Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/32—Radiation-absorbing paints
• • 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
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
  • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
• • 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
  • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
  • C08K3/013—Fillers, pigments or reinforcing additives
• • 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
  • C09D127/00—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 halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—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 halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/06—Homopolymers or copolymers of vinyl chloride
• • 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
  • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/40—Coatings comprising at least one inhomogeneous layer
  • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
  • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
  • C03C2217/48—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase having a specific function
  • C03C2217/485—Pigments
• • 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
  • C08K2201/00—Specific properties of additives
  • C08K2201/011—Nanostructured additives

Definitions

• the present invention relates to a coating composition that can provide protection from exposure to ultra violet (“UV”) light or UV and visible light having wavelengths from less than 200nm and up to 500 or 550 run.
• UV ultra violet
• the present invention relates to a coating composition that can be applied to containers that are used for storage of products that are light sensitive.
• products include, but are not limited to, foods, beverages, and pharmaceuticals.
• Uncoloured clear containers are known to fail to protect light sensitive contents of the containers from the deleterious effect of UV light or UV and visible light.
• Fully opaque or deep amber coloured containers are less attractive than clear containers in situations where consumers wish to see and inspect the contents of the containers .
• a particular deleterious effect of UV and visible light on beverages such as beer or wine is the generation of off-flavours called "lightstrike” .
• the human nose is particularly sensitive to such off-flavours and therefore the use of containers with UV and visible light protection is important for such products.
• hops that are chemically modified so as to remove the chemical precursor of the molecules responsible for the off-flavours .
• these molecules are also the chemicals that contribute to the bitter flavour that is sought by beer drinkers.
• the resulting beer is considerably less attractive to many consumers .
• metal oxides can strongly absorb in the UV and visible regions of the light spectra.
• metal oxides have lacked the clarity and the transparency to be suitable for use as additives for coatings to be applied to containers where it is important to be able to view the contents of the containers.
• a coating composition that includes a carrier and a pigment dispersed in the carrier, and the pigment includes nanoparticles of a UV light absorber such that the coating composition is capable of absorbing a significant amount of the incident UV light up to 360nm or nanoparticles of a UV and visible light absorber such that the coating composition is apable of absorbing a significant amount of the incident UV and visible light up to 550nm, and the absorber includes an inorganic material.
• nanoparticles is understood herein to mean that the particles are small enough to appear transparent with no haze in visible light.
• nanoparticles that is based on a particular size range of particles.
• preferred nanoparticles are particles less than lOOnm (0.1 microns) equivalent spherical diameter.
• nanoparticles include no significant concentration of particles that exceed lOOnm (as determined by Transmission Electron Microscopy) and have effective colloidal stabilisation with no aggregation, agglomeration or flocculation of individual particles, both as a liquid coating composition and as a coating of the coating composition.
• nanoparticles are particles less than 50nm (0.05 microns) equivalent spherical diameter.
• One suitable type of inorganic material of the absorber is iron oxides.
• Iron oxide-based absorbers are suited particularly for forming coloured transparent coatings of the coating composition.
• Iron oxide-based absorbers are also suited particularly for absorbing the UV and visible region of the light spectra.
• Another, although not the only other, suitable type of inorganic material of the absorber is zinc oxides.
• Zinc-oxide-based absorbers are suited particularly for forming colourless transparent coatings of the coating composition.
• Zinc-oxide-based absorbers are also suited particularly for absorbing the UV region of the light spectra.
• the pigment may include more than one type of absorber.
• the pigment further includes nanoparticles of a pigment that provides or contributes to the colour of the coating composition.
• the pigment may include blue or green pigments or a combination of pigments that result in blue or green pigments .
• the pigment further includes nanoparticles of blue or green pigments that cause the coating composition to be a transparent blue or green colour.
• the pigment includes nanoparticles of yellow or red iron oxide absorber pigments and blue or green pigments that cause the coating composition surprisingly to be a transparent blue or green colour.
• the combination of pale yellow or red iron oxide absorber pigments and blue or green pigments creates a coating composition having good UV and visible light absorption characteristics whilst being a transparent blue or green appearance - an attractive commercial proposition.
• the carrier is capable of acting as
• the carrier is a polymeric material.
• the carrier may be a composite of a number of materials that have a range of characteristics.
• the materials may include materials that have dispersant characteristics predominantly, materials that have film- forming characteristics predominantly, and materials that have dispersant and film forming characteristics.
• the film forming material is selected from the group that includes polyurethanes, polyesters, polyolefins, polyvinyls (including polyvinyl chlorides) and polyacrylics .
• a substrate having a coating of the above- described coating composition.
• the substrate may be formed from any suitable material.
• suitable materials are glass and plastics materials.
• the substrate forms a wall of a container, such as a bottle, and the coating is on an outer surface of the container.
• the thickness of the coating is no more than 100 microns.
• the coating thickness is no more than 50 microns.
• the thickness of the coating is related to the level of protection required and to the concentration of the UV light or UV and visible light (“UV/Vis”) absorber in the pigment in the coating composition. Specifically, a range of different combinations of (i) the concentration of the UV/Vis absorber and (ii) the coating thickness can provide a given level of protection.
• UV/Vis UV and visible light
• the concentration of the UV/Vis absorber and the coating thickness may be preferable to vary the concentration of the UV/Vis absorber and the coating thickness between the above- described two extremes to provide a given level of protection.
• the coating thickness be in the range of 0.1-2 microns.
• the coating thickness is 0.1-1.5 microns and more preferably 0.3-1.5 microns.
• smooth, UV and visible light absorptive blue coatings may be applied as cold end coatings at coating thicknesses of 0.3 to 1 microns.
• a method of forming a coating composition capable of absorbing UV light up to 360nm or UV and and visible light up to 550nm which method includes a step of wet milling a carrier and a pigment to form a comminuted dispersion of the pigment in the carrier, and the pigment including nanoparticles of an absorber capable of absorbing UV light or UV and visible light up to 550nm.
• the carrier includes a dispersant in order to prevent floccs forming during the wet milling step.
• Preferred dispersants include:
• the wet milling step is carried out at a low solids content.
• the solids content is 5-30 by weight.
• the solids content is 15-25% by weight .
• the wet milling step includes wet stirred media milling (bead milling) in batch, continuous passes, or continuous recirculation modes using small beads ( ⁇ 0.7mm diameter) with a power input of more than 0.5kW per litre of shell volume for a prolonged period until the required transparency is achieved.
• the wet milling step may be as described in
• a method of forming a coating of a coating composition capable of absorbing UV and visible light up to 550nm on a substrate which method includes the steps of:
• the coating composition may be applied to the substrate by any suitable means, such as spraying or roller-coating the coating composition onto the substrate.
• the method includes adding further carrier to the coating composition formed in step (a) and thereby diluting the coating composition to a required pigment volume concentration prior to applying the substrate in step (b) .
• the further carrier is a film forming material .
• the pigment volume concentration is a pigment volume concentration
• the pigment volume concentration is 30-40%.
• the substrate is a wall of a container and step (b) is part of a container manufacturing method.
• the container is a glass container.
• Glass container manufacturing for example glass bottle manufacturing, typically includes two stages during which coatings may be applied to the bottle surface.
• a hot end coating is applied to glass using chemical vapour deposition techniques immediately after forming a glass container when the surface temperature of the container may be 600°C or higher.
• the HEC is typically a ceramic material such as tin oxide and serves both to protect the glass surface from damage and also to provide a substrate for the cold end coating.
• a cold end coating is applied after a glass container has been annealed at a surface temperature of 120-180°C.
• the CEC consists of an organic coating that provides the glass surface with the necessary lubricity for high speed passage through automatic inspection and filling lines. Some coatings also serve to protect the glass surface from abrasion damage and to preserve the inherent strength of the glass .
• Cold end coatings may be based on silicone waxes, polyethylene, polyvinyl alcohol, stearic acid, oleic acid, polyurethane, polyester, polyolefins, and polyacrylics.
• the coating composition of the present invention may be applied to a glass container in a cold end stage of bottle manufacture.
• the coating thickness is 0.1-1.5 microns.
• the carrier of the cold end coating is the carrier of the coating composition of the invention.
• the carrier of the coating composition is a water-based thermoplastic acrylic or polyurethane or polyester material and the coating composition is applied to a container surface at the CEC stage.
• thermosetting setting acrylic or polyurethane or polyester material may be used under specialised application conditions unrelated to cold end coating.
• FIG 1 compares the UV/Vis shielding properties of clear, green and amber glass used in beer bottles, displayed as UV/Vis absorbance
• FIG 2 compares the UV/Vis shielding properties of clear, green and amber glass used in beer bottles, displayed as UV/Vis transmittance
• FIG 3 compares the UV/Vis shielding properties of (i) a coating composition (formulation A) in accordance with the invention as described in Example 1, (ii) clear glass, and (iii) amber glass used in beer bottles, displayed as UV/Vis absorbance;
• FIG 4 compares the UV/Vis absorbance of the composition used in Figure 3 against the UV/Vis absorbance of commercial glass products
• FIGS 5 and 6 compares the UV/Vis absorbance of a 1 microns film of coating composition (formulation B) in accordance with the invention as described in Example 1 and commercial glass products;
• FIG 7 compares the UV/Vis absorbance of a 0.5 microns film of coating composition (formulation RH503) in accordance with the invention as described in Example 4 and amber glass;
• FIG 8 compares the UV/Vis absorbance of a 0.6 microns film of coating composition (formulation RH502, RH504, RH505 blend) in accordance with the invention as described in Example 4 and amber glass; and
• FIG 9 compares the UV/Vis absorbance of a film of a ZnO-based coating composition in accordance with the invention as described in Example 5 and a control coating.
• Formulation A - based on a thermosetting acrylic carrier.
• the coating composition included:
• TOY is an iron oxide yellow pigment supplied commercially by Johnson Matthey under the product name Trans Oxide Yellow AC0500.
• TOR is an iron oxide supplied by Johnson Matthey under the product name Trans Oxide Red AC1000.
• Formulation B - based on a polyethylene emulsion as a carrier.
• the coating composition was similar to formulation A, with the exception that it was (i) aqueous, (ii) included 20 parts per hundred of pigment of Orotan 731 (a polycarboxylic dispersant) pre-prepared as the ammonium salt as a replacement for the solsperse 3000; and (iii) included a commercially available polyethylene emulsion product (used as a cold end coating in glass bottle manufacture and sold under the trade name DURACOTE) as a replacement for the acrylic resin of formulation A.
• the colour of the coating compositions was virtually indistinguishable from the traditional green glass used for beer bottles.
• the coating provided generally superior protection against UV light in the harmful wavelengths between 350nm and 500nm.
• the absorbance of the coating on the quartz slide was comparable to that of the amber bottle. However, the results should be considered in the context that a quartz slide has no absorbance in the wavelengths measured and that the film thickness was only 1 micron.
• UV/Vis absorbance of formulation B was also compared with that of a green glass beer bottle as shown in Figure 6.
• the UV/Vis protection offered by the coating formulation was very similar to, or better than, amber glass.
• the transparent coating formulations in accordance with the invention tested in this example contained 5-100nm diameter nanoparticles of iron oxide and other pigments dispersed in carriers having dispersant and film- forming characteristics.
• the coating formulations were formed in accordance with the following standardized procedure.
• a 1 litre stainless steel vessel of 100mm internal diameter was fitted with a water jacket for cooling.
• a rotor shaft carrying 4 plain, 6mm thickness, 90mm diameter, circular discs made of ultra high molecular weight polyethylene were placed in the vessel .
• the net volume of the mill was 850 ml. This net volume was charged to 85% with 0.268kg of 0.4 to 0.7mm diameter partially stabilized zirconia beads (47% voidage) .
• a lid was bolted and sealed to the top of the mill with the rotor shaft passing through a hole and stirrer guide in the lid. 400ml of each of the mill base formulations set out below were charged to the mill. The actual weight of the additions was determined according to density.
• the amount of mill base added was 0.88kg.
• the rotor was driven at a rate such that the peripheral speed of the discs was 10 m/s, ie 2100rpm for the 90mm diameter discs. Milling of each of the formulations, with ambient temperature water passing through the cooling jacket, was continued for at least two hours.
• nano-milling is very intensive by comparison with mere dispersive milling of pigments for paint and inks.
• intensity measured as litres of mill base per litre of bulk beads per hour
• the milling produced 0.3 litres or less compared to 9 litres or more produced in conventional milling, with beads of several mm diameter, of pigments for ink and paint.
• the transparent coating formulations contained 5-100nm diameter nanoparticles of iron oxide and other pigments dispersed in carriers having dispersant and film-forming characteristics.
• the carrier was also required to be film forming and mechanically and pasteurisation resistance.
• the dispersants used in the formulations were:
• polycarboxylate dispersants for aqueous media including a proportion of polyaerylie acid as an ammonium salt
• the coating formulations were low in viscosity, 5 to lOcP, and had negligible rheological yield value, ie they were Newtonian.
• the coating formulations had the following compositions and characteristics.
• Formulation 1 blue-green light protective cold-end coating additive - 12% Fe 2 0 3 PR101 - 8% PY124 - 3% CuPc- PB15:3 aq - 18pph Joncryl 61HV- lOp Dispex A40. Milled for 2.25 hr. Strong pure bottle green - clear.
• Formulation 2 amber light protective coating additive - 18% Fe 2 0 3 PR101 - 4% PY124 1.5% CuPc-PB15:3 aq - 18pph Joncryl 61HV - lOpph Dispex A40. Milled for 2 hr. Dark amber - clear. The colour changes intensity less with variation in film thickness on spraying.
• Formulation 3 blue-green light protective cold-end coating additive - 12% Fe 2 0 3 PR101 - 2.3% PY124 - 8.8% CuPc-PB15:3 aq. Milled for 2 hr. Strong blue green - very clear. The colour is more blue-green than formulation 1.
• Formulation 4 increased level of Fe 2 0 3 PRIOlfor more protection at lower thickness - 09F(506) 18% Fe2O3-PR101 - 4% PY124 1.5%CuPc-PB15:3 aq. - 18pph Joncry 161HV - 10 pph Dispex. Milled for 1.75hr. Gold-Brown - very clear.
• Formulation 6 10% Fe 2 0 3 - 12% Pigment Green - 36 1% CuPc aq. - 18p Joncryl 61HV - lOpph Dispex. Milled for 3 hr. Bright green - clear. Pigment Green 36 yields a purer green than combinations of blue and yellow 03J (475) .
• Pigment Green 36 yields a purer green than combinations of Blue and Yellow 03J (474).
• Formulation 8 (468) 10.3% Fe 2 0 3 - 13.7% PG36 aq. - 18p Joncryl 61HV - lOpph Dispex. Milled for 2 hr. Yellow green - clear.
• Clear dispersions of the formulations produced by the milling procedure were diluted to 35% pigment volume concentration with resins, as is appropriate, such as polyethylene aqueous emulsion for cold-end coating or aqueous or solvent borne acrylic or solvent borne polyurethane resin.
• the diluted formulations were applied to glass or clear plastic to form coatings of about 1 microns film thickness, sometimes as thin as 0.5 or 0.3 microns, yet providing the protection exceeding that of amber glass and film properties required.
• Haze of 0.5 to 1 microns thick coatings of the formulations was less than 15% as measured on the Cary Spectrophotometer.
• the mill base was milled, firstly pass by pass, then by recirculation from a well-stirred vessel to a 1.2 litre Drais Double Chamber Process Bead Mill.
• the DCP mill may be fitted with a 0.25mm aperture bead separation screen, but was operated without a bed separation screen, and charged with 3.7kg of 0.4 to 0.7mm diameter partially stabilised zirconia beads.
• the rotor speed was at maximum rate and a pumping rate, using a progressing cavity of 5 to 151/min was maintained for 16 hours. At this point the mill base was clearly transparent.
• the resultant coating composition was tested as a cold end coating by mixing 2 parts of the mill base and 1 part of DIC Duracote 20% polyethylene coating emulsion in an homogeniser.
• the resultant coating composition was sprayed onto hot glass panels and hot glass bottles from a 130°C oven to a dry film thickness of 1.0 micron as measured by a Talysurf Surface Profile Analyser.
• Absorbance of the coating composition exceeded the absorbance of amber glass.
• Absorbance of both the coating composition and amber glass exceeded the value of 1.0 (10% transmission at 500nm) and exceeded 2.0 (1% transmission) at less that 470nm down to 200nm in the UV region.
• composition of the formulations is set out below:
• Formulation RH503 was prepared by milling in the 1 litre stainless steel mill described in Example 2 to produce a transparent coating formulation. The milling time was 6 hours. A coating of the formulation was formed and tested in accordance with the procedure described in Example 2. The coating thickness was 0.5 microns . Figure 7 illustrates the performance of the coating.
• Formulations RH502, RH504 and RH505 were prepared by milling in a glass container in a shaker mill to produce transparent coating formulations. The milling time was 48 hours. A coating of a blend of the formulations was formed and tested in accordance with the procedure described in Example 2. The coating thickness was 0.6 microns. Figure 8 illustrates the performance of the coating.
• the formulation was prepared by adding 35% 20nm ZnO(s) to 15 pph (based on solids) of Avecia Solsperse

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• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
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• Polymers & Plastics (AREA)
• Paints Or Removers (AREA)
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• 2002
  • 2002-04-19 CA CA002444705A patent/CA2444705A1/en not_active Abandoned
  • 2002-04-19 KR KR10-2003-7013673A patent/KR20040007500A/ko not_active Application Discontinuation
  • 2002-04-19 EP EP02717855A patent/EP1392782A4/en not_active Withdrawn
  • 2002-04-19 RU RU2003133667/04A patent/RU2003133667A/ru not_active Application Discontinuation
  • 2002-04-19 JP JP2002583513A patent/JP2004534114A/ja not_active Withdrawn
  • 2002-04-19 HU HU0303820A patent/HUP0303820A3/hu unknown
  • 2002-04-19 WO PCT/AU2002/000490 patent/WO2002085992A1/en not_active Application Discontinuation
  • 2002-04-19 MX MXPA03009547A patent/MXPA03009547A/es not_active Application Discontinuation
• 2003
  • 2003-10-17 NO NO20034646A patent/NO20034646L/no not_active Application Discontinuation
  • 2003-11-18 HR HR20030941A patent/HRP20030941A2/xx not_active Application Discontinuation

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