Patent Description:
In the underwater of oceans, rivers, lakes, and the like, a large number of aquatic fouling organisms such as barnacles, sea squirts, tubeworms, common mussels, fresh-water mussel, Bugula neritina, green laver, sea lettuce and the like exist.

Conventionally, there has been a problem that above aquatic fouling organisms adhere onto the object which is used or exists in underwater, such as ships; fishing tools such as fishing nets (aquaculture nets, fixed nets, and the like), and fishing net accessories; jetties, tetrapods, port facilities, buoys, pipelines, bridges, water pipes of power plants, submarine bases, submarine oil drilling facilities, and other underwater structures. In particular, when ships and the like are immersed underwater for a long period of time, the afore-mentioned aquatic fouling organisms adhere and grow at the contacting portions with water. This would trigger decrease in ship speed, decrease in water flow rate and the like, resulting in significant economic and resource losses. Accordingly, in order to prevent the adhesion of aquatic fouling organisms, the application of antifouling coating has been considered to solve the problem.

Patent literature <NUM> discloses an antifouling coating composition containing a polyether having an alkoxysilylalkylcarbamate bonded to the terminal.

Patent literature <NUM> discloses an antifouling coating composition comprising a polysiloxane-based binder system comprising one or more polysiloxane components modified with hydrophilic oligomer/polymer moieties, and one or more biocides. The hydrophilic oligomer/polymer moieties comprise alkoxysilylalkyl groups bonded to the polysiloxane skeleton. In the cured paint coat, the polysiloxane-based binder system forms a binder matrix facilitating and controlling leaching of the biocide(s).

Patent literature <NUM> discloses an antifouling coating composition comprising a modified fluorosilane nano-polymer compound comprising perfluoropolyethylene (PFPE) modified at both terminals by hydrosilylation.

However, according to the study of the present inventor, it became apparent that the antifouling coating film formed by using the antifouling coating composition of patent literature <NUM> does not have good water resistance.

The present invention has been made in view of such circumstances, and provides an antifouling coating composition capable of forming an antifouling coating film having excellent water resistance.

According to the present invention, an antifouling coating composition is provided comprising an alkoxysilylalkyl terminal-modified polyether (A) and a bleeding oil (B); wherein, the alkoxysilylalkyl terminal-modified polyether(A) is structured by bonding an alkoxysilylalkyl group to an oxygen atom at a terminal of a polyether chain, and a content of the bleeding oil (B) is <NUM> to <NUM> parts by mass with respect to <NUM> parts by mass of the polyether (A).

The present inventors have conducted intensive studies to solve the afore-mentioned problems, and have found that the afore-mentioned problems can be solved by an antifouling coating composition containing an alkoxysilylalkyl terminal-modified polyether, thereby leading to completion of the present invention.

The antifouling coating composition of present invention includes an alkoxysilylalkyl terminal-modified polyether (A)which is structured by bonding an alkoxysilylalkyl group to an oxygen atom at a terminal of a polyether chain.

The polyether (A) is structured by bonding an alkoxysilylalkyl group to an oxygen atom at the terminal of a polyether chain, which is formed by alternately and repeatedly bonding an oxygen atom and an alkylene.

The polyether chain can be a linear chain or a branched chain. The polyether chain preferably has a repeating structure represented by the chemical formula (<NUM>).

When the polyether chain is linear, the alkoxysilylalkyl group is preferably bonded to both terminals, and when the polyether chain is a branched chain, the alkoxysilylalkyl group is preferably bonded to all the terminals. The alkoxysilylalkyl group is preferably a dialkoxysilylalkyl group or a trialkoxysilylalkyl group. The alkyl group is preferably a linear alkyl having <NUM> to <NUM> carbon atoms (preferably <NUM> to <NUM>), and is more preferably propyl. The alkoxysilylalkyl group is preferably represented by the chemical formula (<NUM>). <CHM>
<CHM>
[wherein, in general formula (<NUM>), * is a binding site, X is C1 to C6 linear or branched alkylene, m is <NUM> or <NUM>, n is <NUM> or <NUM>, a is <NUM> or <NUM>].

The alkoxysilylalkyl group binds to the oxygen atom at the terminal of the polyether chain at the site *. The number of carbons of X is, particularly for example,<NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and may be within the range between any two of the numerical values exemplified here.

As a commercially available polyether(A), MS POLYMER S203H, MS POLYMER S303H, MS POLYMER S810, MS POLYMER S202, MS POLYMER SAX220, MS POLYMER SAX400, MS POLYMER SAX510, MS POLYMER SAX530, MS POLYMER SAX580, MS POLYMER SAX590 (all available from Kaneka Corporation), GENIOSIL STD-E15, GENIOSIL STD-E35, GENIOSIL STD-E10, GENIOSIL STD-E30, GENIOSIL XB <NUM>, GENIOSIL XM20 (all available from Wacker Chemie AG), SPUR+1015LM, SPUR+<NUM>, SPUR+3100HM, SPUR+3200HM (all available from Momentive Performance Material, Inc. ), EXCESTAR ES-S2410, EXCESTAR ES-S2420, EXCESTAR ES-S3430, EXCESTAR ES-S3630 (all available from AGC Company) can be mentioned.

The polyether (A) undergoes a hydrolysis and condensation reaction in the presence of moisture (which may be moisture in the air) to form rubber. Specifically, the hydrolyzed alkoxysilyl group in the polyether (A) undergoes a condensation reaction to form a polyether rubber, which forms a film.

The reaction temperature of such condensation reaction is usually <NUM> or lower, preferably <NUM>.

The weight average molecular weight of the polyether (A) is preferably <NUM> to <NUM>,<NUM>,<NUM>, more preferably <NUM>,<NUM> to <NUM>,<NUM>, and even more preferably <NUM>,<NUM> to <NUM>,<NUM>. Two or more kinds having different weight average molecular weights can be used in combination.

A bleeding oil (B) is a component which bleeds out at the surface of the coating film formed with the composition of the present invention, thereby providing antifouling properties.

As the bleeding oil (B), in particular, silicone oil, graft copolymer including acrylic polymer and dimethylpolysiloxane, perfluorinated polyether oil, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hardened castor oil and the like can be mentioned. One of these compounds can be used alone, or two or more of these compounds can be used in combination.

As the silicone oil, silicone oil which have been conventionally used for a silicone rubber based antifouling coating can be used.

The viscosity of the bleeding oil is preferably <NUM> to <NUM>,<NUM><NUM>·s, more preferably <NUM> to <NUM>,<NUM><NUM>·s.

The silicone oil can be categorized into straight silicone oil and modified silicone oil. Here, in the composition of the present invention, either one of these can be used.

As the straight silicone oil, for example, dimethyl silicone oil, methylphenyl silicone oil, diphenyl silicone oil, methylhydrogen silicone oil and the like can be mentioned. Any of these straight silicone oils can be used. Here, methylphenyl silicone oil and the like are preferable.

As a commercially available straight silicone oil, KF-<NUM>, KF-<NUM>, KF-<NUM>, KF-<NUM>, KF-<NUM>, KF-<NUM>, HIVAC-F-<NUM>, X-<NUM>-<NUM>, KF-<NUM>, (all available from Shin-Etsu Chemical Co. ); DOWSIL 200Fluid, DOWSIL 510Fluid, DOWSIL SH510Fluid, DOWSIL SH550Fluid, DOWSIL 550Fluid, DOWSIL SH710 Fluid (all available from DuPont Toray Specialty Materials K. ) Bluesil FLD47V100, Bluesil FLD47V500, Bluesil FLD47V1000, Bluesil FLD550 (all available from Bluestar Silicon Materials Co. ); TSF451, TSF4300, TSF437, TSF400, TSF401, TSF484, TSF433, TSF431 (all available from Momentive Performance Material, Inc. ) and the like can be mentioned.

Modified silicone oil can be categorized as alkyl aralkyl modification, amino modification, carboxyl modification, epoxy modification, polyether modification, alkyl aralkyl·polyether modification, polyglycoside modification, polyglycerin modification, polyglycerin·alkyl modification, carbinol modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, higher fatty acid amide modification, hydrophilic specialized modification, higher alkoxy modification, higher fatty acid containing modification, fluorine modification and the like, depending on the type of the modification. Any of these modified silicone oil can be used. Particularly, silicone oil of amino modification, alkyl aralkyl modification, epoxy modification, polyether modification or alkyl aralkyl·polyether modification and the like are preferable.

As a commercially available alkyl aralkyl modified silicone oil, KF-<NUM>, KF-<NUM>, KF-<NUM>, KF-7235B, X-<NUM>-<NUM>, X-<NUM>-<NUM> (all available from Shin-Etsu Chemical Co. ); TSF4421, XF42-<NUM>, XF42-B3629 (all available from Momentive Performance Material, Inc. ) can be mentioned.

As a commercially available amino modified silicone oil, DOWSIL BY <NUM>-<NUM> Fluid, DOWSIL <NUM>-<NUM> U Fluid (all available from The Dow Chemical Company); FZ3712, AFL-<NUM> (all available from ENEOS NUC Corporation); KF-<NUM>, KF-<NUM>, KF-<NUM>, X-<NUM>-<NUM>, KF-<NUM>, X-<NUM>-<NUM>, KF-<NUM> (all available from Shin-Etsu Chemical Co. ); TSF4700, TSF4701 (all available from Momentive Performance Material, Inc. ) can be mentioned.

As a commercially available carboxyl modified silicone oil, DOWSIL BY <NUM>-<NUM> Fluid (available from The Dow Chemical Company); FXZ3707 (available from ENEOS NUC Corporation); X-<NUM>-3701E, X-<NUM>-<NUM>, X-<NUM>-162C (all available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available epoxy modified silicone oil, DOWSIL BY <NUM>-<NUM> Fluid, DOWSIL BY <NUM>-<NUM> Fluid (all available from The Dow Chemical Company); L-<NUM>, T-<NUM> (all available from ENEOS NUC Corporation); KF-<NUM>, KF-<NUM>, KF-<NUM> (all available from Shin-Etsu Chemical Co. ); TSF4730, YF3965 (all available from Momentive Performance Material, Inc. ) can be mentioned.

As a commercially available polyether modified silicone oil, DOWSIL SH28 Paint Additive, DOWSIL SF8428 Fluid, DOWSIL SF8427 Fluid, DOWSIL FZ-<NUM>, DOWSIL FZ-<NUM>, DOWSIL FZ-<NUM>, DOWSIL FZ-<NUM>, DOWSIL BY <NUM>-<NUM> (all available from The Dow Chemical Company); KF-<NUM>, KF-<NUM>, KF-<NUM>, KF-<NUM>, KF-<NUM>, X-<NUM>-<NUM>, X-<NUM>-<NUM> (available from Shin-Etsu Chemical Co. ); TSF4440, TSF4441, TSF4445, TSF4446, TSF4452, TSF4460 (all available from Momentive Performance Material, Inc. ); BELSIL OW <NUM>, BELSIL DMC <NUM>, BELSIL DMC <NUM> (all available from Wacker Chemie AG) can be mentioned.

As a commercially available alkyl aralkyl·polyether modified silicone oil, DOWSIL SF8416 Fluid (available from The Dow Chemical Company); X-<NUM>-<NUM>, X-<NUM>-<NUM> (all available from Shin-Etsu Chemical Co. ); TSF4450 (available from Momentive Performance Material, Inc. ) can be mentioned.

As a commercially available polyglycoside modified silicone oil, BELSIL SPG <NUM> VP (available from Wacker Chemie AG) can be mentioned.

As a commercially available polyglycoside alkyl modified silicone oil, BELSIL WO <NUM> (available from Wacker Chemie AG) can be mentioned.

As a commercially available polyglycerin modified silicone oil, KF-<NUM>, KF-<NUM>, KF-<NUM> (all available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available polyglycerin·alkyl modified silicone oil, KF-<NUM> (available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available carbinol modified silicone oil, X-<NUM>-<NUM>, X-<NUM>-160AS, KF-<NUM>, KF-<NUM>, KF-<NUM>, X-<NUM>-170DX, X-<NUM>-<NUM> (all available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available higher fatty acid ester modified silicone oil, X-<NUM>-<NUM> (available from Shin-Etsu Chemical Co. ); TSF410, TSF411 (all available from Momentive Performance Material, Inc. ) can be mentioned. As a commercially available higher fatty acid amide modified silicone oil, KF-<NUM> (available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available graft copolymer including acrylic polymer and dimethylpolysiloxane, KP-<NUM>, KP-<NUM>, KP-<NUM>, KP-<NUM>, KP-<NUM>, KP-<NUM> (all available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available fluorine modified silicone oil, FL-<NUM>, X-<NUM>-<NUM>, FL-<NUM> (all available from Shin-Etsu Chemical Co. ) can be mentioned.

As a commercially available perfluorinated polyether oil, FLUOROLINK E10-H, FLUOROLINK 5147X, FLUOROLINK S10, FLUOROLINK MD700, FLUOROLINK AD1700, FLUOROLINK P54, FLUOROLINK TLS <NUM>, FLUOROLINK F10, FLUOROLINK P56, FLUOROLINK A10P, FLUOROLINK PA100E, FOMBLIN HC/<NUM>, FOMBLIN HC/<NUM>, FOMBLIN HC/R, FOMBLIN HC/OH-<NUM>, FOMBLIN HC/SA-<NUM> (all available from Solvay SA) can be mentioned.

As a commercially available polyoxyethylene fatty acid ester, polyoxyethylene oleate (product name: NIKKOL MYO-6V, available from Nikko Chemicals Co. ), polyoxyethylene laurate (product name: NIKKOL MYL-<NUM>, available from Nikko Chemicals Co. ), dioleate PEG-<NUM> (product name: EMALEX DEG-di-O, available from Nihon Emulsion Co. ), dioleate PEG-<NUM> (product name: EMALEX 300di-O, available from Nihon Emulsion Co. ), polyoxyethylene (<NUM>) lanolin (product name: Aqualose L30, available from Croda International plc), polyoxyethylene (<NUM>) lanolin (product name: PEG-75Flake, available from NK Chemical), polyoxyethylene (<NUM>) castor oil (product name NIKKOL CO-<NUM>, available from Nikko Chemicals Co. ), hydrogenated polyoxyethylene (<NUM>) castor oil (product name: NIKKOL CO-<NUM>, available from Nikko Chemicals Co. ) can be mentioned.

The content of the above bleeding oil (B) in the composition of the present invention is <NUM> to <NUM> parts by mass with respect to <NUM> parts by mass of the above polyether (A) and preferably <NUM> to <NUM> parts by mass. When the content of the bleeding oil (B) is less than <NUM> parts by mass, the antifouling effect may not be exhibited for a long period of time. When the content of the bleeding oil (B) is more than <NUM> parts by mass, the strength of the obtained coating film may decrease, and the antifouling effect may not be maintained.

The antifouling coating composition of the present invention may contain a curing catalyst, filler, an antifouling agent, a solvent, a coating film-forming component other than the polyether (A), a plasticizer, a release modifier, a pigment such as a colored pigment, a constitutional pigment, and an anticorrosion pigment, a dehydrating agent, an anti-sagging agent, a silane coupling agent as necessary.

Examples of the curing catalyst include metal curing catalysts:.

These can be used alone, or two or more of these can be used in combination.

The composition of the present invention can further contain inorganic filler and/or organic filler for the purpose of controlling flowability and thixotropic property, or for the purpose of improving mechanical strength of the coating film.

As the inorganic filler, for example, calcium carbonate, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, sedimented barium sulfate, barite powder, titanium dioxide, calcined kaolin, calcined kaolin surface-treated with aminosilane, diatom earth, aluminum hydroxide, fine-grained alumina, magnesium oxide, magnesium carbonate, zinc oxide, zinc carbonate, red oxide, iron oxide, fumed metal oxide, quartz powder, talc, zeolite, bentonite, glass fiber, carbon fiber, fine mica powder, fused silica powder, fine silica powder, fumed silica, precipitated silica, wet silica, dry silica, or hydrophobic fumed silica obtained by treating these with organosilicon compound such as methyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, hexamethylcyclotrisiloxane and okramethylcyclotetrasiloxane, phthalocyanine blue, carbon black and the like can be mentioned.

As the organic filler for example, powder of synthetic resin such as polypropylene, polyvinylchloride, polystyrene, acryl silicone and the like can be mentioned.

Inorganic filler and/or organic filler can be used alone, or two or more of these can be used in combination.

The content of the inorganic filler in the composition of the present invention is usually from <NUM> to <NUM> parts by mass with respect to <NUM> parts by mass of polyether (A), and preferably from <NUM> to <NUM> parts by mass. This content may be, for example, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, <NUM>, and may be within the range between any two of the numerical values exemplified here.

The composition of the present invention can further contain an antifouling agent. As the antifouling agent, for example, inorganic agent and organic agent can be mentioned.

As the inorganic agent, for example, cuprous oxide, cuprous thiocyanate (generic name: copper rhodanide), copper powder, copper carbonate, copper chloride, copper-nickel alloy, brass, silver chloride, silver nitrate, and the like can be mentioned. Among these, cuprous oxide and copper rhodanide are preferable. Cuprous oxide surface-treated with glycerin, sucrose, stearic acid, lauric acid, rishitin, mineral oil and the like is more preferred in terms of long-term stability during storage.

As the organic agent, for example, copper <NUM>-mercaptopyridine-N-oxide (generic name: copper pyrithione), zinc <NUM>-mercaptopyridine-N-oxide (generic name: zinc pyrithione), zinc ethylenebis dithiocarbamate (generic name: Zineb), zinc dimethyldithiocarbamate (generic name: Ziram), a complex compound of manganese N,N'-ethylenebis (dithiocarbamate) and zinc N,N'-ethylenebis (dithiocarbamate) (generic name: Mancozeb), pyridine-triphenylborane, <NUM>,<NUM>-dichloro-<NUM>-n-octyl-<NUM>-isothiazolone (generic name: SEA-NINE <NUM>), <NUM>,<NUM>-dichlorophenyl-N-N-dimethylurea (generic name: Diuron), <NUM>-methylthio-<NUM>-t-butylamino-<NUM>-cyclopropylamino-s-triazine (generic name: Irgarol <NUM>), <NUM>-(p-chlorophenyl)-<NUM>-cyano-<NUM>-bromo-<NUM>-trifluoromethylpyrrole (generic name: Tralopyril), (±) <NUM>-[<NUM>-(<NUM>,<NUM>-dimethylphenyl)ethyl]-<NUM>-imidazole (generic name: Medetomidine), N-{[dichloro(fluoro)methyl]sulfanyl}-N',N'-dimethyl-N-p-tris sulfamide (generic name: Tolylfluanid), N-(dichlorofluoromethylthio)-N-(dimethylaminosulfonyl)aniline (generic name: Dichlofluanid), N-[(<NUM>-hydroxy-<NUM>-methoxyphenyl)methyl]-<NUM>-methyl-<NUM>-nonenamide (generic name: Capsaicin), <NUM>,<NUM>-dihydro-<NUM>,<NUM>-dioxonaphto[<NUM>,<NUM>-b]-<NUM>,<NUM>-dithi-ine-<NUM>,<NUM>-dicarbonitrile (generic name: Dithianon), Avermectin Bla, Avermectin Blb and the like can be mentioned. One or two or more of these antifouling agents can be used in combination.

The composition of the present invention is usually dissolved or dispersed in organic solvent (preferably an organic solvent). Accordingly, the composition can be suitably used as coating. As the solvent, for example, xylene, toluene, hexane, heptane, octane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, <NUM>-ethoxyethyl acetate, propanol, isoamyl alcohol, n-butanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol tertiary butyl ether, ethylene glycol monobutyl ether, <NUM>-methoxy-<NUM>-methyl-<NUM>-butanol, ethylene glycol monopropyl ether, ethylene glycol phenyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, ethylene glycol, diethylene glycol, propylene glycol, decamethylcyclopentasiloxane, octamethyltrisiloxane, aromatic hydrocarbon, aliphatic hydrocarbon, white spirit, alicyclic hydrocarbon based solvent, naphthene based hydrocarbon, mineral spirit, aliphatic solvent naphtha, isoparaffin, normal paraffin, glycol-based ester and the like can be mentioned.

These organic solvents can be used alone, or two or more of these solvents can be used in combination.

Examples of the coating film-forming components other than the polyether (A) include silicone modified epoxy resins, acrylic resins, trialkylsilyl (meth) acrylate copolymer resins, polyester resins, polyester polyol resins, biodegradable bio-polyester resins, epoxy resins, maleic acid copolymer resins, silicone modified acrylic resins, fluoropolymers, polybutene resins, urethane resins, urethane rubbers, polyester-modified silicones, silicone rubbers, nitrile rubbers, isoprene rubbers, natural rubbers, polyamide resins, polybutadiene resins, both terminal hydroxyl groups polybutadiene, styrene butadiene copolymer resins, ethylene vinyl acetate copolymer resins, petroleum resins, alkyd resins, vinyl ether-vinyl chloride copolymer resins, vinyl chloride resins, chloride rubber, chlorinated polyolefin resin. These can be used alone, or two or more of these can be used in combination.

As the plasticizer, for example, phosphate esters, phthalate esters, adipate esters, sebacate esters, epoxidized soybean oil, alkyl vinyl ether polymer, polyalkylene glycols, t-nonyl pentasulfide, vaseline, polybutene, tris(<NUM>-ethylhexyl) trimellitate, silicone oil, chlorinated paraffin, paraffin and the like can be mentioned. These can be used alone, or two or more of these can be used in combination. The content of the plasticizer is usually approximately <NUM> parts by mass or less with respect to <NUM> parts by mass of the polyether (A), preferably <NUM> to <NUM> parts by mass.

As the release modifier, for example, monocarboxylic acid, and salts thereof such as rosin, rosin derivative, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, versatic acid, trimethyl isobutenyl cyclohexene carboxylic acid, and metal salts thereof, or the alicyclic hydrocarbon resin, coumaron resin can be mentioned. These can be used alone, or two or more of these can be used in combination.

As the rosin derivative, hydrogenated rosin, disproportionated rosin, maleic acid modified rosin, formylated rosin, polymerized rosin, rosin ester, hydrogenated rosin ester, and the like can be exemplified.

Among these, rosin, rosin derivative, naphthenic acid, versatic acid, trimethyl isobutenyl cyclohexene carboxylic acid or metal salts thereof are preferable.

As the dehydrating agent, zeolite, gypsum anhydride, calcium sulfate hemihydrate (NP3D, manufactured by Noritake Company), tetramethoxy silane, tetraethoxy silane, methyl trimethoxy silane, vinyl trimethoxy silane, methyl triisopropenoxy silane, ethyl triisopropenoxy silane, vinyl triisopropenoxy silane and the like can be mentioned. These can be used alone, or two or more of these can be used in combination.

Examples of the anti-sagging agent include fatty acid amide, polyethylene oxide, silica, fumed silica. These can be used alone, or two or more of these can be used in combination.

The antifouling coating composition of the present invention can be prepared by mixing and dispersing the polyether (A), and if necessary, bleeding oil (B), cross-linking agent, inorganic filler, antifouling agent, organic solvent, plasticizer, dehydrating agent and the like, using high-speed disperser such as paint shaker, mixer, and dissolver; ultrasonic homogenizer, ball mill, planetary ball mill, pearl mill, wet jet mill, and grinder.

The antifouling coating composition of the present invention can be provided as one-pack coating or two or more multi-pack coating. When the composition is provided as the two or more multi-pack coating, each of the mixture containing one or a plurality of components is packaged and stored in a separate container. For example, when a mixture containing one or more types of the polyether (A) is designated as liquid a, and a mixture containing one or more types of curing catalyst is designated as liquid b, the antifouling coating composition of the present invention is prepared by mixing liquid a and liquid b.

The method for antifouling treatment of the present invention is characterized in that the afore-mentioned antifouling coating composition is used to form an antifouling coating film on the surface of an object that is subjected to coating.

Since curing of the coating composition of the present invention proceed gradually by absorbing moisture in air, it is preferable to prepare the composition just before use and apply the composition as soon as possible after preparation.

As the object that is subjected to coating, ships; fishing tools such as fishing nets (aquaculture nets, fixed nets and the like), fishing net accessories; jetties, tetrapods, port facilities, buoys, pipelines, bridges, water pipes of power plants, submarine bases, submarine oil drilling facilities, and other underwater structures and the like can be mentioned.

The antifouling coating film of the present invention can be formed by applying the antifouling coating composition on the surface (entirely or partially) of the object that is subjected to coating.

Application of the antifouling coating composition can be performed by applying the composition one time, or by overcoating the composition by plurality of times by known coating method.

Examples of the coating method include brush coating, spray coating, dipping, flow coating, and spin coating. These coating methods can be employed singly or in combination.

After the coating, the curing proceeds by absorbing moisture (moisture in air for example), thereby forming the antifouling coating film of the present invention. Curing proceeds also at ambient temperature (<NUM>). Here, for example, curing can be accelerated by heating up to approximately <NUM>.

The antifouling coating film can be formed by using the composition of the present invention.

The thickness of the antifouling coating film can be suitably selected depending on the type of the object that is subjected to coating. Usually, a coating film of <NUM> to <NUM>, preferably <NUM> to <NUM> is applied per one coating, and it is appropriate that the coating film is applied a plurality of times to achieve a film thickness of <NUM> to <NUM> after curing.

The coated object of the present invention has the antifouling coating film on its surface. The coated object of the invention can have the antifouling coating film on its entire surface, or on its partial surface.

The coated object of the present invention can exhibit the antifouling effect continuously. Accordingly, the coated object can be suitably used as the ship (in particular, ship bottom), fishing tools, structures submerged in seawater, and the like.

Examples and the like are provided hereinafter, and further clarify characteristics of the present invention. The present invention, however, is not limited to these Examples and the like.

To a four-necked flask equipped with a thermometer, a cooler, a stirrer, and a dropping funnel, <NUM> of xylene (containing ethylbenzene) and <NUM> of n-butanol (initial solvent) was charged, followed by introduction of nitrogen gas, and then the solvent was stirred while maintaining at <NUM>. Then, a mixture of <NUM> of <NUM>-ethylhexyl acrylate, <NUM> of isononyl acrylate, <NUM> of isodecyl acrylate, <NUM> of <NUM>-propyl heptyl acrylate, <NUM> of isostearyl acrylate, <NUM> of n-butyl acrylate, <NUM> of lauryl acrylate, <NUM> of lauryl methacrylate, <NUM> of mixture of lauryl methacrylate and tridecyl methacrylate, <NUM> of methyl methacrylate, <NUM> of styrene, <NUM> of vinyl acetate, <NUM> of tetrahydrofurfuryl acrylate, <NUM> of <NUM>-methoxyethyl acrylate, <NUM> of <NUM>-methoxyethyl methacrylate, <NUM> of methoxypolyethylene glycol methacrylate, <NUM> of <NUM>-(<NUM>-ethoxyethoxy) ethyl acrylate, <NUM> of triisopropylsilyl methacrylate, <NUM> of triisopropylsilyl acrylate, <NUM> of silicone modified acrylate(Mn=<NUM>), <NUM> of silicone modified acrylate(Mn= <NUM>), <NUM> of <NUM>-mercaptopropyl trimethoxysilane, <NUM> of <NUM>,<NUM>,<NUM>,<NUM>-tetramethylbutylperoxy-<NUM>-ethylhexanoate(initial addition), <NUM> of xylene(containing ethylbenzene) was added dropwise thereto over <NUM> hours while maintaining the temperature at <NUM>. Then, after stirring at <NUM> for <NUM> hour, <NUM> of <NUM>,<NUM>,<NUM>,<NUM> - tetramethylbutylperoxy-<NUM>-ethylhexanoate (late addition) was added three times every hour. After stirring for <NUM> hours at the same temperature, <NUM> of xylene (containing ethylbenzene) (diluting solvent) was added, and the mixture was cooled to room temperature to obtain copolymer solution P1. The heating residue and Mw of P1 are shown in Table <NUM>.

Using the monomers, polymerization initiators, and solvents shown in Table <NUM>, the polymerization reaction was carried out in the same manner as in Production Example <NUM> under each reaction temperature condition to obtain copolymer solutions P2, P3. Table <NUM> shows the heating residue and Mw of P2, P3. The numerical value in the table is mass%.

The antifouling coating compositions of the examples and comparative examples were prepared according to the formulations shown in Table <NUM> to Table <NUM>. Examples <NUM>, <NUM>, <NUM>, <NUM> are reference examples.

The details of the antifouling agents and other additives in the above tables are as follows.

Water resistance test and antifouling tests were conducted on the antifouling coating compositions of the Examples and Comparative Examples according to the following methods. The two-pack antifouling coating compositions were mixed just before testing. The test results are shown in Table <NUM> to Table <NUM>.

As shown in the above table, the coating films formed using the antifouling coating compositions of all the Examples had excellent water resistance and antifouling properties. On the other hand, the coating films formed using the antifouling coating compositions of the Comparative Examples did not have good water resistance.

Epoxy based primer HEMPADUR QUATTRO XO <NUM> (available from HEMPEL A/S) was applied on a hard vinyl chloride plate (<NUM> x <NUM> x <NUM>) so that the dried film thickness would be <NUM>. Subsequently, the sample for test was applied thereon so that the thickness of the dried coating film would be <NUM>, followed by curing at room temperature for <NUM> hours, thereby obtaining the test plate. An X-shaped cut that reaches the antifouling coating was made using a cutter, and then the water resistance was evaluated for <NUM> months by immersing in seawater at <NUM>.

Epoxy based primer HEMPADUR QUATTRO XO <NUM> (available from HEMPEL A/S) was applied on a hard vinyl chloride plate (<NUM> x <NUM> x <NUM>) so that the dried film thickness would be <NUM>. Further, silicone based tie coat HEMPASIL NEXUS X-TEND <NUM> (available from HEMPEL A/S) was applied so that the dried film thickness would be <NUM>. Subsequently, the sample for test was applied thereon so that the thickness of the dried coating film would be <NUM>, followed by curing at room temperature for <NUM> days. The test plate was immersed at <NUM> below sea level in Owase Bay for <NUM> months, and the test plate fouling due to attached objects was examined after <NUM> months, and <NUM> months.

Claim 1:
An antifouling coating composition comprising an alkoxysilylalkyl terminal-modified polyether (A) and a bleeding oil (B); wherein
the alkoxysilylalkyl terminal-modified polyether (A) is structured by bonding an alkoxysilylalkyl group to an oxygen atom at a terminal of a polyether chain, and
a content of the bleeding oil (B) is <NUM> to <NUM> parts by mass with respect to <NUM> parts by mass of the polyether (A).