WO2016038363A1 - Composition anti-salissures - Google Patents

Composition anti-salissures Download PDF

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Publication number
WO2016038363A1
WO2016038363A1 PCT/GB2015/052605 GB2015052605W WO2016038363A1 WO 2016038363 A1 WO2016038363 A1 WO 2016038363A1 GB 2015052605 W GB2015052605 W GB 2015052605W WO 2016038363 A1 WO2016038363 A1 WO 2016038363A1
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WO
WIPO (PCT)
Prior art keywords
composition according
antifouling
resin
copper
hydrophilic
Prior art date
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PCT/GB2015/052605
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English (en)
Inventor
Richard Foster
Original Assignee
Richard Foster
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Publication date
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Publication of WO2016038363A1 publication Critical patent/WO2016038363A1/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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/085—Copper

Definitions

  • the present invention relates to an antifouling composition, in particular to an antifouling composition comprising copper as an antifouling agent.
  • the composition finds use in situations where fouling is to be prevented, in particular in the protection against fouling of marine and water-borne craft.
  • Copper is known to be toxic to marine plants and animals and has been employed for a considerable time as an antifouling agent. It is known to sheath articles or structures in environments that render them susceptible to fouling in copper or an alloy of copper. In the past, copper 1 oxide, often referred to as red copper oxide, has been used in paints and coatings to prevent fouling. More recently, coatings have been formed using a composition comprising metallic copper powder suspended in a carrier, such as a resin. Compositions of this latter type have gained popularity due to their ability to provide protection for extended periods of time, in some cases up to and exceeding ten years. Compositions comprising metallic copper suspended in a carrier may be applied to a surface as a coating, for example to the hull of a boat or ship. Alternatively, or in addition, the composition may be incorporated into the hull composition, for example during moulding.
  • US 3,219,505 concerns a treatment of surfaces to prevent fouling, the treatment comprising applying to the surface a water impermeable, thermosetting resin containing particles of copper.
  • the resin is lightly sanded after application to the surface, in order to expose copper at the surface of the resin.
  • the surface being treated may be coated with a glass fibre cloth prior to application of the copper/resin composition.
  • the copper/resin composition may also be used in the manufacture of an article by impregnating a glass fibre cloth with the aforementioned copper/resin composition.
  • the treatment is particularly suited for the hulls of boats and other articles that are immersed in water when in use.
  • GB 2084488 proposes a method of moulding an article to be protected from fouling, the method comprising applying to the surface of a mould a composition comprising a powder of copper or a copper alloy and a catalysed fluid resin. A layer of glass fibres and resins is applied to the composition. After curing, the moulding is removed from the mould. The surface of the resin is lightly abraded to reveal the copper or copper alloy at the surface.
  • GB 2084488 discloses a coating to treating a structure to prevent biofouling, the coating comprising the aforementioned copper or copper alloy/resin mixture.
  • EP 0 046 354 discloses a development of the coating of GB 2084488.
  • EP 0 046 354 discloses that resin-based compositions containing powdered copper or copper alloy may be formed from polyester and similarly curable resins providing that the resin has an acid value below about 10 mg KOH/g, more preferably less than 5 mg KOH/g.
  • the resins employed in EP 0 046 354 are those cured by free-radical initiated cross-linking mechanisms, such as polyesters, vinyl esters and urethane acrylates. Abrasion of the surface of the composition once applied is generally required. To avoid the need to abrade the surface of the composition to expose copper, it is necessary to employ high loadings of copper or copper alloy in the composition.
  • compositions according to the disclosure of GB 2084488 and EP 0 046 354 found a measure of commercial success, in particular for use as a gel coat in the manufacture of a moulded boat hull, prior to the hull being laminated.
  • the need to abrade the coating to reveal the copper at the surface of the coating is not practical and leads to technical problems.
  • the use of high copper loadings to avoid the need to abrade the surface is not practical.
  • EP 0499817 discloses an antifouling coating composition comprising a copper alloy powder as an antifouling agent.
  • An antifouling coating composition is described in each of JP 06088044, JP 04356567 JP 06057179 and JP 06057180.
  • an epoxy resin-based antifouling composition was developed and commercialised.
  • the composition was intended to avoid the need to abrade the surface in order to reveal copper.
  • the composition comprised copper powder bound in an epoxy resin matrix.
  • the resin matrix included a water soluble resin, such as an ethylene vinyl alcohol resin or the like, with the intention that the water soluble resin would dissolve in use, leaving the epoxy resin matrix porous, allowing the copper to leach to the surface.
  • Products employing this composition have been made commercially available under the trade names CoppercoatTM and Copper 2000TM.
  • the principle of rendering an epoxy-based copper antifouling composition porous to water has been successfully developed and commercialised in the current commercial product CopperplusTM.
  • the product comprises copper dispersed in an epoxy resin matrix.
  • the resin matrix is rendered porous by the inclusion of methyl diproxitol, which leaches out of the matrix over time, exposing the dispersed copper.
  • Epoxy resin is a good binder for coating compositions.
  • epoxy resin is virtually impermeable to water. Modification of the epoxy resin matrix is therefore required in order to achieve the porosity necessary to allow the composition to be effective as an antifouling treatment, if abrasion of the surface of the composition to reveal the copper antifouling agent is to be avoided.
  • the permeability of modified epoxy resin binders is affected by the degree of cure of the binder. This is in turn affected by the ambient temperature at the time the resin composition is applied as a coating. The permeability is also affected by temperature over time, for a month or more after application. Other factors that affect the performance of an epoxy-based copper antifouling composition are the ratio of hardener to resin employed. In addition, over the lifetime of the coating, unreacted epoxy groups in the matrix can
  • an improved antifouling composition is provided when copper powder is dispersed in a resin matrix comprising a hydrophilic resin component and a compatible hydrophobic resin component.
  • the present invention provides an antifouling composition comprising:
  • compositions of the present invention exhibits improved antifouling performance.
  • the composition exhibits a leaching rate of copper that is controllable and is unaffected by the ambient conditions both during and after the application of the composition.
  • the presence in the resin binder matrix of a hydrophilic resin component renders the resin binder system permeable. This in turn allows the composition to absorb water, thus allowing copper ions to diffuse to the surface of the coating, without the need to abrade the composition once applied. It has been found that the leaching rate of copper from the composition is readily controlled by varying the proportions of the hydrophilic and hydrophobic components of the resin binder matrix.
  • the composition comprises a copper antifouling agent.
  • the presence of copper in the composition provides the required antifouling activity. Copper may be present in the composition in any suitable form that provides an antifouling action at the surface of the composition when applied.
  • the antifouling action is provided by the presence of copper ions at the surface of the composition, which are oxidised to form copper 1 oxide, which is the active agent in preventing fouling.
  • the copper antifouling agent present in the composition may be any copper-containing compound or composition that is able to generate copper ions upon contact with water.
  • the copper antifouling agent is most preferably present in a finely divided form, in particular as a powder, more particularly as a spherical powder.
  • the copper antifouling agent comprises copper metal.
  • the copper antifouling agent may comprise a copper alloy that exhibits an antifouling activity.
  • copper-containing alloys include alloys of copper and nickel, such as copper/nickel alloys having a ratio of copper and nickel of from 90:10 to 99:1 parts by weight.
  • a copper/nickel alloy having a ratio of copper and nickel of 90:10 is effective as an antifouling agent and exhibits a low leaching rate for the copper.
  • the copper antifouling agent may comprise a copper-containing compound, for example copper 1 oxide.
  • the copper antifouling agent may be present in the antifouling composition in any suitable amount, in particular to provide the required antifouling protection when the composition is applied to a surface to be protected.
  • the composition may comprise at least 30% by weight of the copper antifouling agent, preferably at least 40%, more preferably at least 50%, still more preferably at least 60% by weight.
  • the copper antifouling agent may be present in the composition in an amount of up to 90% by weight, more preferably up to 80% by weight, still more preferably up to 70% by weight.
  • An amount of the copper antifouling agent in the range of from 50 to 80% by weight is preferred, more preferably in the range of from 60 to 70% by weight.
  • the copper antifouling agent is dispersed in the resin binder matrix.
  • the resin binder matrix comprises a hydrophilic resin component and a hydrophobic resin component. It is preferred that the hydrophobic resin component constitutes the major portion of the resin binder matrix, with the hydrophilic resin component forming the minor component of the resin binder matrix.
  • the leaching rate of copper from the composition is dependent upon the amount of hydrophilic resin component present in the resin binder matrix, relative to the amount of hydrophobic resin component. This provides a means for accurately controlling the copper leaching rate of the composition when applied and in use.
  • the weight ratio of the hydrophilic resin component to the hydrophobic resin component in the resin matrix is preferably at least 1 :1 .5, that is the resin component comprises at least 60% by weight of the hydrophobic resin, more preferably at least 1 :2, that is the resin component comprises at least 67% by weight of the hydrophobic resin, still more preferably at least 1 :3, that is the resin component comprises at least 75% by weight of the hydrophobic resin.
  • the weight ratio of the hydrophilic resin component to the hydrophobic resin component in the resin matrix may be up to 1 :20, that is the resin component comprises up to 95% by weight of the hydrophobic resin, more preferably up to 1 :15, that is the resin component comprises up to 94% by weight of the hydrophobic resin, still more preferably up to 1 :10, that is the resin component comprises up to 91 % by weight of the hydrophobic resin.
  • the resin binder matrix may comprise the hydrophilic resin component in an amount of up to 40% by weight, more preferably up to 30% by weight.
  • the resin binder matrix preferably comprises at least 5% by weight of the hydrophilic resin component, more preferably at least 10%, still more preferably at least 15%.
  • the hydrophilic resin component is preferably present in the resin binder matrix in an amount of from 5 to 35% by weight, more preferably from 10 to 30%, still more preferably from 15 to 25% by weight.
  • the resin binder matrix may comprise the hydrophobic resin component in an amount of up to 60% by weight, more preferably up to 70% by weight.
  • the resin binder matrix may comprise up to 95% by weight of the
  • hydrophobic resin component more preferably up to 90%, still more preferably up to 85%.
  • the hydrophobic resin component is preferably present in the resin binder matrix in an amount of from 65 to 95% by weight, more preferably from 70 to 90% by weight, still more preferably from 75 to 85% by weight.
  • the hydrophobic resin component may be a hydrophobic resin or a resin monomer or precursor that can be cured to form a hydrophobic resin, for example by reaction with a hardener. Such resin systems are known in the art.
  • Suitable hydrophobic resin components for inclusion in the resin binder matrix are known in the art and commercially available. Suitable hydrophobic resin components are any resin components that can be used to form a resin matrix for use as a coating on a surface to be treated and protected.
  • the hydrophobic resin component may be a thermosetting resin or a thermoplastic resin system.
  • Thermosetting resin systems are preferred, as they produce more durable coatings.
  • Suitable hydrophobic resins for forming coatings include epoxy resins.
  • Epoxy resin systems can be formulated to include a hydrophilic component, such as a polyoxyethylene.
  • the polyoxyethylene may be included in either the resin monomers or the hardener components. However, as the curing of the epoxy resin occurs over time, the extent and rate of curing vary according to the ambient temperature.
  • epoxy resins are not preferred for use in the composition of the present invention.
  • hydrophobic resins for use in the composition of the present invention are preferably those that have their extent of cure less dependent upon ambient temperature.
  • the temperature-dependency of the resin is preferably within an acceptable range, that is the properties of the resin are not significantly varied across the range of temperatures to which the resin will be exposed during preparation of the coating and its subsequent use.
  • Preferred hydrophobic resins are polyurethane resins, acrylic resins, polyester resins and epoxyester resins.
  • Polyurethane resins are particularly preferred.
  • the hydrophobic resin is a water-borne polyurethane prepared from a hardener, in particular an isocyanate and a resin, in particular a polyol.
  • a hardener in particular an isocyanate
  • a resin in particular a polyol.
  • an excess of the hardener is used, ensuring that most, if not all, of the resin reacts with the hardener, with the remaining hardener reacting with the water. In this way, further reaction of the hydrophobic resin components is prevented.
  • the resin binder matrix of the composition further comprises a hydrophilic resin component.
  • the hydrophilic resin component is present in the resin matrix formed by the hydrophobic resin component.
  • the hydrophilic resin component and the hydrophobic resin component are present as a physical mixture within the matrix, for example in the form of an interpenetrating polymer network.
  • the hydrophobic resin component and the hydrophilic resin component are chemically linked within the resin matrix. Such a chemical linkage is preferably achieved by selecting the hydrophobic resin and the hydrophilic resin to react with the same hardener, in particular an isocyanate hardener.
  • the hardener for the system is one that reacts with water, in particular an isocyanate. In this way, any excess unreacted hardener reacts with water, such as moisture in the atmosphere, within a short period of time after the coating has been applied.
  • the hardener preferably an isocyanate, has a low reactivity with water, preferably substantially no reactivity with water. In this way, adhesion of the composition to a surface may be improved, in particular when applying the composition to a surface in damp or wet conditions.
  • the resin matrix may be formed by reacting each of the hydrophobic resin component and the hydrophilic resin component with a different, respective hardener. In such a case, it is still preferred that the two resin
  • a particularly preferred hardener for use in the composition is an isocyanate.
  • Suitable isocyanates are known in the art and are commercially available.
  • the isocyanate component comprises or is prepared from a polyisocyanate, that is a compound having two or more isocyanate groups.
  • the isocyanate may be aliphatic, alicyclic or aromatic.
  • the isocyanate component comprises one or more aromatics.
  • isocyanates In a particularly preferred embodiment, the isocyanate is a
  • polyisocyanate derived from xylene, that is an aromatic diisocyanate that is an aromatic diisocyanate.
  • Particularly preferred isocyanate xylene-derivatives are xylene diisocyanates bearing one or more substituents on each methyl moiety, in particular one or more alkyl groups, preferably lower alkyl groups, more preferably to C 4 alkyl groups, especially methyl.
  • One particularly preferred isocyanate to form or prepare the hardener is tetramethyl xylene diisocyanate.
  • the hardener is an isocyanate formed by the reaction of a polyisocyanate, preferable a diisocyanate, for example tetramethyl xylene diisocyanate, with a polyol.
  • the hardener is formed by reacting the polyisocyanate with the polyol.
  • the polyisocyanate is present in a molar excess, preferably at least twice the molar amount required to react with the polyol. In this way, the polyol reacts with isocyanate groups of the polyisocyanate, leaving unreacted isocyanate moieties available to form the reactive hardener.
  • the reaction of the polyisocyanate with the polyol also improves the miscibility of the isocyanate with water, which is advantageous when using a polyisocyanate that is not readily miscible with water, such as tetramethyl xylene diisocyanate.
  • the hydrophilic resin component in use, the hydrophilic resin component, as a result of being chemically bound and/or physically retained within the resin binder matrix, remains in the resin binder matrix and the coating, once applied.
  • the cured hydrophilic resin component acts to absorb water into the resin binder matrix. The water so absorbed dissolves the copper antifouling agent present in the composition, producing copper ions. The copper ions leach to the surface of the composition and form copper 1 oxide at the surface, which in turn acts as the active agent to prevent fouling.
  • the hydrophilic resin component may be a hydrophilic resin monomer. The resin monomer is cured to form the hydrophilic resin component.
  • Suitable monomers include acid group-containing hydrophilic unsaturated monomers and salts thereof, nonionic hydrophilic unsaturated monomers and cationic hydrophilic unsaturated monomers. Oligomers and resins formed with the aforementioned monomers may also be used as the hydrophilic resin component of the resin binder matrix of the composition.
  • acid group-containing hydrophilic unsaturated monomers examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, acryloyloxy propionic acid, vinyl-sulfonic acid, styrene- sulfonic acid, 2-(meth)acrylamide-2-methyl propane sulfonic acid, 2-(meth)acryloyl ethane sulfonic acid, 2-(meth)acryloyl propane sulfonic acid, and sulfoethoxy polyethylene glycol mono(meth)acrylate, and salts thereof.
  • nonionic hydrophilic unsaturated monomers include acrylamides, such as acrylamide, methacrylamide, N-ethyl (meth)acrylamide, N-n-propyl
  • (meth)acrylamide N-isopropyl (meth)acrylamide, ⁇ , ⁇ -methyl (meth)acrylamide
  • acrylates and methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- hydroxypropyl (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, polyethylene glycol mono(meth)acrylate
  • pyridines such as vinyl pyridine
  • piperidines such as N-acryloyl piperidine
  • pyrrolidones such as N-acryloyl pyrrolidine
  • cationic hydrophilic unsaturated monomers include certain acrylates and acrylamides, such as ⁇ , ⁇ -dimethylaminoethyl (meth)acrylate, N,N- diethylaminoethyl (meth)acrylate, ⁇ , ⁇ -dimethyl-aminopropyl (meth)acrylate, N,N- dimethylaminopropyl (meth)acrylamide, and quaternary salts thereof.
  • oligomers and resins formed with the above monomers may also be used as the hydrophilic resin component to form the resin binder matrix of the composition.
  • the composition comprises a monomer or precursor for one or both of the resin components, these are reacted and cured as described above to form the resin matrix in the final coating or layer formed using the composition.
  • Preferred hydrophilic components for use in the resin binder matrix of the composition are polyoxyethylene polyols and vinyl pyrrolidone.
  • Polyoxyethylene polyols and polyoxyethylene/oxypropylene copolymer polyols are particularly preferred hydrophilic resin components for use in the composition of the present invention.
  • Polyoxyethylene polyols are solids at room temperature, with the exception of very low molecular weight products.
  • Copolymer polyols with ethylene oxide and propylene oxide are liquids at room temperature.
  • the resin binder matrix comprises a hydrophobic resin component and a hydrophilic resin component.
  • the hydrophobic resin component and the hydrophilic resin component together form the resin matrix in the cured composition, in which the copper antifouling agent is dispersed.
  • the hydrophilic and hydrophobic resin components are selected to be compatible with one another.
  • the hydrophobic resin component and the hydrophilic resin component are suitable to be cured together in a mixture, more preferably with the use of a single hardener composition, as noted above.
  • the hydrophilic resin may be combined with the hydrophobic resin before the hardener is added.
  • the hydrophilic resin component may be combined with the hardener, before being added to the hydrophobic resin for curing.
  • the hardener may be selected to impart the required hydrophilic or hydrophobic properties to one of the resin components.
  • a hydrophilic hardener may be prepared by reacting a hydrophilic component, such as a polyoxyethylene, with an isocyanate to form a hydrophilic hardener.
  • the hydrophilic resin component should also be compatible with the method of curing the hydrophobic resin component.
  • the hydrophilic resin component should not interfere with the curing of the hydrophobic resin component to form the resin matrix.
  • the hydrophilic and hydrophobic properties of the resin components must be retained when the components are mixed and are cured together.
  • the hydrophobic resin component is a hydroxylated acrylic resin, preferably present in the form of an emulsion, and the hydrophilic resin component is a polyoxyethylene polyol, which when reacted form a polyurethane resin matrix.
  • the polyurethane resin is typically formed by a reaction involving an isocyanate, preferably a water miscible isocyanate, which is used as the basis for a hardener.
  • the polyoxyethylene polyol may be combined with the hydrophobic resin component or may be used to prepare a prepolymer with an isocyanate for use as the hardener system.
  • the resin binder matrix may comprise a single hydrophobic resin component or a mixture of two or more such components. Similarly, the resin binder matrix may comprise a single hydrophilic resin component or a mixture of two or more thereof.
  • the composition of the present invention is provided as a coating or layer on the surface of an article, item or structure.
  • the resin binder system is cured and in the form of a resin matrix having the copper antifouling agent dispersed therethrough.
  • the composition may be applied to the surface in any suitable form to provide the aforementioned coating that is effective in preventing fouling by aquatic plants and animals.
  • the composition of the present invention is provided as an uncured formulation, such as a paint composition.
  • the composition comprises the resin components in the form of monomers, pre-polymers and/or precursors that are subsequently cured to form the coating as described above.
  • the composition is preferably provided with a separate hardener composition, as is common practice in the art, such that when the two compositions are combined the resin components cure to form the aforementioned resin matrix.
  • the present invention provides a composition for applying to a surface to provide an antifouling coating thereon, the composition comprising:
  • a resin composition comprising:
  • the resin composition and the hardener composition being combined, whereby the hydrophobic resin precursor and the hydrophilic resin precursor react with the hardener composition to form a resin matrix containing the copper antifouling agent.
  • the hardener composition may comprise a hardener component for reacting with each of the hydrophobic resin precursor and the hydrophilic resin precursor. More preferably, a single hardener component for reacting with both the resin components is employed.
  • the hydrophilic resin precursor may be present in combination with the hydrophobic resin precursor. Alternatively, or in addition thereto, the hydrophilic resin precursor or the hydrophobic resin precursor may be present in the hardener composition.
  • compositions of this embodiment may comprise one or more additional components, for example components that aid the composition being applied to the surface.
  • additional components for example components that aid the composition being applied to the surface.
  • Other components included in coating compositions that may be present in the composition of the present invention are known in the art.
  • the composition may be free of a solvent. More preferably, the composition comprises one or more solvents. Suitable solvents are known in the art and include organic solvents and water. Water is a preferred solvent, as it has a low
  • the solvent is present in a sufficient amount to facilitate application of the uncured composition to the surface being treated. Higher solvent amounts reduce the relative amount of copper antifouling agent in the composition, in turn making application of the composition to the surface easier.
  • a solvent is preferably employed for higher melting point resin components, in particular those that are solid at room or ambient temperatures.
  • the resin component may be dissolved in the solvent.
  • the resin component may be dispersed in the solvent, in particular as an emulsion.
  • the resin binder matrix of the coating composition comprises an acrylic resin as the hydrophobic resin component.
  • the acrylic resin is provided in the form of an emulsion of acrylic monomers in water.
  • the emulsion is polymerised to form a dispersion of particles of solid resin in water.
  • Embodiments of the composition of the present invention that are intended for use as a gel coat, for example for application in a mould, are most preferably free of solvent.
  • the solvent is preferably present in an amount of from 0 to 60% by weight of the composition, more preferably from 1 to 50%, still more preferably from 2 to 40%, more preferably still from 5 to 30% by weight.
  • a particularly preferred solvent content of the composition is from 10 to 25% by weight.
  • Other components that may be present in the composition of this embodiment are known in the art and include, for example, one or more air release agents, one or more surface wetting agents and one or more thickeners. Suitable components are commercially available.
  • the hydrophobic resin component of the resin binder system is a polyurethane resin.
  • the preferred hydrophilic resin component for use in a polyurethane binder system is a polyoxyethylene polyol.
  • the permeability of a copper antifouling agent bound in a polyurethane binder system can be readily controlled by varying the amount of the polyoxyethylene polyol component in the composition. It is well known in the polyurethane industry that, unlike propylene, ethylene oxide containing polyols are water absorbing and consequently they are not normally used in the industry. However suitable polyoxyethylene polyols and
  • polyoxyethylene/oxypropylene copolymer polyols are made in large quantities for other applications such as lubricants and, hence are readily available.
  • Polyoxyethylene polyols and polyoxyethylene/oxypropylene copolymer polyols are particularly preferred hydrophilic resin components for use with polyurethane resin binder systems.
  • Polyoxyethylene polyols are solids at room temperature, with the exception of very low molecular weight products.
  • Copolymers with propylene oxide are liquids at room temperature.
  • Polyoxyethylene/oxypropylene copolymer polyols having an ethylene oxide to propylene oxide (EO/PO) of 70/30 or 75/25 are preferred, as noted above.
  • the present invention provides a method of preparing an antifouling coating containing a copper antifouling agent, the method comprising:
  • composition of the present invention is applied to a surface to provide an antifouling coating or layer.
  • the present invention provides a method of forming an antifouling coating, the method comprising applying to a surface a composition as hereinbefore described.
  • the surface to which the composition is applied may be the surface of an article, such as the hull of a water borne craft or the surface of a submerged structure.
  • the composition may be applied to the surface of a mould, for example to form a gel coat, as part of the moulding process for an article, such as the hull of a water borne craft.
  • the present invention provides an article, such as a water borne vessel, comprising an antifouling composition as hereinbefore described on at least a portion of the surface thereof.
  • An antifouling composition comprising a hydrophobic resin component was prepared having the components set out in Table 1 :
  • a composition was prepared having the components indicated in Table 3.
  • Air release agent (10% wt in water) 5.88 (Dow Corning Additive 62TM)
  • Polyurethane thickener (20% wt in water) 7.83 (Rheovis PU 1270TM)
  • the above components were mixed and formed a smooth paint.
  • the paint exhibited superior application properties compared with known epoxy resin bound systems.
  • the efficacy of the antifouling composition of Table 2 in terms of the rate at which copper was leached from the composition, was tested using the procedure set out in British Standard EN ISO 15181 -1 :2007 Parts 1 and 2. Sea water filtered through a 10 micron filter was used in place of the artificial sea water called for in the standard test procedure.
  • the composition of the present invention exhibited excellent leaching rates of copper from the composition. Compared with the composition of Example 1 , it can be seen that the composition of the present invention, comprising both a hydrophilic resin component and a hydrophobic resin component in the resin binder matrix, exhibited superior leaching rates for the copper antifouling agent.
  • the leaching rate of the composition of Example 2 could be easily controlled by varying the amount of the hydrophilic resin precursor, that is the high ethylene oxide polyol, present in the composition, that is by adjusting the ratio of the hydrophilic and hydrophobic resin components.
  • the leaching rate could be readily increased by increasing the amount of high ethylene oxide polyol present in the composition, relative to the amount of the hydroxylated acrylic component.
  • An antifouling composition was prepared having the components indicated ' Table 5 below.
  • Air release agent (20% wt in water) 4.5 (Dow Corning Additive 62TM)
  • Polyurethane thickener (20% wt in water) 25 (Rheovis PU 1270TM)
  • the composition was found to have excellent antifouling properties.

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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne une composition anti-salissures, la composition comprenant un agent anti-salissures à base de cuivre ; et une matrice liante de résine comprenant un constituant de résine hydrophile et un constituant de résine hydrophobe. La présente invention décrit également une composition à appliquer sur une surface afin d'obtenir un revêtement anti-salissures sur celle-ci, la composition comprenant une composition de résine comprenant un agent anti-salissures à base de cuivre ; un précurseur de résine hydrophile ; un précurseur de résine hydrophobe; et une composition de durcisseur ; la composition de résine et la composition de durcisseur étant combinées à l'utilisation, ce par quoi le précurseur de résine hydrophobe et le précurseur de résine hydrophile réagissent avec la composition de durcisseur pour former une matrice de résine contenant l'agent anti-salissures à base de cuivre. Un procédé de préparation d'un revêtement anti-salissures contenant un agent anti-salissures à base de cuivre comprend la détermination du taux de lixiviation de l'agent anti-salissures à base de cuivre nécessaire pour le revêtement ; l'utilisation d'un mélange comprenant l'agent anti-salissures à base de cuivre, un constituant de résine hydrophobe et un constituant de résine hydrophile, le rapport du constituant de résine hydrophobe et du constituant de résine hydrophile étant choisi pour obtenir le taux de lixiviation déterminé ; et le durcissement du mélange.
PCT/GB2015/052605 2014-09-12 2015-09-09 Composition anti-salissures WO2016038363A1 (fr)

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GB1416128.5 2014-09-12
GB1416128.5A GB2530071B (en) 2014-09-12 2014-09-12 Antifouling composition

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WO2016038363A1 true WO2016038363A1 (fr) 2016-03-17

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563784A (zh) * 2020-04-29 2021-10-29 中环海化(厦门)船舶智能涂料有限公司 一种石墨铜粉基接触型防污涂料及制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499817A1 (fr) * 1991-01-30 1992-08-26 Dai Nippon Toryo Co., Ltd. Composition de revêtement anti-salissure
WO2005068563A1 (fr) * 2004-01-14 2005-07-28 Richard John Foster Revetements antisalissure comprenant une poudre metallique de cuivre et un additif fugitif
EP2206755A1 (fr) * 2007-10-31 2010-07-14 Chugoku Marine Paints, Ltd. Composition de revêtement anti-coloration contenant un composé à base de cuivre et ayant une résistance à la formation de biofilm et une stabilité au stockage améliorées

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2857933B2 (ja) * 1991-01-30 1999-02-17 大日本塗料株式会社 防汚塗料組成物
JP2857934B2 (ja) * 1991-01-30 1999-02-17 大日本塗料株式会社 防汚塗料組成物
JP2857935B2 (ja) * 1991-01-30 1999-02-17 大日本塗料株式会社 防汚塗料組成物
JP2857932B2 (ja) * 1991-01-30 1999-02-17 大日本塗料株式会社 防汚塗料組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0499817A1 (fr) * 1991-01-30 1992-08-26 Dai Nippon Toryo Co., Ltd. Composition de revêtement anti-salissure
WO2005068563A1 (fr) * 2004-01-14 2005-07-28 Richard John Foster Revetements antisalissure comprenant une poudre metallique de cuivre et un additif fugitif
EP2206755A1 (fr) * 2007-10-31 2010-07-14 Chugoku Marine Paints, Ltd. Composition de revêtement anti-coloration contenant un composé à base de cuivre et ayant une résistance à la formation de biofilm et une stabilité au stockage améliorées

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113563784A (zh) * 2020-04-29 2021-10-29 中环海化(厦门)船舶智能涂料有限公司 一种石墨铜粉基接触型防污涂料及制备方法

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GB201416128D0 (en) 2014-10-29
GB2530071A (en) 2016-03-16
GB2530071B (en) 2017-02-15

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