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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/06—Polyurethanes from polyesters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/08—Anti-corrosive paints
  • C09D5/10—Anti-corrosive paints containing metal dust
  • C09D5/103—Anti-corrosive paints containing metal dust containing Al
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
  • C23C22/82—After-treatment
  • C23C22/83—Chemical after-treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D2252/00—Sheets
  • B05D2252/02—Sheets of indefinite length
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
  • B05D3/0254—After-treatment
  • B05D3/0263—After-treatment with IR heaters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/50—Multilayers
  • B05D7/51—One specific pretreatment, e.g. phosphatation, chromatation, in combination with one specific coating
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
  • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
• • E—FIXED CONSTRUCTIONS
  • E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
  • E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
  • E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
  • E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
  • E06B9/26—Lamellar or like blinds, e.g. venetian blinds
  • E06B9/38—Other details
  • E06B9/386—Details of lamellae
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12014—All metal or with adjacent metals having metal particles
  • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
  • Y10T428/12049—Nonmetal component

Definitions

• the present invention relates to anticorrosion compositions for coating metal surfaces and to a process for coating metal surfaces with aluminum-containing organic coatings.
• DE-C-3412234 describes a conductive and weldable corrosion protection primer for electrolytically thin-galvanized, phosphated or chromated and deformable sheet steel.
• This anticorrosive primer consists of a mixture of more than 60% zinc, aluminum, graphite and / or molybdenum disulfide and another anticorrosive pigment and 33 to 35% of an organic binder and about 2% of a dispersing agent or catalyst.
• organic binder polyester resins and / or epoxy resins and their derivatives are proposed.
• WO 99/24515 discloses a conductive and weldable anticorrosion composition for coating metal surfaces, characterized in that it comprises a) from 10 to 40% by weight of an organic binder containing aa) at least one epoxy resin) at least one hardener selected from guanidine, substituted guanidines, substituted ureas, cyclic tertiary amines and mixtures thereof ac) at least one blocked polyurethane resin b) 0 to 15% by weight of a silicate-based anticorrosion pigment c) 40 to 70% by weight of powdered zinc, aluminum, graphite and / or molybdenum sulfide , Carbon black, iron phosphide d) 0 to 30 wt .-% of a solvent.
• an organic binder containing aa) at least one epoxy resin) at least one hardener selected from guanidine, substituted guanidines, substituted ureas, cyclic tertiary amines
• WO 01/85860 describes a conductive and weldable anti-corrosion composition for coating metal surfaces, characterized in that, based on the total composition, a) from 5 to 40 wt .-% of an organic binder containing aa) at least one epoxy resin ab) at least one Hardener selected from cyanoguanidine,
• an anticorrosive pigment c) 40 to 70% by weight of conductive pigment selected from pulverulent zinc, aluminum, graphite, molybdenum sulfide, carbon black and iron phosphide d) 0 to 45% by weight a Wegsmitttels and, if desired, up to 50 wt .-% further active ingredients or auxiliaries, wherein the proportions of the components add up to 100 wt .-%.
• a number of coating compositions for metals containing particles of metallic aluminum are known.
• the aluminum is here especially as Conducting pigment used so that the coatings thus obtained can be electrically welded and optionally electrocoated. These coatings serve as a basis for subsequent painting and are not intended to be either the only organic coating or, if desired, coated with a clearcoat.
• This zinc coated (“galvanized”) steel may be overcoated, however, the adhesion of the paint to the zinc layer may be problematic and may require special pre-treatment, but often the zinc coated steel is used unpainted or, if necessary, clear coated because of the silver appearance Due to the cathodic protective effect of the zinc layer, which can also be passivated by environmental influences, the underlying steel does not rust as long as the zinc layer is still closed It can take decades for galvanized steel to show red rust.
• the galvanizing of steel is therefore a classic and widespread measure for corrosion protection.
• galvanizing is energy consuming and increases the thickness of the material and thus the total material consumption. Therefore, there is a need for a process which gives a similar appearance and corrosion protection to galvanized steel as galvanizing.
• the present invention provides such a method and a means to be employed therewith.
• the first aspect of the present invention relates to an agent for coating metal surfaces based on crosslinking polyester resins as an organic binder, characterized in that the agent, based on its total mass, 4 to 20 wt .-% aluminum flakes and not more than 0.1 wt. Containing% isocyanate group-containing compounds.
• the crosslinking polyester resins are particularly suitable for permanently entrapping the aluminum flakes and fixing them on the metal surface, resulting in a coating with good anti-corrosive properties.
• the composition according to the invention contains not more than 0.1% by weight, preferably not more than 0.01% by weight and particularly preferably no detectable isocyanate groups at all. containing compounds. Due to the absence of isocyanate or polyurethanes, the coating is particularly insensitive to environmental influences and in particular to sunlight.
• a content of 4 to 20 wt .-% aluminum flakes causes the cured coating at a desired thickness between about 3 and about 30 microns optically completely covers the underlying metal surface.
• the metal surface then visually looks as if it had been electrolytically galvanized. Due to the anti-corrosive effect of the coating, red rust formation in the case of steel coated in this way is suppressed in the long term.
• the agent thus gives the steel coated herewith similar optical and corrosion protection properties as galvanized steel. However, the energy required to apply the coating is less than that for galvanizing.
• the layer obtained with the agent according to the invention is lighter than a galvanizing layer, so that material is saved compared to a galvanizing. Suitable aluminum flakes are commercially available.
• the agents may, for example, have a mean surface diameter in the range of 20 to 60 ⁇ m, preferably 30 to 50 ⁇ m, and a thickness in the range of 0.3 to 1 ⁇ m, preferably in the range of 0.4 to 0.6 ⁇ m.
• the agent contains, based on its total mass, 5 to 12 wt .-% aluminum flakes.
• the anticorrosive effect of the agent according to the invention can be improved if it is added to it, based on its total mass, from about 2 to about 10% by weight, in particular from about 3 to about 7% by weight, of corrosion inhibitors and / or anticorrosion pigment.
• Anticorrosion pigments can be selected, for example, from calcium or zinc phosphates, magnesium oxide, in particular in nanoscale form, fine-grained or very fine-grained barium sulfate and anticorrosive pigments based on calcium silicate. The latter are preferred because of their particularly good effectiveness.
• the inventive composition based on its total mass, 20 to 50 wt .-% and in particular 30 to 40 wt .-% organic binder and 30 to 70 wt .-%, in particular 50 to 60 wt .-% solvent, wherein the Sum of the proportions of solvent and organic binder due to the presence of other ingredients such as at least the aluminum flakes not greater than 96 wt .-%, preferably not greater than 90 wt .-% and in particular not greater than 70 wt .-%.
• the components of the organic binder are usually commercially available as a solution or dispersion in organic solvent. Due to the use of such raw materials, the coating composition according to the invention is also solvent-containing. The presence of solvent has a favorable effect on the viscosity of the agent. This should in particular be adjusted so that the agent can be applied by conventional methods of coil coating on a running metal strip. The viscosity at the temperature at which the agent is applied to the metal strip can be adjusted by varying the amount of solvent to the desired range. It may therefore be advantageous if the inventive agent except the solvent content of the raw materials additionally contains solvent.
• the solvent may be, for example, so-called "solvent naphtha", diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, cyclohexanone, diacetone alcohol, diethylene glycol, propylene glycol n-butyl ether, methoxypropyl acetate, methoxypropanol, butanol, in particular isobutanol, xylene or more commonly used in the field of paints and paints solvents.
• solvent naphtha diethylene glycol monobutyl ether acetate, propylene glycol methyl ether, cyclohexanone, diacetone alcohol, diethylene glycol, propylene glycol n-butyl ether, methoxypropyl acetate, methoxypropanol, butanol, in particular isobutanol, xylene or more commonly used in the field of paints and paints solvents.
• the coating composition of the invention preferably contains at least one hydroxylated polyester resin and a crosslinking component therefor.
• the hydroxylated polyester resin preferably has an average molecular weight in the range of 2,000 to 15,000, more preferably in the range of about 3,000 to about 10,000.
• gel permeation chromotography can be selected. In general, however, molecular weights are given in the technical product data sheets of the manufacturers, which can be used for the purpose of the present invention.
• a melamine-formaldehyde crosslinking agent is preferably used as the crosslinking component for the hydroxylated polyester resin.
• a methoxymethylmelamine can be used, which is usually present as a secondary amine and is alkoxylated on the nitrogen.
• Such crosslinking agents are commercially available and often contain solvents.
• the crosslinking reaction upon curing of the organic binder can be improved and accelerated if the agent additionally contains at least one acidic crosslinking catalyst, preferably a weakly acidic crosslinking catalyst.
• This is preferably in blocked form, so that the crosslinking reaction starts only at a temperature which is above the storage and application temperature of the agent.
• a nonionic blocked acidic cross-linking catalyst is suitable, which is activated at a temperature of above 110 0C.
• Such catalysts for melamine formaldehyde-based stoving lacquers are commercially available and are usually present as a solution in an organic solvent (eg xylene).
• such an agent is used, which, based on the total mass of the composition, 15 to 40 wt .-%, preferably 20 to 35 wt .-% hydroxylated polyester resin, 2 to 10 wt .-%, preferably 3 to 8 wt .-% crosslinking component for the hydroxylated polyester resin, 0.05 to 1 wt .-%, preferably 0.1 to 0.5 wt .-% acidic crosslinking catalyst.
• the composition according to the invention may contain further additives which are customary in the field of organic coating compositions.
• these may be fillers, anti-settling agents, defoamers or leveling agents.
• the agent according to the invention may contain inorganic fillers, for example based on mica, quartz and / or chlorite.
• the average particle size should be compatible with the desired coating thicknesses and preferably not above 5 ⁇ m.
• the filler should preferably contain no more than 1% by weight of particles larger than 15 ⁇ m.
• the agent preferably contains from about 2 to about 20% by weight, in particular from about 4 to about 10% by weight, based on its total weight of fillers.
• a second aspect of the present invention resides in a process for coating metal strip, particularly non-galvanized steel strip by strip, characterized by i) purifying the strip if necessary, ii) contacting the strip with an acidic treating solution which is on the steel surface produces a conversion layer containing not more than 1 mg of chromium per m 2 and then with or without intermediate rinsing with water, iii) coated with an agent as described above having such a wet film thickness to give a layer coverage in the range of 3 to 30 microns after curing, and iv) the applied in step iii) wet layer by IR radiation or by heating the tape a substrate temperature in the range of 120 to 280 0 C, preferably in the range of 230 to 250 0 C hardens.
• metal strips are coated which have been coated immediately before with a metal coating, for example with zinc or zinc alloys, electrolytically or by hot dipping, it is not necessary to clean the metal surfaces before carrying out the conversion treatment (ii). If the metal strips have already been stored and in particular provided with corrosion protection oils, a purification step is necessary before carrying out step (ii).
• the conversion solution to be used in step (ii) may be a layer-forming or non-layer-forming phosphating solution known in the art.
• an acidic treatment solution which contains, as a layer-forming component, complex fluorides of silicon and in particular of titanium and / or zirconium.
• the conversion solution may contain organic polymers such as, for example, polyacrylates or amino-substituted polyvinylphenol derivatives.
• Addition of nanoscale silica or nanoscale alumina to the conversion solution in step (ii) may result in further improved corrosion protection and adhesion properties.
• nanoscale means particles which on average have a particle diameter of less than 1000 nm, in particular of less than 500 nm.
• steps (ii) and (iii) are carried out as a strip treatment process, wherein the liquid treatment agent is applied in step (iii) in such an amount that after hardening the desired layer thickness in the range of 3 to 30 microns.
• the coating composition may vary according to various methods are applied, which are familiar in the art. For example, applicator rolls can be used to directly adjust the desired wet film thickness. Alternatively, one may immerse the metal strip in the coating agent or spray it with the coating agent, after which the desired wet film thickness is adjusted by means of squeeze rolls.
• the coated sheet is heated to the required drying or crosslinking temperature for the organic coating.
• the layer thickness is preferred. If it is desired to have a layer thickness of more than about 10 ⁇ m and in particular more than about 15 ⁇ m, it may be advisable to carry out the coating in two stages, with the agent applied in each stage being cured in each case.
• This process sequence is thus characterized in that the two steps iii) and iv) are carried out in duplicate and in the first step pair iii) + iv) a layer support in the range of 3 to 15 .mu.m and then in the second step pair iii) + iv) another layer support in the range of 10 to 27 microns applies.
• a layer thickness in the range of 5 ⁇ m and in the second step pair a layer thickness in the range of 20 ⁇ m can be applied. Further conceivable combinations are: about 10 ⁇ m in the first coating step and about 15 ⁇ m in the second coating step or about 12 ⁇ m in the first coating step and likewise about 12 ⁇ m in the second coating step.
• the present invention comprises a band or a sheet or component produced therefrom, which is obtainable by the method according to the invention. Depending on the intended use, the coating thickness may vary and the coating may or may not be overcoated.
• the layer support produced in steps iii) and iv) is in the range of 3 to 10 .mu.m, whereupon at least one further lacquer layer is applied which does not represent a clearcoat.
• the coating according to the invention therefore acts as a primer for a subsequent coating.
• Such opaque painted sheets can be used or produced for example in vehicle construction or in the manufacture of household appliances or metal furniture. You can then each form the outside of the products mentioned.
• the overpainting may be, for example, a cathodic dip paint or a powder paint.
• the coating applied according to the invention is present after curing in step iv) with a layer thickness in the range from about 3 to about 15 ⁇ m and in particular in the range from about 8 to about 14 ⁇ m. It then provides sufficient corrosion protection to serve as a so-called “backside coating” without further overcoating, so it covers the interior surfaces of, for example, vehicles, furniture or household appliances, which are not very corrosive enough, so that no further overpainting is required ,
• the coating according to the invention is to lie on the outside of the articles produced from the coated substrate and if it is not or should be overcoated with a clearcoat, it is preferred to produce a total of one coat in the range of about 20 to 30 .mu.m. Preferably this is produced according to the above-described two-stage process in which steps iii) and iv) are carried out twice in succession.
• a metal strip or a sheet or component produced therefrom is obtained, in which the coating applied according to the invention is either not coated on the surface of the component or at best coated with a clearcoat.
• the galvanizing-like appearance of the coating according to the invention is visible, which may be desirable for aesthetic reasons.
• the coating according to the invention serves, so to speak, as a "galvanizing substitute.” Both the visual impression and the anticorrosive effect of a galvanized steel surface are produced in a cost-effective manner, without having to resort to galvanizing, which is more energy consuming and more expensive.
• the strip or a sheet metal or component produced therefrom is preferably used for the production of household appliances or architectural parts, in particular for building walls or roofs or for the outer covering of building walls or roofs.
• the coated in this embodiment sheets can therefore be used for all applications for which one currently uses not painted or possibly provided with a clear coat galvanized steel.
• these can also be rain gutters on buildings or ducts of air conditioning systems or for supply or exhaust air ducts, for example.
• so coated material for railing or for posts for example, used as a carrier for traffic lights or traffic signs.
• fences, gates, guardrails, containers such as garbage containers are other uses for the material coated according to the invention as a "galvanizing substitute".
• an agent according to the invention can be composed as follows (quantities in% by weight, based on the total mass):

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Other Surface Treatments For Metallic Materials (AREA)
• Chemical Treatment Of Metals (AREA)

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• 2006
  • 2006-12-28 DE DE102006062500A patent/DE102006062500A1/de not_active Ceased
• 2007
  • 2007-11-20 AU AU2007341515A patent/AU2007341515A1/en not_active Abandoned
  • 2007-11-20 BR BRPI0720642-9A patent/BRPI0720642A2/pt not_active IP Right Cessation
  • 2007-11-20 RU RU2009128735/05A patent/RU2009128735A/ru not_active Application Discontinuation
  • 2007-11-20 CN CNA200780048446XA patent/CN101573187A/zh active Pending
  • 2007-11-20 WO PCT/EP2007/062572 patent/WO2008080700A1/de active Application Filing
  • 2007-11-20 EP EP07822746A patent/EP2106299A1/de not_active Withdrawn
  • 2007-11-20 JP JP2009543414A patent/JP2010514866A/ja active Pending
  • 2007-11-20 KR KR1020097015778A patent/KR20090122195A/ko not_active Application Discontinuation
• 2009
  • 2009-06-26 US US12/492,851 patent/US20090324983A1/en not_active Abandoned

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