glass beads having a diameter of 1.5 to 2.5 mm to produce a coating composition.
  • Test Example 1 (Paint stability test) The coating compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 4 were sealed in 100 ml wide-mouth tin cans and stored in a 45 ° C. incubator for 3 months. Measured with a viscometer. Evaluation was performed by the following method.
  • ⁇ Viscosity change of the paint from 500 to 5000 mPa ⁇ s / 25 ° C (slightly thickened)
  • ⁇ Viscosity change of the paint is over 5000 mPa ⁇ s / 25 ° C.
  • Test Example 2 Coating adhesion test
  • the coating adhesion test was performed in accordance with the provisions of JIS K-5600-5-6. Specifically, the coating compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 4 were dried on a blasted tin plate (75 ⁇ 150 ⁇ 2 mm) with a dry coating thickness of about 100 ⁇ m. After being applied and dried at 40 ° C. for 1 day, an adhesion test was conducted. Evaluation was performed by the following method. The dried coating film was cut with a cutter with 11 vertical and horizontal scratches reaching the base (tinplate) in a grid pattern to make 100 squares of 2 mm square.
  • a cellophane tape (Nichiban Co., Ltd., tape width: 24 mm) is applied to the 100 squares so that no air bubbles enter, and one end of this tape is held in hand to quickly peel it off.
  • Test Example 3 Coating film flexibility test
  • the coating compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 4 were applied to a blasted tin plate (75 ⁇ 150 ⁇ 2 mm) so that the thickness as a dry coating film was about 100 ⁇ m. After drying at 0 ° C. for one day, the state of the folded coating film was confirmed by visual observation at 90 degrees. Evaluation was performed by the following method. :: Almost no cracks occurred ⁇ : Fine cracks occurred ⁇ : Large cracks occurred ⁇ : Part of the coating film was easily peeled Table 3 shows the results. From Table 3, it can be seen that the coating films formed using the coating compositions of the present invention (Examples 1 to 19) hardly generate cracks in the flexibility test. Further, in Example 5 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer was 80% by mass, the flexibility was slightly inferior compared to the other examples.
  • Test Example 4 (Rotary test) A rotating drum having a diameter of 515 mm and a height of 440 mm was attached to 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 the seawater constant and an automatic pH controller for keeping the pH of the seawater constant were attached. Two test plates were prepared according to the following method. First, a rust preventive coating film was formed by applying a rust preventive paint (vinyl A / C) on a hard PVC plate (75 ⁇ 150 ⁇ 1 mm) so that the thickness after drying was about 50 ⁇ m and drying.
  • a rust preventive paint (vinyl A / C)
  • the coating compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 4 were each applied on the rust-preventing coating film so that the thickness after drying was about 300 ⁇ m.
  • the obtained coated material was dried at 40 ° C. for 3 days to prepare a test plate having a dry coating film having a thickness of about 300 ⁇ m.
  • One of the produced test plates was fixed to the rotating drum of the rotating device of the apparatus so as to contact seawater, and the rotating drum was rotated at a speed of 20 knots. Meanwhile, the temperature of the seawater was kept at 25 ° C. and the pH was kept at 8.0 to 8.2, and the seawater was changed every week.
  • each test plate is measured with a laser focus displacement meter at the initial stage and every 3 months after the start of the test, and the dissolved film thickness is calculated from the difference ( ⁇ m / month ) In addition, the said measurement was performed for 24 months and the said coating-film melt
  • the coating films formed using the coating compositions of the present invention have a dissolution amount in seawater of about 3 to 5 ⁇ m per month (annual average). Recognize. Further, it can be seen that the coating film formed using the coating composition of the present invention is stably dissolved for a long period of time because the coating film dissolution rate is suppressed to some extent. And since the coating film formed using the coating composition of this invention is excellent in water resistance, and does not produce a crack, a hair crack, etc., it can maintain antifouling performance for a long period of time.
  • Example 5 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer was 80% by mass, the state of the coating film after 24 months was slightly inferior compared to the other examples.
  • the coating film formed using the coating composition of Comparative Example 3 cannot exhibit sufficient antifouling performance because the dissolution rate of the coating film is very small.
  • the coating film is too hard, the water resistance is poor, and abnormalities of the coating film such as cracks and peelings occur during the test.
  • the coating film formed using the coating composition of Comparative Example 4 cannot exhibit antifouling performance for a long time because the dissolution rate of the coating film in seawater increases with time.
  • Comparative Example 1 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer was 54% by mass, the coating state after 24 months was good, but the average coating after 12 to 24 months It was found that the dissolution amount was greatly reduced from the initial to 12 months, and the dissolution rate of the coating film was not stable. Furthermore, in Comparative Example 2 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer is 85% by mass, the coating state after 24 months is poor and the average coating amount dissolved after 12 to 24 months is low. It was found that the coating film dissolution rate was not stable because the coating film dissolution rate was larger than that of the initial to 12 months.
  • Test Example 5 Anti-fouling test
  • the coating compositions obtained in Examples 1 to 19 and Comparative Examples 1 to 4 were applied on both sides of a hard PVC plate (100 ⁇ 200 ⁇ 2 mm) so that the thickness as a dry coating film was about 200 ⁇ m.
  • the obtained coated material 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.
  • the test plate was immersed in 1.5 m below the sea surface in Owase City, Mie Prefecture, and the test plate was observed for fouling due to deposits for 24 months. Evaluation was performed by visually observing the state of the coating film surface, and was judged according to the following criteria.
  • ⁇ No fouling organisms such as shellfish and algae adhere, and there is almost no slime.
  • ⁇ Level at which fouling organisms such as shellfish and algae are not attached, and slime is thin (approx. ⁇ : No fouling organisms such as shellfish and algae adhere, but the slime is so thick that the surface of the coating cannot be seen and cannot be removed even if wiped with a brush.
  • ⁇ Level at which fouling organisms such as shellfish and algae adhere
  • Example 5 The results are shown in Table 5. From Table 5, it can be seen that the coating films formed using the coating compositions of the present invention (Examples 1 to 19) are free from the attachment of fouling organisms such as shellfish and algae after a 36-month test. However, in Examples 1 and 5 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer was 55% by mass or 80% by mass, the antifouling performance slightly decreased after 36 months. On the other hand, in the example in which this ratio is 60 to 70% by mass, the antifouling performance was not deteriorated even after 36 months. In Examples 7 to 8 and Examples 18 to 19 containing the metal carboxylate-containing copolymer, the antifouling performance slightly decreased after 36 months.
  • the antifouling performance was not deteriorated even after 36 months.
  • the coating film formed using the coating composition of Comparative Example 1 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer is 54% by mass has a thin slime deposit after 24 months. After 36 months, fouling organisms were attached.
  • Comparative Example 2 in which the proportion of t-butyldiphenylsilyl acrylate in the copolymer was 85% by mass a thin slime adhered after 24 months and a thick slime adhered after 36 months.
  • fouling organisms such as shellfish and algae adhered violently to the coating film formed using the coating compositions of Comparative Examples 3 and 4.

Abstract

La présente invention concerne une composition de revêtement anti-encrassement ayant une excellente stabilité au stockage à long terme. Elle concerne également un copolymère ayant une structure spécifique qui est utilisé pour former un film de revêtement anti-encrassement ayant une grande sécurité environnementale et capable de maintenir des performances stables de solubilité du film de revêtement et anti-encrassement sans provoquer de défauts du film de revêtement tels que des fissures dans l'eau de mer pendant une longue période. La présente invention concerne spécifiquement une composition de revêtement anti-encrassement qui contient un copolymère (A) obtenu en copolymérisant 55-80% en poids de monomère acrylate de tertiobutyldiphénylsilyle (a) et 20-45% en poids d'un monomère éthyléniquement insaturé (b) autre que le monomère (a), et dans laquelle le monomère (b) est composé d'au moins un type de monomère choisi dans le groupe comprenant le méthacrylate de méthyle, le (méth)acrylate de butyle et le (méth)acrylate de 2-méthoxyéthyle.
PCT/JP2011/066155 2010-08-25 2011-07-14 Composition de revêtement anti-encrassement, copolymère pour composition de revêtement anti-encrassement et article recouvert d'un revêtement ayant une surface fournie avec un film de revêtement anti-encrassement formé en utilisant ladite composition WO2012026237A1 (fr)

Priority Applications (2)

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CN201180040531.8A CN103080249B (zh) 2010-08-25 2011-07-14 防污涂料组合物、防污涂料组合物用共聚物、表面具有使用该组合物形成的防污涂膜的被涂物
SG2013006036A SG187606A1 (en) 2010-08-25 2011-07-14 Antifouling coating composition, copolymer for antifouling coating composition, and coated article having surface that is provided with antifouling coating film which is formed using the composition

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JP2010188583A JP4769331B1 (ja) 2010-08-25 2010-08-25 防汚塗料組成物、防汚塗料組成物用共重合体、該組成物を用いて形成される防汚塗膜を表面に有する塗装物
JP2010-188583 2010-08-25

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WO2014096102A1 (fr) 2012-12-19 2014-06-26 Jotun A/S Copolymère d'ester de silyle
WO2014175140A1 (fr) * 2013-04-24 2014-10-30 日東化成株式会社 Composition de peinture antisalissure, copolymère pour composition de peinture antisalissure et procédé de fabrication correspondant, et objet peint recouvert en surface d'un film de peinture antisalissure formé à partir de ladite composition
GB202107159D0 (en) 2021-03-23 2021-06-30 Jotun As Monitoring a vessel
US11111406B2 (en) 2018-07-03 2021-09-07 Nippon Paint Marine Coatings Co., Ltd. Copolymer and antifouling coating composition containing the same
WO2021180588A2 (fr) 2020-03-09 2021-09-16 Jotun A/S Robot de nettoyage de coque
WO2022200430A1 (fr) 2021-03-23 2022-09-29 Jotun A/S Surveillance de la propreté d'une surface immergée d'un objet stationnaire

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JP2016033210A (ja) * 2014-07-28 2016-03-10 日本曹達株式会社 コーティング剤
JP6494743B2 (ja) * 2015-03-23 2019-04-03 関西ペイント株式会社 防汚塗料組成物、及びそれによって被覆された物品
GB201703457D0 (en) * 2017-03-03 2017-04-19 Jotun As Composition
KR102526940B1 (ko) 2017-03-27 2023-05-02 미쯔비시 케미컬 주식회사 다공질막, 막 모듈, 수 처리 장치, 및 다공질막의 제조 방법
ES2928802T3 (es) * 2018-04-20 2022-11-22 Nitto Kasei Co Ltd Composición de recubrimiento antiincrustante
JP7287648B2 (ja) * 2019-03-15 2023-06-06 日東化成株式会社 防汚塗料組成物
CN111171678A (zh) * 2020-02-24 2020-05-19 中环海化(厦门)船舶智能涂料有限公司 一种含铜及铜合金粉的铜粉基接触型防污涂料及制备方法

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WO2014096102A1 (fr) 2012-12-19 2014-06-26 Jotun A/S Copolymère d'ester de silyle
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JPWO2014175140A1 (ja) * 2013-04-24 2017-02-23 日東化成株式会社 防汚塗料組成物、防汚塗料組成物用共重合体の製造方法、該組成物を用いて形成される防汚塗膜を表面に有する塗装物
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WO2014175140A1 (fr) * 2013-04-24 2014-10-30 日東化成株式会社 Composition de peinture antisalissure, copolymère pour composition de peinture antisalissure et procédé de fabrication correspondant, et objet peint recouvert en surface d'un film de peinture antisalissure formé à partir de ladite composition
CN105209561B (zh) * 2013-04-24 2019-02-12 日东化成株式会社 防污涂料组合物、防污涂料组合物用共聚物及其制造方法、表面具有使用该组合物形成的防污涂膜的涂装物
CN105209561A (zh) * 2013-04-24 2015-12-30 日东化成株式会社 防污涂料组合物、防污涂料组合物用共聚物及其制造方法、表面具有使用该组合物形成的防污涂膜的涂装物
US11111406B2 (en) 2018-07-03 2021-09-07 Nippon Paint Marine Coatings Co., Ltd. Copolymer and antifouling coating composition containing the same
EP3617240B1 (fr) * 2018-07-03 2021-12-01 Nippon Paint Marine Coatings Co., Ltd. Résine liante pour un revêtement antisalissure
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