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WO2008038967A1 - Anti-fouling paint composition - Google Patents

Anti-fouling paint composition Download PDF

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Publication number
WO2008038967A1
WO2008038967A1 PCT/KR2007/004655 KR2007004655W WO2008038967A1 WO 2008038967 A1 WO2008038967 A1 WO 2008038967A1 KR 2007004655 W KR2007004655 W KR 2007004655W WO 2008038967 A1 WO2008038967 A1 WO 2008038967A1
Authority
WO
WIPO (PCT)
Prior art keywords
fouling
paint composition
fouling paint
weight
parts
Prior art date
Application number
PCT/KR2007/004655
Other languages
French (fr)
Inventor
Sang-Ki Ahn
Original Assignee
Sang-Ki Ahn
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020070076439A external-priority patent/KR100913938B1/en
Application filed by Sang-Ki Ahn filed Critical Sang-Ki Ahn
Publication of WO2008038967A1 publication Critical patent/WO2008038967A1/en

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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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • 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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1637—Macromolecular compounds
    • C09D5/165—Macromolecular compounds containing hydrolysable groups

Definitions

  • the present invention relates to an anti-fouling paint composition which uses an environmental-friendly anti-fouling agent or anti-fouling additive unlike a conventional anti-fouling paint composition using only an anti-fouling agent with strong toxicity, thereby reducing environmental contamination and having improved anti-fouling properties, and more particularly, to an anti-fouling paint composition which uses a basic inorganic salt as an anti-fouling agent or an anti-fouling additive, thereby having improved anti-fouling properties.
  • Anti-fouling paint compositions are for preventing or controlling deposition of seawater and the attachment and growth of marine organisms which cause contamination of a surface of a paint film.
  • an anti-fouling paint composition which includes copolymers of tributyltinmethacrylate, methylmethacrylate, or the like and copper oxide (Cu 2 O) as an anti-fouling paint with excellent anti-fouling properties is painted on the bottom of a ship.
  • the copolymer constituting the anti-fouling paint composition is hydrolyzed in seawater to release an organotin compound such as bistributyltinoxide (Bu 3 Sn-O-SnBu 3 where Bu is a butyl group) or tributyltinhalide (Bu 3 SnX where X is a halogen atom), and thereby shows anti-fouling properties.
  • the copolymer is hydrolysable and is a self-polishing type copolymer
  • the hydrolyzed copolymer itself can be water-soluble, and thereby is dissolved in seawater.
  • resin residues do not remain on a surface of a paint film at the bottom of a ship, and the paint film is constantly active.
  • the organotin compound described above has very strong toxicity and as such there is a high possibility that marine contamination, deformed fish or deformed seashells may be produced as an unwanted side affect, thereby potentially harming underwater ecosystems through the food chain, or the like. Due to the problems, there is a need for developing a tin free anti-fouling paint which can replace conventional organotin anti-fouling paints.
  • organotin free anti-fouling paints are disclosed in Korean Patent Publication No. 2005-0010681 , and the like.
  • the organotin free anti-fouling paints still use another kind of toxic anti-fouling agent, and thus the toxicity problem still exists. Therefore, there is still a need for developing an environmental-friendly anti-fouling agent or anti-fouling additive.
  • the present invention provides an anti-fouling paint composition which uses an environmental-friendly anti-fouling agent or anti-fouling additive, thereby having improved anti-fouling properties.
  • an anti-fouling paint composition including an inorganic salt as an anti-fouling agent or anti-fouling additive and a self-polishing polymer as a binder.
  • the present invention provides an anti-fouling paint composition, including an inorganic salt as an anti-fouling agent or anti-fouling additive and a self-polishing polymer as a binder.
  • the inventor of the present application found that when a basic inorganic salt was added to a conventional anti-fouling paint or when a part of the anti-fouling agent or anti-fouling additive was replaced with a basic inorganic salt, anti-fouling properties were significantly improved, thus completing the present invention.
  • the basic inorganic salt does not individually cause environmental contamination, and as such is environmental-friendly. Therefore, the amount of a conventional anti-fouling agent or anti-fouling additive which has strong toxicity used in a paint can be significantly reduced compared to a conventional anti-fouling paint or can be reduced to nothing to obtain anti-fouling performance similar to that of the conventional anti-fouling paint.
  • the inorganic salt used in the anti-fouling paint composition may be a metal salt of hypochlorous acid, a metal salt of chloric acid, a metal salt of chlorous acid, a metal salt of carbonic acid, sodium carbonate, sodium hydroxide (NaOH), or the like.
  • the metal used in the inorganic salt may be at least one metal selected from the group consisting of an alkali metal and an alkali earth metal.
  • the alkali metal may be Li, Na, K, Rb, or the like.
  • the alkali earth metal may be Mg, Ca, Sr, or the like.
  • the metal can be a mixture of the alkali metal and the alkali earth metal.
  • the inorganic salt has a basic property, and may be any inorganic salt which has anti-fouling properties when being basic.
  • the inorganic salt may be, but is not limited to, NaCIO, KCIO 3 , NaCIO 3 , NaCIO 2 , Na 2 Co 3 , NaHCo 3 , NaOH, or the like. Not to limit the scope of the present invention but to provide a better understanding of the present invention, the cause as to why the inorganic salts described above show anti-fouling properties will now be described.
  • the inorganic salts When the inorganic salts are used in an anti-fouling paint, it is considered that when the anti-fouling paint contacts seawater, the inorganic salts maintain strong base condition in a binder, or generate chlorine gas, thereby preventing bacteria or microorganism from proliferating in water. When the proliferating of the bacteria or microorganism in water is prevented, diatomaceous earth, slime, or the like which is attached to the bacteria or microorganism does not exist. Therefore, it is regarded that macrophytes or the like do not proliferate in the end. In particular, the inorganic salts rarely have toxicity that a conventional anti-fouling agent or anti-fouling additive has, which is environmental-friendly, and thus is more suitable for further enhanced maritime environmental regulation.
  • the inorganic salt may further comprise an acid corresponding to the salt.
  • NaCIO may comprise hypochlorous acid. This configuration can be made by equilibrium of the salt with the acid corresponding to the salt.
  • an amount of the inorganic salt may be in the range of from 1 to 50 parts by weight with respect to 10O parts by weight of the binder.
  • the amount of the inorganic salt is less than 1 part by weight with respect to 100 parts by weight of the binder, the anti-fouling properties are deteriorated.
  • the amount of the inorganic salt is greater than 50 parts by weight with respect to 100 parts by weight of the binder, a paint film is not easily adhered to an object such as a bottom of a ship body.
  • the inorganic salt can be used by being prepared as an aqueous solution containing water, if necessary.
  • the inorganic salt can be used as it is by being mixed with distilled water.
  • the aqueous solution may further comprise tourmaline and iron (III) chloride (FeCIs).
  • FeCIs iron (III) chloride
  • an organic solvent may not be used at all in the anti-fouling paint composition. In this case, the anti-fouling paint composition can be more environmental-friendly.
  • the anti-fouling paint composition may further comprise tourmaline as the anti-fouling additive.
  • the tourmaline is an antibiotic stone, and prevents bacteria or microorganism which propagates in the bottom of a ship or an underwater structure from being produced. It is considered that the anti-fouling properties are improved due to an interaction between the tourmaline and the inorganic salt.
  • the tourmaline may be represented by Formula 1 below, and the tourmaline is mainly produced in China, Japan, Brazil, and the like. ⁇ Formula 1 >
  • the tourmaline may be, but is not limited to, NaMg 3 Cr 6 Si 6 Oi 8 (BO 3 ) S (OH), NaMg 3 AI 6 Si 6 Oi 8 (BOs) 3 (OH),
  • the tourmaline may be any tourmaline used in the art.
  • the anti-fouling paint composition comprises 1-50 parts by weight of the inorganic salt and 1-100 parts by weight of the tourmaline with respect to 100 parts by weight of the binder.
  • the amount of the tourmaline is greater than 100 parts by weight with respect to 100 parts by weight of the binder, the difficulty of forming of a paint film is increased.
  • the amount of the tourmaline is less than 1 part by weight with respect to 100 parts by weight of the binder, anti-fouling effects can not be substantially obtained.
  • the self-polishing polymer may comprise a polymer prepared using at least one ethylenically unsaturated monomer selected from a carboxylic acid derivative and a sulfonic acid derivative which generates an acid group in hydrolysis, but is not limited thereto.
  • the self-polishing polymer may be any self-polishing polymer used in the art.
  • the self-polishing polymer may comprise a polymer prepared using at least one monomer selected from the group consisting of a monomer containing a trialkylsilyl group and a (meth)acrylate-based monomer.
  • the polymer may be Zn acrylate, Cu acrylate, or the like.
  • the monomer containing a trialkylsilyl group used in preparing the polymer may be trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tripropylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tributylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, trihexylsilyl (meth)acrylate, trioctylsilyl (meth)acrylate, tridodecylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, butyldimethylsilyl (meth)acrylate, octyldibutylsilyl (meth)acrylate, or the like.
  • the (meth)acrylate-based monomer may be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl (meth)acrylate, or the like.
  • the self-polishing polymer may further comprise a vinyl-based unsaturated monomer.
  • the vinyl-based unsaturated monomer may be styrenes, vinylesters, or the like.
  • the vinyl-based unsaturated monomer may be styrene, vinyltoluene, methylstyrene, vinylacetate, vinylbenzoate, vinylpropionate, vinylbutyrate, or the like.
  • the self-polishing polymer may be prepared by random copolymerization using various known polymerization such as solution polymerization, bulk polymerization, emulsification polymerization, or suspension polymerization in the presence of a radical polymerization initiator.
  • the anti-fouling paint composition of the present invention may further comprise general components used in a conventional anti-fouling paint, in addition to the inorganic salt and the self-polishing polymer.
  • the components may comprise an anti-fouling agent, a pigment, a thickening agent, an organic solvent, a dehumidifying agent, an anti-sagging agent, an anti-flooding agent, a thixotropic agent, a solidification preventing agent, a stabilizing agent, a dispersant, an anti-foaming agent, and the like.
  • a fluorinated resin can be optionally used.
  • the fluorinated resin may be any fluorinated resin used in the art, for example, a fluorinated polysiloxane-based resin, a fluorinated polyester-based resin, or the like.
  • the fluorinated resins are used as a kind of additive, and thus although any kind of fluorinated resin can be used, it does not have a bad impact on achieving the objective of the present invention.
  • the anti-fouling agent used as another essential component may be any anti-fouling agent known in the art.
  • the known anti-fouling agent may be an inorganic compound, a metal-containing organic compound, and a metal-free organic compound.
  • the inorganic compound may include a Cu compound (for example, copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, a conventionally preferred cuprous oxide), zinc sulfate, zinc oxide, zinc sulfide, nickel sulfate, and a Cu-Ni alloy.
  • a Cu compound for example, copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, a conventionally preferred cuprous oxide
  • zinc sulfate zinc oxide
  • zinc sulfide nickel sulfate
  • a Cu-Ni alloy for example, copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, a conventionally preferred cuprous oxide
  • the metal-containing organic compound may be an organo-copper compound, an organo-nickel compound, and an organo-zinc compound.
  • the metal-containing organic compound which can be used may be ethylene bisdithiocarbamate (maneb), propineb, or the like.
  • organo-copper compound may include copper nonylphenol-sulfonate, copper bis(ethylenediamine) bis(dodecylbenzenesulfonate), copper acetate, copper naphtenate, copper pyrithione, and copper bis(pentachlorophenolate).
  • organo-nickel compound may include nickel acetate and nickel dimethyldithiocarbamate.
  • organo-zinc compound may include zinc acetate, zinc carbamate, bis(dimethylcarbamoyl) zinc ethylene-bis(dithiocarbamate), zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylene-bis(dithiocarbamate).
  • a mixed metal-containing organic compound may include (polymeric) manganese ethylene bis(dithiocarbamate) complexed with zinc (mancozeb).
  • Examples of the metal-free organic compound may include N-trihalomethylthiophthalimide, trihalomethylthiosulfamide, dithiocarbamic acid, N-arylmaleimide, 3-(substituted amino)-1 ,3-thiazolidine-2,4-dione, a dithiocyano compound, a triazine compound, oxathiazine, and the like.
  • Examples of N-trihalomethylthiophthalimide may include
  • N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide examples include dithiocarbamic acid may include bis(dimethylthiocarbamoyl)disulfide, ammonium N-methyldithiocarbamate, and ammonium ethylene bis(dithiocarbamate).
  • dithiocarbamic acid may include bis(dimethylthiocarbamoyl)disulfide, ammonium N-methyldithiocarbamate, and ammonium ethylene bis(dithiocarbamate).
  • trihalomethylthiosulfamide examples include N-(dichlorofluoromethylthio- N',N'-dimethyl-N-phenylsulfamide and N-(dichlorofluoromethylthio)-
  • N-arylmaleimide may include N-(2,4,6-trichlorophenyl)maleimide, N-4-tolylmaleimide,
  • 3-(substituted amino)-1 ,3-thiazolidine-2,4-dione may include 2-(thiocyanomethylthio)benzothiazole, 3-benzylideneamino-1 , 3-thiazolidine-2,4-dione,
  • dithiocyano compound may include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene.
  • the triazine compound may be
  • 2-methylthio-4-butylamino-6-cyclopropylamino-s-triazine examples include 1 ,4,2-oxathiazine and mono- and di-oxides thereof.
  • organic compound which does not contain a metal may include 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyl-dichlorophenylurea,
  • the anti-fouling paint composition of the present invention may use at least one anti-fouling agent selected from the anti-fouling agents described above.
  • the amount of the anti-fouling agent used may be in the range of from 0.1 to 90 wt%, preferably in the range of from 0.1 to 80 wt%, and more preferably in the range of from 1 to 60 wt%, with respect to a solid content of the anti-fouling paint film composition.
  • the anti-fouling paint composition of the present invention may further include an anti-fouling additive in order to more improve the performance of the anti-fouling agent.
  • the anti-fouling additive can act as either an anti-fouling agent or an anti-fouling additive.
  • anti-fouling agent when two anti-fouling agents are used, one can be referred to as an anti-fouling agent, and the other can be referred to as an anti-fouling additive.
  • the anti-fouling paint composition of the present invention may further include a pigment (or a filler), a solvent, and an additive.
  • the anti-fouling paint composition can include at least one "active pigment" which is dissolved in a small amount in seawater.
  • the active pigment has a seawater solubility such that the pigment particles do not survive at a surface of the paint.
  • the active pigment overall uniformly induces a force where seawater which moves relative to the paint affects a paint film, and minimizes a local corrosion of the paint film, thereby removing abnormal products formed in a process of coating a paint.
  • the sparlingly soluble pigment has been long used in a self-polishing anti-fouling paint.
  • the active pigment may include cuprous thiocyanate, cuprous oxide, zinc oxide, cupric acetate meta-arsenate, zinc chromate, zinc dimethyl dithiocarbamate, zinc ethylene bis(dithiocarbamate), and zinc diethyl dithiocarbamate.
  • a preferred pigment which is dissolved in a small amount may be zinc oxide, cuprous oxide, or cuprous thiocyanate.
  • the anti-fouling paint composition may include at least one pigment which is highly insoluble in seawater such as titanium dioxide, talc, or ferric oxide.
  • An amount of the pigment which is highly insoluble in seawater may be in the range of 40 wt% or less with respect to total weight of total pigment components.
  • the pigment which is highly insoluble in seawater delays corrosion of the paint composition.
  • the organic solvent may include an aromatic hydrocarbon such as xylene or toluene; an aliphatic hydrocarbon such as hexane and heptane; esters such as ethyl acetate and butyl acetate; amides such as N-methylpyrolidone or N,N-dimethylformamide; alcohols such as propyl alcohol, isopropyl alcohol, or butyl alcohol; dioxane; tetrahydrofuran; ethers such as diethyl ether; and ketones such as methylethylketone, methylisobutylketone, or isoamylketone.
  • water can be used as a solvent.
  • the solvent may be used alone or in combination.
  • the anti-fouling paint composition of the present invention can introduce an additive component.
  • the additive component may be any additive which is conventionally used in a coating composition, for example, a dehumidifying agent, an anti-sagging agent, an anti-flooding agent, a thixotropic agent, a solidification preventing agent, a stabilizing agent, a drying agent, a film strength adjusting agent, and an anti-foaming agent.
  • the anti-fouling paint composition of the present invention may include a benzoic acid, hydroxypyridine, a zinc or copper salt of a benzoic acid, a metal salt of hydroxypyridine, or mixtures thereof, as the stabilizing agent.
  • the anti-fouling paint composition of the present invention may include cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose; and polyvinyl alcohol), polyvinyl pyrolidone), poly(ethylene glycol), a salt of polyacrylic acid, a salt of acrylic acid/acrylamide copolymer, or the like, as the thickening agent.
  • the anti-fouling paint composition according to the present invention uses a basic inorganic salt as an anti-fouling agent or an anti-fouling additive, thereby having significantly improved anti-fouling properties, and alleviating or preventing environmental contamination problems that a conventional anti-fouling agent has.
  • An anti-fouling paint composition was prepared by adding, to 47 parts by weight of a binder, 30 parts by weight of a 33 wt% aqueous solution of sodium hypochlorite, 8 parts by weight of tourmaline, 10 parts by weight of zinc oxide, 2 parts by weight of
  • BYK-323(BYK-Chemie GMBH, Lot No 0110282870-01) as a dispersant 5 parts by weight of Sea-Nine 211 (Product of Rohm & Haas Company) as an anti-fouling additive, and 3 parts by weight of xylene as a solvent.
  • the binder comprised 25 parts by weight of zinc acrylate, 20 parts by weight of rosin, and 2 parts by weight of fluororesin(fluoropolyether).
  • An anti-fouling paint composition was prepared in the same manner as in Example 1 , except that 1.42 parts by weight of a 33 wt% aqueous solution of sodium hypochlorite and 4.7 parts by weight of tourmaline were added to 47 parts by weight of a binder.
  • An anti-fouling paint composition was prepared in the same manner as in Example 1 , except that 71.21 parts by weight of a 33 wt% aqueous solution of sodium hypochlorite and 47 parts by weight of tourmaline were added to 47 parts by weight of a binder.
  • A/F 795 (product name of KCC, Korea) was used as it was.
  • Comparative Example 2 lntersleek 757 (product name of International Marine Coatings) was used as it was.
  • An epoxy-based anticorrosive coat of a thickness of 200 ⁇ m, a sealer coat of a thickness of 100 ⁇ m, and the anti-fouling paint compositions prepared by Example 1 were with an interval of 24 hours sequentially coated on a sandblasted steel plate with the size of 20mmX50mmx2mm, and the resultants were cured and dried at room temperature for one week to prepare a sample. The same procedure was repeated for Examples 2 and 3 and Comparative Examples 1 and 2.
  • the samples were positioned at 1m below from sea level using raft-type test devices (pontoons) installed off Dadaepo, Korea (hereinafter, referred to as location "A") and off Gijang, Korea (hereinafter, referred to as location "B”).
  • the extent of contamination of paint films due to attachment of marine life was observed every two weeks after the positioning of the samples, and anti-fouling properties were evaluated according to standards described below.
  • the anti-fouling paint composition has significantly improved anti-fouling properties compared to a conventional anti-fouling paint composition.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Provided is an anti-fouling paint composition including an inorganic salt used as an anti-fouling agent or an anti-fouling additive and a self-polishing polymer used as a binder. The anti-fouling paint composition uses a basic inorganic salt as an anti-fouling agent or an anti-fouling additive, and thereby has significantly improved anti-fouling properties, and alleviates or prevents environmental contamination problems associated with a conventional anti-fouling agent.

Description

ANTI-FOULING PAINT COMPOSITION
TECHNICAL FIELD
The present invention relates to an anti-fouling paint composition which uses an environmental-friendly anti-fouling agent or anti-fouling additive unlike a conventional anti-fouling paint composition using only an anti-fouling agent with strong toxicity, thereby reducing environmental contamination and having improved anti-fouling properties, and more particularly, to an anti-fouling paint composition which uses a basic inorganic salt as an anti-fouling agent or an anti-fouling additive, thereby having improved anti-fouling properties.
BACKGROUND ART
Anti-fouling paint compositions are for preventing or controlling deposition of seawater and the attachment and growth of marine organisms which cause contamination of a surface of a paint film.
When the bottom of a ship body, an underwater structure, or the like is exposed underwater for a long period of time, animals such as shellfish, oysters, sea mussel, or barnacles, plants such as sea lettuces (seaweeds), and any other kind of aquatic organisms such as underwater bacteria may be attached to a surface thereof and then proliferate. Thus, the appearance of the bottom of the ship body, the underwater structure, or the like may become degraded or functions thereof may be lost. In particular, when the aquatic organisms are attached to the bottom of a ship body and then proliferate, surface roughness of whole outside hull of a ship is increased so that the speed of the ship is reduced, or fuel consumption is increased. To remove aquatic organisms from the bottom of a ship, there is a need for a large amount of effort and a long-term operation is required. In addition, when a viscous fluid (clay materials), slime, or the like is attached onto bacteria which is attached to an underwater structure and then proliferates, thereby decaying the bacteria, or when viscous large-scale organisms are attached to an underwater structure (for example: a steel structure) and then proliferate, thereby damaging a paint film which prevents corrosion of the underwater structure, strength of function of the underwater structure is degraded, and thus lifespan of the underwater structure is significantly reduced.
Generally, to prevent these problems, an anti-fouling paint composition which includes copolymers of tributyltinmethacrylate, methylmethacrylate, or the like and copper oxide (Cu2O) as an anti-fouling paint with excellent anti-fouling properties is painted on the bottom of a ship. The copolymer constituting the anti-fouling paint composition is hydrolyzed in seawater to release an organotin compound such as bistributyltinoxide (Bu3Sn-O-SnBu3 where Bu is a butyl group) or tributyltinhalide (Bu3SnX where X is a halogen atom), and thereby shows anti-fouling properties. In addition, since the copolymer is hydrolysable and is a self-polishing type copolymer, the hydrolyzed copolymer itself can be water-soluble, and thereby is dissolved in seawater. Thus, resin residues do not remain on a surface of a paint film at the bottom of a ship, and the paint film is constantly active.
However, the organotin compound described above has very strong toxicity and as such there is a high possibility that marine contamination, deformed fish or deformed seashells may be produced as an unwanted side affect, thereby potentially harming underwater ecosystems through the food chain, or the like. Due to the problems, there is a need for developing a tin free anti-fouling paint which can replace conventional organotin anti-fouling paints.
Examples of organotin free anti-fouling paints are disclosed in Korean Patent Publication No. 2005-0010681 , and the like. However, the organotin free anti-fouling paints still use another kind of toxic anti-fouling agent, and thus the toxicity problem still exists. Therefore, there is still a need for developing an environmental-friendly anti-fouling agent or anti-fouling additive.
DETAILED DESCRIPTION OF THE INVENTION TECHNICAL PROBLEM
The present invention provides an anti-fouling paint composition which uses an environmental-friendly anti-fouling agent or anti-fouling additive, thereby having improved anti-fouling properties.
TECHNICAL SOLUTION
According to an aspect of the present invention, there is provided an anti-fouling paint composition, including an inorganic salt as an anti-fouling agent or anti-fouling additive and a self-polishing polymer as a binder.
Hereinafter, the present invention will be described in more detail. The present invention provides an anti-fouling paint composition, including an inorganic salt as an anti-fouling agent or anti-fouling additive and a self-polishing polymer as a binder.
The inventor of the present application found that when a basic inorganic salt was added to a conventional anti-fouling paint or when a part of the anti-fouling agent or anti-fouling additive was replaced with a basic inorganic salt, anti-fouling properties were significantly improved, thus completing the present invention. The basic inorganic salt does not individually cause environmental contamination, and as such is environmental-friendly. Therefore, the amount of a conventional anti-fouling agent or anti-fouling additive which has strong toxicity used in a paint can be significantly reduced compared to a conventional anti-fouling paint or can be reduced to nothing to obtain anti-fouling performance similar to that of the conventional anti-fouling paint. The inorganic salt used in the anti-fouling paint composition may be a metal salt of hypochlorous acid, a metal salt of chloric acid, a metal salt of chlorous acid, a metal salt of carbonic acid, sodium carbonate, sodium hydroxide (NaOH), or the like.
The metal used in the inorganic salt may be at least one metal selected from the group consisting of an alkali metal and an alkali earth metal. The alkali metal may be Li, Na, K, Rb, or the like. The alkali earth metal may be Mg, Ca, Sr, or the like. The metal can be a mixture of the alkali metal and the alkali earth metal.
The inorganic salt has a basic property, and may be any inorganic salt which has anti-fouling properties when being basic. The inorganic salt may be, but is not limited to, NaCIO, KCIO3, NaCIO3, NaCIO2, Na2Co3, NaHCo3, NaOH, or the like. Not to limit the scope of the present invention but to provide a better understanding of the present invention, the cause as to why the inorganic salts described above show anti-fouling properties will now be described. When the inorganic salts are used in an anti-fouling paint, it is considered that when the anti-fouling paint contacts seawater, the inorganic salts maintain strong base condition in a binder, or generate chlorine gas, thereby preventing bacteria or microorganism from proliferating in water. When the proliferating of the bacteria or microorganism in water is prevented, diatomaceous earth, slime, or the like which is attached to the bacteria or microorganism does not exist. Therefore, it is regarded that macrophytes or the like do not proliferate in the end. In particular, the inorganic salts rarely have toxicity that a conventional anti-fouling agent or anti-fouling additive has, which is environmental-friendly, and thus is more suitable for further enhanced maritime environmental regulation.
In addition, the inorganic salt may further comprise an acid corresponding to the salt. For example, NaCIO may comprise hypochlorous acid. This configuration can be made by equilibrium of the salt with the acid corresponding to the salt.
In the anti-fouling paint composition, an amount of the inorganic salt may be in the range of from 1 to 50 parts by weight with respect to 10O parts by weight of the binder. When the amount of the inorganic salt is less than 1 part by weight with respect to 100 parts by weight of the binder, the anti-fouling properties are deteriorated. When the amount of the inorganic salt is greater than 50 parts by weight with respect to 100 parts by weight of the binder, a paint film is not easily adhered to an object such as a bottom of a ship body. The inorganic salt can be used by being prepared as an aqueous solution containing water, if necessary. For example, the inorganic salt can be used as it is by being mixed with distilled water. The aqueous solution may further comprise tourmaline and iron (III) chloride (FeCIs). When the inorganic salt is prepared as an aqueous solution, an organic solvent may not be used at all in the anti-fouling paint composition. In this case, the anti-fouling paint composition can be more environmental-friendly.
The anti-fouling paint composition may further comprise tourmaline as the anti-fouling additive. The tourmaline is an antibiotic stone, and prevents bacteria or microorganism which propagates in the bottom of a ship or an underwater structure from being produced. It is considered that the anti-fouling properties are improved due to an interaction between the tourmaline and the inorganic salt.
The tourmaline may be represented by Formula 1 below, and the tourmaline is mainly produced in China, Japan, Brazil, and the like. <Formula 1 >
(Ca, K, Na)(AI, Fe, Li, Mg, Mn)3(AI, Cr, Fe, V)6(BOs)3(Si, Al, B)6Oi8(OH, F)4 More particularly, the tourmaline may be, but is not limited to, NaMg3Cr6Si6Oi8(BO3)S(OH), NaMg3AI6Si6Oi8(BOs)3(OH),
Na(LiL51AlL5)AI6Si6Oi8(BOs)3(OH), CaFe2+ 3(MgAI5)Si6Oi8(BO3)3(OH), (Fe2+ 2AI)AI6Si6Oi8(BO3)s(OH), Ca(Li2AI)AI2Si6Oi8(BO3)S(OH)3,
(Mg2AI)AI6Si6OiS(BO3)S(OH), NaAI3AI6Si6Oi8(BO3)3O3,
NaFe3+ 3(Fe3+ 4Mg2)Si6O18(BO3)3(OH)s, (LiAI2)AI6Si6Oi8(BO3)3(OH),
NaFe2+ SAI6Si6Oi8(BOs)3(OH), CaMg3(MgAI5)Si6Oi8(BO3)s(OH)3,
NaMg3V6Si6Oi8(BO3)3(OH), or the like. In addition, the tourmaline may be any tourmaline used in the art.
Preferably, the anti-fouling paint composition comprises 1-50 parts by weight of the inorganic salt and 1-100 parts by weight of the tourmaline with respect to 100 parts by weight of the binder. When the amount of the tourmaline is greater than 100 parts by weight with respect to 100 parts by weight of the binder, the difficulty of forming of a paint film is increased. When the amount of the tourmaline is less than 1 part by weight with respect to 100 parts by weight of the binder, anti-fouling effects can not be substantially obtained.
In the anti-fouling paint composition, the self-polishing polymer may comprise a polymer prepared using at least one ethylenically unsaturated monomer selected from a carboxylic acid derivative and a sulfonic acid derivative which generates an acid group in hydrolysis, but is not limited thereto. In addition, the self-polishing polymer may be any self-polishing polymer used in the art. In particular, the self-polishing polymer may comprise a polymer prepared using at least one monomer selected from the group consisting of a monomer containing a trialkylsilyl group and a (meth)acrylate-based monomer. For example, the polymer may be Zn acrylate, Cu acrylate, or the like. More particularly, the monomer containing a trialkylsilyl group used in preparing the polymer may be trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tripropylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tributylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, trihexylsilyl (meth)acrylate, trioctylsilyl (meth)acrylate, tridodecylsilyl (meth)acrylate, ethyldimethylsilyl (meth)acrylate, butyldimethylsilyl (meth)acrylate, octyldibutylsilyl (meth)acrylate, or the like.
The (meth)acrylate-based monomer may be methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, methoxyethyl (meth)acrylate, or the like. The self-polishing polymer may further comprise a vinyl-based unsaturated monomer. The vinyl-based unsaturated monomer may be styrenes, vinylesters, or the like. More particularly, the vinyl-based unsaturated monomer may be styrene, vinyltoluene, methylstyrene, vinylacetate, vinylbenzoate, vinylpropionate, vinylbutyrate, or the like. The self-polishing polymer may be prepared by random copolymerization using various known polymerization such as solution polymerization, bulk polymerization, emulsification polymerization, or suspension polymerization in the presence of a radical polymerization initiator.
The anti-fouling paint composition of the present invention may further comprise general components used in a conventional anti-fouling paint, in addition to the inorganic salt and the self-polishing polymer.
The components may comprise an anti-fouling agent, a pigment, a thickening agent, an organic solvent, a dehumidifying agent, an anti-sagging agent, an anti-flooding agent, a thixotropic agent, a solidification preventing agent, a stabilizing agent, a dispersant, an anti-foaming agent, and the like.
In addition, a fluorinated resin can be optionally used. The fluorinated resin may be any fluorinated resin used in the art, for example, a fluorinated polysiloxane-based resin, a fluorinated polyester-based resin, or the like. The fluorinated resins are used as a kind of additive, and thus although any kind of fluorinated resin can be used, it does not have a bad impact on achieving the objective of the present invention.
In the anti-fouling paint composition of the present invention, the anti-fouling agent used as another essential component may be any anti-fouling agent known in the art. The known anti-fouling agent may be an inorganic compound, a metal-containing organic compound, and a metal-free organic compound.
Examples of the inorganic compound may include a Cu compound (for example, copper sulfate, copper powder, cuprous thiocyanate, copper carbonate, copper chloride, a conventionally preferred cuprous oxide), zinc sulfate, zinc oxide, zinc sulfide, nickel sulfate, and a Cu-Ni alloy.
The metal-containing organic compound may be an organo-copper compound, an organo-nickel compound, and an organo-zinc compound. In addition, the metal-containing organic compound which can be used may be ethylene bisdithiocarbamate (maneb), propineb, or the like.
Examples of the organo-copper compound may include copper nonylphenol-sulfonate, copper bis(ethylenediamine) bis(dodecylbenzenesulfonate), copper acetate, copper naphtenate, copper pyrithione, and copper bis(pentachlorophenolate). Examples of the organo-nickel compound may include nickel acetate and nickel dimethyldithiocarbamate. Examples of the organo-zinc compound may include zinc acetate, zinc carbamate, bis(dimethylcarbamoyl) zinc ethylene-bis(dithiocarbamate), zinc dimethyldithiocarbamate, zinc pyrithione, and zinc ethylene-bis(dithiocarbamate). Examples of a mixed metal-containing organic compound may include (polymeric) manganese ethylene bis(dithiocarbamate) complexed with zinc (mancozeb).
Examples of the metal-free organic compound may include N-trihalomethylthiophthalimide, trihalomethylthiosulfamide, dithiocarbamic acid, N-arylmaleimide, 3-(substituted amino)-1 ,3-thiazolidine-2,4-dione, a dithiocyano compound, a triazine compound, oxathiazine, and the like. Examples of N-trihalomethylthiophthalimide may include
N-trichloromethylthiophthalimide and N-fluorodichloromethylthiophthalimide. Examples of dithiocarbamic acid may include bis(dimethylthiocarbamoyl)disulfide, ammonium N-methyldithiocarbamate, and ammonium ethylene bis(dithiocarbamate). Examples of trihalomethylthiosulfamide may include N-(dichlorofluoromethylthio- N',N'-dimethyl-N-phenylsulfamide and N-(dichlorofluoromethylthio)-
N',N'-dimethyl-N-(4-methylphenyl)sulfamide. Examples of N-arylmaleimide may include N-(2,4,6-trichlorophenyl)maleimide, N-4-tolylmaleimide,
N-3-chlorophenylmaleimide, N-(4-n-butylphenyl)maleimide, N-(anilinophenyl)maleimide, and N-(2,3-xylyl)maleimide. Examples of 3-(substituted amino)-1 ,3-thiazolidine-2,4-dione may include 2-(thiocyanomethylthio)benzothiazole, 3-benzylideneamino-1 , 3-thiazolidine-2,4-dione,
3-(4-methylbenzylideneamino)-1 ,3-thiazolidine-2,4-dione, 3-(4-methylbenzylideneamino)-1 ,3-thiazolidine-2,4-dione, 3-(2-hydroxybenzylideneamino)-1 ,3-thiazolidine-2,4-dione,
3-(4-dimethylaminobenzylideamino)-1 ,3-thiazolidine-2,4-dione, and
3-(2,4-dichlorobenzylideneamino)-1 ,3-thiazolidine-2,4-dione. Examples of the dithiocyano compound may include dithiocyanomethane, dithiocyanoethane, and 2,5-dithiocyanothiophene. The triazine compound may be
2-methylthio-4-butylamino-6-cyclopropylamino-s-triazine. Examples of oxathiazine may include 1 ,4,2-oxathiazine and mono- and di-oxides thereof.
Other examples of the organic compound which does not contain a metal may include 2,4,5,6-tetrachloroisophthalonitrile, N,N-dimethyl-dichlorophenylurea,
4,5-dichloro-2-n-octyl-4-isothiazoline-3-on,
N-dimethyl-N'-phenyl-(N-fluorodichloromethylthio)sulfamide, tetramethylthiuramdisulfide, 3-iodo-2-propynylbutyl carbamate, 2-(methoxycarbonylamino)benzimidazole, 2,3)5,6-tetrachloro-4-(methylsulfonyl)pyridine, diiodomethyl-p-tolyl sulfone, phenyl(bispyridine)bismuth dichloride, 2-(4-thiazolyl)benzimidazole, dihydroabietyl amine, N-methylol formamide, and pyridine triphenylborane.
The anti-fouling paint composition of the present invention may use at least one anti-fouling agent selected from the anti-fouling agents described above. The amount of the anti-fouling agent used may be in the range of from 0.1 to 90 wt%, preferably in the range of from 0.1 to 80 wt%, and more preferably in the range of from 1 to 60 wt%, with respect to a solid content of the anti-fouling paint film composition. When the amount of the anti-fouling agent is too low, anti-fouling effects are not obtained. When the amount of the anti-fouling agent is too high, defects such as cracks or detachment may occur in a paint film formed thereof, thereby degrading the anti-fouling effects. The anti-fouling paint composition of the present invention may further include an anti-fouling additive in order to more improve the performance of the anti-fouling agent.
The anti-fouling additive can act as either an anti-fouling agent or an anti-fouling additive.
For example, when two anti-fouling agents are used, one can be referred to as an anti-fouling agent, and the other can be referred to as an anti-fouling additive.
The anti-fouling paint composition of the present invention may further include a pigment (or a filler), a solvent, and an additive. The anti-fouling paint composition can include at least one "active pigment" which is dissolved in a small amount in seawater. The active pigment has a seawater solubility such that the pigment particles do not survive at a surface of the paint. The active pigment overall uniformly induces a force where seawater which moves relative to the paint affects a paint film, and minimizes a local corrosion of the paint film, thereby removing abnormal products formed in a process of coating a paint. The sparlingly soluble pigment has been long used in a self-polishing anti-fouling paint. Examples of the active pigment may include cuprous thiocyanate, cuprous oxide, zinc oxide, cupric acetate meta-arsenate, zinc chromate, zinc dimethyl dithiocarbamate, zinc ethylene bis(dithiocarbamate), and zinc diethyl dithiocarbamate. A preferred pigment which is dissolved in a small amount may be zinc oxide, cuprous oxide, or cuprous thiocyanate.
The anti-fouling paint composition may include at least one pigment which is highly insoluble in seawater such as titanium dioxide, talc, or ferric oxide. An amount of the pigment which is highly insoluble in seawater may be in the range of 40 wt% or less with respect to total weight of total pigment components. The pigment which is highly insoluble in seawater delays corrosion of the paint composition.
Examples of the organic solvent may include an aromatic hydrocarbon such as xylene or toluene; an aliphatic hydrocarbon such as hexane and heptane; esters such as ethyl acetate and butyl acetate; amides such as N-methylpyrolidone or N,N-dimethylformamide; alcohols such as propyl alcohol, isopropyl alcohol, or butyl alcohol; dioxane; tetrahydrofuran; ethers such as diethyl ether; and ketones such as methylethylketone, methylisobutylketone, or isoamylketone. In addition, water can be used as a solvent. The solvent may be used alone or in combination.
The anti-fouling paint composition of the present invention can introduce an additive component. The additive component may be any additive which is conventionally used in a coating composition, for example, a dehumidifying agent, an anti-sagging agent, an anti-flooding agent, a thixotropic agent, a solidification preventing agent, a stabilizing agent, a drying agent, a film strength adjusting agent, and an anti-foaming agent. In addition, the anti-fouling paint composition of the present invention may include a benzoic acid, hydroxypyridine, a zinc or copper salt of a benzoic acid, a metal salt of hydroxypyridine, or mixtures thereof, as the stabilizing agent.
The anti-fouling paint composition of the present invention may include cellulose derivatives such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose; and polyvinyl alcohol), polyvinyl pyrolidone), poly(ethylene glycol), a salt of polyacrylic acid, a salt of acrylic acid/acrylamide copolymer, or the like, as the thickening agent.
ADVANTAGEOUS EFFECTS The anti-fouling paint composition according to the present invention uses a basic inorganic salt as an anti-fouling agent or an anti-fouling additive, thereby having significantly improved anti-fouling properties, and alleviating or preventing environmental contamination problems that a conventional anti-fouling agent has.
BEST MODE
Hereinafter, the present invention will be described more specifically with reference to the following examples. The following examples are only for illustrative purposes and are not intended to limit the scope of the invention. Preparation of anti-fouling paint composition Example 1
An anti-fouling paint composition was prepared by adding, to 47 parts by weight of a binder, 30 parts by weight of a 33 wt% aqueous solution of sodium hypochlorite, 8 parts by weight of tourmaline, 10 parts by weight of zinc oxide, 2 parts by weight of
AI(OH)3, 2 parts by weight of titanium dioxide (TiO2), 0.01 parts by weight of Disper
BYK-323(BYK-Chemie GMBH, Lot No 0110282870-01) as a dispersant, 5 parts by weight of Sea-Nine 211 (Product of Rohm & Haas Company) as an anti-fouling additive, and 3 parts by weight of xylene as a solvent.
The binder comprised 25 parts by weight of zinc acrylate, 20 parts by weight of rosin, and 2 parts by weight of fluororesin(fluoropolyether). Example 2
An anti-fouling paint composition was prepared in the same manner as in Example 1 , except that 1.42 parts by weight of a 33 wt% aqueous solution of sodium hypochlorite and 4.7 parts by weight of tourmaline were added to 47 parts by weight of a binder.
Example 3
An anti-fouling paint composition was prepared in the same manner as in Example 1 , except that 71.21 parts by weight of a 33 wt% aqueous solution of sodium hypochlorite and 47 parts by weight of tourmaline were added to 47 parts by weight of a binder.
Comparative Example 1
A/F 795 (product name of KCC, Korea) was used as it was. Comparative Example 2 lntersleek 757 (product name of International Marine Coatings) was used as it was.
Anti-fouling properties test
An epoxy-based anticorrosive coat of a thickness of 200μm, a sealer coat of a thickness of 100μm, and the anti-fouling paint compositions prepared by Example 1 were with an interval of 24 hours sequentially coated on a sandblasted steel plate with the size of 20mmX50mmx2mm, and the resultants were cured and dried at room temperature for one week to prepare a sample. The same procedure was repeated for Examples 2 and 3 and Comparative Examples 1 and 2.
The samples were positioned at 1m below from sea level using raft-type test devices (pontoons) installed off Dadaepo, Korea (hereinafter, referred to as location "A") and off Gijang, Korea (hereinafter, referred to as location "B"). The extent of contamination of paint films due to attachment of marine life was observed every two weeks after the positioning of the samples, and anti-fouling properties were evaluated according to standards described below.
5 class: a state where marine life was not attached
4 class: a state where a thin film formed of an organic compound was formed
3 class: a state where an area of vegetable contamination was 30% or less of an effective area of a sample
2 class: a state where an area of vegetable contamination was more than 60% of an effective area of a sample
1 class: a state where animal contamination occured Table 1
Figure imgf000011_0001
Figure imgf000012_0001
As shown in Table 1 , the anti-fouling paint composition has significantly improved anti-fouling properties compared to a conventional anti-fouling paint composition.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.

Claims

1. An anti-fouling paint composition comprising an inorganic salt used as an anti-fouling agent or an anti-fouling additive and a self-polishing polymer used as a binder.
2. The anti-fouling paint composition of claim 1 , wherein the inorganic salt comprises at least one compound selected from the group consisting of a metal salt of hypochlorous acid, a metal salt of chloric acid, a metal salt of chlorous acid, a metal salt of carbonic acid, sodium carbonate, and sodium hydroxide (NaOH).
3. The anti-fouling paint composition of claim 2, wherein the metal used in the inorganic salt is at least one metal selected from the group consisting of an alkali metal and an alkali earth metal.
4. The anti-fouling paint composition of claim 1 , comprising 1-50 parts by weight of the inorganic salt with respect to 100 parts by weight of a binder.
5. The anti-fouling paint composition of claim 1 , further comprising tourmaline as the anti-fouling additive.
6. The anti-fouling paint composition of claim 5, comprising 1-50 parts by weight of an inorganic salt and 1-100 parts by weight of tourmaline with respect to 100 parts by weight of a binder.
7. The anti-fouling paint composition of claim 1 , comprising water.
8. The anti-fouling paint composition of claim 1 , wherein the self-polishing polymer is polymer prepared using at least one ethylenically unsaturated monomer selected from a carboxylic acid derivative and a sulfonic acid derivative which generates an acidic group in hydrolysis.
9. The anti-fouling paint composition of claim 1 , wherein the self-polishing polymer is a polymer prepared using at least one monomer selected from the group consisting of a monomer containing a trialkylsilyl group and a (meth)acrylate-based monomer.
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US10428450B2 (en) * 2012-07-25 2019-10-01 Johns Manville Glass fiber reinforced facer mat
CN105542540A (en) * 2016-01-15 2016-05-04 武汉理工大学 A kind of Al2O3 nanoparticle-reinforced chrome-free Dacromet anti-corrosion coating, coating and preparation method thereof
CN106675240A (en) * 2016-12-14 2017-05-17 刘兴旺 Environment-friendly metal protective coating
CN109423157A (en) * 2017-06-29 2019-03-05 洛阳尖端技术研究院 A kind of coating and preparation method thereof
CN109852123A (en) * 2019-02-19 2019-06-07 杭州琻泰环境科技有限公司 Titania modified anion fireproof coating and preparation method thereof
CN113025085A (en) * 2021-03-03 2021-06-25 滁州格锐矿业有限责任公司 Water-based industrial paint with corrosion resistance and processing method thereof

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