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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
• • 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
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
• • 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
  • C09D5/1687—Use of special additives
• • 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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B63—SHIPS OR OTHER WATERBORNE VESSELS; RELATED EQUIPMENT
  • B63B—SHIPS OR OTHER WATERBORNE VESSELS; EQUIPMENT FOR SHIPPING 
  • B63B59/00—Hull protection specially adapted for vessels; Cleaning devices specially adapted for vessels
  • B63B59/04—Preventing hull fouling
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
  • C08K2003/3045—Sulfates

Definitions

• the present invention relates to an antifouling coating composition and a coated object having, on its surface, an antifouling coating film formed using the composition.
• Aquatic fouling organisms such as barnacles, tubeworms, common mussels, Bugula neritina, sea squirts, green laver, sea lettuce, and slimes attach to ships (especially ship bottoms), fishing tools such as fishing nets and fishing net accessories, and structures submerged in seawater such as power plant aqueducts, leading to dysfunction, impaired appearance, and other problems of the ships and so on.
• Patent Literature 1 Since a conventional organic tin-containing copolymer has been banned, triorganosilyl group-containing copolymers which have low toxicity and are environment-friendly have been developed, and have been used for antifouling coating materials (Patent Literature 1).
• the antifouling coating material can exert the long-term stable dissolution of the coating film, the coating film after long-term soaking in seawater tends to cause coating film defects such as a crack.
• various proposals have been presented, including blending the triorganosilyl ester-containing copolymer with an additional resin, a plasticizer, other various additives, etc.
• the additional resin-blended antifouling coating material has improved coating film properties regarding a crack, etc., to some degree, the material cannot achieve the long-term stable dissolution of the coating film any more (Patent Literatures 3 to 6).
• the plasticizer-blended antifouling coating material hardly exerts an advantageous effect.
• the coating film properties regarding a crack, etc. are improved to some degree.
• the coating film is fragile and the dissolution of the coating film becomes too large.
• the antifouling coating material blended with fiber as another additive can produce an effect of preventing a coating film defect such as a crack.
• the dissolution of the coating film is decreased such that the long-term stable dissolution of the coating film cannot be achieved (Patent Literature 7).
• An aspect of the present invention provides an antifouling coating composition
• R 1 is a hydrogen atom or a methyl group; and R 2 , R 3 , and R 4 are the same or different from each other and each represents a C 3-6 alkyl group branched at an ⁇ -position or a phenyl group) and (b) an ethylenically unsaturated monomer copolymerizable with the triorganosilyl(meth)acrylate monomer; and (B) calcium sulfate hydrate.
• the present inventor have addressed the problems of developing an antifouling coating composition that can maintain the stable coating film dissolution property and antifouling performance of a coating film without causing coating film defects such as a crack during long-term seawater treatment.
• the present invention provides the antifouling coating compositions having excellent storage stability and can produce an antifouling coating film with increased antifouling performance maintained for an extended period of time.
• An antifouling coating composition comprises: (A) a triorganosilyl ester-containing copolymer obtained from a mixture of (a) a triorganosilyl(meth)acrylate monomer represented by general formula (1):
• R 1 is a hydrogen atom or a methyl group; and R 2 , R 3 , and R 4 are the same or different from each other and each represents a C 3-6 alkyl group branched at the ⁇ -position or a phenyl group) and (b) an ethylenically unsaturated monomer copolymerizable with the triorganosilyl(meth)acrylate monomer; and (B) calcium sulfate hydrate.
• a copolymer (A) of the present invention is produced by copolymerization of the monomer (a) and the monomer (b). The following specifically describes methods of synthesizing the monomer (a), the monomer (b), and the copolymer (A).
• Examples of the C 3-6 alkyl group branched at the ⁇ -position include isopropyl group, s-butyl group, t-butyl group, 1-ethylpropyl group, 1-methylbutyl group, 1-methylpentyl group, 1,1-dimethylpropyl group, 1,1-dimethylbutyl group, and thexyl group.
• the invention enables formation of an antifouling coating film which is unlikely to cause coating film defects and is excellent in water resistance by selecting specific groups for R 2 , R 3 , and R 4 .
• R 2 , R 3 , and R 4 are the same or different from each other, and are each preferably isopropyl group, s-butyl group, t-butyl group, or phenyl group, and more preferably isopropyl group.
• Examples of the monomer (a) include triisopropylsilyl(meth)acrylate, tri-s-butylsilyl(meth)acrylate, triphenylsilyl(meth)acrylate, diisopropyl-s-butylsilyl(meth)acrylate, diisopropyl-t-butylsilyl(meth)acrylate, diisopropylthexylsilyl(meth)acrylate, diisopropylphenylsilyl(meth)acrylate, isopropyl-di-s-butylsilyl(meth)acrylate, isopropyl-diphenylsilyl(meth)acrylate, diphenylthexlysilyl(meth)acrylate, and t-butyldiphenylsilyl(meth)acrylate.
• triisopropylsilyl(meth)acrylate tri-s-butylsilyl(meth)acrylate, and t-butyldiphenylsilyl(meth)acrylate are preferred, and triisopropylsilyl(meth)acrylate is more preferred.
• triorganosilyl(meth)acrylate monomers are used singly or in combination.
• the monomer (b) is an ethylenically unsaturated monomer copolymerizable with the monomer (a).
• the monomer (b) include: (meth)acrylic esters such as methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, t-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, lauryl(meth)acrylate, 2-methoxyethyl acrylate, 2-methoxypropyl acrylate, 4-methoxybutyl acrylate, 2-ethoxyethyl(meth)acrylate, ethylene glycol monomethyl ether(meth)acrylate, propylene glycol monomethyl ether(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, dimethylaminoethyl(
• (meth)acrylic esters are preferred, and methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate, i-butyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and 2-methoxyethyl acrylate are more preferred.
• the monomer (b) may be used singly or in combination as a monomer component of the copolymer (A).
• the copolymer (A) is obtained by polymerizing a mixture of the monomer (a) and the monomer (b).
• the content of the monomer (a) in the mixture is preferably from about 20 to 70% by mass, and more preferably from about 30 to 60% by weight.
• the coating film formed using the resultant antifouling coating composition can exhibit the stable coating film dissolution property, and it can maintain an antifouling effect for a long period of time.
• the glass-transition temperature (Tg) of the copolymer (A) is preferably from about 20 to 80° C. and is more preferably from about 30 to 70° C.
• Tg is from about 20 to 80° C.
• the coating film hardness is hardly dependent on water temperature or air temperature, and thus suitable hardness and strength can be maintained for a long time. Consequently, coating film defects such as cold flow, crack, and peel-off are unlikely to occur.
• the copolymer (A) has a weight-average molecular weight (Mw) of preferably from 10,000 to 100,000 and more preferably from 20,000 to 70,000.
• Mw weight-average molecular weight
• the coating films are not brittle and have a suitable dissolving rate, so that a desired antifouling effect can be effectively exerted.
• One example of the method for measuring the Mw is gel permeation chromatography (GPC).
• the copolymer (A) may be any one of a random copolymer, alternate copolymer, periodical copolymer, and block copolymer between the monomer (a) and the monomer (b).
• the copolymer (A) can be prepared by polymerizing the monomer (a) and the monomer (b) under the presence of, for example, a polymerization initiator.
• polymerization initiator used in the polymerization reaction those similar to the below-described polymerization initiator can be used singly or in combination.
• preferable polymerization initiator include AIBN, in particular, and t-butyl peroxy-2-ethyl hexanoate.
• the molecular weight of the copolymer A can be adjusted by suitably selecting the amount of the polymerization initiator used.
• polymerization methods include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization.
• the solution polymerization is preferable because it allows the copolymer A to be prepared easily and accurately.
• an organic solvent may be added, if necessary.
• the organic solvent include aromatic hydrocarbon-based solvents (e.g., xylene, toluene); aliphatic hydrocarbon-based solvents (e.g., hexane, heptane);ester-based solvents (e.g., ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate); alcohol-based solvents (e.g., isopropyl alcohol, butyl alcohol); ether-based solvents (e.g., dioxane, diethyl ether, dibutyl ether); and ketone-based solvents (e.g., methyl ethyl ketone, methyl isobutyl ketone).
• aromatic hydrocarbon-based solvents are preferable, and xylene is more preferable. These solvents may be used singly or in combination.
• the reaction temperature in the polymerization reaction may be suitably selected depending on the type of the polymerization initiator, etc., and is usually from about 70 to 140° C. and preferably from about 80 to 120° C.
• the reaction time necessary for the polymerization reaction may be suitably selected depending on the reaction temperature, etc., and is usually from about 4 to 8 hours.
• the polymerization reaction is preferably conducted under an inert gas (e.g. nitrogen gas and argon gas) atmosphere.
• the amount of the copolymer (A) in the composition of the present invention is not particularly limited, and is usually from 20 to 70% by mass and preferably 40 to 60% by mass with respect to the solid content of the composition of the present invention.
• the amount of the copolymer A is from 20 to 70% by mass, the suitable dissolving rate and properties of the coating film in seawater can be achieved.
• the long-term stable surface renewal can remain constant and a desired antifouling effect can be effectively exerted.
• the coating film can exert excellent recoating performance.
• the content of the calcium sulfate hydrate (B) of the present invention is from 5 to 50% by mass with respect to the solid content of the composition of the present invention, and more preferably from 10 to 30% by mass.
• the content of the calcium sulfate hydrate (B) is within the above range, not only the initial (a stage before soaking in seawater) coating film strength is increased, but also no coating film defects (e.g., cracks) occur in the antifouling coating film after soaking in seawater for a given period. In addition, an effect of optimizing the coating film dissolving rate can be exerted.
• use of the calcium sulfate hydrate can achieve, for example, increased smoothness (hydrophilicity on the coating film surface), impact resistance, adhesiveness, and/or block resistance.
• the content of the calcium sulfate hydrate (B) is specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45, or 50% by mass with respect to the solid content of the composition of the present invention, or may be between any two of the above-described values.
• Examples of the calcium sulfate hydrate (B) of the present invention include calcium sulfate dihydrate and calcium sulfate hemihydrate.
• the calcium sulfate dihydrate is included, in particular, the above effect can be markedly exerted.
• the calcium sulfate hydrate (B) has an average particle size of usually less than 50 ⁇ m. From the viewpoint of crack resistance, the size is preferably from 1 to 10 ⁇ m.
• calcium sulfate dihydrate can be prepared by, for example, grinding, crystallization, or precipitation.
• calcium sulfate hemihydrate can be prepared by heating a raw plaster material at high temperatures.
• calcium sulfate hemihydrate may be a by-product during a technical step such as a process for producing phosphorous acid and/or hydrogen fluoride. Further, commercially available products may also be used as the calcium sulfate hydrate.
• the content proportion of the copolymer (A) to the calcium sulfate hydrate (B) is from 0.4 to 3 by mass ratio when converted to a solid content. In this case, the effect of optimizing the coating film dissolving rate can be markedly exerted. When the content proportion is from 0.6 to 1.5, the above effect can be exerted further.
• This mass ratio is specifically, for example, 0.4, 0.5, 0.6, 1, 1.5, 2, 2.5, or 3, or may be between any two of the above-described values.
• the antifouling coating composition of the present invention may further contain, as necessary, an antifoulant (C), a release modifier (D), a plasticizer (E), another resin (F), and the like in addition to the copolymer (A) and the calcium sulfate hydrate (B).
• an antifoulant C
• D release modifier
• E plasticizer
• F another resin
• the addition can improve the antifouling effect.
• antifoulants (C) there is no limitation to the antifoulants (C) as long as they have a killing or repelling effect against aquatic fouling organisms.
• examples can include inorganic and organic antifoulants.
• inorganic antifoulants examples include cuprous oxide, copper thiocyanate (general name: copper rhodanide), cupronickel, and copper powder. Among them, cuprous oxide and copper rhodanide are particularly preferred.
• organic antifoulants examples include: organic copper compounds such as 2-mercaptopyridine-N-oxide copper (general name: copper pyrithione) and the like; organic zinc compounds such as 2-mercaptopyridine-N-oxide zinc (general name: zinc pyrithione), zinc ethylene bis(dithio carbamate) (general name: zineb), zinc bis(dimethyldithiocarbamate) (general name: ziram), dizinc bis(dimethyldithiocarbamate)ethylenebis(dithiocarbamate) (general name: polycarbamate) and the like; organic boron compounds such as pyridine-triphenylborane, 4-isopropyl pyridyl-diphenylmethyl borane, 4-phenyl pyridiyl-diphenyl borane, triphenylboron-n-octadecyl amine, triphenyl[3-(2-ethylhexyloxy)propy
• zinc pyrithione particularly preferred are zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropyl pyridyl-diphenylmethyl borane, bethoxazine, zineb, Sea-Nine 211, and Irgarol 1051. More preferred are copper pyrithione, zinc pyrithione, pyridine-triphenylborane, and bethoxazine.
• cuprous oxide preferred are cuprous oxide, copper rhodanide, zinc pyrithione, copper pyrithione, pyridine-triphenylborane, 4-isopropyl pyridyl-diphenylmethyl borane, bethoxazine, zineb, Sea-Nine 211, Irgarol 1051, tolylfluanid, and dichlofluanid. More preferred are cuprous oxide, copper pyrithione, zinc pyrithione, pyridine-triphenylborane, and bethoxazine.
• the amount of the antifoulant (C) in the composition of the present invention is not particularly limited, and is usually from 0.1 to 75% by mass and preferably from 1 to 60% by mass with respect to the solid content of the composition of the present invention. When the amount of the antifoulant (C) is less than 0.1% by mass, a sufficient antifouling effect might not be obtained. When the amount of the antifoulant (C) is over 75% by mass, the obtained coating film is fragile and adherence of the coating film to an object to be coated is weak, and thus the coating film does not sufficiently exhibit the function as an antifouling coating film.
• Examples of the release modifier (D) include rosin, a rosin derivative and a metal salt thereof, monocarboxylic acid and a salt thereof, and an alicyclic hydrocarbon resin.
• Examples of the rosin include tall oil rosin, gum rosin, and wood rosin.
• Examples of the rosin derivative include hydrogenated rosin, disproportionated rosin, maleinized rosin, formylated rosin, and polymerized rosin.
• a reaction product of a metal compound with rosin can be used as a metal salt of the rosin or a metal salt of rosin derivative.
• Examples of the metal salt include a zinc (or copper) salt of gum rosin, a zinc (or copper) salt of wood rosin, and a zinc (or copper) salt of tall oil rosin.
• Examples of the metal salt of the rosin derivative include a zinc (or copper) salt of hydrogenated rosin, a zinc (or copper) salt of disproportionated rosin, a zinc (or copper) salt of maleinized rosin, a zinc (or copper) salt of formylated rosin, and a zinc (or copper) salt of polymerized rosin.
• Examples of the monocarboxylic acid include C 5-30 fatty acid, synthetic fatty acid, and naphthenic acid.
• Examples of a salt of the monocarboxylic acid include copper salts, zinc salts, magnesium salts, and calcium salts.
• Examples of the commercially available alicyclic hydrocarbon resin include Quintone 1500, 1525L, and 1700 (product name; manufactured by ZEON CORPORATION).
• the composition preferably contains at least one member selected from the group consisting of rosin, a rosin derivative, and a metal salt thereof as the release modifier (D).
• the composition more preferably contains a copper or zinc salt of rosin or a rosin derivative.
• the amount of the release modifier (D) in the composition of the present invention is usually from 1 to 80 parts by mass and preferably from 10 to 50 parts by mass with respect to 100 parts by mass of the copolymer (A).
• the amount of the release modifier (D) is less than 1 part by mass, the effect of preventing attachment of aquatic fouling organisms, in particular, during rigging cannot be expected.
• the amount of the release modifier (D) is over 80 parts by mass, defects such as cracks and peeling tend to occur in the coating film, and thus the effect of preventing attachment of aquatic fouling organisms might not be sufficiently exhibited.
• the amount of the release modifier (D) is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, or 80 parts by mass with respect to 100 parts by mass of the copolymer (A). The amount may be between any two of the above-described values.
• plasticizer (E) By adding the plasticizer (E) to the antifouling coating composition of the present invention, it is possible to improve the plasticity of the composition, and as a result it is possible to suitably form a strong coating film.
• plasticizer (E) examples include: phosphate esters such as tricresyl phosphate, trioctylphosphate, triphenyl phosphate and the like; phthalate esters such as dibutyl phthalate, dioctyl phthalate and the like; adipate esters such as dibutyl adipate, dioctyl adipate and the like; sebacate esters such as dibutyl sebacate, dioctyl sebacate and the like; epoxidized oils and fats such as epoxidized soybean oil, epoxidized linseed oil and the like; alkyl vinyl ether polymers such as methyl vinyl ether polymer, ethyl vinyl ether polymer and the like; polyalkylene glycols such as polyethylene glycol, polypropylene glycol and the like; and t-nonylpentasulfide, vaseline, polybutene, tris(2-ethyl)
• the amount of the plasticizer (E) in the composition of the present invention is usually from 0.1 to 20 parts by mass and preferably from 0.5 to 10 parts by mass with respect to 100 parts by mass of the copolymer (A).
• Another resin (F) is added to the antifouling coating composition of the present invention. This makes it possible to reduce cost without impairing the effects of the present invention. Also, a synergistic effect with the resin (F) properties can be obtained.
• Examples of another resin (F) include a (meth)acrylic resin, an alkyd resin, a polyester resin, a chlorinated rubber resin, and a vinyl resin.
• Another resin (F) can be added to the composition of the present invention to such a degree that the suitable dissolving rate and properties of the coating film in seawater are not impaired. Its amount is from 1 to 200 parts by mass and preferably from 20 to 100 parts by mass with respect to 100 parts by mass of the copolymer (A).
• the antifouling coating composition of the present invention may include a pigment, a dye, an antifoaming agent, an anti-sagging agent, a dispersant, an antisettling agent, a dehydrating agent, and an organic solvent. These additives can be added to such an extent that the suitable dissolving rate and properties of the coating film in seawater are not impaired.
• Example of the pigment include zinc oxide, red iron oxide, talc, titanium oxide, silica, calcium carbonate, barium sulfate, calcium oxide, and magnesium oxide. They can be used singly or in combination.
• Examples of the dye include various kinds of organic dyes soluble in an organic solvent.
• antifoaming agent examples include a silicone resin-based antifoaming agent and an acryl resin-based antifoaming agent.
• anti-sagging agent examples include fatty acid amide wax and oxidized polyethylene.
• dehydrating agent examples include silicates such as a synthetic zeolite-based adsorbent, orthoesters, tetraethoxysilane and the like, and isocyanates. They can be used singly or in combination.
• organic solvent examples include an aliphatic solvent, an aromatic solvent, a ketone-based solvent, an ester-based solvent, an ether-based solvent, and the like which are usually used in the antifouling coating material. They can be used singly or in combination.
• the antifouling coating composition of the present invention can be manufactured, for example, by mixing and dispersing a mixed solution containing the copolymer (A) and the calcium sulfate hydrate (B) by use of a disperser.
• the amounts of the copolymer (A) and the calcium sulfate hydrate (B) in the mixed solution may be suitably adjusted such that the resulting antifouling coating composition contains the copolymer (A) and the calcium sulfate hydrate (B) as described above.
• the mixed solution is preferably obtained by dissolving or dispersing, in a solvent, various materials such as the copolymer (A) and the calcium sulfate hydrate (B).
• a solvent those similar to the above organic solvent may be used.
• the disperser for example, the one which can be used as a micro-pulverizer can be suitably used.
• a commercially available homo mixer, sand mill, bead mill, or the like can be used.
• the mixed solution may be mixed and dispersed by use of a stirrer-equipped container containing glass beads for mixing and dispersing.
• the antifouling treatment of the invention is characterized in that an antifouling coating film is formed using the above-explained antifouling coating composition on the surface of an object that is subjected to coating.
• the antifouling treatment of the present invention can prevent adhesion of aquatic fouling organisms by the gradual dissolution of the surface of the antifouling coating film such that the surface of the coating film is continually renewed. After the dissolution of the coating film, the antifouling effect can be continuously exhibited by recoating the composition.
• Examples of objects on which a coating film can be formed include ships (in particular, ship bottoms), fishing tools, and structures submerged in seawater.
• Examples of the fishing tools include fishing nets for use in aquaculture or in fixed netting, and fishing net accessories such as ropes and floats attached to fishing nets.
• Examples of the structures submerged in seawater include power plant aqueducts, bridges, and port facilities.
• the antifouling coating film can be formed by applying the antifouling coating composition to the surface (entirely or partially) of an object onto which the coating film is to be formed.
• the coating method include brush coating, spray coating, dipping, flow coating, and spin coating. These coating methods may be employed singly or in combination.
• the coating composition is dried after the application.
• the drying temperature may be room temperature.
• the drying time may be suitably selected depending on the thickness of the coating film, etc.
• the antifouling coating film produced using the above antifouling coating composition according to an embodiment of the present invention can exhibit the suitable dissolving rate and properties of the coating film in seawater.
• the long-term stable surface renewal can remain constant and a desired antifouling effect can be effectively exerted.
• the coating film can advantageously exert excellent recoating performance.
• the thickness of the antifouling coating film may be suitably selected depending on types of an object on which the coating film is to be formed, the navigation speed of a ship, the seawater temperature, etc. For example, when the object on which the coating film is to be formed is a ship bottom, the thickness of the antifouling coating film is usually from 50 to 500 ⁇ m and preferably from 100 to 400 ⁇ m.
• the antifouling coating film of the present invention has a suitable hardness. Specifically, the antifouling coating film of the present invention has an hardness enough to cause no coating film defects such as cold flow.
• the coated object of the present invention has the antifouling coating film on its surface.
• the coated object of the present invention may have the antifouling coating film on the entire surface thereof or on the partial surface thereof.
• the coated object of the present invention is provided with a coating film having long-term stable surface renewal and excellent recoating performance because the suitable dissolving rate and properties of the coating film in seawater are improved. Accordingly, the coated object can be preferably applied for the above ships (in particular, ship bottoms), fishing tools, structures submerged in seawater, etc.
• the antifouling coating film when the antifouling coating film is formed on the surface of a ship bottom, the antifouling coating film gradually dissolves from the surface, so that the coating film surface is always renewed. This prevents the adhesion of aquatic fouling organisms.
• the hydrolysis rate of the antifouling coating film is desirably controlled.
• ships benefit from the antifouling effect for a long period of time.
• the adhesion and accumulation of aquatic fouling organisms are barely observed and the antifouling effect is exhibited for a long time.
• the surface of the antifouling coating film is basically free from cracking or peeling even after a long period of time. Accordingly, it is unnecessary to completely remove the existing coating film before re-forming a new coating film.
• the antifouling coating film can be effectively formed. This makes it possible to continuously maintain the antifouling effect in a simple and inexpensive manner.
• % denotes “% by mass”. Viscosity was determined at 25° C. using a Brookfield viscometer. The weight-average molecular weight (Mw) was determined by gel permeation chromatography (GPC) (using a polystyrene standard). GPC was performed under the following conditions.
• the non-volatile content was determined by heating for 1 hour at 125° C.
• the mixture was cooled and filtrated to obtain the gum rosin zinc salt xylene solution D-1 containing a zinc salt of the resin acids (a transparent dark brown solution; the solid content: about 50%).
• the resulting xylene solution had a non-volatile content of 50.2%.
• Calcium sulfate dihydrate a reagent, manufactured by Wako Pure Chemical Industries, Ltd.
• Calcium sulfate hemihydrate a reagent, Kishida Chemical Co., Ltd.
• Cuprous oxide product name “NC-301”, with an average particle size of 3 ⁇ m, manufactured by Nissin Chemco, Ltd.
• Copper pyrithione product name “Copper Omadine”, manufactured by Arch Chemicals, Inc.
• Chlorinated paraffin product name “TOYOPARAX 150”, manufactured by Tosoh Corporation.
• Calcium sulfate (anhydrate) a special grade chemical, manufactured by Kishida Chemical Co., Ltd.
• Calcium carbonate a reagent, manufactured by Wako Pure Chemical Industries, Ltd.
• Barium sulfate a reagent, manufactured by Wako Pure Chemical Industries, Ltd.
• Silica a special grade chemical, manufactured by Kishida Chemical Co., Ltd.
• Bentonite product name “Kunipia-F”, manufactured by KUNIMINE INDUSTRIES CO., LTD.
• Talc product name “Crown Talc 3S”, manufactured by MATSUMURA INDUSTRIES Co., Ltd.
• Zinc oxide product name “Zinc Oxide Type II”, manufactured by Seido Chemical Industry Co., Ltd.
• Red iron oxide product name “TODA COLOR EP-13D”, manufactured by Toda Pigment Corp.
• Titanium oxide product name “FR-41”, manufactured by FURUKAWA CO., LTD.
• Tetraethoxysilane a special grade chemical, manufactured by Kishida Chemical Co., Ltd.
• Fatty acid amide-based thixotropic agent product name “Dispalon A603-20X” containing 20% xylene paste as a principal component, manufactured by Kusumoto Chemicals, Ltd.
• a tank was provided, in the center thereof, with a rotating drum with a diameter of 515 mm and a height of 440 mm in order to allow the rotation of the drum by means of a motor.
• the tank was also provided with: a cooling apparatus for keeping the temperature of seawater constant; and an automatic pH controller for keeping the pH of the seawater constant.
• an anti-corrosive coating film was formed by applying an anti-corrosive coating material (a vinyl-based A/C) to a hard vinyl chloride plate (75 ⁇ 150 ⁇ 1 mm) such that the thickness after drying would be about 50 ⁇ m, followed by drying.
• an anti-corrosive coating material a vinyl-based A/C
• a hard vinyl chloride plate 75 ⁇ 150 ⁇ 1 mm
• Each of the antifouling coating compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 13 was applied onto the anti-corrosive coating film such that the thickness after drying would be about 300 ⁇ m.
• the applied coating was dried for 3 days at 40° C., such that a test plate having the dry coating film with a thickness of about 300 ⁇ m was prepared.
• test plates One of the thus-prepared test plates was secured to the rotating drum of the rotary apparatus of the above-mentioned equipment and was made to contact the seawater, and the rotating drum was rotated at a speed of 20 knots.
• the seawater temperature was maintained at 25° C. and the pH at 8.0 to 8.2; the seawater was replaced once every week.
• the initial thickness of the coating film and the remaining thickness of the coating film was measured every 3 months from the beginning of the test were determined using a laser focus displacement meter for each test plate, and the thickness of the dissolved coating film was calculated from the difference therebetween to give the dissolving amount of the coating film per month ( ⁇ m/month). The measurement was conducted for 24 months, and the dissolving amount of the coating film was calculated every 12 months.
• the test plate was dried, and the surface of each coating film was visually inspected to evaluate the state of the coating film.
• Example 2 The results are shown in Table 2. It can be seen from Table 2 that the coating films formed using the coating compositions of the invention (Examples 1 to 11) were dissolved in seawater in amounts of about 2 to 6 ⁇ m per month (annual average). In addition, in the coating films formed using the coating compositions of the invention the dissolving rate is somewhat low, so that they are dissolved stably for an extended period of time. Furthermore, the coating films formed using the coating compositions of the invention are excellent in water resistance, and do not develop cracks or hairline cracks. In this way, the antifouling effect can be maintained for a long time.
• the coating films formed using the coating compositions of Comparative Examples 4 and 5 have low water resistance, and thus develop coating film defects such as cracks or peel-offs during the test. Furthermore, the coating films formed using the coating compositions of Comparative Examples 1 to 3 and 6 to 13 are superior in water resistance, but develop cracks after the long-term use. Moreover, the coating films formed using the coating compositions of Comparative Examples 9 and 13 have an increased initial dissolving rate of the coating film in seawater, but have a reduced dissolving rate after 12 months. That is, the above coating films cannot exhibit the antifouling effect for a long period.
• Each of the coating compositions obtained in Examples 1 to 11 and Comparative Examples 1 to 13 was applied to both surfaces of a hard vinyl chloride plate (100 ⁇ 200 ⁇ 2 mm) such that the thickness of the dry coating film would be about 200 ⁇ m.
• the applied coating was dried for 3 days at room temperature (25° C.), such that a test plate having a dry coating film with a thickness of about 200 ⁇ m was prepared.
• These test plates were immersed at 1.5 m below sea level in Owase City, Mie Prefecture, Japan, and fouling of each test plate was examined for 12 months.
• the evaluation was conducted by visual inspection for the state of the surface of the coating film in accordance with criteria shown below.
• fouling organisms such as shellfish, algae, and/or slime are attached, after 12-month immersion, to the coating films formed using the coating compositions of Comparative Examples 1 to 13.

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