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WO2009076722A1 - Procédé de protection d'une surface contre l'encrassement biologique - Google Patents

Procédé de protection d'une surface contre l'encrassement biologique Download PDF

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Publication number
WO2009076722A1
WO2009076722A1 PCT/AU2008/001869 AU2008001869W WO2009076722A1 WO 2009076722 A1 WO2009076722 A1 WO 2009076722A1 AU 2008001869 W AU2008001869 W AU 2008001869W WO 2009076722 A1 WO2009076722 A1 WO 2009076722A1
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WIPO (PCT)
Prior art keywords
groups
poly
fouling
polymeric material
ethylene glycol
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/AU2008/001869
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English (en)
Inventor
Richard Wetherbee
John Francis Quinn
Angus Phillip Rayner Johnston
Georgina Such
Maeve Rose Eason Hubbard
Thomas Paul Davis
Francesco Caruso
Paolo Giuseppe Molino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Melbourne
NewSouth Innovations Pty Ltd
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University of Melbourne
NewSouth Innovations Pty Ltd
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Priority claimed from AU2007906976A external-priority patent/AU2007906976A0/en
Application filed by University of Melbourne, NewSouth Innovations Pty Ltd filed Critical University of Melbourne
Publication of WO2009076722A1 publication Critical patent/WO2009076722A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D5/1693—Antifouling paints; Underwater paints as part of a multilayer system
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/02—Homopolymers or copolymers of vinylamine
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/005—Modified block copolymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2438/00—Living radical polymerisation
    • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Definitions

  • the present invention relates to a method of protecting a surface from biological fouling.
  • the present invention finds particular application in the protection of the surface of objects that are used in aquatic environments, particularly marine environments.
  • the present invention also relates to kits for use in the methods of the present invention.
  • Bio fouling of surfaces is a constant problem in the modern world and is almost endemic as it can be observed in almost every environment into which man has spread.
  • biological fouling include the growth of mosses and lichen on structures such as buildings, bridges and the like, the growth of mould in buildings and the fouling of objects that come into contact with aquatic environments such as boats, pilings and the like.
  • Biological fouling of man-made surfaces by aquatic organisms is a significant economic and environmental issue. Colonization of surfaces exposed to aquatic environments by bacteria, protists (e.g., diatoms and Ulva), fungi, tubeworms, sponges, barnacles, mollusks (e.g., clams, oysters, periwinkles and mussels) and other marine organisms can lead to deterioration of the surface coating, necessitating frequent re- application, and having a significant aesthetic impact. Where the coated surface is on a mobile vessel (such as a ship's hull), biological fouling can lead to significant increases in drag and, therefore, reduced fuel efficiency. Biological fouling also increases the downtime for commercial vessels, as repeated repainting becomes required.
  • protists e.g., diatoms and Ulva
  • fungi fungi
  • tubeworms e.g., tubeworms, sponges, barnacles
  • mollusks e.g.,
  • copper compounds such as copper oxide have been used extensively in marine coatings (see, for example, US 5,302,192). While less toxic than organotin compounds, these compounds also tend to accumulate to unsatisfactorily high levels in areas of heavy maritime traffic. Moreover, while effective against some of the larger fouling organisms, such as barnacles, the copper oxide based antifouling paints have never been as effective against fouling by bacteria and some protists, particularly diatoms and the green seaweed Ulva that often dominate biofilms. Therefore, there exists a real need for the development of antifouling surfaces that do not leach inorganic toxins into the marine environment, and which are effective against a wide variety of aquatic fouling species.
  • US Application 20070129461 discloses the use of a polymeric matrix incorporating an ionic monomer, wherein the ionic monomer is associated with an organic cationic biocide.
  • the cationic biocide used is selected from among the polysubstituted cationic guanidinium derivatives, quaternary ammonium cations and pyridinium derivatives. While representing a move away from inorganic biocidal compounds, this invention nevertheless involves the use of toxic chemical species.
  • US 5,218,059 discloses the use of a non-toxic antifouling paint based on silicone resin.
  • a certain proportion of non-curable silicone is incorporated into the coating, with the effect that the non-curable molecules eventually leach to the surface where they disrupt the interaction of biofouling organisms, thereby facilitating foul release.
  • US 6,265,515 discloses the use of a fluorinated silicone elastomer in the production of antifouling surfaces.
  • the use of the fluorinated polymer is aimed at the production of a highly hydrophobic surface, in which the non-polar fluorine sites prevent the formation of hydrogen bonds with the biopolymer adhesive secreted by biofouling organisms, thereby resisting colonization by biofouling organisms.
  • US 2003/01 13547 also discloses the use of fluorinated surfaces in the reduction of marine biofouling. In this case, the fluorinated surface is derived from the incorporation of a fluorinated polyol into a polyurethane.
  • US Application 20070258940 discloses the application of cellulose esters in the preparation of toughened hydrophilic surfaces which resist microbial adhesion.
  • the application of the ester is such that the formation of pores and imperfections in the surface is minimized.
  • Crosslinkers are employed so as to ensure that there is appropriate stability for the coatings on items which are submerged in water.
  • US 6,241 ,898 discloses the use of a combination of surfactants (poly(ethylene oxide- co-propylene oxide) and various alkylsulfosuccinates) to block the adhesion of biofouling organisms to surfaces.
  • This approach requires the addition of the surfactants to the process stream (which are then free in solution, rather than attached to the surface per se). While this approach is effective in closed systems, it is obviously not a practicable method for reducing the attachment of organisms to ocean going vessels and marine structures and devices.
  • US 6,039,965 discloses the application of block copolymers incorporating ethylene oxide units in solution as a means of preventing microbial adhesion to surfaces.
  • this document disclosed the prevention of bacterial adhesion inside closed systems, for example, in a cooling system or in a pulp and paper making facility.
  • Other aspects discussed include the prevention of microbial adhesion onto plastic surfaces.
  • WO 99/01514 discloses the application of polymers which have a broad spectrum anti-fouling capability derived from the incorporation of isothiazolones and/or furanones. These compounds were found to have an anti-fouling capability at very low concentrations of released compound. Moreover, the degradability of these compounds make them a preferable alternative to toxic inorganics. Nevertheless, the expense of incorporating "boutique" compounds such furanones (some of which are derived from Australian red seaweed Delisea pulchra) into a commodity such as marine paint is a significant limitation.
  • the present invention has arisen from the inventors' discovery that the surface of an object can be protected from biological fouling by applying to the surface an anti-fouling composition containing a polymeric material, the polymeric material (i) having side chains containing polymeric moieties that inhibit biological fouling. It has been found that such anti- fouling compositions are most efficiently applied by providing a first functional group on the surface of the object and incorporating a second functional group on the polymeric material in the antifouling composition and applying the anti-fouling composition to the surface of the object under conditions suitable for forming a bond between the first functional group and the second functional group.
  • the anti-fouling layer need not necessarily be the outer layer. This is because in circumstances where a further layer is added to a layer formed from the anti-fouling composition the side chains can penetrate or poke though the further layer leading to the effect that at least a portion of the polymeric moieties that inhibit biological fouling will be present on or projecting from the surface of the treated article even if the layer containing these materials is not the outer layer. This has the net effect that the anti-fouling property of the treated object will be more resilient to degradation as the layer containing the anti-fouling agent is harder to remove from the object (not being an outer layer).
  • the present invention provides a method of protecting a surface of an object from biological fouling, the method including
  • the steps of the method may be repeated from 1 to 100 times. In some specific embodiments of the invention, the steps of the method may be repeated from 1 to 10 times. In some specific embodiments of the invention, the steps of the method may be repeated from 1 to 5 times. In some embodiments the steps of the method may be repeated once. In some other embodiments the steps of the method may be repeated twice. In still other embodiments, the steps of the method may be repeated three times. In still other embodiments, the steps of the method may be repeated four times. In still other embodiments, the steps of the method may be repeated five times.
  • the step of providing the first functional group on the surface of the object may be carried out using any method known in the art.
  • providing a first functional group on the surface of the object includes activation of the surface.
  • activation of the surface includes oxidation of the surface.
  • activation of the surface includes acidification of the surface.
  • activation of the surface includes reaction of the surface with a chemical entity to provide a first functional group on the surface.
  • the invention provides a method of protecting a surface of an object from biological fouling, the method including: (a) applying a primer composition including a material containing a first functional group to the surface of the object;
  • the steps of the method may be repeated from 1 to 100 times. In some specific embodiments of the invention, the steps of the method may be repeated from 1 to 10 times. In some specific embodiments of the invention, the steps of the method may be repeated from 1 to 5 times. In some embodiments the steps of the method may be repeated once. In some other embodiments the steps of the method may be repeated twice. In still other embodiments, the steps of the method may be repeated three times. In still other embodiments, the steps of the method may be repeated four times. In still other embodiments, the steps of the method may be repeated five times.
  • the primer composition may contain any suitable material that contains the first functional group.
  • the primer composition contains a polymeric material containing the first functional group.
  • the primer composition contains a polymeric material containing hydroxy groups.
  • the primer composition contains polyvinyl alcohol) as such a polymeric material.
  • the primer composition for use in the methods of the invention contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups, or a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the primer composition for use in the methods of the invention contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups.
  • a primer composition of this type is a primer composition that contains a polyamine.
  • the polyamine may be any suitable polyamine although in some specific embodiments the polyamine is selected from the group consisting of poly(ethyleneimine), poly(allylamine hydrochloride) and poly(vinylamine hydrochloride).
  • the primer composition for use in the methods of the invention contains a polymeric material containing a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the primer composition for use in the methods of the invention contains a block, gradient, star or random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol), or a block, gradient, star or random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the primer composition for use in the methods of the invention is a random copolymer.
  • the random copolymer may be any suitable random copolymer although in some embodiments the primer composition contains a random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the primer composition contains a random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the polymeric material in the anti-fouling composition contains epoxide groups.
  • the epoxide groups are located in side chains of the polymeric material in the anti-fouling composition.
  • the polymeric material in the anti-fouling composition is a copolymer of glycidyl acrylate and/or glycidyl methacrylate and a polymerisable ester monomer of poly(ethylene glycol).
  • the anti-fouling composition contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups.
  • the anti-fouling composition contains a polymeric material containing a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the anti-fouling composition contains a copolymer prepared by polymerization of a polymerisable ester monomer of poly(ethylene glycol) and a sulfonated ethylenically unsaturated monomer.
  • the sulfonated ethylenically unsaturated monomer is 4-styrene sulfonate.
  • the anti-fouling composition contains a block copolymer of sodium 4-styrenesulfonate and poly(ethylene glycol) methyl ether acrylate.
  • the anti-fouling composition contains a random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the anti-fouling composition contains a random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the composition either primer or anti- fouling contains a copolymer formed by polymerisation of a polymerisable ester monomer and another monomer.
  • polymerisable ester monomers may be employed in the present invention although in some embodiments the polymerisable ester monomer is selected from the group consisting of poly(ethylene glycol) acrylates, poly(ethylene glycol) methacrylates, poly(ethylene glycol) methyl ether acrylates and poly(ethylene glycol) methyl ether methacrylates.
  • the anti-fouling composition can contain a polymeric material having side chains which inhibit biological fouling.
  • the polymeric material has side chains containing one or more ethylene oxide units.
  • each side chain contains between 1 and 1000 ethylene oxide units.
  • each side chain contains between 1 and 100 ethylene oxide units.
  • each side chain contains between 1 and 20 ethylene oxide units.
  • each side chain contains between 3 and 12 ethylene oxide units.
  • Typical equipment suitable for protection by the methods of the invention may include water intakes, piping systems, condensers, evaporators, valves, inlets, outlets and heat exchangers.
  • Other materials and equipment suitable for protecting by the methods of the invention include those used in small scale water treatment and desalination apparatus. Such materials include membranes and filters, for example reverse osmosis membranes and particulate filters.
  • Typical equipment may include water intakes, piping systems, condensers, evaporators, valves, inlets, outlets and heat exchangers.
  • the invention provides a kit for use in protecting a surface from biological fouling the kit including:
  • the primer composition contains a polymeric material containing the first functional group.
  • the first functional groups are hydroxy groups.
  • the polymeric material containing the first functional group is polyvinyl alcohol).
  • the primer composition contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups, or a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the primer composition contains a polymeric material containing a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the primer composition contains a block, gradient, star or random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol), or a block, gradient, star or random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the random copolymer may be any suitable random copolymer although in some embodiments the primer composition contains a random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol). In other embodiments the primer composition contains a random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the polymeric material in the anti-fouling composition contains epoxide groups.
  • the epoxide groups are located in side chains of the polymeric material in the anti-fouling composition.
  • the polymeric material in the anti-fouling composition is a copolymer of glycidyl acrylate and/or glycidyl methacrylate and a polymerisable ester monomer of poly(ethylene glycol).
  • the anti-fouling composition contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups, or a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the anti-fouling composition contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups.
  • the anti-fouling composition contains a polymeric material containing a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the anti-fouling composition contains a copolymer prepared by polymerization of a polymerisable ester monomer of poly(ethylene glycol) and a sulfonated ethylenically unsaturated monomer.
  • the sulfonated ethylenically unsaturated monomer is 4-styrene sulfonate.
  • the anti-fouling composition contains a block copolymer of sodium 4-styrenesulfonate and poly(ethylene glycol) methyl ether acrylate.
  • the anti-fouling composition contains a random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the anti-fouling composition can contain a polymeric material having side chains which inhibit biological fouling.
  • the polymeric material has side chains containing one or more ethylene oxide units.
  • each side chain contains between 1 and 1000 ethylene oxide units.
  • each side chain contains between 1 and 100 ethylene oxide units.
  • each side chain contains between 1 and 20 ethylene oxide units.
  • each side chain contains between 3 and 12 ethylene oxide units.
  • Figure 3 shows the chemical structure of the random copolymer of glycidyl methacrylate and PEG methyl ether methacrylate.
  • Figure 4 shows the build-up of PSS-PEG 2/PAH and PSS/PAH multilayer films, as measured by UV-Vis spectrophometer.
  • the polyelectrolyte concentrations were 1 mg ml 1 in an aqueous solution also containing 0.5 M NaCI.
  • Figure 5 shows the incorporation of rhodamine isothiocyanate-labelled PAH into PSS-PEG 2/PAH and PSS/PAH multilayer films, as measured by UV-Vis spectrophometry.
  • the polyelectrolyte concentrations were 1 mg ml 1 in an aqueous solution also containing 0.5 M NaCI.
  • Figure 6 shows the AFM images of (top) (PSS-PEG 2/PAH) 21 - and (bottom) (PSS/PAH) 21 - coated silicon surfaces.
  • the step decrease in thickness on the left section of each image is the result of scalpel blade scratching, from which dry coating thickness is measured.
  • Figure 11 shows the frequency responses for the settlement of the diatom Haslea sp. upon (a) native gold, (b) (PSS-PEG 2/PAH) 1 PSS-PEG 2, (c) (PSS-PEG 2/PAH) 2 PSS-PEG 2 and (d) (PSS-PEG 2/PAH) 3 PSS-PEG 2 over an 18 h period.
  • the frequency response induced by Haslea sp. on (PSS-PEG 2/PAH) 3 PSS-PEG 2 was less than the natural drift of the instrument, indicating negligible adhesion.
  • Figure 13 shows the frequency responses for the settlement of the diatom Amphora coffeaeformis upon (a) native gold and (b) (PSS-PEG 1/PAH) 3 PSS-PEG 1 over an 18 h period.
  • the frequency response induced by A. coffeaeformis on (PSS-PEG 1/PAH) 3 PSS-PEG 1 was less than the natural drift of the instrument, indicating negligible adhesion.
  • Figure 14 shows the frequency responses for the settlement of the diatom Amphora coffeaeformis upon (a) native gold, (b) PEI-PSS-PEG 2, (c) (PSS-PEG 2/PAH) 1 PSS-PEG 2, (d) (PSS-PEG 2/PAH) 2 PSS-PEG 2 and (e) (PSS-PEG 2/PAH) 3 PSS-PEG 2 over an 18 h period.
  • the frequency response induced by A is induced by A.
  • Figure 16 shows the frequency responses for settlement of zoospores of the green alga Ulva sp. upon (a) native gold, (b) PEI-PSS-PEG 2, (c) (PSS-PEG 2/PAH) 1 PSS-PEG 2, (d) (PSS-
  • Figure 19 shows the frequency responses for the settlement of the diatom Haslea sp. upon (a) native gold and (b) (PVA/PEG EPO ⁇ ) 2 over an 18 h period. Cells were introduced into the
  • Figure 20 shows the frequency responses for the settlement of the diatom Haslea sp upon
  • Figure 23 shows representative images illustrating the bacterial colonisation upon acid washed glass (a,b), lntersleek 700 (c,d), PEG1 (e,f) & PEG2 (g,h) after 6 days of immersion in the ocean. Control images of areas upon the substrate surface not exposed to shear (a,c,e,g) are compared to areas exposed to shear forces (b,d,f,h).
  • Figure 24 shows the mean number of Haslea sp. cells adhered to (a) lntersleek 700®, (b) acid washed glass, (c) (PVA/PEG EP ox)i, (d) (PVA/PEG EPO ⁇ )2 and (e) (PVA/PEG E POX) 3 following exposure to shear stress of 60 Lmin 1 and 120 Lmin 1 for 5 min in a fully turbulent flow chamber. Cells were settled for 6h prior to analysis. Data shown are means of three replicate slides for each treatment.
  • Figure 25 shows the percentage area cover of Ulva sp. zoospores on (a) lntersleek 700® (b) acid washed glass, (c) (PVA/PEG EPO ⁇ )i, (d) (PVA/PEG EPO ⁇ )2 and (e) (PVA/PEG EP ox) 3 following exposure to shear stress of 60 Lmin '1 and 120 Lmin '1 for 5 min in a fully turbulent flow chamber. Cells were settled for 6h prior to analysis. Data shown are means of three replicate slides for each treatment. DETAILED DESCRIPTION OF THE INVENTION
  • biological fouling when used herein refers to the fouling of a surface by biological organisms when exposed to an environment capable of hosting such organisms. It includes the direct adsorption of organic fouling molecules onto the surface, attachment of organisms such as bacteria, protists, fungi, tubeworms, sponges, barnacles, mollusks, and other aquatic organisms to the surface, growth of said organisms on the surface, and deposits left by said organisms on the surface.
  • the method of the present invention may be applied to the protection of the surfaces of a broad range of objects from biological fouling. In essence the methods may be applied to the surface of any object that requires protection from biological fouling. As stated previously the methods of the invention find particular application in the protection of the surfaces of objects in aquatic environments, particularly marine environments.
  • the object is exposed to an aquatic environment. In certain embodiments, the object is exposed to marine environments. In certain embodiments, the object is exposed to estuarine environments. In other embodiments, the object is exposed to process water in an industrial environment. In other embodiments, the object is exposed to freshwater environments.
  • the object to be subjected to the methods of the present invention is a means of transport used in an aquatic environment.
  • objects of this type includes a ship, boat, yacht, dinghy, submarine, ferry, speedboat, frigate, aircraft carrier, minesweeper, ice breaker, rowboat, skiff, jet ski, ketch, yawl, sloop, schooner, tanker, barge, or tugboat.
  • the object to be subjected to the methods of the invention is a recreational object used in an aquatic environment.
  • objects of this type include a surfboard, boogey board, windsurfer or waterski.
  • the object to be subjected to the methods of the invention is a functional object that is generally exposed to an aquatic environment either permanently or intermittently during use.
  • objects of this type include a buoy, pier, wharf, jetty, beacon, breakwater, oil rig, fish farm fence, shark net, fishing net, pontoon, crab pot, lobster pot, shark cage or dock.
  • the object to be subjected to the methods of the invention are components of a larger object. In these circumstances the object may be treated whilst part of the larger item or it may be treated as an individual item either by removal from the larger item or before it is added to the larger item. Examples of objects of this type include a keel, fin, mast, sail, rudder, propeller, periscope or cabin.
  • the object to be subjected to the methods of the invention are the glass surfaces of aquaria (domestic and commercial), ornamental rocks and statuary in ponds, underwater viewing vessels such as glass bottomed boats, semi- submersibles.
  • the objects range from such large objects as ships (supertankers and the like) to quite small components such as the propeller of a boat.
  • the surface of the object to be treated is typically a surface that is either constantly or intermittently in contact with the aquatic environment. This for example in relation to a boat or a ship the surface is typically the hull or a portion thereof. Nevertheless other surfaces such as the deck or inner surface of ballast water tanks of the ship or boat may also benefit from the method of the present invention.
  • the first step in the method of the invention is the provision of a first functional group on the surface of the object.
  • the nature of this step will vary considerably depending upon the base nature of the surface to be protected. For example in certain circumstances the process of manufacture of the surface in the construction of the object will lead to a surface that inherently has the required first functional groups on the surface.
  • the first functional group may be inherent to the surface, such as hydroxyl groups provided by the surface of wood.
  • first functional group is not inherent on the surface it is necessary to introduce a first functional group onto the surface. This may be carried out in a number of ways.
  • the first functional group may be introduced by activation of the surface.
  • Activation of the surface may be carried out in a number of ways known in the art.
  • the surface may be activated by direct chemical modification of the surface leading to a surface with first functional groups thereon.
  • this may be by oxidation with an oxidizing agent, such as an inorganic oxidizing agent or an organic oxidizing agent.
  • the functional group can be provided by exposing the surface to radiation, such as ultraviolet, visible infrared or gamma radiation.
  • a functional group may be provided on the surface by acidification of the surface.
  • the first functional group is provided on the surface by reaction of the surface with a chemical entity to provide a first functional group on the surface.
  • the nature of the chemical entity used in the reaction of the surface will vary based on a number of variables such as the nature of the surface and the chemical moieties inherently present thereon and the desired first functional group to be provided on the surface.
  • the first functional group may be selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups, phosphonate groups, protonated primary amino groups, protonated secondary amino groups, protonated tertiary amino groups, quaternary ammonium groups, acyl bromide groups, acyl chloride groups, aldehyde groups, alkene groups, alkyne groups, amide groups, primary, secondary or tertiary amine groups, anhydride groups, azide groups, nitrile groups, carboxylic acid groups, epoxide groups, hydroxyl groups, isocyanate groups, isothiocyanate groups and thiol groups.
  • a skilled worker in the field would be able to determine suitable methodology for the insertion of a functional group of this type.
  • the chemical groups extending from the surface are selected from the group consisting of protonated primary amino groups, protonated secondary amino groups, hydroxy groups, alkyne groups and azide groups.
  • the nature of the first functional group will typically be determined based on the nature of the second functional group of the antifouling composition used in the invention as the intention is that the first functional group and the second functional group be complementary such that they will form a bond.
  • the first functional group may be provided on the surface using the methods described above the maximum flexibility in selection of the first functional group is provided by applying to the surface a primer composition which includes a material containing the first functional group.
  • the primer composition which includes a material containing the first functional group.
  • the primer composition may be any suitable primer composition although it typically contains a polymeric material containing the first functional group.
  • a large number of suitable polymeric materials may be used with the identity of the polymeric material to be used in the primer composition being chosen in order to provide the desired first functional group.
  • a suitable polymeric material for use in the primer composition is a polymeric material having functional groups which are able to undergo reaction with an epoxide group.
  • Suitable polymeric materials include those having hydroxyl groups, amine groups and thiol groups. Such polymer materials may be formed by copolymerization or homopolymerization of an appropriate precursor monomer, or by post synthesis modification of a polymer. Examples of suitable polymeric materials having hydroxyl groups include polyvinyl alcohol) or polyvinyl phenol).
  • polymeric materials having amine groups include polymeric materials such as poly(ethyleneimine), poly(allylamine) poly(N,N- dimethylaminoethyl methacrylate), poly(N,N-dimethylaminoethyl acrylate),or poly(vinylamine).
  • polymeric materials having thiol groups include poly(methacrylic acid) conjugated with cystamine in the presence of dithiothreitol, or poly(acrylic acid) conjugated with cystamine in the presence of dithiothreitol.
  • Other hydroxy-, amine- and thiol- containing polymers or copolymers suitable for use with the invention would be known to one having skill in the art.
  • a suitable polymeric material for use in a primer composition is a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups, or a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the primer composition contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups.
  • the first functional group will desirably be a positively charged species when the antifouling composition contains a polymeric material that contains a negatively charged second functional group.
  • the primer composition contains a polymeric material containing a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the first functional group will desirably be a negatively charged species when the antifouling composition contains a polymeric material that contains a positively charged second functional group.
  • the material in the primer composition containing the first functional groups may also be chosen such that the first functional group is suitable for reaction with the second functional group to form a covalent bond.
  • the formation of the bond between the chemical group extending from the surface and the chemical moiety on the polymeric material is a so called "click" reaction.
  • the reaction is a condensation reaction.
  • the reaction is a ring opening reaction.
  • the reaction is a cyclization reaction. In each of these instances the material in the primer composition will be chosen to provide the desired first functional group to achieve the desired reaction
  • the formation of the bond between the chemical group extending from the surface and the chemical moiety on the polymeric material occurs via the formation of a heterocyclic ring structure.
  • the heterocyclic ring is formed in the presence of a catalyst.
  • the catalyst includes a metal selected from the group consisting of Au, Ag, Hg, Cd, Zr, Ru, Fe, Co, Pt, Pd, Ni, Cu, Rh and W. More preferably, the catalyst includes a metal selected from the group consisting of Ru, Pt, Ni, Cu and Pd. Even more preferably, the catalyst includes Cu(I).
  • the heterocyclic ring formation occurs in the absence of a catalyst. The use of elevated temperature or pressure reaction conditions or irradiation (such as by microwaves), may eliminate the need to use a catalyst.
  • the bonds formed between the chemical groups extending from the surface and the chemical moieties in the polymeric material result in the formation of a 1 ,2,3-triazole. In some embodiments, this occurs by the Cu(I) catalysed variant of the Huisgen 1 ,3-dipolar cycloaddition.
  • the primer composition include a material containing click functional groups.
  • An example of a suitable click chemistry functional group is an alkyne group or an azide group.
  • the primer composition contains a block, gradient, star or random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol), or a block, gradient, star or random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the copolymer is a random copolymer.
  • the selection of the first functional group on the material in the primer composition will depend upon the identity of the second functional group on the polymeric material of the anti- fouling composition.
  • the identity of the first functional group will be chosen to be complementary with the identity of the functional group on the polymeric material of the anti- fouling composition.
  • the second functional group will be an azide.
  • the first functional group is an azide then the second functional group will be an azide.
  • a number of complementary click functional group pairings are known in the art and a skilled addressee can easily select a required combination.
  • the primer composition typically utilizes a suitable solvent for the material containing the first functional group.
  • the identity of the solvent will typically be determined based on a number of variables such as cost and compatibility with the material containing the first functional group.
  • suitable solvents include water, C 1-10 alcohols, C 1 . 10 ketones, C 1- - I O ethers, aromatic solvents, heteroaromatic solvents, C 1- - I 0 alkanes, N,N-di(C 1 . 10 )alkyl amides, C 3 - 10 cycloalkanes, halogenated solvents, tetrahydrofuran, C 1-6 glycol, dimethylsulfoxide and dioxane.
  • the solvent is chosen from the group consisting of water, ethanol, methanol or acetone.
  • the solvent is a mixture of at least two of the solvents listed above.
  • the solvent is water.
  • the polymeric moieties which inhibit biological fouling include vinyl pyrrolidone units or ethylene oxide units. In some embodiments, the polymeric moieties which inhibit biological fouling include ethylene oxide units.
  • the methods of the invention utilize an antifouling composition containing a polymeric material, the polymeric material (i) having side chains containing one or more ethylene oxide units and (ii) containing a second functional group.
  • the identity of the polymeric material used in the anti-fouling composition will be determined based on the identity of the first functional groups on the surface and vice versa.
  • the polymeric material of the primer composition includes a hydroxyl- thiol- or amino-containing polymeric material
  • some suitable polymeric materials for use in the antifouling material will include those having epoxide groups.
  • the epoxide groups may be added to the polymer by co-polymerizing an epoxide containing monomer or by modification of an appropriate precursor polymer with an appropriate reagent post- polymerization.
  • those epoxide groups may be disposed in the polymer backbone, on side chains or on the chain ends of polymeric branches. If disposed on side chains, the epoxide groups may be located in separate branches to the polymeric moieties which inhibit biological fouling, or in the same branches that inhibit biological fouling. If disposed in the sidechains that inhibit biological fouling, the epoxide groups may be located at the end of the side chain closest to the polymeric backbone, or at the end of the side chain furthest from the polymeric backbone.
  • the epoxide groups may be incorporated into the polymer by using an epoxide functional monomer such as glycidyl acrylate or glycidyl methacrylate in the synthesis of the polymer, by reacting a pre-formed polymer with a reagent suitable for forming epoxide groups on the polymer chain, or by conjugating a preformed polymer with an appropriate reagent having epoxide groups.
  • an epoxide functional monomer such as glycidyl acrylate or glycidyl methacrylate
  • polymeric materials suitable for use in the antifouling composition include copolymers of glycidyl acrylate with poly(ethylene glycol) acrylate, glycidyl acrylate with poly(ethylene glycol) monomethyl ether acrylate, glycidyl methacrylate with poly(ethylene glycol) methacrylate, glycidyl methacrylate with poly(ethylene glycol) monomethyl ether methacrylate, glycidyl methacrylate with poly(ethylene glycol) acrylate, glycidyl methacrylate with poly(ethylene glycol) monomethyl ether acrylate, glycidyl methacrylate with poly(ethylene glycol) monomethyl ether acrylate, glycidyl methacrylate with poly(ethylene glycol) acrylate, and glycidyl methacrylate with poly(ethylene glycol) monomethyl ether acrylate.
  • the anti-fouling composition contains a polymeric material containing a positively charged species selected from the group consisting of protonated primary amino, protonated secondary amino, protonated tertiary amino and quaternary ammonium groups, or a negatively charged species selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups and phosphonate groups.
  • the copolymer is prepared by polymerization of a polymerisable ester monomer of poly(ethylene glycol) and a sulfonated ethylenically unsaturated monomer. Any suitable sulfonated ethylenically unsaturated monomer may be used although a particularly suitable monomer of this type is 4-styrene sulfonate.
  • the anti-fouling composition contains a block copolymer of sodium 4-styrenesulfonate and poly(ethylene glycol) methyl ether acrylate.
  • the polymeric material having side chains containing polymeric moieties which inhibit biological fouling used in the anti-fouling composition is typically a copolymer prepared from polymerization of a polymerisable ester of poly(ethylene glycol) and another monomer.
  • the polymerisable ester of poly(ethylene glycol) is typically chosen from the group consisting of poly(ethylene glycol) acrylates, poly(ethylene glycol) methacrylates, poly(ethylene glycol) methyl ether acrylates and poly(ethylene glycol) methyl ether methacrylates.
  • the polymeric material is a block, gradient, star or random copolymer of the polymerisable ester of poly(ethylene glycol), wherein there is at least one other monomer in the copolymer.
  • the side chains containing one or more ethylene oxide units contain between 1 and 1000 ethylene oxide units. In some specific embodiments, the side chains one or more ethylene oxide units contain between 1 and 100 ethylene oxide units. In some specific embodiments the side chains containing one or more ethylene oxide units contain between 1 and 20 ethylene oxide units. In some more specific embodiments, the side chains containing one or more ethylene oxide units contain between 3 and 12 ethylene oxide units. In these circumstances it is typical that the other monomer used in the polymerization process provides the second functional group. As such the identity of the monomer used in the copolymerisation reaction will be selected to provide the desired group.
  • the second functional group in the polymeric material in the anti-fouling composition which form bonds with the first functional groups on the surface is typically selected from the group consisting of carboxylate groups, sulfonate groups, sulfate groups, phosphonate groups, protonated primary amino groups, protonated secondary amino groups, protonated tertiary amino groups, quaternary ammonium groups, acyl bromide groups, acyl chloride groups, aldehyde groups, alkene groups, alkyne groups, amide groups, primary, secondary or tertiary amine groups, anhydride groups, azide groups, nitrile groups, carboxylic acid groups, epoxide groups, hydroxyl groups, isocyanate groups, isothiocyanate groups and thiol groups.
  • the second functional group in the polymeric material is selected from the group consisting of sulfonate groups, alkyne groups and azide groups.
  • the anti-fouling composition contains a random copolymer of an acrylate with pendant alkyne groups and a polymerisable ester monomer of poly(ethylene glycol). In some other specific embodiments the anti-fouling composition contains a random copolymer of an acrylate with pendant azide groups and a polymerisable ester monomer of poly(ethylene glycol).
  • the first functional group is provided by a layer of a block, gradient, star or random copolymer of an acrylate with pendant azide groups and poly(ethylene glycol) methyl ether acrylate and the polymeric material is a block, gradient, star or random copolymer of an acrylate with pendant alkyne groups and poly(ethylene glycol) methyl ether acrylate.
  • the first functional group is a chemical moiety on the surface and the second functional group is a chemical moiety on the polymeric material of the anti- fouling composition and the bond formed between the first functional group and the second functional group is a covalent bond.
  • the chemical moieties in the polymeric material in the anti-fouling composition are typically selected from the group consisting of acyl bromide groups, acyl chloride groups, aldehyde groups, alkene groups, alkyne groups, amide groups, primary, secondary or tertiary amine groups, anhydride groups, azide groups, nitrile groups, diazonium groups, sulfonyl chloride groups, carboxylic acid groups, epoxide groups, aziridine groups, hydroxyl groups, isocyanate groups, isothiocyanate groups and thiol groups.
  • the covalent bonds formed by the reaction of the first functional group and the second functional group in the polymeric material in the anti-fouling composition are typically selected from the group consisting of amide, ester, urethane, carbamate, urea, allophonate, biuret, isocyanurate, imine, heterocycle, ether, alkyl, cycloalkyl, thiocarbamate, disulfide, sulfide, anhydride, amine, azide and sulfonamide.
  • the anti-fouling composition typically utilizes a suitable solvent for the polymeric material containing the ethylene oxide moieties.
  • a suitable solvent for the polymeric material containing the ethylene oxide moieties.
  • the identity of the solvent will typically be determined based on a number of variables such as cost and compatibility with the polymeric material containing the ethylene oxide moieties.
  • suitable solvents include water,
  • the solvent is chosen from the group consisting of water, ethanol, methanol or acetone. In some embodiments the solvent is a mixture of at least two of the solvents listed above. In some specific embodiments the solvent is water.
  • the anti-fouling composition includes further additives.
  • the additives are selected from the group consisting of mineral acids, bases and ionic salts.
  • the additive is sodium chloride.
  • the additive is dilute aqueous hydrochloric acid.
  • the additive is dilute aqueous sodium hydroxide.
  • the anti-fouling composition may contain additional additives that enhance the surface. Examples of such additives include pigments and the like.
  • the functional groups in the polymeric material are provided by using monomers which contain the functional group in synthesising the polymeric material.
  • the monomers containing the functional groups are acrylic, styrenic, allylic, vinylic or methacrylic monomers.
  • the functional groups are incorporated into the polymeric material after the polymeric material has been prepared from reactive precursor.
  • the monomers containing the functional groups are styrene derivatives containing acyl bromide groups, acyl chloride groups, aldehyde groups, alkene groups, alkyne groups, amide groups, primary, secondary or tertiary amine groups, anhydride groups, azide groups, nitrile groups, diazonium groups, sulfonyl chloride groups, carboxylic acid groups, epoxide groups, aziridine groups, hydroxyl groups, isocyanate groups, isothiocyanate groups and thiol groups, esters of methacrylic acid containing acyl bromide groups, acyl chloride groups, aldehyde groups, alkene groups, alkyne groups, amide groups, primary, secondary or tertiary amine groups, anhydride groups, azide groups, nitrile groups, diazonium groups, sulfonyl chloride groups, carboxylic acid groups, epoxide groups, aziridine groups,
  • the functional groups in the polymeric materials are provided by preparing the polymeric material using the monomers allylamine, sodium A- styrenesulfonate, sodium acrylate, sodium methacrylate, acrylic acid, methacrylic acid, sodium 4-vinylbenzoate, 4-vinylbenzoic acid, te/t-butyl acrylate, te/t-butyl methacrylate, A- vinylbenzyl-N,N,N-trimethylammonium chloride, acrylonitrile, vinylbenzyl chloride, glycidyl methacrylate, glycidyl acrylate, propargyl acrylate, methacryloyl chloride, acryloyl chloride, methacryloyl bromide, acryloyl bromide, 4-vinylaniline, crotonaldheyde, acrylamide, N, N- dimethylaminoethyl methacrylate, 4-vinylphenol, vinyl a
  • the primer composition and the anti-fouling composition may be applied using any technique known in the art.
  • the compositions may be applied by spraying, dipping or painting and the appropriate procedures in order to utilize these techniques would be known to a skilled addressee.
  • primer - anti-fouling composition once (i.e. primer - anti-fouling composition - primer - anti-fouling composition).
  • the application of the primer and antifouling composition may also be repeated twice. In some other cases it may be desirable to repeat application of the primer and antifouling composition three times. In still other cases it may be desirable to repeat the application of the primer and antifouling composition four times. In some certain cases it may be desirable to repeat the application of the primer and antifouling composition five times. In principle, the applications may be repeated as many times as desired by the applicator.
  • a primer composition is used there may be a lag time between the application of the primer composition and the ant-fouling composition (a cure time).
  • the anti-fouling composition is applied to the surface immediately after the primer composition. In some embodiments, there is a defined time between application of the primer composition and application of the anti-fouling composition.
  • drying is accomplished by heating.
  • drying is accomplished by exposing the surface to a stream of gas (such as air or nitrogen).
  • the surface is allowed to dry naturally.
  • the present invention also provides kits containing a primer composition and an anti- fouling composition as described above.
  • the PSS-PEG block copolymer system is applied to the surface by first adsorbing a layer of polyamine (poly(ethyleneimine) or poly(allylamine hydrochloride)) to provide positively charged groups on the surface. These positively charged sites facilitate the attachment of the negatively charged sodium sulfonate domains.
  • the process can be repeated a number of times, using the layer-by-layer (LbL) process to alternately layer the PSS-PEG with poly(allylamine hydrochloride) (PAH). In this case electrostatic interactions promote the assembly.
  • a first layer of the click-PEG was attached electrostatically to a surface, the surface having been pretreated so as to provide protonated amine groups on the surface. This was achieved by first adsorbing a layer of polyamine (poly(ethyleneimine) or poly(allylamine hydrochloride)) to provide positively charged groups on the surface.
  • polyamine poly(ethyleneimine) or poly(allylamine hydrochloride)
  • Example 2 Synthesis of Poly(ethylene glycol) 3 acrylate with alkyne functionality (click-PEG-Alk)
  • Poly(ethylene glycol) 3 acrylate with alkyne functionality (click-PEG-Alk) was synthesized using a similar procedure with a molar ratio of approximately 350:50:1 methoxy terminated poly(ethylene glycol) 3 acylate (1 .712 g), acrylic acid (1 .01 g) and the above RAFT agent (7.5 mg). 10 wt % Azobisisobutyronitrile (0.2 mg) relative to the RAFT agent was also added along with 3ml dioxane.
  • the solution was purged using three freeze thaw cycles on a Schlenk line and then polymerized at 60 ° C in a constant temperature oil bath (36 h).
  • the polymer was stirred overnight with propargyl amine (0.010 g) in the presence of 1 -[3'- (dimethylamino)propyl]-3-ethylcarbodiimide (0.150 g).
  • the product was dialyzed for 7 days and then freeze dried.
  • the monomer sodium 4-styrenesulfonate (6g, 0.029 moles) was dissolved in 20 ml_ distilled water.
  • 3-Benzyl(sulfanylthiocarbonyl)sulfanylpropanoic acid (0.1387 g, 0.0005 moles) and initiator, 4,4'-azobis-4-cyanopentanoic acid (ACPA) (28.6mg, 0.0001 moles) were dissolved in 10 mL ethanol.
  • ACPA 4,4'-azobis-4-cyanopentanoic acid
  • the polymerization was initiated by immersing the glass vial in an oil bath set at 7OO, and the polymerization allowed to proceed for 16 h.
  • the polymer (PSS-RAFT) was purified by precipitating into acetone, filtering, and drying in a fumehood overnight. Close to 100% conversion was achieved.
  • the M n determined by NMR was 14,600 g mol "1 , which is close the calculated M n of 12,400 g mol "1 .
  • Block polymer PSSPEG was synthesized by chain extending the above PSS-RAFT.
  • a water- soluble thermal initiator 4,4'-azobis-4-cyanopentanoic acid (ACPA) was used for polymerization, which was conducted in water and at 7OC Specifically, the monomer polyethylene glycol methyl ether acrylate, PEGMEA (2.2704g, 0.005 moles), macroRAFT agent sodium polystyrene sulphonate, PSS-RAFT (1.24g, 0.0001 moles), and initiator, ACPA (5.6mg, 0.00002 moles) were weighed into a glass vial. Distilled water (13 ml.) was added to dissolve all components.
  • ACPA 4,4'-azobis-4-cyanopentanoic acid
  • the mixture was then degassed on a Schlenk line and blanketed with nitrogen after three degassing cycles.
  • the polymerization was started by immersing the glass vial in an oil bath set at 7OO for 1 hour.
  • the polymer was purified by dialysis followed by freeze drying. 86.7% conversion was determined by 1 H NMR (D 2 O as solvent).
  • Substrates (glass slides, quartz slides and gold QCM electrodes) were coated with PSS-PEG films by an alternate adsorption procedure.
  • the substrate was initially exposed to an aqueous solution of polyethyleneimine for 5 minutes (1 mg ml 1 , also containing 0.5 M NaCI), and was then rinsed with water.
  • the substrate was then exposed to an aqueous solution of PSS-PEG (1 mg ml 1 , also containing 0.5 M NaCI) for 5 minutes, and was then rinsed again in water.
  • the slides were prepared by depositing a layer of PEI onto the glass slide/QCM crystal from a 1 mg ml 1 solution containing 0.5 M NaCI. The slides were rinsed 3 times in water after each polymer deposition. A layer of PAA-Az (1 mg ml 1 ) was electrostatically deposited onto the PEI surface to facilitate covalent attachment of the subsequent PEG-AIk layer. The "click" PEG layers were assembled by alternately coating the surface with PEG- AIk or PEG-Az from the solution containing 0.5 mg ml 1 polymer, 0.36 mg ml 1 copper sulfate and 0.88 mg ml 1 sodium ascorbate.
  • PSS-PEG 2/PAH films The characterization of PSS-PEG 2/PAH films was performed with UV-Vis spectrophotometry, atomic force microscopy and dual polarization interferometry.
  • UV-Vis Spectrophotometry UV-visible spectra were collected using an Agilent 8453 single beam UV-Vis spectrophotometer. A PEI-coated quartz slide blank was taken before each measurement. PSS has an absorption peak at 227 nm, while FITC-PAH has an adsorption peak at 565 nm. Fig. 4 and Fig. 5 revealed that the PSS-PEG 2/PAH multilayer film assembles linearly and follow a build up regime that is very similar to that of the conventional PSS/PAH system.
  • Dual Polarization lnterferometry Measurements were carried out on an Analight Bio200 dual polarization interferometer (Farfield Scientific Ltd., Cheshire, U.K.). A continuous flow of deionised water with an adjustable pump rate was introduced into the instrument using a dual syringe pump (Harvard Apparatus PHD 2000, Holliston, MA). The DPI chip was illuminated using light from a helium neon laser (632.8 nm), which is split equally into two beams and transverses both the reference and the sensing waveguides before exiting the structure to form Young's interference fringes in the far-field.
  • a helium neon laser 632.8 nm
  • QCM Q-Sense QCM-D300 with a Q-Sense Axial Flow Cell (QAFC301 ) (Q-Sense AB, Vastra Fr ⁇ lunda, Sweden).
  • the system was initially equilibrated with deionized water at 23.35 ⁇ 0.025 Q C. Once all resonant overtone parameters were within the range stipulated by the manufacturer, the system was pre-equilibrated with sterile, enriched seawater K-medium used to culture the cells (Keller, M. D., Selvin, R. C, Claus, W. and Guillard, R. R. L. 1987. "Media for the culture of oceanic ultraphytoplankton" J. Phycol.
  • PSS-PEG2/PAH and PSS-PEG1/PAH test surfaces QCM experiments utilising comparable cell concentrations of the diatom species Haslea sp. (Fig. 7 and Fig. 8) and Amphora coffeaeformis (Fig. 9) revealed remarkably similar trends for cells settled upon each of the test surfaces.
  • Haslea sp. induced negligible parameter responses when settled upon PSS-PEG 1 & PSS-PEG 2, producing f shifts of -5 Hz and -1 Hz, and D shifts of 2 and 3, respectively.
  • There was also negligible impact noticeable on the click-PEG surface Fig.
  • Haslea sp. settlement experiments on PSS-PEG 2/PAH test surfaces The adhesion of Haslea sp. to the unmodified control surface (i.e. gold) induced a strong frequency response, concluding at - 56.51 Hz at 18 h (see Fig. 5). This is a significant deviation from the natural drift of the instrument, indicating strong adhesive interaction between cells and the sensor surface.
  • the settlement of Haslea sp. on (PSS-PEG 1/PAH) 3 PSS-PEG 1 and (PSS-PEG 2/PAH) 3 PSS-PEG 2 induced maximum frequency responses of - 6.99 Hz and -5.91 Hz respectively (Fig. 10; Fig. 1 1 d.
  • FIG. 17 illustrates the frequency (/) and dissipation (D) responses recorded over a 5 hr period upon the injection of zoospores of Ulva sp. onto either a native cleaned gold sensor surface, or surface modified by the adsorbing of either PSS, PSS-PEG 1 or PSS-PEG 2.
  • PSS-PEG 1 generated large parameter shifts
  • PSS-PEG 2 produced only negligible frequency (-3 Hz) and dissipation (2) shifts over the 5 hr study.
  • the PSS surface induced a minor frequency shift of -5 Hz and dissipation shift of 2. The parameter shifts are significant for several reasons.
  • zoospores Upon adhesion to a surface, zoospores secrete an adhesive pad which provides permanent adhesion to a surface. Previous to this, the cells are actively moving throughout the chamber, searching for a suitable surface on which to adhere. Therefore, if zoospores actively bind to the substrate surface upon the sensor, significant parameter shifts would be expected as illustrated for the PSS-PEG 1 surface, and to a lesser degree the native gold surface. However, if there is a minimal response in the f and D parameters, then there is no adhesive interaction between the zoospores and the substrate.
  • Example 10 Microscope observations of diatom settlement Microscope slides were imaged using a Panasonic digital 3CCD camera set upon a
  • Diatom cells inoculated onto the gold quickly settle and move over the surface, secreting adhesive mucilage and generating a response by the QCM crystal.
  • diatoms On the PSS surface, diatoms likewise settle and instantly start moving over the surface.
  • diatoms are shown to adhere strongly to gold, but weakly to the PSS.
  • the fact that cells move quickly on the PSS surface indicates that there is enough adhesion to at least generate sufficient traction for movement.
  • Diatoms do not show normal settlement behaviour when placed over the PSS-PEG 1 and PSS-PEG 2 surfaces discussed above. Cells were not seen to adhere to the surface even after several hours, and instead tend to adhere to one another to form clumps of cells that appear to accumulate just off the surface.
  • the PSS-PEG surfaces and the click-PEG surface are not recognized by the organisms as surfaces, even after several hours. Eventually, some contact is made with the PSS-PEG 1 surface, and this does allows some movement. With the exception of the gold surface, diatoms are easily removed from the other surfaces by gentle agitation and even mild shear from the flow chamber is not required.
  • Microscope slides were placed in a plastic quadriperm dish, which was subsequently filled with sterile seawater. Seawater with zoospores was then injected above slides and the zoospores observed over time using a Nikon inverted microscope at low and medium magnification. A haemocytometer was used to ensure that the cell concentration in suspension was consistent for all experiments.
  • Example 12 Assays of bacterial adhesion to PSS-PEG 2/PAH test surfaces
  • the slide surface with adhered organisms was stained and fixed by drawing a solution of 20 mg ml71 Hoechst 33342 (trihydrochloride) (Molecular Probes: H 1399) fluorescent stain in 2.5% glutaraldehyde in sterile filtered seawater under the coverslip and the coverslip sealed with Valap (Vaseline, Paraffin and lanolin in a 1 :1 :1 ratio).
  • Valap Valap
  • the outer edge of the Valap seal was subsequently coated with a thin layer of nail varnish to enhance the seal.
  • EPS extracellular polymeric substances
  • Fig. 23 contains representative images of the substrate surfaces that were either subjected to a simple shear stress test (b,d,f,h) or not subjected to shear stress (a,c,e,g).
  • Example 15 Flow chamber adhesion assays Slides were placed in plastic quadriperm dishes and these were filled with sterile seawater. A 2ml_ aliquot of sterile seawater with cells was added to each quadriperm dish. The concentration of cell suspensions used in all experiments was consistent, as determined with a haemocytometer. Cells were allowed to settle for 6 h at 16O under Sylvania 15W Cool White fluorescent lamps.
  • the slides were mounted onto the slide holder from quadriperm dishes filled with Instant Ocean®.
  • the slide holder is resident in an open tank continuous to the flow channel, and is constantly in the aqueous environment. Slides were subjected to a flow rate of either 60 L min '1 or 120 L min '1 for 5 min. For each flow rate, three replicate assays were performed. As a control, fouling was analysed on three slides which had not been exposed to shear.

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Abstract

La présente invention concerne un procédé de protection d'une surface contre un encrassement biologique. La présente invention peut être utilisée, en particulier, à des fins de protection de la surface d'objets utilisés en milieu aquatique et, en particulier, en milieu marin. La présente invention concerne également des nécessaires utilisables dans le cadre des procédés de la présente invention.
PCT/AU2008/001869 2007-12-19 2008-12-19 Procédé de protection d'une surface contre l'encrassement biologique Ceased WO2009076722A1 (fr)

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AU2007906976A AU2007906976A0 (en) 2007-12-19 Method of Protecting a Surface from Biological Fouling
AU2007906976 2007-12-19

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2700660A1 (fr) * 2012-08-24 2014-02-26 Rohm and Haas Company Polymère d'alkylamine encombré
US20140083931A1 (en) * 2012-03-05 2014-03-27 Chung Yuan Christian University Anti-biofouling Membrane for Water-Treatment
WO2016046523A1 (fr) * 2014-09-22 2016-03-31 Novabiotics Limited Utilisation de la cystamine pour le traitement d'infections bacteriennes et fongiques
WO2016166084A1 (fr) * 2015-04-13 2016-10-20 Basf Se Procédés pour réduire l'encrassement de surfaces
US9782423B2 (en) 2010-12-14 2017-10-10 Novabiotics Limited Antibiotic compositions comprising an antibiotic agent and cysteamine
US10384167B2 (en) 2013-11-21 2019-08-20 Oasys Water LLC Systems and methods for improving performance of osmotically driven membrane systems
JP2019183021A (ja) * 2018-04-12 2019-10-24 東洋インキＳｃホールディングス株式会社 バイオフィルム形成抑制コート剤及びバイオフィルム形成抑制積層体
JP2020038059A (ja) * 2017-08-31 2020-03-12 東洋インキＳｃホールディングス株式会社 蛋白質、細胞又は微生物の接着抑制剤、並びにその用途
WO2021212155A1 (fr) * 2020-04-17 2021-10-21 Kraton Polymers Llc Composition de peinture antimicrobienne
WO2021212153A3 (fr) * 2020-04-17 2021-11-25 Kraton Polymers Llc Composition de pulvérisation antimicrobienne
WO2021212147A3 (fr) * 2020-04-17 2021-12-02 Kraton Polymers Llc Équipement de protection biosécurisé et ses procédés de fabrication
WO2022120393A3 (fr) * 2020-12-02 2022-09-01 Maxwell Biosciences, Inc. Traitements de surface utilisant des analogues peptidiques antimicrobiens immobilisés

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0040498A1 (fr) * 1980-05-09 1981-11-25 M & T Chemicals B.V. Polymères à propriétés biocides
WO2002000785A1 (fr) * 2000-06-26 2002-01-03 Dupont Teijin Films Us Limited Partnership Film polymere
WO2003080747A1 (fr) * 2002-03-26 2003-10-02 Jotun As Polymere filmogene et peinture antisalissure
JP2004202385A (ja) * 2002-12-25 2004-07-22 Chugoku Marine Paints Ltd プライマー防汚塗膜または複合防汚塗膜で被覆された水中構築構造物塗装体、および水中構築構造物の防汚方法
US20070021529A1 (en) * 2003-09-25 2007-01-25 Ndsu Research Foundation Polymeric materials with anti-fouling activity
US20070129461A1 (en) * 2005-12-01 2007-06-07 University Of Victoria Innovation And Development Corporation Antifouling polymeric agent for marine applications

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0040498A1 (fr) * 1980-05-09 1981-11-25 M & T Chemicals B.V. Polymères à propriétés biocides
WO2002000785A1 (fr) * 2000-06-26 2002-01-03 Dupont Teijin Films Us Limited Partnership Film polymere
WO2003080747A1 (fr) * 2002-03-26 2003-10-02 Jotun As Polymere filmogene et peinture antisalissure
JP2004202385A (ja) * 2002-12-25 2004-07-22 Chugoku Marine Paints Ltd プライマー防汚塗膜または複合防汚塗膜で被覆された水中構築構造物塗装体、および水中構築構造物の防汚方法
US20070021529A1 (en) * 2003-09-25 2007-01-25 Ndsu Research Foundation Polymeric materials with anti-fouling activity
US20070129461A1 (en) * 2005-12-01 2007-06-07 University Of Victoria Innovation And Development Corporation Antifouling polymeric agent for marine applications

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11020414B2 (en) 2010-12-14 2021-06-01 Novabiotics Limited Antimicrobial compositions with cysteamine
US9782423B2 (en) 2010-12-14 2017-10-10 Novabiotics Limited Antibiotic compositions comprising an antibiotic agent and cysteamine
US20140083931A1 (en) * 2012-03-05 2014-03-27 Chung Yuan Christian University Anti-biofouling Membrane for Water-Treatment
EP2700660A1 (fr) * 2012-08-24 2014-02-26 Rohm and Haas Company Polymère d'alkylamine encombré
US10384167B2 (en) 2013-11-21 2019-08-20 Oasys Water LLC Systems and methods for improving performance of osmotically driven membrane systems
WO2016046523A1 (fr) * 2014-09-22 2016-03-31 Novabiotics Limited Utilisation de la cystamine pour le traitement d'infections bacteriennes et fongiques
US10850238B2 (en) 2015-04-13 2020-12-01 Solenis Technologies, L.P. Processes for reducing the fouling of surfaces
WO2016166084A1 (fr) * 2015-04-13 2016-10-20 Basf Se Procédés pour réduire l'encrassement de surfaces
EA038493B1 (ru) * 2015-04-13 2021-09-07 Басф Се Способ уменьшения загрязнения поверхности, его применение, полимер для уменьшения биозагрязнения мембраны и мембрана
AU2016249717B2 (en) * 2015-04-13 2021-10-28 Solenis Technologies Cayman, L.P. Processes for reducing the fouling of surfaces
JP2020038059A (ja) * 2017-08-31 2020-03-12 東洋インキＳｃホールディングス株式会社 蛋白質、細胞又は微生物の接着抑制剤、並びにその用途
JP7192314B2 (ja) 2017-08-31 2022-12-20 東洋インキＳｃホールディングス株式会社 蛋白質、細胞又は微生物の接着抑制剤、並びにその用途
JP2023027114A (ja) * 2017-08-31 2023-03-01 東洋インキＳｃホールディングス株式会社 蛋白質、細胞又は微生物の接着抑制剤、並びにその用途
JP7425946B2 (ja) 2017-08-31 2024-02-01 ａｒｔｉｅｎｃｅ株式会社 蛋白質、細胞又は微生物の接着抑制剤、並びにその用途
JP2019183021A (ja) * 2018-04-12 2019-10-24 東洋インキＳｃホールディングス株式会社 バイオフィルム形成抑制コート剤及びバイオフィルム形成抑制積層体
WO2021212155A1 (fr) * 2020-04-17 2021-10-21 Kraton Polymers Llc Composition de peinture antimicrobienne
WO2021212153A3 (fr) * 2020-04-17 2021-11-25 Kraton Polymers Llc Composition de pulvérisation antimicrobienne
WO2021212147A3 (fr) * 2020-04-17 2021-12-02 Kraton Polymers Llc Équipement de protection biosécurisé et ses procédés de fabrication
WO2022120393A3 (fr) * 2020-12-02 2022-09-01 Maxwell Biosciences, Inc. Traitements de surface utilisant des analogues peptidiques antimicrobiens immobilisés

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