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
  • C09D5/24—Electrically-conducting paints
• • 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
  • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
• • 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
• • 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
  • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
• • 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
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10D—INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
  • H10D64/00—Electrodes of devices having potential barriers
  • H10D64/01—Manufacture or treatment
  • H10D64/011—Manufacture or treatment of electrodes ohmically coupled to a semiconductor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/20—Electrodes
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/20—Electrodes
  • H10F77/206—Electrodes for devices having potential barriers
  • H10F77/211—Electrodes for devices having potential barriers for photovoltaic cells
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F77/00—Constructional details of devices covered by this subclass
  • H10F77/30—Coatings
  • H10F77/306—Coatings for devices having potential barriers
  • H10F77/311—Coatings for devices having potential barriers for photovoltaic cells
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
  • H10P14/46—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials using a liquid
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy

Definitions

• the invention relates to a composition for printing electrodes on a substrate containing electrically conductive particles, glass frit and solvent.
• compositions containing electrically conductive particles and glass frit dispersed in a solvent are especially used to print electrodes on semiconductor substrates. Use find such printed semiconductor substrates, for example as solar cells.
• the composition is applied to the substrate by a conventional printing method.
• a printing method for example, ink jet printing or laser printing are suitable.
• the composition generally contains silver particles. These may be platy or spherical. Mixtures of platelet-shaped and spherical silver particles are also known.
• the composition contains a solvent. Usually, organic solvents are used. However, this has the disadvantage that in the further processing after printing, the solvent escapes from the composition and thus enters the environment. So that the composition does not proceed, a polymer material is usually also included, with which the composition is first bound to the semiconductor material. After printing, the composition is generally fired. Upon firing, the polymer material decomposes and is removed from the tracks. The glass frit contained in the composition melts and binds the printed conductor tracks containing the electrically conductive particles to the substrate.
• a composition in paste form which can be used for producing a light-receiving surface electrode of a solar cell is described, for example, in WO 2007/089273.
• the paste contains silver particles having a specific surface area of 0.2 to 0.6 m 2 / g, glass frit, resin binder and diluent.
• the diluent used is an organic solvent.
• a composition containing silver powder with two different average diameters is described in EP-A 1 775 759. In addition to the silver powder, the composition also contains glass frit and an organic carrier. The proportion of silver in the electrode material is 75 to 95 wt .-%.
• a paste for producing electrodes of solar cells which contains 85 to 99 wt .-% of a conductive metal component and 1 to 15 wt .-% of a glass component and an organic portion is described in WO 2006/132766.
• the disadvantage of this known composition is that the organic substances contained therein are liberated during drying after application of the composition or during firing.
• the object of the present invention is to provide a composition for printing electrodes in which less organic material is released to the environment during drying and firing.
• the object is achieved by a composition for printing electrodes on a substrate, the 30 to 90 wt .-% electrically conductive particles, 0 to 7 wt .-% glass frit, 0, 1 to 5 wt .-% of at least one absorbent for laser radiation , 0 to 8 wt .-% of at least one matrix material, 0 to 8 wt .-% of at least one organometallic compound, 3 to 50 wt .-% of water as a solvent, 0 to 65 wt .-% of at least one retention aid and 0 to 5 wt .-% of at least one additive, each based on the total mass of the composition contains.
• composition according to the invention is particularly suitable for printing electrodes with a laser printing method.
• Electrically conductive particles contained in the composition may be particles of any geometry made of any electrically conductive material.
• electrically conductive particles contained in the composition include silver, gold, aluminum, platinum, palladium, tin, nickel, cadmium, gallium, indium, copper, zinc, iron, bismuth, cobalt, manganese, chromium, vanadium, titanium or mixtures or alloys thereof.
• the mean particle size of the particles used is preferably in the range from 3 nm to 100 ⁇ m. More preferably, the mean particle size is in the range of 100 nm to 50 ⁇ and in particular in the range of 500 nm to 10 ⁇ .
• the particles used can have any desired shape known to those skilled in the art.
• the particles may be platy or spherical.
• Spherical is also understood to mean particles whose real form deviates from the ideal spherical shape.
• spherical particles may also have a drop-shaped shape or be flattened due to their production.
• Suitable particles which can be used to prepare the composition are known to those skilled in the art and are commercially available. Particular preference is given to using spherical silver particles.
• the advantage of the spherical particles is their improved rheological behavior compared to platelet-shaped particles.
• a composition containing spherical particles has a lower viscosity than a composition with platelet-shaped particles.
• a composition containing spherical particles exhibits a large viscosity reduction on shear.
• high fill levels of up to about 90% can be achieved, in which the composition remains printable.
• two or more different types of electrically conductive particles are used, this can be done by mixing the varieties.
• the particles of different varieties may differ in material, shape and / or size.
• the proportion of electrically conductive particles in the composition is in the range of 50 to 90 wt .-%.
• the proportion is preferably in the range from 70 to 87% by weight and in particular in the range from 75 to 85% by weight.
• the composition contains solvent.
• the solvent used is water which is present in the composition in an amount of from 3 to 20% by weight.
• the proportion of water in the composition in the range of 5 to 15 wt .-% and in particular in the range of 6 to 12 wt .-%. Since water generally evaporates relatively quickly, the addition of a retention agent, a so-called retarder, is necessary to slow evaporation.
• the retention agent is present in the composition in a proportion of 0 to 65 wt .-%, preferably in a proportion of 0.5 to 10 wt .-% and in particular in a proportion in the range of 0.8 to 4 wt .-% before ,
• Suitable retention aids are polar, water-binding solvents.
• Suitable polar, water-binding solvents are, for example, glycerol, glycols, for example ethylene glycol, propylene glycol, polyglycols such as diethylene glycols, polyethylene glycols (for example PEG200), polypropylene glycol, alkanolamines, for example methyldiethanolamine, ethyldiethanolamine, n-methylpyrrolidone, polyethyleneimines, polyvinylamine , Polyvinylformamide or mixtures thereof.
• Particularly preferred as retention aids are glycerol and polyethylene glycols. These have a high surface tension, whereby a running of the composition on the surface of the substrate to be printed is reduced. As a result, clearer structures are printable.
• a matrix material is furthermore contained.
• Water-soluble or water-dispersible polymers or polymer mixtures are preferably used as the matrix material.
• Suitable polymers which can be used as matrix material are, for example, acrylate dispersions and acrylate copolymers, for example styrene acrylates, alkali-soluble acrylate resins and copolymers thereof, maleic anhydride copolymers, for example styrene-maleic acid dispersions, alkyd resin dispersions, styrene-butadiene dispersions, cellulose derivatives, in particular hydroxyalkyl celluloses, Carboxyalkylcelluloses, polyester dispersions, polyvinyl alcohols, in particular partially or completely hydrolyzed polyvinyl alcohols, hydrolyzed vinyl acetate copolymers, for example grafted polyethylene glycol-vinyl acetate copolymers, polyvinylpyrrolidone and vinylpyrrolidone copolymers, polyethyleneimines, polyvinylamine, polyvinylformamide, hyperbranched polycarbonates, polyglycols, polyurethane dispers
• the composition contains a glass frit in a proportion in the range of 0 to 7 wt .-%.
• the proportion of glass frit in the range of 1, 5 to 4 wt .-% and in particular in the range of 2 to 3.5 wt .-%.
• glass frits are, for example, bismuth oxide-based glasses.
• Glass frits suitable for the composition contain in particular bismuth oxide, silicon oxide and / or tellurium oxide.
• the proportion of tellurium oxide is preferably in the range of 0.01 to 10 wt .-%.
• the proportion of bismuth oxide is preferably in the range of 40 to 95 wt .-%. More preferably, the proportion of bismuth oxide is in the range of 50 to 80 wt .-% and in particular in the range of 60 to 75 wt .-%.
• the proportion of silicon oxide is preferably in the range from 0 to 30 wt .-%, in particular in the range of 1 to 4 wt .-%, each based on the mass of the glass frit.
• the glass frit may additionally contain boron oxide.
• the proportion of boron oxide is preferably in the range from 0.1 to 10% by weight, in particular in the range from 0.5 to 8% by weight and in a particularly preferred embodiment in the range from 1 to 4% by weight. %.
• the glass frit may contain zinc oxide and / or alumina.
• the proportion of zinc oxide is in the range of 0 to 15 wt .-% and the proportion of aluminum oxide in the range of 0 to 3 wt .-%.
• metal oxides which may be contained in the glass frit are, for example, silver oxide (Ag 2 O), antimony oxide (Sb 2 O 3 ), germanium oxide (GeO 2 ), indium oxide (ln 2 O 3 ), phosphorus pentoxide (P 2 O 5 ). , Vanadium pentoxide (V 2 0 5 ), niobium pentoxide (Nb 2 0 5 ) and tantalum pentoxide (Ta 2 0 5 ).
• the amount of Ag 2 O, P 2 O 5 , V 2 O 5 , Nb 2 O 5 and / or Ta 2 O 5 which may be contained in the glass frit, is in the range of about 0 to 8 wt.
• the content of ln 2 O 3 and / or Sb 2 O 3 in the glass frit is preferably in the range of 0 to 5% by weight.
• one or more alkali oxides usually Na 2 O, Li 2 O and / or K 2 O may be contained in the glass frit.
• the proportion of alkali metal oxides in the glass frit is in each case in the range from 0 to 3 wt .-%.
• alkaline earth metal oxides may also be contained in the glass frit. Commonly contained alkaline earth oxides are BaO, CaO, MgO and / or SrO.
• the proportion of alkaline earth oxides in the glass frit is in each case in the range from 0 to 8 wt .-%.
• essentially lead-free means that no lead is added to the glass frit and that the proportion of lead in the glass frit is less than 1000 ppm.
• the composition according to the invention also contains at least one organometallic compound.
• the proportion of the organometallic compound in the composition is in the range of 0 to 5 wt .-%, preferably in the range of 1 to 3 wt .-% and in particular in the range of 1, 5 to 2.5 wt .-%.
• Suitable organometallic compounds which can be used are metal carboxylates, metal propionate, metal alkoxides, complex compounds of a metal or a mixture thereof. Furthermore, the organometallic compounds may also contain aromatic or aliphatic groups. Suitable carboxylates are, for example, formates, acetates or propionates. Suitable alkoxides are, for example, methoxide, ethanolate, propanolate, butoxide, pentanoate, hexanolate, heptanolate, octanolate, nonanolate, decanolate, undecanolate and dodecanolate.
• the metal of the organometallic compound is preferably selected from the group consisting of aluminum, bismuth, zinc and vanadium.
• the organometallic compound may contain boron or silicon.
• Suitable organometallic compounds that can be used are, for example, bismuth (III) acetate, triphenyl bismuth, bismuth (III) hexafluoropentanedionate, bismuth (III) tetramethylheptanedionate, bismuth neodecanoate, bismuth (III) -2-ethylhexanoate, bismuth carbonate oxide, bismuth subgallate hydrate , Bismuth (III) gallate base hydrate, bismuth (III) subsalicylate, bismuth (III) tris (2,2,6,6-tetramethyl-3,5-heptanedionate), triphenylbis- bis (III) carbonate, tris (2-) methoxyphenyl) -bismuthine.
• organometallic compounds are bismuth (III) acetate, bismuth (III) 2-ethylhexanoate, bismuth carbonate oxide, bismuth subgallate hydrate, bismuth (III) gallate base hydrate, bismuth (III) subsalicylate.
• the composition may also contain other additives. Additives which may be included in the composition are, for example, dispersants, thixotropic agents, plasticizers, wetting agents, defoamers, driers, crosslinkers, complexing agents, conductive polymer particles and / or absorbents for laser radiation.
• the additives can be used in each case individually or as a mixture of two or more of the additives.
• the proportion of additives in the composition is generally in the range of 0 to 5 wt .-%, preferably in the range of 0.1 to 3 wt .-% and in particular in the range of 0.1 to 2 wt .-%.
• dispersant When a dispersant is used as the additive, it is possible to use only one dispersant or more dispersants.
• dispersants known to the person skilled in the art for use in dispersions and described in the prior art are suitable.
• Preferred dispersants are surfactants or surfactant mixtures, for example anionic, cationic, amphoteric or nonionic surfactants.
• Suitable cationic and anionic surfactants are described, for example, in "Encyclopedia of Polymer Science and Technology", J. Wiley & Sons (1966), Vol. 5, pp. 816-818 and in “Emulsion Polymerization and Emulsion Polymers", Editors P. Lovell and M. El-Asser, published by Wiley & Sons (1997), pages 224 to 226.
• thixotropic agents When thixotropic agents are added as an additive, for example, organic thixotropic agents may be used.
• Thickeners that can be used are, for example, polyacrylic acid, polyurethanes or hydrogenated castor oil.
• Plasticizers, wetting agents, defoamers, drying agents, crosslinkers, complexing agents and conductive polymer particles which can be used are those which are conventionally used in dispersions and are known to the person skilled in the art.
• absorbants for the energy of the energy source such as the laser.
• absorbants for the energy of the energy source
• Suitable absorbents for laser radiation have a high absorption in the laser wavelength range. Particularly suitable are absorbents which have a high absorption in the near infrared and in the longer wavelength VIS range of the electromagnetic spectrum. Such absorbents are particularly suitable for absorbing the radiation of high-performance solid-state lasers, for example Nd: YAG lasers and IR diode lasers. Suitable absorbents for the laser radiation are, for example, in the infrared spectral region strongly absorbing dyes such as phthalocyanines, naphthalocyanines, cyanines, quinones, metal complex dyes such as dithiols or photochromic dyes.
• inorganic pigments in particular intensively colored inorganic pigments such as chromium oxides, iron oxides or iron oxide hydrates.
• the amount of carbon black in the composition is in the range of 0 to 5% by weight.
• the proportion is in the range of 0.01 to 3 wt .-% and in particular in the range of 0.5 to 2 wt .-%.
• any carbon black known to the person skilled in the art can be used as carbon black.
• Such radicals are known to the person skilled in the art and are commercially available.
• absorbents it is also possible to use nanoparticles of silver, gold, platinum, palladium, tungsten, nickel, tin, iron, indium tin oxide, tungsten oxide, titanium carbide or titanium nitride as absorbers for laser radiation.
• elemental carbon for example in the form of carbon black, carbon nanotubes, graphenes or graphite
• Another advantage of using silver, gold, platinum, palladium, tungsten, nickel, tin, iron, indium tin oxide or titanium carbide is that these materials are electrically conductive.
• the use of the nanoparticles reduces the electrical conductivity of the printed interconnects to a much lesser extent, or preferably does not lower them.
• these materials do not oxidize when fired, In particular, they do not give gaseous compounds which can lead to a porosity of the printed conductors and thereby to a reduction of the conductivity.
• Titanium carbide as an absorbent can burn, but the amount of carbon released is much less than the amount released when using elemental carbon as the absorbent.
• the nanoparticles are spherical particles.
• Spherical particles in the context of the present invention means that the particles have a substantially spherical shape, but the real particles may also have deviations from the ideal spherical shape.
• the real particles may also be flattened or have a teardrop shape. Also other deviations from the ideal spherical shape, which can occur due to production, are possible.
• the nanoparticles are spherical particles, they preferably have a diameter in the range of 2 to 100 nm.
• spherical nanoparticles with a particle diameter in the range from 2 to 50 nm are particularly suitable.
• the diameter of the spherical particles is in the range of 6 nm.
• the proportion of nanoparticles in the composition is in particular in the range from 0.5 to 12% by weight.
• the nanoparticles are prisms having an edge length in the range of 15 to 1000 nm and a height of 3 to 100 nm.
• the shape of the prisms is variable. The shape depends, among other things, on the laser radiation used.
• the base area of the prisms can thus be designed, for example, in the form of an arbitrary polygon, for example a triangle or a pentagon.
• the prisms used as nanoparticles are generally plasmon resonators whose absorption behavior is adapted to the wavelength of the laser used.
• the adaptation to the wavelength of the laser used takes place, for example, by the edge length of the prisms and by the cross-sectional area. For example, different cross-sectional areas and different edge lengths each have a different absorption behavior.
• the height of the prisms also exerts an influence on the absorption behavior.
• the proportion of nanoparticles present as prisms in the composition is preferably in the range from 3 to 10% by weight.
• spherical particles or prisms as an absorber for laser radiation
• the nanoparticles are generally stabilized during production, in particular for transport, by suitable additives.
• the additives are usually not removed, so that they are then also contained in the composition.
• the proportion of stabilizing additives is generally at most 15% by weight, based on the mass of nanoparticles.
• additives for stabilizing the nanoparticles for example, long-chain amines, for example dodecylamine can be used.
• Further additives which are suitable for stabilizing the nanoparticles are, for example, octylamine, decylamine, oleic acid and polyethyleneimines.
• absorbers for laser radiation are inorganic pigments, nanoparticles of silver, gold, platinum, palladium, tungsten, nickel, tin, iron, indium tin oxide, tungsten oxide, titanium carbide or titanium nitride, in particular of silver, fine-particle carbon species or finely divided lanthanum hexaboride (LaB 6 ).
• inorganic pigments nanoparticles of silver, gold, platinum, palladium, tungsten, nickel, tin, iron, indium tin oxide, tungsten oxide, titanium carbide or titanium nitride, in particular of silver, fine-particle carbon species or finely divided lanthanum hexaboride (LaB 6 ).
• the amount of absorbent added will be selected by those skilled in the art depending on the desired properties of the dispersion layer. In this case, the skilled person will additionally take into account that the added absorbent not only affects the speed and efficiency of the transfer of the composition by the laser, but also affects other properties such as the adhesion of the composition to the substrate to be printed or the printed circuit traces.
• the preparation of the composition according to the invention is carried out, for example, by intensive mixing and dispersion in units known to the person skilled in the art. This includes, for example, mixing the components in a dissolver or comparable intensively dispersing aggregate, dispersing in an agitated ball mill or a powder fluidizer when producing large quantities.
• the application of the composition according to the invention to a substrate can be carried out by any method known to the person skilled in the art. For example, a coating with a printing process, such as screen printing, pad printing, inkjet printing, offset printing or laser printing is possible.
• the layer thickness applied during printing preferably varies in the range from 0.01 to 100 ⁇ m, more preferably between 0.1 and 50 ⁇ m, and particularly preferably in the range from 5 to 30 ⁇ m.
• the layers applied with the composition according to the invention can be both full-surface and structured.
• the composition according to the invention is applied to the substrate by a printing process in which the composition undergoes a change in volume and / or position by means of an energy-emitting device that emits energy in the form of electromagnetic waves, thereby transferring the composition the substrate takes place.
• an energy-emitting device that emits energy in the form of electromagnetic waves

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• Chemical & Material Sciences (AREA)
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• Microelectronics & Electronic Packaging (AREA)
• Conductive Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
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• Printing Plates And Materials Therefor (AREA)
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• 2010
  • 2010-09-01 US US13/394,011 patent/US9396833B2/en not_active Expired - Fee Related
  • 2010-09-01 EP EP10747636.8A patent/EP2474004B1/de not_active Not-in-force
  • 2010-09-01 JP JP2012527305A patent/JP5984671B2/ja not_active Expired - Fee Related
  • 2010-09-01 ES ES10747636.8T patent/ES2536696T3/es active Active
  • 2010-09-01 KR KR1020127008776A patent/KR101874125B1/ko not_active Expired - Fee Related
  • 2010-09-01 CN CN201080042425.9A patent/CN102576575B/zh not_active Expired - Fee Related
  • 2010-09-01 WO PCT/EP2010/062775 patent/WO2011026852A1/de not_active Ceased
  • 2010-09-01 TW TW099129532A patent/TWI553663B/zh not_active IP Right Cessation
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