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WO2008149134A2 - Composition anti-salissures - Google Patents

Composition anti-salissures Download PDF

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Publication number
WO2008149134A2
WO2008149134A2 PCT/GB2008/050385 GB2008050385W WO2008149134A2 WO 2008149134 A2 WO2008149134 A2 WO 2008149134A2 GB 2008050385 W GB2008050385 W GB 2008050385W WO 2008149134 A2 WO2008149134 A2 WO 2008149134A2
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WO
WIPO (PCT)
Prior art keywords
antifouling composition
composition
antifouling
component
marine bacteria
Prior art date
Application number
PCT/GB2008/050385
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English (en)
Other versions
WO2008149134A3 (fr
Inventor
Keith Martin Macgregor
Original Assignee
Si Laboratories Limited
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Publication date
Application filed by Si Laboratories Limited filed Critical Si Laboratories Limited
Publication of WO2008149134A2 publication Critical patent/WO2008149134A2/fr
Publication of WO2008149134A3 publication Critical patent/WO2008149134A3/fr

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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
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/002—Use of waste materials, e.g. slags
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/006—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels to produce glass through wet route
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C12/00—Powdered glass; Bead compositions
    • 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
    • C08K3/40—Glass
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
    • 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
    • C08K2003/0812—Aluminium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen

Definitions

  • the present invention relates to an antifouling composition applied to a surface to prevent or reduce fouling, in particular in a marine environment.
  • Fouling on underwater surfaces of seaborne vessels such as boats can seriously affect their performance, in particular their speed, acceleration and fuel efficiency, as well as in some cases hasten surface corrosion, which can reduce lifetime and encourage further fouling. Once fouling has taken hold it will not be removed through motion of the boat whereto it is attached, and prolonged fouling will damage the substrata of a boat.
  • an antifouling composition comprising a marine bacteria combating material; wherein the marine bacteria combating material has a negative zeta potential.
  • the marine bacteria combating material preferably has a permanent surface negative charge.
  • Zeta potential is essentially a measure of surface electrostatic properties, and is a theoretical property exhibited by all colloid particles and surfaces within a dispersion medium (eg. sea water) .
  • Zeta potential is a universal measure of the electrical potential difference between a dispersion medium and the stationary layer (or interfacial double layer) of fluid associated with the dispersed particle or surface.
  • the zeta potential of the marine bacteria combating material may be more negative than -25mV, is preferably more negative than -3OmV, preferably more negative than -
  • the marine bacteria combating material is preferably a marine bacteria repelling material.
  • marine bacteria is repelled through electrostatic forces.
  • the combating material is also believed to exhibit catalytic activity which serves to dissociate molecules such as water and oxygen to form highly reactive free radicals.
  • the radicals cause a redox reaction with organic molecules, such as those present in the cell wall of marine bacteria.
  • the marine bacteria combating material is therefore self-sterilizing and actively resists biofouling .
  • the marine bacteria combating material may be a siliceous component, preferably comprising silicon dioxide.
  • the siliceous component is in particulate form.
  • a suitable average particle size for the particulate siliceous component may be from 0.001 to 1000 microns, preferably from 0.01 to 500 microns, more preferably from 0.1 to 100 microns, and most preferably from 5 to 40 microns, as measured by use of a particle image analyser.
  • the particulate siliceous component may be described as a powder.
  • the siliceous component may comprise up to 80 wt% of the antifouling composition, preferably up to 50 wt%, preferably up to 20 wt%, more preferably 0.001 to 20 wt%, preferably 0.01 to 12 wt%, most preferably 0.1 to 8 wt%.
  • the siliceous component may have the required zeta potential following mechanical treatment to form particles of the preferred particulate size.
  • the siliceous component may have the required zeta potential as a result of chemical processing, most preferably by treatment of a suitable precursor with a base, preferably hydroxide ions.
  • the siliceous component preferably comprises a glass component .
  • the glass component may comprise any kind of glass, including high-quartz glass (sometimes called just "quartz sand"), borosilicate glass, or soda-lime glass.
  • high-quartz glass sometimes called just "quartz sand”
  • borosilicate glass or soda-lime glass.
  • the glass is conventionally coloured, e.g. by addition of certain chemical compounds, for example metal oxides such as manganese oxide, cobalt oxide, chromium oxide, sulphur compounds and iron oxides, especially ferric oxide.
  • metal oxides such as manganese oxide, cobalt oxide, chromium oxide, sulphur compounds and iron oxides, especially ferric oxide.
  • Coloured glasses containing one or more of the preceding additive compounds are especially preferred glass components for use in the present invention.
  • iron oxides especially ferric oxide .
  • glasses with a negative surface charge give especially good enhancement of efficacy, owing to a bacteria repelling effect.
  • Preferred glass particles have a zeta potential more negative than - 30 mV.
  • glass particles for use in the present invention preferably have a negative surface charge.
  • a negative surface charge may arise in glass particles due to the chemical nature of the glass, and/or chemical treatment (e.g. with acid or alkali), and/or mechanical treatment, for example when pulverising glass pieces to form the particles or when subjecting glass particles to shear forces.
  • chemical treatment e.g. with acid or alkali
  • mechanical treatment for example when pulverising glass pieces to form the particles or when subjecting glass particles to shear forces.
  • glass particles are injected into the air stream of a jet engine for the purpose of cleaning the jet engine.
  • Another is when glass particles are passed tangentially between the adjacent edges of two rapidly counter-rotating ceramic circular plates.
  • Negatively charged glass particles may simply be purchased on the open market.
  • One example is glass cullet material used to manufacture insulating material.
  • a particulate glass component for use in the present invention may be made by grinding pieces of glass in an industrial grinding apparatus.
  • the pieces of glass may be made by breaking glass artefacts, for example bottles and j ars .
  • Recycled glass is very suitable as a base material for a particulate glass component of the present invention.
  • plain glass may produce a negatively charged surface due to reaction of (SiOH) species in the glass with hydroxyl ions in the water, forming Si(OH) 2 - species on the surface, glass having a pre-charged negative surface is preferred.
  • the composition may also comprise an additional chemical compound, especially of iron, tin, zinc or titanium, preferably selected from the group: ferric oxide, titanium dioxide, zinc oxide, zinc acetate, zinc octoate, zinc chloride, zinc bromide, titanium tetrachloride, u-n-cclvlti.. ⁇ -b- ⁇ .zoyl- ⁇ -nc L hyl-2- 4- v f" r ,v -/-p «r- , ar ⁇ una r ⁇ - ]''':rri, ⁇ , ⁇ ⁇ I , ⁇ " s ⁇ ,” an ado t .
  • an additional chemical compound especially of iron, tin, zinc or titanium
  • the antifouling composition may further comprise a fluoropolymer component, especially a fluoropolymer component which increases the hydrophobicity of the polymer matrix composition.
  • the fluoropolymer component may comprise a fluoropolymer selected from the group including: Teflon®, polyvinylfluoride, and polymers of 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-Dodecafluoroheptyl acrylate, 2,2, 3, 3, 4, 4, 4-Heptafluorobutyl acrylate, 1,1,1,3,3,3- Hexafluoroisopropyl acrylate, 2,2,3,3,4,4,5,5- Octafluoropentyl acrylate, 2,2,3,3,4,4,5,5- Octafluoropentyl methacrylate, 2, 2, 3, 3, 3-Pentafluoropropyl acrylate, 2, 2, 3, 3-Tetrafluoropropyl acrylate or mixtures thereof.
  • the polymer of 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl acrylate is particularly preferred.
  • All such fluoropolymers are readily available commercially, or easily synthesised through standard polymerisation of the respective fluoromonomers .
  • the fluoropolymer component comprises a fluoroalkyl acrylate copolymer, preferably including any of the above monomers, or copolymers of any two or more of the above species.
  • the fluoropolymer component comprises a homopolymer.
  • the fluoropolymer component preferably comprises 0.01 to 10 wt% of the antifouling composition, preferably 0.01 to 2 wt%, more preferably 0.1 to 1.5 wt%, most preferably 0.5 to 1.0 wt%.
  • the antifouling composition preferably comprises a matrix material.
  • the matrix comprises a polymer matrix.
  • the matrix comprises a water-repelling material .
  • composition is preferably "slippy" to the touch when in the form of a dried coating on a substrate.
  • water dropped onto a coating formed from the composition forms beads, which may readily run off it, for example when it is tilted by 10° from the horizontal.
  • the composition may comprise as particulate material an aluminium component.
  • the composition may comprise a carbon component such as carbon black.
  • the aluminium component may comprise aluminium metal.
  • the aluminium component may comprise a water-insoluble compound, for example aluminium oxide or an aluminium silicate .
  • the particulate aluminium or carbon component is in a suitable particulate form that it can be readily dispersible within a coating composition.
  • a suitable particle size of the particulate aluminium or carbon component may be from 1 to 25 microns, more preferably from 2 to 20 microns, preferably from 5 to 10 microns .
  • Particle sizes herein are measured by use of a particle image analyser.
  • the particulate aluminium or carbon component may be described as a powder.
  • the aluminium or carbon component comprises aluminium or carbon platelets, which further enhance the "slippiness" of the composition, when coated, and also coat the substrate such that the platelets mutually overlap to form a barrier, giving protection against water ingress into and osmosis through the said substrate.
  • the aluminium or carbon component is delivered into the composition in a liquid vehicle, preferably a hydrocarbon solvent, preferably C5-C12, more preferably white spirits.
  • a liquid vehicle preferably a hydrocarbon solvent, preferably C5-C12, more preferably white spirits.
  • the weight ratio, aluminium or carbon component to vehicle is between 9:1 and 1:9, more preferably between 7:3 and 3:7, and most preferably between 6:4 and 4:6, so as to form a mobile slurry with the aluminium or carbon prior to mixing with other components of the antifouling composition.
  • the antifouling composition comprises an aluminium or carbon component it preferably comprises up to 5 wt% of the aluminium or carbon component and more preferably 0.01 to 2.5 wt%, and most preferably 0.05 to
  • the matrix preferably comprises a polymeric silicon- containing compound, and preferably two or more such compounds.
  • the compositions comprise at least one siloxane and at least one silane.
  • a polymerisable siloxane or siloxane polymer or oligomer is present.
  • the curing process is moisture activated in air as a result of the moisture content of the atmosphere.
  • Suitable siloxane polymers or oligomers may include dimethylpolysiloxane, diethylpolysiloxane, diphenylpolysiloxane, dimethoxypolysiloxane, diethoxypolysiloxane, dimethylpolysiloxane ethoxylate, poly [methyl (3, 3, 3-trifluoropropyl) siloxane] , hexamethyldisiloxane, hexaethyldisiloxane, hexaphenyldisiloxane, 1,1,3, 3-tetramethyldisiloxane, 1,1,3, 3-tetraethyldisiloxane, 1,1,3,3- tetraisopropyldisiloxane, 1, 3-diethoxy-l, 1,3,3- tetramethyldisiloxane, 1, 3-dimethyltetravinyldisiloxane, pentamethyldisilox
  • Such siloxane polymers may comprise up to 70 wt% of the overall antifouling composition, preferably up to 65 wt%, and more preferably 35 to 55 wt%.
  • Suitable silanes may include tetraethyl silane, tetraallyl silane, tetraphenyl silane, tetrakis (3- fluorophenyl) silane, tetrakis (p-tolyl) silane, ethyltriacetoxysilane, isobutyl (trimethoxy) silane, triacetoxy (vinyl) silane, triethoxy (ethyl) silane, triethyl (trifluoromethyl) silane, trimethoxy (vinyl) silane, trimethyl (phenyl) silane, trimethyl (vinyl) silane, tris (2- methoxyethoxy) (vinyl) silane, l-phenyl-2- trimethylsilylacetylene, 3-trimethylsiloxy-l-propyne, 3- [ tris (trimethylsiloxy) silyl] propyl methacrylate, allyl (4- methoxyphenyl
  • Such silanes may typically comprise up to 20 wt% of the overall antifouling coating composition, but more preferably 1 to 10 wt%.
  • the silanes suitably act as crosslinking agents, catalysts, tensile elasticity control, and adhesion promoters.
  • the polymer matrix may further comprise a siloxanolate of the formula:
  • M can be any monovalent metal ion, preferably an alkali metal; or an ammonium ion, preferably tetraalkylammonium, more preferably tetramethylammonium.
  • a siloxanolate comprises up to 10% wt/wt of composition, preferably 1-5%.
  • the composition contains alkanes, preferably Cu to Ci 5 .
  • the alkanes are isoparaffins
  • the alkanes may constitute up to 55 wt% of the overall composition, but more preferably 20 to 55 wt%.
  • Alkanes are believed to be solvent carriers or diluents for the polymer; as they evaporate the hydrolysis gradually increases to form the final matrix.
  • the matrix composition due to its extreme hydrophobic properties has, it is believed, an unusual antifouling property in that bacterial organisms, which are the base for marine growth contamination, will attempt to colonise the underwater surface. However, not being able to adhere, the lipids which are part of the bacterial membrane will spread attempting to secure adhesion. Ultimately this action will result in bursting of the bacterial membrane and deactivation of the microorganism. This effect is enhanced by inclusion into the matrix of the component with high zeta potential.
  • compositions may be sprayable but are preferably spreadable by means of an implement such as a roller or brush.
  • an implement such as a roller or brush.
  • an antifouling composition with a negative zeta potential there is provided an antifouling composition with a negative zeta potential.
  • an antifouling composition which substantially repels marine bacteria through electrostatic forces .
  • the electrostatic forces result from the antifouling composition having a negative zeta potential.
  • the electrostatic forces result from a marine bacteria combating material.
  • an antifouling composition comprising a marine bacteria combating material; wherein the marine bacteria combating material repels bacteria through electrostatic forces.
  • an antifouling composition comprising a glass component.
  • the glass component preferably has a negative zeta potential as defined above in relation to the first aspect, but this is not essential in this fifth aspect. It may not be material in all embodiments.
  • the antifouling composition further comprises a matrix material.
  • an antifouling composition comprising:
  • a matrix material comprising:
  • a particulate material comprising: - 0.01 to 2.5 wt% aluminium or aluminium oxide or aluminium silicate; and/or
  • the glass component preferably has a negative zeta potential as defined above in relation to the first aspect, but this is not essential in this sixth aspect. It may not be material in all embodiments.
  • a coated substrate wherein the coating comprises a composition of any of the first to sixth aspects .
  • the coating may be applied in one pass, or preferably one or more passes, and most preferably from two to four passes .
  • the coating may undergo further processing once applied; preferably curing in air.
  • the thickness of the final coating is preferably between 50 microns to 2000 microns, more preferably between 100 microns to 1000 microns, and most preferably between 250 microns and 650 microns.
  • a method of preparing a marine bacteria combating material comprising particulating a siliceous component .
  • the method comprises particulating the siliceous component so as to exhibit a negative zeta potential, preferably more negative than -25mV, preferably more negative than -3OmV, more preferably -4OmV, more preferably -5OmV, and most preferably -6OmV.
  • the siliceous component requires no chemical treatment when particulating.
  • the siliceous component is derived from glass.
  • the glass may be waste glass, such as waste bottles.
  • a method for preparing an antifouling composition comprising mixing together the marine bacteria combating material and additional components of the antifouling compositions of any of the first to sixth aspects, to form a sprayable or spreadable product.
  • the marine bacteria combating material may be prepared separately, premixing the marine bacteria combating material with a hydrocarbon solvent to form a mobile slurry which may then be further mixed with the additional components to give a uniform antifouling composition.
  • a tenth aspect of the present invention involves a method of protecting underwater structures from fouling, and preferably corrosion, comprising:
  • the substrate to be treated is clean (for example grease free) and without corrosion damage (for example perforations or crusting) .
  • composition is suitable for the treatment of any surface, though a surface would preferably be selected from the group: fibreglass, metal alloys (including aluminium/aluminium alloy), steel, iron, wood, painted surfaces, conventional antifouling paint, and rubber bitumen .
  • a surface would preferably be selected from the group: fibreglass, metal alloys (including aluminium/aluminium alloy), steel, iron, wood, painted surfaces, conventional antifouling paint, and rubber bitumen .
  • no more than four, and more preferably no more than two coats are applied in any one antifouling treatment program.
  • the applied coating (s) should be left for 24 hours and more preferably 48 hours to cure.
  • antifouling compositions may tolerate temperatures from -40 0 C to 200 0 C after curing.
  • An eleventh aspect of the invention involves the use of the compositions described in any of the first to sixth aspects to prevent fouling on underwater structures, and preferably those from the group including boats, ships, submarines, submarine oil field facilities, underwater tunnels, fishing nets, water intakes, pipelines, jetties, breakwaters, groynes, buoys and bridges.
  • the antifouling coatings herein disclosed should last for at least 5 years, more likely at least 10 years and most likely at least 20 years.
  • antifouling compositions of the present invention include:
  • a polymer matrix material - a particulate marine bacteria combating material; and an optional metal component.
  • the particulate marine bacteria combating material is a siliceous component, whereas the optional metal component is an aluminium component.
  • the siliceous component has particles with a negative surface charge. This negative surface charge is believed to provide a source of electrostatic repulsion to colloidal bacteria particles, which themselves appear generally to exhibit a negative surface charge. Since fouling and the accumulation of marine growth typically starts with bacterial fouling, the repulsion of bacteria is considered to be a crucial factor in the development of improved antifouling compositions.
  • Zeta potentials a theoretical property exhibited by all colloid particles and surfaces within a dispersion medium (eg. sea water) .
  • Zeta potential is a universal measure of the electrical potential difference between a dispersion medium and the stationary layer (or interfacial double layer) of fluid associated with the dispersed particle or surface .
  • a zeta potential (positive or negative) essentially reflects the polarity and magnitude of the charge at the actual surface of a dispersed particle. Therefore, two particles having a high zeta potential of the same polarity will tend to repel. Two particles having either low zeta potentials or zeta potentials of opposite polarity will tend to attract, thus accounting for their tendency to coagulate or flocculate. Zeta potentials are therefore also a useful indication of whether two types of particles will form a stable emulsion or not.
  • zeta potential is seen as an important measure of the affinity of bacteria, dispersed in marine environments, for surfaces coated with antifouling compositions.
  • siliceous components have been produced which exhibit highly negative zeta potentials. Such siliceous components are then ideal for use in antifouling compositions .
  • the siliceous component is generated through compacting coloured glass bottles, flushing with 2M citric acid, and processing in a high speed cyclone to produce glass particles between 5 and 40 microns in size.
  • An equally useful siliceous component is generated through feeding powdered glass (preferably derived from coloured glass bottles) through two grooved metal or ceramic circular plates separated by 20 microns and spinning at high speed in opposite directions.
  • Both methods yield glass particles of approximately 20 microns with highly negative zeta potential.
  • the siliceous component is generated through the hydrolysis of tetraethyl orthosilicate (TEOS) obtained from Sigma-Aldrich.
  • TEOS tetraethyl orthosilicate
  • a sol-gel is formed between TEOS and hydrochloric acid solution, by heating the two components together at 50 0 C for 1 hour. The sol-gel is then dried at 150 0 C to produce a fine powder of silicon dioxide having an average particle size of below 20 microns.
  • sol-gel may also be formed using ammonia or ethyl alcohol and/or a process of air drying.
  • EXAMPLE 3 The zeta potentials of the siliceous components formed from Examples 1 and 2 were subsequently measured.
  • Example 1 and 2 silicon dioxide product A sample of each of Example 1 and 2 silicon dioxide product was made up in a Zetasizer Nano cell (folded capillary cell) as a 0.5% w/v dispersion in deionised water.
  • the dispersant had an RI (refractive index) of 1.33, a viscosity of 0.8872 cP at ambient temperature, and a dielectric constant of 78.5.
  • Each sample was at pH 6.8 and was analysed at 25°C.
  • Example 1 sample -47.2 mV
  • Example 2 sample -25.0 mV
  • siliceous component formed from ground coloured glass was deemed preferable for compositions of the present invention.
  • a control antifouling composition was made by blending the following components: - 3 . 0 % w/w tetraethyl s i lane 54 . 8 % w/w i soparaf f ins , Cn-Ci 5
  • the first four components were blended, followed by the aluminium fines.
  • Two additional antifouling compositions were formed: the first by blending 10% w/w of the siliceous component of Example 1 into the control antifouling composition; and the second by blending 10% w/w of the siliceous component of Example 2 into the control antifouling composition.
  • compositions were then individually packaged in airtight paint tins, with the intention of later brushing from the tins onto a suitable substrate, e.g. a boat hull, or conveying to a sprayer apparatus.
  • a suitable substrate e.g. a boat hull, or conveying to a sprayer apparatus.
  • the thickness of a typical coat after application of two layers and curing in air is 150 to 400 microns.
  • the composition feels "slippy" and is not wetted by water: water dropped onto the coated substrate held horizontally forms beads; inclining the substrate even a small amount, e.g. 10°, causes the beads to run off the surface .
  • Example 4 Three test plates were coated using the compositions of Example 4: the first with the control antifouling composition; the second with the coating containing silicon dioxide of Example 1; and the third with the coating containing silicon dioxide of Example 2.
  • Example 1 and Example 2 coatings were found to be substantially free of bacterial marine growth (as assessed by eye) , albeit Example 2 showed signs of minor accumulation of bacteria.
  • the control antifouling composition clearly had bacterial accumulations.
  • coatings formed from all the compositions are resistant to fouling. Such fouling as does form is poorly adhered and can be quickly removed, for example, by mild rubbing or by spraying with water. Application of a second such coating, if wished, is easily achieved; the first and second coatings bond well together.
  • An antifouling composition was made by blending the following components:
  • the first four components were blended, followed by the ground glass powder.
  • the composition was then packaged in airtight paint tins, with the intention of later brushing from the tins onto a suitable substrate, e.g. a boat hull, or conveying to a sprayer apparatus .
  • the thickness of a typical coat after application of two layers and curing in air is 150 to 420 microns.
  • the composition feels "slippy" and is not wetted by water: water dropped onto the coated substrate held horizontally forms beads; inclining the substrate even a small amount, e.g. 10°, causes the beads to run off the surface.
  • Coatings formed from the composition did not have any marine growth during six months' immersion in seawater. Such fouling as does form is poorly adhered and can be quickly removed, for example, by mild rubbing or by spraying with water. Application of a second such coating, if wished, is easily achieved; the first and second coatings bond well together.
  • An antifouling composition was made by blending the following components:
  • the first six components were blended, followed by the aluminium fines.
  • the composition was then packaged in airtight paint tins, with the intention of later brushing or spraying onto a hull or undersurface intallation, for example of a jetty, breakwater, buoy or bridge.
  • the thickness of a typical coat after application of two layers and curing in air is 150 to 400 microns.
  • the composition feels "slippy" and is not wetted by water: water dropped onto the coated substrate held horizontally forms beads.
  • Coatings formed from the composition are resistant to fouling. Such fouling as does form is poorly adhered and can be quickly removed, for example, by mild rubbing or by spraying with water. Application of further coating, if wished, is easily achieved; successive coatings bond well together .
  • compositions of Examples 4 to 7 are all found to have enhanced antibacterial and antifouling properties when blended with 2% w/w titanium dioxide.
  • the titanium dioxide acts as a photocatalyst in the presence of UV light, to further create a hostile environment for bacteria. This is believed to be the result of the localised generation of oxygen gas, especially whilst the coating is exposed to UV light such as from the sun.
  • compositions of Examples 4 to 8 were further enhanced in terms of their hydrophobic properties through the addition of 1% w/w of a fluoropolymer such as the polymerised adduct of 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl acrylate (available from Sigma-Aldrich) .
  • a fluoropolymer such as the polymerised adduct of 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl acrylate (available from Sigma-Aldrich) .
  • a fluoropolymer such as the polymerised adduct of 2, 2, 3, 3, 4, 4, 5, 5-octafluoropentyl acrylate (available from Sigma-Aldrich) .
  • Such fluoropolymers particularly improved the compositions of Example 4 in terms of their bacteria combating properties and also their general hydrophobicity .
  • An antifouling composition was made by blending the following components:
  • the components were blended and then packaged in airtight paint tins, with the intention of later brushing from the tins onto a suitable substrate, e.g. a boat hull, or conveying to a sprayer apparatus .
  • a suitable substrate e.g. a boat hull, or conveying to a sprayer apparatus .
  • Hydroxy-terminated polydimethylsiloxane has a viscosity of 500 P (50 Pa. s) and serves as the foundation of the composition and is cross-linked on curing by the various silanes present.
  • Non-hydroxy terminated polydimethylsiloxane has a viscosity of 10 P (1 Pa. s) and is a plasticizer which allows a flexible substrate coated with the above composition to be flexed without cracking the coating.
  • N-beta- (aminoethyl) -gamma- aminopropylmethyldimethoxysilane is an adhesion promoter which helps the composition initially adhere to a substrate to be coated before curing takes place.
  • the isoparaffinic solvent acts as a diluent or thinning agent to provide the composition with a consistency conducive to spreadability .
  • the thickness of a typical coat after application of two layers and curing in air is 150 to 400 microns.
  • the composition feels "slippy" and is not wetted by water: water dropped onto the coated substrate held horizontally forms beads; inclining the substrate even a small amount, e.g. 10°, causes the beads to run off the surface .
  • Coatings formed from the composition are resistant to bio-fouling in marine environments and did not have any marine growth during six months' immersion in seawater.
  • Such fouling as does form is poorly adhered and can be quickly removed, for example, by mild rubbing or by spraying with water.
  • Application of a second such coating if wished, is easily achieved; the first and second coatings bond well together.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention porte sur une composition anti-salissures appliquée à une surface pour empêcher ou réduire les salissures, en particulier dans un environnement marin. La présente invention porte en outre sur une composition anti-salissures comprenant un matériau combattant les bactéries marines, ce dernier ayant un potentiel zêta négatif. Les compositions anti-salissures de la présente invention combattent essentiellement les bactéries marines par des forces électrostatiques.
PCT/GB2008/050385 2007-06-02 2008-05-28 Composition anti-salissures WO2008149134A2 (fr)

Applications Claiming Priority (2)

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GBGB0710574.5A GB0710574D0 (en) 2007-06-02 2007-06-02 Antifouling composition
GB0710574.5 2007-06-02

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WO2008149134A3 WO2008149134A3 (fr) 2009-01-29

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172275A (zh) * 2011-12-23 2013-06-26 富港电子（东莞）有限公司 抗菌触摸面板及其制造方法
WO2017020147A1 (fr) * 2015-08-03 2017-02-09 天津纳微华瑞科技有限公司 Peinture et revêtement fonctionnels composites anti-encrassement et antitraînée de type cationique
KR20170060642A (ko) * 2015-11-24 2017-06-02 한국기계연구원 표면 개질을 통해 우수한 내오염성을 갖는 세라믹 분리막 및 그 수처리 방법
US9896601B2 (en) 2015-05-27 2018-02-20 Gaco Western, LLC Dirt pick-up resistant silicone compositions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217408A (en) * 1967-03-22 1970-12-31 United States Steel Corp Antifoulant composition and method
GB1542064A (en) * 1976-04-29 1979-03-14 Standard Telephones Cables Ltd Biocidal compositions
EP0851009A2 (fr) * 1996-12-24 1998-07-01 Matsushita Electric Works, Ltd. Composition de revêtemnt antiadhésive et anti-fouling et articles revêtus
EP0903398A2 (fr) * 1997-09-23 1999-03-24 Exxon Research And Engineering Company Graisse lubrifiante contenant une amine alcoxylée comme inhibiteur de corrosion
WO2001094487A2 (fr) * 2000-06-02 2001-12-13 Microphase Coatings, Inc. Composition de revetement antisalissure
US20060142413A1 (en) * 2003-02-25 2006-06-29 Jose Zimmer Antimicrobial active borosilicate glass

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217408A (en) * 1967-03-22 1970-12-31 United States Steel Corp Antifoulant composition and method
GB1542064A (en) * 1976-04-29 1979-03-14 Standard Telephones Cables Ltd Biocidal compositions
EP0851009A2 (fr) * 1996-12-24 1998-07-01 Matsushita Electric Works, Ltd. Composition de revêtemnt antiadhésive et anti-fouling et articles revêtus
EP0903398A2 (fr) * 1997-09-23 1999-03-24 Exxon Research And Engineering Company Graisse lubrifiante contenant une amine alcoxylée comme inhibiteur de corrosion
WO2001094487A2 (fr) * 2000-06-02 2001-12-13 Microphase Coatings, Inc. Composition de revetement antisalissure
US20060142413A1 (en) * 2003-02-25 2006-06-29 Jose Zimmer Antimicrobial active borosilicate glass

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172275A (zh) * 2011-12-23 2013-06-26 富港电子（东莞）有限公司 抗菌触摸面板及其制造方法
US9896601B2 (en) 2015-05-27 2018-02-20 Gaco Western, LLC Dirt pick-up resistant silicone compositions
WO2017020147A1 (fr) * 2015-08-03 2017-02-09 天津纳微华瑞科技有限公司 Peinture et revêtement fonctionnels composites anti-encrassement et antitraînée de type cationique
KR20170060642A (ko) * 2015-11-24 2017-06-02 한국기계연구원 표면 개질을 통해 우수한 내오염성을 갖는 세라믹 분리막 및 그 수처리 방법
KR102006133B1 (ko) * 2015-11-24 2019-08-02 한국기계연구원 표면 개질을 통해 우수한 내오염성을 갖는 세라믹 분리막 및 그 수처리 방법

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GB0710574D0 (en) 2007-07-11
WO2008149134A3 (fr) 2009-01-29

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