Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • 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
  • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
  • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
  • B05D5/067—Metallic effect
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B22—CASTING; POWDER METALLURGY
  • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
  • B22F9/00—Making metallic powder or suspensions thereof
• • 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
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
• • 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
  • C09D5/24—Electrically-conducting paints
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K1/00—Printed circuits
  • H05K1/02—Details
  • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
  • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
  • H05K1/097—Inks comprising nanoparticles and specially adapted for being sintered at low temperature
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
  • H05K2203/01—Tools for processing; Objects used during processing
  • H05K2203/0104—Tools for processing; Objects used during processing for patterning or coating
  • H05K2203/013—Inkjet printing, e.g. for printing insulating material or resist
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
  • H05K3/00—Apparatus or processes for manufacturing printed circuits
  • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
  • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
  • H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
  • H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
• • 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
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/298—Physical dimension

Definitions

• the invention is based on finely divided metal particles and metal suspensions for the production of electrically conductive layers.
• plastic components generally have good mechanical properties and sometimes also good optical properties (such as the transparency of polycarbonate), most engineering plastics are electrical insulators.
• inks filled with metal particles in the nanometer range for example, using the inkjet technology, it is possible to print narrow, electrically conductive webs of practically any desired geometry, for example on plastic films. It is particularly desirable in this case that the line width of such interconnects reaches or falls below about 20 ⁇ m. From this limit, structures are usually difficult to recognize for the human eye and a disturbing optical effect on transparent components is eliminated.
• Another possibility is to produce printed conductors with the fineness described above, ie which are visually difficult or impossible to detect on surfaces (structures with a line width ⁇ 20 ⁇ m), in particular on polymeric substrates, by forming the substrate in a pretreatment step with the necessary structuring is provided to subsequently fill the resulting structuring with the conductive material.
• the following additional requirements must be met, which were not all accessible with the previously known inks.
• the electrical conductors must be both temperature resistant (ie briefly up to 400 0 C) and mechanically flexible, the metal particle inks used for their production should allow the production of webs of a line thickness of 100 microns and below (up to 20 microns), and cheaper and easier to process than known conductive pastes. This results in the requirement for a significantly lower viscosity when ink-jet processes are to be used, a suitable wetting and spreading capacity and smaller particles than conventional conductive pastes. In particular, the wetting behavior and spreading capacity must be taken into account for the presented possibility of filling the depressions of prestructured surfaces.
• the ink should also have a low contact angle ( ⁇ 45 °) on the selected substrate and / or the highest possible surface tension (> 10mN / m).
• a specific electrical conductivity of the printed, dried and heat-treated ink should be achieved significantly better than 10 2 ⁇ "1 cm " 1 .
• Heat treatment should be carried out in particular at 140 0 C, the
• the interconnects should also have a particularly good adhesion to common substrates, especially polycarbonate.
• a special requirement for such ink is that the particle size of the metal particles should be substantially smaller than 20 microns and that the ink via a low viscosity (less than 150 mPa »s) has. It also appears advantageous if the particles used in the formulation are suitable for forming dense packages after the printing process, which lead to the desired conductivity of the printed structure even at low concentration and low processing temperature.
• PVD physical vapor deposition
• RW Vest Metallo-organic Materials for Improved Thick Film Reliability, Nov. 1, 1980, Final Report, Contract N00163-79-C-0352, National Avionic Center
• the required temperature is to produce a conductivity at 250 0 C. ie far above the possible application temperature for many engineering plastics.
• US patents US-A-5,882,722 and US-A-6,036,889 describe a conductive formulation containing metallic particles, a precursor and an organic solvent which forms conductive structures only at a temperature above 200 ° C. Also here is the viscosity of the formulation so high that this formulation can not be processed in principle in an ink-jet printer.
• Formulations based on easily decomposable silver compounds as low-viscosity solutions with low sintering temperature are content of the disclosure WO 03/032084 (A2).
• low decomposition temperatures are reported, which, however, are not deposited with specific conductivities of the structures obtained.
• the lowest temperature at which a conductive coating is achieved with a silver formulation is reported as 185 ° C.
• WO 2006 / 072959A2 discloses a method by means of which metal nanoparticles which could be used, for example, for ink-jet printing can be obtained. This nanoparticles are obtained with sizes smaller than 20 nm and unknown size distribution. A bimodal distribution is not disclosed.
• the usable content of resulting formulations is in the range of 0.5-80% by weight. Furthermore, it is disclosed that in the production process a pre-reduction of silver acetate by means of water-soluble polymers is necessary in order, inter alia, to prevent the agglomeration of the nanoparticles obtained.
• WO 2005/0136638 uses a mixture of silver and gold nanoparticles. From a good conductivity is spoken here from a sintering temperature of 200 0 C.
• EP 1 493 780 A1 describes a silver paste which is very highly conductive after temperature treatment at 150 ° C., but this formulation is too viscous to be printed by means of ink-jet.
• Cabot offers the product "Cabot InkJet Silver Conductor AG-IJ-G-100-Sl", which is a silver ink that can be applied by inkjet technology and does not support adhesion to plastics such as polycarbonate mentioned.
• HARIMA offers the "NP Series Nano-Paste" product line, which is a low viscosity silver nanoparticle ink.
• HARIMA gives Sintering temperatures of 210-230 0 C on. The processing temperature makes the paste unsuitable for printing on polymers.
• the above objects can be achieved by the silver-containing formulation described below.
• articles made of polycarbonate for example, by dip coating or casting and subsequent heat treatment particularly easy and inexpensive evenly coated with a thin shiny layer of silver adhesion.
• a formulation according to the invention it is possible with a formulation according to the invention to produce visually difficult or unrecognizable printed conductors (width ⁇ 20 ⁇ m, for example on polycarbonate) on pre-structured surfaces by filling the structuring.
• the lowest possible silver concentrations in the lacquer used and low layer thicknesses are to be preferred, since even a very thin silver layer is sufficient to produce a continuous reflective layer and silver is an expensive educt for such a formulation.
• the above particular task of printing plastics is z. B. solved using a silver-containing formulation with a printer, such as a piezo ink jet
• Printer can be applied to a substrate, such as polycarbonate, and after or during the application (or both) is heated so that a layer with desired electrical conductivity can form.
• the invention relates to a silver-containing, disperse, water-containing formulation comprising at least
• the formulation has a viscosity of at most 150 mPa ⁇ s.
• the formulation is further characterized by forming a low contact angle (i.e. ⁇ 45 ° on polycarbonate) with the substrate and having the highest possible surface tension (> 10mN / m).
• the contact angle is below 30 ° and / or the surface tension of the formulation above 20mN / m.
• Particularly preferred here is the contact angle below 10 ° and / or the surface tension of the formulation over 40 mN / m.
• the contact angle is measured on polycarbonate at 25 ° C and under normal conditions.
• the sum of the parts by weight of the components of the formulation is in particular 100 parts by weight.
• the dispersing aid comprises at least one agent selected from the group: alkoxylates, alkylolamides, esters, amine oxides, alkylpolyglucosides, alkylphenols, arylalkylphenols, water-soluble homopolymers, water-soluble random copolymers, water-soluble block copolymers, water-soluble graft polymers, in particular polyvinyl alcohols, copolymers of polyvinyl alcohols and polyvinyl acetates, polyvinylpyrrolidones, Cellulose, starch, gelatin, gelatin derivatives, amino acid polymers, polylysine, polyaspartic acid, polyacrylates, polyethylene sulfonates, polystyrenesulfonates, polymethacrylates, condensation products of aromatic sulfonic acids with formaldehyde, naphthalenesulfonates, lignosulfonates, copolymers of acrylic monomers, polyethyleneimines,
• the dispersing aid is particularly preferably selected from the series: polyvinylpyrrolidone, block copolyether and block copolyether with polystyrene blocks.
• the film former d) is preferably selected from the series: polydimethylsiloxane, polyacrylate, ammonium salts of polyacrylates, siloxanes, wax combinations, copolymers with pigment-active groups, low molecular weight polymers, hydroxyethyl cellulose, polyvinyl alcohol or from the group of the above-mentioned dispersing aids, particularly preferably z.
• the additive e) is preferably selected from the series: pigments, defoamers, light stabilizers, optical brighteners, corrosion inhibitors, antioxidants, algicides, plasticizers, thickeners, surface-active substances.
• pigments defoamers, light stabilizers, optical brighteners, corrosion inhibitors, antioxidants, algicides, plasticizers, thickeners, surface-active substances.
• Pluronic PE 10400 from BASF, Ludwigshafen
• the conductive polymer f) is preferably selected from the series: polypyrrole, polyaniline, polythiophene, polyphenylenevinylene, polyparaphenylene, polyethylenedioxythiophene, polyfluorene, polyacetylene, more preferably polyethylenedioxythiophene in combination with polystyrenesulfonic acid.
• a particularly preferred formulation is characterized in that the silver particles a) have an effective particle diameter of 10 to 150 nm, preferably 40 to 80 nm, determined by laser correlation spectroscopy.
• the silver particles a) are preferably present in the formulation in a proportion of 1 to 20 parts by weight, more preferably 2 to 6 parts by weight.
• the content of dispersing assistant c) is preferably 0.02 to 5 parts by weight, particularly preferably 0.04 to 2 parts by weight.
• a particularly advantageous formulation is obtained by subjecting the silver sol to membrane filtration with a filtration fineness of at most 100,000 Da for purification and concentration.
• Another object of the invention is the use of the formulation according to the invention for the production of electrically conductive and / or optically reflective coatings, in particular of printed conductors of a line width of less than 100 microns, preferably less than 80 microns.
• the invention also provides a method for producing printed conductors of a line width of less than 100 ⁇ m, preferably less than 80 ⁇ m, which is characterized in that the new formulation is printed on a substrate surface with the aid of the inkjet technique and in particular at a temperature of at most 140 0 C for removing water residues and optionally solvents and optionally for sintering existing silver particles is heat treated.
• a method for producing printed conductors having a line width of less than 20 microns in which the new formulation is introduced into the predetermined patterning of the substrate, wherein the structuring has a line width of ⁇ 20 microns, and the applied Formulation especially at a temperature of at most 140 0 C for the removal of water and optionally solvent is heat treated.
• Subject of the invention is also a substrate, in particular a transparent plastic substrate comprising an electrically conductive and / or optically reflective coating, which is obtainable from a formulation according to the invention.
• a substrate which is characterized in that the electrically conductive coating conductor tracks of a line width of less than 100 microns, preferably less than 80 microns, wherein the conductivity in the interconnects is at least 7 * 10 6 S / m.
• the new formulation has silver particles with a bimodal size distribution as described above. It has surprisingly been found that the bimodal distribution is advantageous for the formation of conductive structures even at a lower content of the silver particles. It can be assumed that this is due to the filling of the resulting gusset volumes between the larger particles by smaller ones. This results in the thermal aftertreatment of the ink larger, continuous contact surfaces. Thus, at lower mass, the resulting formulation will have the same conductivity of an ink approximately monodisperse distribution at approximately the same effective diameter, or higher at the same mass content and same effective diameter.
• a formulation containing silver nanoparticles, solvents, film formers, dispersing aids and possibly other additives Preferably, it contains small silver nanoparticles containing, essentially, an effective diameter of 75 nm with a bimodal distribution in a low concentration of 0.5 to 20% by weight, preferably 2 to 5% by weight, whereby only a small amount Amount of dispersants is necessary.
• a low post-treatment temperature of 140 0 C is sufficient to achieve high conductivities.
• the formulation can be applied to polycarbonate, for example, by ink-jet printing, dipping, flooding or casting, then dried and annealed at 140 ° C for several hours. This gives very well adhering, electronically conductive structures or, in a two-dimensional application, optically reflective layers, both with high adhesion to polycarbonate.
• the silver sols preferably used in the formulation are prepared from Ag 2 O by reduction with a reducing agent, such as aqueous formaldehyde solution (FA), after prior addition of a dispersing aid.
• a reducing agent such as aqueous formaldehyde solution (FA)
• the Ag 2 O sols are prepared by rapid mixing of silver nitrate solution with NaOH by rapid stirring batchwise or by using a micromixer according to the still unpublished German patent application with the file number 10 2006 017 696 in a continuous process.
• the content of the patent application with the file reference 10 2006 017 696 belongs to the disclosure content of the present patent application.
• the Ag 2 O nanoparticles are reduced with FA in excess in a batch process and finally purified by centrifugation or membrane filtration, preferably by membrane filtration.
• This production method is particularly advantageous because the amount of organic auxiliaries bound on the surface of the silver nanoparticles can be kept low and furthermore a bimodal size distribution can be obtained.
• FIG. 1 shows the photomicrograph of a coating according to the invention of polycarbonate after a scratch test.
• FIG. 2 shows the photomicrograph of a coating according to the prior art after a scratch test.
• a 0.054 molar silver nitrate solution was admixed with a mixture of a 0.054 molar sodium hydroxide solution and the dispersing aid Disperbyk 190 (manufacturer BYK Chemie) (1 g / l) in a volume ratio of 1: 1 and stirred for 10 minutes. A brown-colored Ag 2 0 nanosol was formed. An aqueous 4.6 molar formaldehyde solution was added to this reaction mixture while stirring so that the molar ratio of Ag + to reducing agent was 1:10. This mixture was heated to 60 0 C, held for 30 min at this temperature and then cooled.
• the particles were purified by centrifugation (60 min at 30,000 rpm) and redispersed by adding ultrasound (1 min) in demineralized water. This process was repeated twice. A colloidally stable sol having a solid content of 5% by weight (silver particles and dispersing aid) was thus obtained. The yield was almost 100%. According to elemental analysis, the silver dispersion contained 3% by weight of Disperbyk 190 based on the silver content after centrifugation. An investigation by means of laser correlation spectroscopy revealed an effective diameter of the particles of 73 nm.
• a 0.054 molar silver nitrate solution was admixed with a mixture of a 0.054 molar sodium hydroxide solution and the dispersing aid Disperbyk 190 (manufacturer BYK Chemie) (1 g / l) in a volume ratio of 1: 1 and stirred for 10 min.
• An aqueous 4.6 molar aqueous formaldehyde solution was added to this reaction mixture while stirring so that the ratio of Ag + to reducing agent is 1:10. This mixture was heated to 6O 0 C, kept at this temperature for 30 min and then cooled.
• 0.05 g of polyvinylpyrrolidone K15, together with 0.04 g of Pluronic PE 10400 and 0.03 g of BYK348 are weighed.
• the resulting formulation is well mixed, resulting in a homogeneous brown-grayish dispersion.
• the resulting ink is particularly well-suited for visual production, i. with the naked eye heavy or unrecognizable lines on pre-structured polycarbonate.
• the ink is poured into the structures on polycarbonate and
• polycarbonate films were coated by "flooding" with the silver dispersion to be tested-also referred to below as ink-by tilting the film and allowing the ink of Examples 1 to 6 to run down over the untreated polycarbonate film. Subsequently, the films were dried and stored at about 140 0 C in air for 17 hours.
• the coating thickness obtained was about 1 .mu.m (in the case of the ink from Example 1) and about 6 .mu.m in the commercially available comparison ink (Cabot InkJet Silver Conductor AG-IJ-G-100-Sl). The higher layer thickness of the comparison ink results from its higher solids content.
• Coatings are scribed several times in parallel and then perpendicular to the substrate.
• the film coated with an ink according to Example 1 surprisingly shows that the adhesion of the silver layer is substantially better (FIG. 1) than the adhesion of the silver layer from the ink according to the prior art
• a cohesive failure is basically a sign of good adhesion between the silver layer and the substrate.
• the layer thicknesses in the present case were about 6 ⁇ m for the ink according to the prior art and about 1 ⁇ m for the ink according to example 1.
• the specific electrical conductivity was measured after about 17 hours of post-treatment at about 140 0 C.
• the line cross-section of the line was determined by means of a white light topography microscope, four contacts with silver conductive adhesive at a distance of 1 cm, 2 cm and 1 cm attached and determined the conductivity of the line by a four-point measurement over a length of 2 cm.
• a polycarbonate film (Makrofol) is dripped with ink from Example 6. The resulting drops are allowed to dry at room temperature and the dried ink is kept at 140 ° C. under air for 17 hours.
• the silvery, shiny drop is placed in an injection mold and overmolded with liquid polycarbonate.
• the resulting pattern shows that under the influence of the high pressure and the high temperatures prevailing during the injection molding, the shape of the silvery-shiny drops does not change optically, so that the ink described in Example 6 is also suitable for use in the back-injection process.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dispersion Chemistry (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Nanotechnology (AREA)
• Conductive Materials (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Paints Or Removers (AREA)
• Powder Metallurgy (AREA)
• Manufacturing Of Electric Cables (AREA)
• Manufacture Of Metal Powder And Suspensions Thereof (AREA)
• Non-Insulated Conductors (AREA)
• Compositions Of Macromolecular Compounds (AREA)

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• 2007
  • 2007-08-06 DE DE102007037079A patent/DE102007037079A1/de not_active Withdrawn
  • 2007-10-12 SG SG2011078482A patent/SG176423A1/en unknown
  • 2007-10-12 JP JP2009533690A patent/JP5954922B2/ja not_active Expired - Fee Related
  • 2007-10-12 MY MYPI20091643A patent/MY146242A/en unknown
  • 2007-10-12 MX MX2009004133A patent/MX2009004133A/es active IP Right Grant
  • 2007-10-12 RU RU2009119426/07A patent/RU2009119426A/ru not_active Application Discontinuation
  • 2007-10-12 EP EP07818947.9A patent/EP2087490B1/de active Active
  • 2007-10-12 CA CA2667219A patent/CA2667219C/en not_active Expired - Fee Related
  • 2007-10-12 WO PCT/EP2007/008876 patent/WO2008049519A1/de not_active Ceased
  • 2007-10-12 CN CN2007800394923A patent/CN101529531B/zh active Active
  • 2007-10-12 BR BRPI0718186-8A2A patent/BRPI0718186A2/pt not_active Application Discontinuation
  • 2007-10-12 KR KR1020097008459A patent/KR101405656B1/ko not_active Expired - Fee Related
  • 2007-10-12 ES ES07818947.9T patent/ES2660666T3/es active Active
  • 2007-10-24 TW TW096139777A patent/TWI426111B/zh active
  • 2007-10-25 US US11/923,887 patent/US7824580B2/en active Active
• 2009
  • 2009-04-23 IL IL198335A patent/IL198335A/en active IP Right Grant
• 2010
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