WO2009104257A1 - Film de revêtement antisalissures évitant la fixation d'organismes aquatiques, son procédé d'obtention et son utilisation - Google Patents

Film de revêtement antisalissures évitant la fixation d'organismes aquatiques, son procédé d'obtention et son utilisation Download PDF

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WO2009104257A1
WO2009104257A1 PCT/JP2008/052878 JP2008052878W WO2009104257A1 WO 2009104257 A1 WO2009104257 A1 WO 2009104257A1 JP 2008052878 W JP2008052878 W JP 2008052878W WO 2009104257 A1 WO2009104257 A1 WO 2009104257A1
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antifouling
group
mol
monomer
polymer hydrogel
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PCT/JP2008/052878
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English (en)
Japanese (ja)
Inventor
龍文 沖野
靖行 野方
克和 北野
薫 岩井
洋治 平沢
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国立大学法人北海道大学
財団法人電力中央研究所
国立大学法人奈良女子大学
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Application filed by 国立大学法人北海道大学, 財団法人電力中央研究所, 国立大学法人奈良女子大学 filed Critical 国立大学法人北海道大学
Priority to PCT/JP2008/052878 priority Critical patent/WO2009104257A1/fr
Priority to JP2009554163A priority patent/JP5569677B2/ja
Publication of WO2009104257A1 publication Critical patent/WO2009104257A1/fr

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    • 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
    • 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

Definitions

  • the present invention relates to an antifouling film to which aquatic organisms do not adhere, an antifouling paint for obtaining the antifouling film, a method for forming the antifouling film, and an antifouling object having the antifouling film on the surface.
  • Patent Document 1 JP-A-2005-34770
  • a polymer hydrogel is a water molecule that is fluidly incorporated into an antifouling coating. From the viewpoint of aquatic organisms, it creates a so-called “bad scaffolding” state so that aquatic organisms do not adhere. is there.
  • This method using a polymer hydrogel has few conventional drawbacks and is highly effective.
  • Patent Document 2 JP-A-2002-380907
  • Patent Document 3 JP-A-2002-380907
  • an object of the present invention is to provide an antifouling film in which an antifouling agent is monomerized and introduced into a matrix of a polymer hydrogel.
  • the present invention relates to an antifouling coating to which aquatic organisms composed of a polymer hydrogel do not adhere, wherein the polymer hydrogel has an antifouling monomer as one of its constituent components, and prevents aquatic organisms from adhering.
  • the object is achieved by providing a dirty coating.
  • the antifouling monomer has the following chemical formula (1) (Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, p represents 0 or 1, and X represents O represents oxygen or —NH—, and Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and is an ether group, carbonyl group, ester group, amino group, amide group, imide group, sulfide A group, a sulfoxide group or a sulfone group may be interposed.) The thing represented by these is preferable.
  • Y is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may interpose an ether group.
  • Y is preferably a linear, branched or cyclic alkyl group having 5 to 12 carbon atoms.
  • the polymer hydrogel of the present invention is a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer. May be obtained by three-dimensionally cross-linking.
  • the antifouling coating of the present invention may contain an antifouling agent in addition to the polymer hydrogel.
  • the present invention also provides a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer,
  • a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer.
  • an antifouling paint for forming an antifouling film containing a crosslinking agent, a catalyst and a solvent.
  • the present invention further provides a vinyl polymer obtained from a vinyl monomer mixture containing 50 to 90 mol% of a hydrophilic monomer, 1 to 20 mol% of an antifouling monomer and 9 to 49 mol% of another copolymerizable monomer,
  • a method for forming an antifouling film characterized in that an antifouling paint containing a crosslinking agent, a catalyst and a solvent is applied to form a film and then immersed in water.
  • the present invention is also an antifouling object composed of a base material and an antifouling film provided on the outermost surface of the base material, wherein the antifouling film is the specific antifouling film described above.
  • an antifouling object to which characteristic aquatic organisms do not adhere is also an antifouling object composed of a base material and an antifouling film provided on the outermost surface of the base material, wherein the antifouling film is the specific antifouling film described above.
  • the base material may be a ship, an underwater structure, a seawater introduction pipe, a fish net, or a submarine cable.
  • an antifouling monomer that is, a monomer capable of exhibiting antifouling properties is synthesized as one of the monomer components at the time of the synthesis of the polymer hydrogel, and the antifouling component is contained in the matrix of the obtained polymer hydrogel.
  • the antifouling film is introduced to keep the antifouling property, and the antifouling component is securely fixed in the antifouling film, so it does not elute into the water and there is an antifouling film As long as the antifouling property is maintained. Further, since the antifouling component is firmly held in the matrix, it does not elute in water, does not contaminate water, and hardly reaches the human body.
  • the antifouling coating of the present invention comprises a polymer hydrogel.
  • the polymer hydrogel of the present invention is considered to have a structure in which highly hydrophilic polymer molecules are three-dimensionally cross-linked and water molecules can be retained or trapped therein.
  • a highly hydrophilic polymer has a predetermined amount of hydrophilic groups in a general polymer skeleton (specifically, a vinyl polymer), and the vinyl polymer is three-dimensionally crosslinked by a crosslinking reaction.
  • an antifouling monomer is blended during the synthesis of the polymer, and an antifouling part is introduced into the matrix of the resulting polymer hydrogel.
  • the polymer hydrogel film is mainly formed from a vinyl polymer that can swell with water to form a hydrogel.
  • a vinyl polymer is preferable because it can be formed by polymerization of various vinyl monomers and various physical quantities (for example, molecular weight, hydrophilic group amount, etc.) can be easily controlled.
  • the vinyl polymer constituting the polymer hydrogel of the present invention comprises a hydrophilic vinyl monomer in an amount of 50 to 90 mol% (preferably 60 to 80 mol%), and an antifouling monomer 1 to 20 mol% (preferably 1 to 10 mol%). Mol%) and other copolymerizable monomers are formed from a vinyl monomer mixture containing 9 to 49 mol% (preferably 20 to 40 mol%). In addition, a vinyl monomer mixture is 100 mol% in total.
  • the hydrophilic vinyl monomer When the hydrophilic vinyl monomer is less than 50 mol%, the obtained vinyl polymer does not exhibit the performance as a hydrogel. On the other hand, when the amount of the hydrophilic vinyl monomer is more than 90 mol%, the water-resistant physical properties (physical properties such as Young's modulus, breaking strength, and elongation rate of the coating film swollen in seawater) of the obtained polymer hydrogel film are lowered. When the amount of the antifouling monomer is less than 1 mol%, the antifouling performance is not exhibited, and the effect of the antifouling coating of the present invention cannot be obtained. When there are more antifouling monomers than 20 mol%, the hydrophilic property of a coating film will fall and the swelling degree will be suppressed.
  • hydrophilic vinyl monomers include cationic vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, allylamine, N-methylallylamine, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl ( (Meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N-hydroxy (meth) acrylamide and vinylpyridine, vinylimidazole, vinylpyrrolidone, etc .; anionic vinyl monomers such as (meth) acrylic acid and its salts, fumaric acid, maleic acid Citraconic acid, itaconic acid, crotonic acid, aconitic acid, 4-pentenoic acid, ⁇ -undecenoic acid and their salts, vinyl sulfonic acid, vinyl benzyl sulfonic acid, 2-acetic acid Rumido 2-methylpropanesulfonic
  • the polymer hydrogel of the present invention contains an antifouling monomer as an essential component of the monomer mixture in addition to the hydrophilic monomer.
  • the antifouling monomer may be various, but preferably the following chemical formula (1): (Wherein R 1 is hydrogen or a methyl group, R 2 and R 3 each independently represent hydrogen or an alkyl group having 1 to 10 carbon atoms, p represents 0 or 1, and X represents O represents oxygen or —NH—, and Y is a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and is an ether group, carbonyl group, ester group, amino group, amide group, imide group, sulfide A group, a sulfoxide group or a sulfone group may be interposed.) Is mentioned.
  • R 2 and R 3 are preferably each independently hydrogen or an alkyl group having 1 to 5 carbon atoms, and more specifically, a methyl group, an ethyl group, or a propyl group. Butyl group, pentyl group and hexyl group.
  • Y is preferably a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms which may intervene with an ether group, and more preferably a linear, branched or cyclic group having 5 to 12 carbon atoms.
  • antifouling monomer examples include 4-isocyanocyclohexyl acrylate, 11-isocyano-11-methyldodecyl acrylate, N- (11-isocyano-11-methyl) dodecylacrylamide, N- (4-isocyanocyclohexyl) Acrylamide, 4-isocyano-4-methylcyclohexyl acrylate, N- (4-isocyano-4-methylcyclohexyl) acrylamide, 10-isocyano-10-methylundecyl acrylate, N- (10-isocyano-10-methyl) undecyl Acrylamide, 8-isocyano-8-methylnonyl acrylate, N- (8-isocyano-8-methyl) nonyl acrylamide, 6-isocyano-6-methylheptyl acrylate, N- (6-isocyano-6-methyl) heptyl Acrylamide, 4-isocyano-4-methyl-hexyl acrylate, N-(
  • More preferred antifouling monomers are 4-isocyanocyclohexyl acrylate, 11-isocyano-11-methyldodecyl acrylate, and N- (11-cyano-11-methyl) dodecyl acrylamide.
  • the hydrophilic vinyl monomer and the antifouling monomer may be copolymerized with other copolymerizable monomers that are copolymerized therewith.
  • other copolymerizable monomers include N-alkyl substituted (meth) acrylamides: eg (meth) acrylamide, (meth) N-acrylol-L-alanine, (meth) aminopropylacrylamide, (meth) N-amino Propylacrylamide, (meth) N-isopropylacrylamide, t-butyl (meth) acrylamide, dimethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, (meth) isobutylacrylamide , (Meth) t-butylaminoethyl acrylate, (meth) diacetone acrylamide, etc .; or (meth) acrylic acid ester: for
  • the monomer copolymerized with the hydrophilic vinyl monomer for forming the polymer hydrogel is not limited to those described above, but a vinyl monomer for introducing a crosslinkable functional group into the obtained vinyl polymer (referred to as “crosslinkable monomer”). .) Is also necessary.
  • Examples of such monomers include two polymerizable vinyl monomers that introduce crosslinkable unsaturated groups into the resulting vinyl polymer, such as vinyl (meth) acrylate, allyl (meth) acrylate, and (meth) acrylic. Examples include, but are not limited to, 2-butenyl acid and 3-methyl-2-butenyl (meth) acrylate.
  • a polymerizable unsaturated group is introduced into the obtained vinyl polymer and is cured at room temperature due to the presence of a curable catalyst called a so-called dryer.
  • crosslinkable monomer is glycidyl (meth) acrylate: for example, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 4-hydroxybutyl (meth) acrylate glycidyl ether, etc. It is done.
  • These monomers are intended for crosslinking reaction with glycidyl groups.
  • a crosslinkable monomer having a glycidyl group a monomer having a carboxyl group as a group capable of reacting with a glycidyl group (that is, an epoxy group) must be used as a part of the hydrophilic monomer.
  • crosslinkable monomers include hydroxyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2- (2-hydroxyethoxy) ethoxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, and these monomers are intended for crosslinking reaction with hydroxyl groups.
  • hydroxyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2- (2-hydroxyethoxy) ethoxy (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, and these monomers are intended for crosslink
  • the other copolymerizable monomer may be a hydrophobic monomer or a water-repellent monomer in order to adjust the water swelling degree and water content of the film.
  • monomers include (meth) alkylalkoxy acrylates: for example, ethyl-3-ethoxy (meth) acrylate, (meth) 2-ethoxyethyl acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meta ) Acrylate, (meth) ethylene glycol methyl ether acrylate, etc .; polyethylene glycol (meth) acrylate: For example, polyethylene glycol mono (meth) with a degree of polymerization (n) of ethylene glycol of about 1 to 10, preferably 1 to 3.
  • the polymer hydrogel is prepared by polymerizing at least one monomer among the vinyl monomers by a conventional method, using a solvent or a polymerization initiator (such as azoisobutyronitrile) as necessary. Can be done. However, the hydrophilic monomer and the antifouling monomer must be present in specific amounts as described above.
  • the vinyl polymer thus prepared (sometimes referred to as “polymer hydrogel prepolymer”) is applied to the surface of the object to be coated when one having two double bonds in the crosslinkable monomer constituting the polymer is used. And dried at room temperature. As a result, cross-linking occurs due to oxidative polymerization or the like of the incorporated vinyl group, and a cross-linked polymer resin coating film having a highly hydrophilic polymer matrix formed therein is obtained.
  • the polymer matrix contains the solvent used during preparation. In this case, a curing catalyst called a so-called dryer is necessary. Specific examples thereof include cobalt, lead, titanium, and nickel-based catalysts.
  • crosslinkable monomers when using a monomer having a glycidyl group, a monomer incorporating an amino group or a monomer having a hydroxyl group, a crosslinking agent (for example, an amine compound, an aldehyde, a polyisocyanate compound) is added at the time of coating. You may mix uniformly. In this case, a three-dimensional crosslinked structure is formed by the action of the crosslinking agent.
  • a crosslinking agent for example, an amine compound, an aldehyde, a polyisocyanate compound
  • amine compounds include alkylamines such as triethylamine, diethylamine, aromatic diamine compounds such as amine methylene bis (2-chloroaniline), trimethylene bis (4-aminobenzoate) 4-aminophenyl sulfone; aliphatic diamine compounds, Examples thereof include dimethylaminopropylamine and 1,2-diaminopropane.
  • aldehydes include glutaraldehyde, phthalaldehyde, and 1,3-bis- (4-formylphenoxy) propane.
  • the polyisocyanate compound includes known ones, but when water is contained as a solvent, measures to avoid reactivity with water are necessary.
  • the former (that is, a system in which a crosslinking agent is not added) is more preferable because good paint workability can be provided.
  • the polymer hydrogel may be mixed with a silicone resin (SiR).
  • SiR silicone resin
  • moisture reaction curable methylsiloxane rubber generator name “RTV silicone rubber”
  • RTV silicone rubber moisture reaction curable methylsiloxane rubber
  • the polymer matrix has very little solvent remaining in the three-dimensional bridge structure after drying, the three-dimensional bridge structure is covered with water or seawater when immersed in water or seawater.
  • the polymer hydrogel membrane of the present invention in which water or seawater is included in the three-dimensional crosslinked structure (that is, swollen with water or seawater) is obtained.
  • the antifouling coating film of the present invention may contain another antifouling agent in the three-dimensional crosslinked structure of the polymer hydrogel.
  • an antifouling monomer is used, an additional antifouling agent is not necessarily required, but the addition of the antifouling agent is not hindered.
  • antifouling agents organic and inorganic. In the present invention, either one or both may be used in combination.
  • the organic antifouling agent suitably used in the present invention may be a known one, and is selected from, for example, nitrile, pyridine, haloalkylthio, organic iodo, thiazole and benzimidazole antibacterial agents. Two or more types may be included. Specific examples of preferable antibacterial agents are listed below.
  • Nitrile antibacterial agents Nitrile antibacterial agents; haloisophthalonitrile compounds (for example, 2,4,5,6-tetrachloroisophthalonitrile, 5-chloro-2,4,6-trifluorophthalonitrile) and haloaryl nitrile compounds ,
  • (B) Pyridine antibacterial agents Halogenated pyridine derivatives (for example, 2-chloro-6-trichloromethylpyridine, 2-chloro-4-trichloromethyl-6-methoxypyridine, 2-chloro-4-trichloromethyl- 6- (2-furylmethoxy) pyridine, di (4-chlorophenyl) pyridinemethanol, sulfonylhalopyridine compounds (2,3,5,6-tetrachloro-4-methylsulfonylpyridine, 2,3,5-trichloro-4 -(n-propylsulfonyl) pyridine) and pyridinethiol-1-oxide compounds (eg, 2-pyridinethiol-1-oxide sodium, 2-pyridinethiol-1-oxide zinc, di (2-pyridinethiol-1-oxide) )),
  • pyridinethiol-1-oxide compounds eg, 2-pyridinethiol-1-oxide sodium, 2-pyridinethiol-1-oxid
  • haloalkylthio antibacterial agents haloalkylthiophthalimide compounds (for example, N-fluorodichloromethylthiophthalimide, N-trichloromethylthiophthalimide), haloalkylthiotetrahydrophthalimide compounds (for example, N-1,1,2,2-tetrachloroethylthio) Tetrahydrophthalimide, N-trichloromethylthiotetrahydrophthalimide), haloalkylthiosulfamide compounds (eg, N-trichlorothio-N- (phenyl) methylsulfamide, N-trichloromethylthio-N- (4-chlorophenyl) methylsulfami N- (1-fluoro-1,1,2,2-tetrachloroethylthio) -N- (phenyl) methylsulfamide, N- (1,1-difluoro-1,2,2-trichloroethy
  • (E) thiazole antibacterial agents ; isothiazolin-3-one compounds (for example, 1,2-benzisothiazolin-3-one, 2- (n-octyl) -4-isothiazolin-3-one, 5-chloro-2- Methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 4,5-dichloro-2-cyclohexyl-4-isothiazolin-3-one), benzthiazole compounds (for example, 2- ( 4-thiocyanomethylthio) -benzthiazole, 2-mercaptobenzthiazole sodium, 2-mercaptobenzthiazole zinc), and isothiazolin-3-one compounds, and
  • benzimidazole antibacterial agents benzimidazole carbamate compounds (for example, methyl 1-H-2-benzimidazole carbamate, methyl butylcarbamoyl-2-benzimidazole carbamate, 6-benzoyl-1H-2-benzimidazole) Methyl carbamate), sulfur-containing benzimidazole compounds (eg, 1H-2-thiocyanomethylthiobenzimidazole, 1-dimethylaminosulfonyl-2-cyano-3-bromo-6-trifluoromethylbenzimidazole), cyclic benzimidazole Compound derivatives (eg, 2- (4-thiazolyl) -1H-benzimidazole, 2- (4-thiazolyl) -1H-benzimidazole, 2- (2-chlorophenyl) -1H-benzimidazole, 2- (1- ( 3,5-dimethylpyrazolyl) -1H-benzimidazole, 2- (2-furyl)
  • the metal-containing antifouling agent examples include, for example, cuprous oxide, rhodan copper, copper naphthenate, copper stearate, zinc oxide, titanium oxide, iron oxide, Examples include zinc bis- (dimethyldithiocarbamate), ethylene-bis- (dithiocarbamate) zinc, ethylene-bis- (dithiocarbamate) manganese, and ethylene-bis- (dithiocarbamate) copper. The most commonly used is cuprous oxide.
  • a part of the antifouling agent may be ionically bonded in the three-dimensional cross-linked structure of the polymer hydrogel membrane of the present invention.
  • the polymer hydrogel film of the present invention may further contain various additives such as a solvent, a plasticizer, a color pigment, an extender pigment, and an elution aid.
  • the solvent preferably used in the present invention may be water or an organic water-soluble solvent.
  • solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol and propylene glycol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, 1,4-dioxane, diethyl ether and ethylene glycol diethyl ether And ethers such as dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone are preferably used.
  • Plasticizers include phthalic acids such as dioctyl phthalate, dimethyl phthalate and dicyclohexyl phthalate, aliphatic dibasic acid esters such as diisobutyl adipate and dibutyl sebacate, glycol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl ester, Examples thereof include phosphate esters such as tricresyl phosphate and trichloroethyl phosphate, and epoxy systems such as epoxidized soybean oil and octyl epoxy stearate.
  • phthalic acids such as dioctyl phthalate, dimethyl phthalate and dicyclohexyl phthalate
  • aliphatic dibasic acid esters such as diisobutyl adipate and dibutyl sebacate
  • glycol esters such as diethylene glycol dibenzoate and pentaerythritol alkyl ester
  • titanium oxide, zircon oxide, carbon black, bengara, phthalocyanine green, quinacridone, emerald green, and phthalocyanine blue can be used.
  • the extender pigments include talc, clay, silica white, alumina white, titanium white, bentonite, barite, precipitated barium sulfate, and the like.
  • ⁇ ⁇ Paraffin can be used as an elution aid.
  • the present invention also provides an object to which the polymer hydrogel film of the present invention is applied as a second embodiment.
  • an object to which the polymer hydrogel membrane of the present invention is applied is an object that comes into contact with water or seawater, and its function, performance, or operability, particularly when aquatic organisms adhere to its surface. It can be greatly influenced by such.
  • Such objects specifically include ships (especially ship bottoms), seawater introduction pipes, for example, bay facilities, offshore excavation facilities, bridges, pipelines, offshore structures such as submarine bases, and fishnets.
  • Antifouling paint Another aspect of the present invention is an antifouling paint containing a hydrophilic vinyl polymer as a main component and containing a solvent and an additive. If necessary, an antifouling agent or a crosslinking agent may be added to the antifouling paint.
  • the antifouling paint of the present invention is used to form the polymer hydrogel film of the present invention.
  • the hydrophilic vinyl polymer as the main component of the antifouling paint of the present invention may be blended in an amount of 1 to 50% by weight, preferably 5 to 35% by weight, based on the total weight of the antifouling paint.
  • an additional antifouling agent is added in an amount of 0 to 40% by weight, preferably 2% with respect to the total weight of the antifouling coating composition.
  • an amount of ⁇ 30% by weight and the total amount of solvent and various additives is 35 to 99% by weight relative to the total weight of the antifouling coating composition, preferably 45 to 90% by weight relative to the total weight of the antifouling coating composition % May be included.
  • the antifouling agent When blending the antifouling agent, the solvent and various additives, they are added to the polymer resin and mixed using a mixer such as a ball mill, roll mill, sand grind mill, etc. A dirty paint composition is obtained.
  • the antifouling paint composition of the present invention may be appropriately diluted after preparation with a water-soluble solvent up to an appropriate use viscosity for application.
  • the antifouling paint of the present invention is applied to the surface of a ship, which is an object to be coated, and then dried at room temperature and crosslinked to form a crosslinked polymer resin coating film.
  • the obtained crosslinked polymer resin coating film contains a very small amount of the solvent used during preparation or preparation of the coating composition in the three-dimensional crosslinked structure inside.
  • the crosslinked polymer resin coating film is immersed in water or sea water (for example, for 0.5 to 7 days) (with the object coated with this film). High polymer resin coating.
  • the polymer hydrogel membrane of the present invention in which water or seawater is included in the three-dimensional crosslinked structure (that is, swollen with water or seawater) is obtained.
  • the polymer hydrogel membrane of the present invention is unlikely to become a foothold for attachment of aquatic organisms (also referred to as “poor scaffold” for aquatic organisms), and as a result, aquatic organisms are difficult to attach.
  • the antifouling monomer is contained in the matrix of the polymer hydrogel film, the polymer hydrogel alone exhibits sufficient antifouling performance without adding an additional antifouling agent. And attachment of aquatic organisms can be more effectively prevented.
  • the antifouling monomer is a matrix of the polymer hydrogel
  • the antifouling agent is not eluted into the water, and the antifouling performance can be continued as long as the antifouling coating exists. Contamination due to elution of antifouling agent into water does not occur. Of course, this does not prevent the addition of a separate antifouling agent to the polymer hydrogel.
  • the performance improves and at the same time the sustainability may increase.
  • the polymer hydrogel film of the present invention is also poor in hydrolyzability, so that the film is difficult to collapse. If antifouling agents are optionally included, they are retained within the three-dimensional cross-linked structure within the membrane and are optionally ionically fixed and cannot be released into water unless the membrane is disrupted. . Therefore, the polymer hydrogel membrane of the present invention not only extends the useful life of the membrane itself but also prevents water contamination.
  • the polymer hydrogel film of the present invention can be used for a long period of time, for example, for at least 2 years, particularly for at least 3 years. It is possible to effectively prevent the attachment of marine organisms.
  • trans-acetic acid-4-formaminocyclohexyl ester (2.32 g, 12.6 mmol) was dissolved in pyridine (10 mL), paratoluenesulfonyl chloride (2.87 g, 15.1 mmol) was added, and the mixture was stirred at room temperature for 18 hours. .
  • To the reaction solution was added saturated brine (50 mL), and the mixture was extracted with ethyl acetate (200 mL). The organic layer was washed with 1M hydrochloric acid aqueous solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate.
  • Trans-acetic acid 4-isocyanocyclohexyl ester (8.15 g, 48.7 mmol) was dissolved in methanol (100 mL), potassium carbonate (10.57 g, 76.4 mmol) was added, and the mixture was stirred at room temperature for 12 hours. The reaction mixture was filtered under reduced pressure, concentrated, and ethyl acetate (200 mL) was added. The organic phase was washed with water and saturated brine, and then dried over sodium sulfate.
  • the obtained 11-bromoundecanoic acid methyl ester (79.93 g, 286 mmol) was added dropwise to a stirred 3M-diethyl ether solution of methylmagnesium bromide (200 mL, 600 mmol) over 2 hours under ice cooling. After further stirring for 12 hours, an aqueous hydrochloric acid solution (200 mL) was added to the reaction mixture, and the mixture was stirred for 5 minutes, and then extracted with ethyl acetate (400 mL). The organic phase was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated aqueous carbonate, and then dried over sodium sulfate. After filtration, the solvent was distilled off to obtain 12-bromo-2-methyl-2-dodecanol (76 g, 272 mmol) in a yield of 95%.
  • the obtained 12-bromo-2-methyl-2-dodecanol (15.06 g, 53.9 mmol) was dissolved in methylene chloride (15 mL), TMSCN (8 mL, 60.0 mmol) was added, and methanesulfonic acid ( 4.5 mL, 69.3 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Then, methanesulfonic acid (5 mL, 77.0 mmol) was further added, and the mixture was further stirred for 1 hour.
  • Production Example 3 Production of Antifouling Monomer (N- (11-Isocyano-11methyldodecyl) -acrylamide) 12-Bromo-2-methyl-2-dodecanol obtained in the same manner as in the synthesis of Production Example 2 ( 73.78 g, 264 mmol) was dissolved in DMF (200 mL), potassium phthalimide (59.05 g, 319 mmol) was added, and the mixture was heated to reflux for 6 hours. The reaction mixture was filtered, and further washed with ethyl acetate (400 mL). The organic phase was washed with 5% aqueous potassium hydroxide solution and saturated brine, and then dried over sodium sulfate.
  • Production Example 9 Production of polymer hydrogel prepolymers F-1 and F-2 (Production of F-1) Acrylic monomers (22.38 g of acrylic acid, 22.02 g of t-butyl methacrylate, 24.21 g of acrylamide, 11.89 g of glycidyl methacrylate, Examples Antifouling monomer C (11-isocyano-11-methyldodecyl acrylate) 8.65 g prepared in 2 and 0.304 g of isobutyronitrile as an initiator, 52.81 g of 2-propanol, 53.4 g of methanol and 26.79 g of water as a stirrer In a 500 ml glass reaction vessel equipped with a condenser and a thermometer, the mixture was heated at 60 ° C. for 73 minutes with stirring under nitrogen gas to obtain 222 g of a polymer hydrogel prepolymer F-1.
  • Acrylic monomers 22.38 g of acrylic acid, 22.02 g of t-
  • Example 1 Preparation of polymer hydrogel membrane and evaluation of immersion in seawater
  • Example 1 Preparation of polymer hydrogel membrane A and evaluation of immersion in seawater Transfer 20 g of polymer hydrogel prepolymer A to a metal stirring vessel, add a cobalt-based reaction catalyst, and rotate about 2000 times. (Rpm) and mixed for 5 minutes.
  • the obtained coating liquid was applied to a test piece made of vinyl chloride with a brush and dried overnight at room temperature to obtain a polymer hydrogel film A.
  • the obtained polymer hydrogel film A coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.
  • Example 2 Preparation of polymer hydrogel membrane B and evaluation of immersion in seawater
  • Polymer hydrogel prepolymer B (20 g) was transferred to a metal stirring vessel, an amine-based reaction catalyst was added, and the mixture was mixed at about 2000 rpm (rpm) for 5 minutes.
  • the obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature.
  • the obtained polymer hydrogel membrane B-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.
  • Example 3 Preparation of polymer hydrogel membrane C and evaluation of immersion in seawater
  • Polymer hydrogel prepolymer C 20 g, was transferred to a metal stirring vessel, an amine-based reaction catalyst was added, and the mixture was mixed at about 2000 rpm (rpm) for 5 minutes. .
  • the obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature.
  • the obtained polymer hydrogel film-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.
  • Example 4 Preparation of polymer hydrogel membrane D and evaluation of immersion in seawater
  • Polymer hydrogel prepolymer D (20 g) was transferred to a metal stirring vessel, a cobalt-based reaction catalyst was added, and the mixture was mixed at about 2000 rpm (rpm) for 5 minutes. .
  • the obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature.
  • the obtained polymer hydrogel membrane D-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.
  • Example 5 Preparation of polymer hydrogel membrane E and evaluation of immersion in seawater
  • Polymer hydrogel prepolymer E-1, 10 g, polymer hydrogel prepolymer E-2, 10 g were transferred to a metal stirring vessel, and amine-based and cobalt-based
  • the reaction catalyst was added and mixed for 5 minutes at about 2000 revolutions (rpm).
  • the obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature.
  • the obtained polymer hydrogel-coated plate was immersed in actual seawater for about 1 month, no adhesion of aquatic organisms was observed.
  • Example 6 Preparation of polymer hydrogel membrane F and evaluation of immersion in seawater
  • Polymer hydrogel prepolymer F-1, 10 g, polymer hydrogel prepolymer F-2, 10 g were transferred to a metal stirring vessel, and amine-based and cobalt-based
  • the reaction catalyst was added and mixed for 5 minutes at about 2000 revolutions (rpm).
  • the obtained coating liquid was applied to a vinyl chloride test piece with a brush and dried overnight at room temperature.
  • the obtained polymer hydrogel-coated plate was immersed in the appropriate water for about 1 month, no adhesion of aquatic organisms was observed.
  • the antifouling coating of the present invention can be applied to any underwater structure and can suppress the adhesion of aquatic organisms for a long time.
  • the method for forming the antifouling coating, the antifouling paint used for forming the antifouling coating, and the antifouling object having the antifouling coating have the same applicability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • Ocean & Marine Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un film de revêtement antisalissures dans lequel un agent antisalissures, se présentant sous la forme d'un monomère, est introduit dans une matrice d'hydrogel à masse moléculaire élevée. Plus précisément, un film de revêtement antisalissures constitué d'un hydrogel à masse moléculaire élevée et évitant la fixation d'organismes aquatiques, est caractérisé en ce que l'hydrogel à masse moléculaire élevée comprend un monomère antisalissures au titre de l'un de ses constituants.
PCT/JP2008/052878 2008-02-20 2008-02-20 Film de revêtement antisalissures évitant la fixation d'organismes aquatiques, son procédé d'obtention et son utilisation WO2009104257A1 (fr)

Priority Applications (2)

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PCT/JP2008/052878 WO2009104257A1 (fr) 2008-02-20 2008-02-20 Film de revêtement antisalissures évitant la fixation d'organismes aquatiques, son procédé d'obtention et son utilisation
JP2009554163A JP5569677B2 (ja) 2008-02-20 2008-02-20 水棲生物が付着しない防汚被膜、防汚被膜を得るための手段およびその使用

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PCT/JP2008/052878 WO2009104257A1 (fr) 2008-02-20 2008-02-20 Film de revêtement antisalissures évitant la fixation d'organismes aquatiques, son procédé d'obtention et son utilisation

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WO2010109855A1 (fr) * 2009-03-24 2010-09-30 国立大学法人北海道大学 Agent antisalissure pour empêcher l'adhésion de parasites aquatiques
JP2013518877A (ja) * 2010-02-02 2013-05-23 エージェンシー フォー サイエンス，テクノロジー アンド リサーチ 官能化された防汚化合物及びその使用
WO2014142035A1 (fr) * 2013-03-13 2014-09-18 株式会社エステン化学研究所 Film de revêtement antisalissure ayant une faible résistance au frottement avec l'eau ou l'eau de mer
JP2019048947A (ja) * 2017-09-11 2019-03-28 三菱ケミカル株式会社 防汚塗料用ポリマー、樹脂組成物、防汚塗料、塗膜、防汚塗料用ポリマーの製造方法、及び防汚材料
CN110358006A (zh) * 2019-05-24 2019-10-22 中国科学院化学研究所 一种可用于海洋防污的水凝胶及其制备方法和用途
JP2021024988A (ja) * 2019-08-07 2021-02-22 日東化成株式会社 防汚塗料組成物
CN114014971A (zh) * 2021-11-25 2022-02-08 中国海洋大学 一种无挥发性有机物的丙烯酸基水凝胶防污材料制备方法及该材料的用途

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JP4476579B2 (ja) * 2003-07-16 2010-06-09 洋治 平沢 水棲生物が付着しない防汚被膜、それを用いた防汚物体、およびそれをうるための防汚塗料

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JP2004525935A (ja) * 2001-03-27 2004-08-26 バイエル アクチェンゲゼルシャフト 防汚剤としてのアルキルアミン誘導体
JP2002370907A (ja) * 2001-06-19 2002-12-24 Japan Science & Technology Corp 水中有害付着生物に対する防汚剤
WO2003067990A1 (fr) * 2002-02-18 2003-08-21 Hokkaido Technology Licensing Office Co., Ltd. Agent de prevention de salissures
WO2006035891A1 (fr) * 2004-09-30 2006-04-06 National University Corporation Tokyo University Of Agriculture And Technology Isonitriles et agents antidépôt pour lutter contre l’adhésion d’organismes aquatiques
JP2006193672A (ja) * 2005-01-17 2006-07-27 Hiroo Iwata 水中生物付着防止塗料

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010109855A1 (fr) * 2009-03-24 2010-09-30 国立大学法人北海道大学 Agent antisalissure pour empêcher l'adhésion de parasites aquatiques
JPWO2010109855A1 (ja) * 2009-03-24 2012-09-27 国立大学法人北海道大学 水中有害付着生物に対する防汚剤
JP2013518877A (ja) * 2010-02-02 2013-05-23 エージェンシー フォー サイエンス，テクノロジー アンド リサーチ 官能化された防汚化合物及びその使用
WO2014142035A1 (fr) * 2013-03-13 2014-09-18 株式会社エステン化学研究所 Film de revêtement antisalissure ayant une faible résistance au frottement avec l'eau ou l'eau de mer
CN105209562A (zh) * 2013-03-13 2015-12-30 株式会社埃斯腾化学研究所 与水或海水的摩擦阻力小的防污涂膜
JPWO2014142035A1 (ja) * 2013-03-13 2017-02-16 株式会社エステン化学研究所 水または海水との摩擦抵抗の小さい防汚塗膜
JP2019048947A (ja) * 2017-09-11 2019-03-28 三菱ケミカル株式会社 防汚塗料用ポリマー、樹脂組成物、防汚塗料、塗膜、防汚塗料用ポリマーの製造方法、及び防汚材料
CN110358006A (zh) * 2019-05-24 2019-10-22 中国科学院化学研究所 一种可用于海洋防污的水凝胶及其制备方法和用途
CN110358006B (zh) * 2019-05-24 2020-10-27 中国科学院化学研究所 一种可用于海洋防污的水凝胶及其制备方法和用途
JP2021024988A (ja) * 2019-08-07 2021-02-22 日東化成株式会社 防汚塗料組成物
JP7321510B2 (ja) 2019-08-07 2023-08-07 日東化成株式会社 防汚塗料組成物
CN114014971A (zh) * 2021-11-25 2022-02-08 中国海洋大学 一种无挥发性有机物的丙烯酸基水凝胶防污材料制备方法及该材料的用途

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