Classifications

• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/32—Processes for applying liquids or other fluent materials using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
  • B05D1/322—Removable films used as masks
• • 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
  • B05D5/02—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a matt or rough surface
• • 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
  • B05D1/00—Processes for applying liquids or other fluent materials
  • B05D1/40—Distributing applied liquids or other fluent materials by members moving relatively to surface
• • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F24—HEATING; RANGES; VENTILATING
  • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
  • F24C15/00—Details
  • F24C15/02—Doors specially adapted for stoves or ranges
  • F24C15/04—Doors specially adapted for stoves or ranges with transparent panels
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
• • 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
  • Y10T428/31504—Composite [nonstructural laminate]

Definitions

• the invention relates to a substrate comprising at least one fully or partially macrostructured layer, processes for their preparation and their use.
• sol-gel technology is often used.
• sol-gel layers are: Layer function: Layer / System
• sol-gel solutions anti-reflective multilayer system SiO 2 -TiO 2 alcoholic Si and Ti alkoxide solutions photocatalytic TiO 2 layer (Anatase) colloidal TiO 2 solution anti-microbial Ag-containing layer colloidal Ag solution
• the sol-gel solutions used have different viscosities. Often, however, this is in the order of magnitude of aqueous solutions and is therefore very low.
• the application of the layers takes place over the entire surface using common Application methods, such as dipping, flooding, spraying, spraying, pouring, brushing, rolling or spinning. As a rule, the layers are cured by a subsequent tempering step.
• WO 97/38810 A1 discloses a process for producing a sintered structure on a substrate, wherein a particle-containing liquid such as a sol-gel solution is applied to a substrate by an ink jet printer and the applied liquid is evaporated by a laser pulse to build a sintered structure in layers ,
• the WO 02/17347 A1 discloses a method for consolidating and patterning a sol-gel composition on a surface of a substrate, wherein a layer of a sol-gel composition is deposited on a surface of a substrate, an electron beam is directed to selected areas of the sol-gel film, to cure the sol-gel film and the uncured areas are removed with a solvent again.
• the EP 0 329 026 A1 to an ink-jet ink and printing method, wherein the ink comprises 90 to 99.9% by weight of an aqueous sol-gel medium, preferably a mixture of carrageenan and water, and 0.1 to 10% by weight of a colorant , and the ink represents a thermally reversible sol-gel ink that is a gel at ambient temperature and is a sol at temperatures between about 40 ° C and 100 ° C.
• the ink is applied as a sol to the substrate where it forms a gel upon cooling.
• the substrate used is almost exclusively paper into which the ink penetrates.
• US Pat. No. 5,970,873 relates to an imaging process comprising imagewise applying a mixture of a sol precursor and a liquid as a thin layer to a substrate and removing the liquid from the thin layer to imagewise form an insoluble, crosslinked, polymeric sol-gel matrix.
• An imaging element made by the process such as a lithographic printing plate, will also be described.
• the image area created in the sol-gel matrix therefore serves as a "negative" to which ink is applied, which is then transferred to a suitable receptor material to reproduce the image.
• the WO 99/33760 a method of providing an article with visually-visible patterns, wherein first at least a surface area of a substrate is masked, then at least one thin layer is applied to the masked and unmasked areas of the surface, and the mask is removed to produce the desired pattern.
• the article produced therewith has at least a first portion carrying a generally transparent thin film selected from metal-containing, semi-metal-containing coatings and combinations thereof, which when viewed under reflected light exhibits a first color and exhibits a second color under light passing therethrough , as well as a second section, visibly different in contrast to the first.
• the sol-gel technology is mentioned, but no explanation is given how this can be done.
• the present invention is based on the object, in a development of the prior art, to provide a flexible, non-expensive and cost-effective method by means of which structures can be produced on a substrate in a simple manner. In particular, it should be possible to provide any substrate with a desired structure.
• the present object is achieved by a substrate according to claim 1.
• the present invention accordingly comprises substrates with a structured coating, wherein a sol-gel solution is used to produce the structured coating.
• structured is to be construed as broad as possible according to the invention and includes, for example, a pattern, logo, image (s), words, a marker, hatching, marking, labels, in one or more defined optical manifestations, functionalities or the like. This structure can be provided over the whole area or only part of the area on a substrate.
• sol-gel system i. a sol which forms a thin, preferably transparent, gel film after drying, which preferably hardens by baking / tempering.
• sol-gel layer in the present invention is intended to represent a layer prepared by a sol-gel method.
• nanosols can be used.
• the average particle diameter of such sols is in the range ⁇ 800 nm, preferably ⁇ 200 nm, particularly preferably ⁇ 100 nm.
• the sol-gel layer is based on one or more metal oxides and is preferably selected from at least one titanium, zirconium, silicon, aluminum, tin, boron or phosphorus oxide or mixtures thereof. Particular preference is given to containing silicon oxide, but it is also possible for other or further metal oxides to be present.
• metal also the semimetals, such as silicon and germanium, understood.
• sol-gel solutions for example, so-called classical sol-gel solutions are used according to the invention, in addition to a suitable amount of desired additives, a metal oxide precursor, a solvent, a minor amount of water for precondensation and a catalyst (acid or base ) or consist of.
• colloidal metal oxide solutions solutions of nanoscale metal oxide powders in water or other solvents are used; In some cases, traditional sol-gel solutions are also mixed with nanoscale metal oxide powders.
• Solvents are usually water or an aqueous / organic solvent, such as, for example, ethanol or acetone. Long-term stable sol-gel solutions may also be stored in purely organic solvents.
• sols are clear and stable solutions with solids contents typically in the range of about 1 to about 30 weight percent.
• the metal oxide contents can also be significantly higher.
• a part of the solvent is evaporated, whereby the particles chemically or physically aggregate and a three-dimensional crosslinking (gelation) takes place. After complete evaporation of the solvent results in a solvent-free coating of a porous sol-gel layer, which under the influence of higher temperatures further networked and thereby hardened and compacted.
• the sol-gel matrix can also be modified chemically in any manner by co-hydrolysis or co-condensation. These modifications are known to the person skilled in the art. Such organically modified sol-gel compounds are known, for example, under the brand ORMOCER® ®.
• the sol-gel coating can be carried out directly in structured form according to process variant (a) according to the invention using various printing techniques.
• process variant (a) according to the invention using various printing techniques.
• the tampon and gravure are mentioned here, as they are particularly well suited for the processing of low-viscosity liquids.
• the sol-gel solution which is converted to the sol-gel layer can be applied directly in structured form:
• Structured liquid coatings can generally be applied to the substrate using known printing technologies, but so far this has not been known for sol-gel solutions used to make functional layers.
• Conventional sol-gel solutions dry very quickly, which can cause great difficulties in printing techniques. Without a modification of the solution, especially the solvents, many methods are unusable because the coating reacts on the transfer medium or in the printing nozzles. It is important that no / hardly any condensation reactions take place during the printing process.
• the present invention now provides ways in which - in contrast to the prior art - known printing technologies can be used, whereby the above problems are minimized or completely avoided.
• sol-gel solutions tailor-made for the special printing technology, which includes, for example, a modification of the viscosity of the solution and / or a suitable choice of the solvent, is the first to be used hitherto unavailable printing technologies accessible.
• a highly viscous sol-gel solution can be used for screen printing.
• sol-gel solutions generally have a comparatively low viscosity
• tampon and intaglio printing in particular are suitable for the production of structured coated articles.
• the application of the sol-gel solution in already structured form according to the process (a) according to the invention is therefore carried out on the substrate, preferably with a low-viscosity sol-gel solution using a known printing process.
• low viscosity is meant in the present invention, a viscosity in the range of about 0.1 to about 10 4 mPa s.
• pigment-filled color formulations which contain a sol-gel solution, for example as a binder, are also preferably used.
• a sol-gel solution for example as a binder
• thickening additives are, for example, cellulose, cellulose ethers, starch, aerosils (pyrogenic silicas), bentones, hydrophobically modified polyoxyethylenes, acrylates, polyurethanes, polyamides, polyolefins, Castor oil and basic sulphonates.
• thickening additives are added and a highly viscous, sufficiently thixotropic sol-gel solution is obtained, the application of the structured coating is also possible by means of screen printing or other printing techniques, such as offset, pad and pad printing.
• a "high-viscosity”, “sufficiently thixotropic” sol-gel solution is understood here to mean that the viscosity-in the absence of shear forces-is above a limit of about 10 3 mPa s, in particular about 10 4 to 10 6 mPa s.
• Thixotropy refers to the property of a non-Newtonian fluid to exhibit a lower viscosity after shearing and to rebuild at rest.
• the sol-gel layer can be applied over the entire surface of the substrate and subsequently structured in further working steps:
• these can be applied directly to the substrate as positive coatings at the points of the layer to be structured (process variant (b1) according to the invention).
• processing variant (b1) according to the invention.
• screen printable Coating used.
• the application of the Abdecklacks can already be done preferably in a structured form.
• a photoresist is used.
• the structuring can also take place after a full-area application of the photoresist in a second step with the aid of an exposure step and subsequent removal of the areas not to be lacquered. Subsequently, the full surface coating of the prepared substrate is carried out using the sol-gel solution.
• (screen) printable paints is preferred over that of photo-resists because they are significantly less expensive and their application is associated with a significantly lower cost.
• solvent or dispersant or solvent mixture suitable for such a process can be used as solvent or dispersant for the sol-gel solution of all processes according to the invention.
• examples are water and alcohols, for example ethanol, or alcohol-water mixtures.
• alcohols for example, alcohols, but also aprotic solvents, such as dioxane, or aqueous solvents can be used.
• the sol-gel layers applied according to the invention which are used in process variants (b1) and (b2) according to the invention, preferably have layer thicknesses in the range from 1 nm to 100 .mu.m, preferably 1 nm to 1 .mu.m, in particular 1 to 200 nm.
• the (preferred) layer thicknesses vary greatly. If only a few monolayers are deposited on the substrate in the case of an easy-to-clean layer, ie the layer thickness moves here in the nm range, it may be preferred if pigment-filled, decorative sol-gel layers are opaque. This is achieved, for example, with layer thicknesses of at least 10 ⁇ m or significantly higher.
• a fully or partially coated layer is to be applied, it is preferably applied by a spraying or dipping method, wherein all other methods known to the person skilled in the art may also be used, e.g. a spin, roll coating (rolling), brushing, pouring or knife coating.
• a spraying or dipping method wherein all other methods known to the person skilled in the art may also be used, e.g. a spin, roll coating (rolling), brushing, pouring or knife coating.
• sol-gel layers which fulfill very specific functions which can be used for commercial products. Drying according to process variant (b1) is preferably carried out in a temperature range from room temperature (25 ° C.) to 300 ° C. until essentially all the solvent has been removed, the solvent of the sol-gel solution being water, alcohol, all known to the person skilled in the art , in particular common, preferably halogen-free, low (boiling point: up to 120 ° C) and high boiling solvent (boiling point: 120 to 250 ° C) and mixtures thereof are preferred.
• the drying time is generally in the range of a few minutes to 1 or more days. In some applications, the quality of the layers thus formed is sufficient, so that no further production step for baking is required. -No preferred drying times can be specified, since these can be very different depending on the application.
• the dried sol-gel layer is subsequently baked.
• a "burn-in" according to variant (b1) in the context of the invention means that the dried sol-gel layer is converted into its final form by chemical reaction, sintering and / or stimulation of diffusion processes.
• the substrate with the applied dried layer for a period of 10 minutes to 3 hours a temperature in the range between room temperature and 800 ° C, preferably between 250 and 800 ° C. exposed.
• Coating lacquers generally can not be exposed to the temperatures necessary for curing the sol-gel layers, so that they are removed before stoving.
• Baking has the advantage that the mechanical and chemical resistance of the layer increases drastically. In some cases, the layer only gets its actually desired function by the burn-in. The coated article in these cases can be used only after the baking step in the respective application.
• Burning in can also specifically influence certain properties of the layer.
• the optical antireflection effect of SiO2 TiO2 -Wechsel Anlagensystemen is critically dependent on the refractive indices of the respective, present in the layer packet individual layers. This in turn is structurally dependent.
• the chemical structure varies depending on the choice of baking conditions.
• the anti-reflection effect of such coating systems inter alia, depends crucially on the conditions during the penetration of the layers.
• the sol-gel layer is preferably already converted into its final form, so that further post-treatment steps are not necessary.
• microstructures are generated which can be used, for example, in semiconductor components, and become visible to the naked eye, for example, only under a microscope.
• macrostructured regions for example coarse-structured, optionally large-area regions, are produced. This means that structures in the order of up to a minimum of about 50 to 100 microns (corresponding to about the width of a hair) can be made, so that always visible to the eye structures are produced.
• a transfer of such Microstructures on macrostructures would not be considered by a person skilled in the art due to the well-known special status of semiconductor technology.
• the evaporation of the solvent or drying according to process variant (b2) is preferably carried out in a temperature range from room temperature to max. 200 ° C until essentially all the solvent has been removed, being used as the solvent of the sol-gel solution, water, alcohol, all known in the art, especially common, preferably halogen-free, low (boiling point: up to 120 ° C) and high boiling solvent (Boiling point: 120 to 250 ° C) and mixtures thereof are preferred.
• the drying time is generally in the range of a few minutes to 1 or more days. Because of the diversity of the layers to be produced, the above information is only an example.
• the patterning of the resist can advantageously be effected by means of suitable (screen) printing methods, i. Applying the resist in structured form, or photolithographically, i. after application, done.
• the sol-gel layer is then removed at the exposed locations, for example with a suitable chemical etching solution.
• a suitable chemical etching solution may be, for example, an aqueous NaOH solution or an aqueous HF solution.
• the covering is again mechanically, chemically or pyrolytically - as already described - removed.
• the Abdecklack which is applied either in a structured form or structured after the order is not baked.
• any known in the art paint can be used.
• paint classes such as: topcoats, Peel-off lacquers, photostructurable lacquers (liquid resists, dry resists).
• Usable commercially available products are, for example: covering lacquer 80 2039 (from Ferro), Wepelan covering lacquer SD 2154 E (Peters), stripping lacquer SD 2962 P (Peters), liquid resist AZ 9260 (from Clariant), liquid resist AZ nLOF 2070 (Clariant), dry resist EtchMaster ES-102 (DuPont) and dry resist Riston 220 (DuPont).
• the sol-gel solution used according to the invention preferably contains further constituents selected from the group consisting of inorganic and / or organic dyes, pigments and / or additives, such as thickener, dispersant, defoamer, anti-settling agent, surface tension modifier, processing aid, deaerator, lubricant and leveling agents, crosslinking additives, primers, and the like.
• Additives can be used, for example, for the specific introduction of specific functionalities.
• organic and / or inorganic dyes or pigments for example, additional color effects can be produced.
• pigments are able to introduce further functionalities, such as IR or UV reflection, into the layer.
• the total amount of all components of the sol-gel solution naturally complements 100% by weight.
• the substrate in the above method provided with one or more structures is not particularly limited in the present invention. Any type of material may be used, such as, for example, plastic, metal, wood, enamel, glass, ceramics, in particular glass-ceramic, preference being given to glass and glass-ceramic substrates.
• alkali-containing float glasses such as borosilicate glasses (eg Borofloat 33, Borofloat 40, Duran from Schott AG, Mainz), as well as alkali-free glasses (eg AF 37, AF 45 from Schott AG, Mainz), aluminosilicate glasses (eg Fiolax, IIIax from Schott AG, Mainz), alkaline earth glasses (eg B 270, BK 7 from Schott AG, Mainz), Li 2 O-Al 2 O 3 -SiO 2 float glass, discolored float glass with an iron concentration below 700 ppm, preferably below 200 ppm and, in a more specific application, soda-lime glasses, particularly the latter being preferred.
• display glasses such as D263 from Schott-DESAG, Grünenplan. In principle, all known technical and optical glasses can be used.
• Typical glass ceramics which are used as alkali-containing glass-ceramics are, for example lithium aluminosilicate (LAS) glass-ceramics, such as CERAN ®, ® or ROBAX ZERODUR ® (all brands of Schott AG, Mainz), but also alkali-free glass ceramics, such as magnesium aluminosilicates (MAS) can be used.
• LAS lithium aluminosilicate
• CERAN ® ®
• ROBAX ZERODUR ® all brands of Schott AG, Mainz
• MAS magnesium aluminosilicates
• the substrate is not particularly limited in the invention not only in terms of the material but also in terms of shape, so that, for example, flat, round, rounded large and small objects can be used. Preference is given to objects made of or with glass and / or glass ceramics of any shape, such as glass tubes, glass lenses, ampoules, carpets, bottles, jugs. Slices, plates or any shaped parts.
• an optionally surface-treated substrate as well as a substrate already provided with a layer, for example a surface-treated or already coated glass.
• the substrate is provided at least on a part of its surface with a macrostructure according to the present invention.
• the entire surface may also be structured or the structure may be present on multiple parts of one or more surfaces.
• the structure can be applied, for example, on one or both sides, according to the shape of a substrate also on several sides.
• substrates tiles, enamel parts, panes, in particular viewing panes, plates, panels, glazings of all kinds, shower enclosures, covers, work and cooking surfaces, as part of refrigerators or freezers, dining or drinking utensils, containers, Fire panels, chimney windows, oven panes as a glass cover for solar energy systems, medical glass, in particular a drug bottles, lenses or covers for displays, a component of hi-fi or computing or telecommunications equipment and the like.
• the invention also relates to the partially or completely macro-structured layers produced according to the invention.
• These can be used, for example, in the form of functional layers, i. the partial or full-surface structured layer has one or more specific functions or properties.
• functional layers structured according to the invention are anti-reflection layers, color layers, decorative layers, photocatalytic layers, antimicrobial layers, anti-virus layers, anti-mold layers, anti-fungicidal layers, anti-algae layers, anti-fogging layers. Layers, cleaning layers, odor neutralizing layers, anti-fingerprint layers, air cleaning layers or combinations thereof.
• glass ceramic plates for a household appliance a glass cover for solar energy systems, as a window of a dishwasher or cookware, such as a steamer, as a fire or medical glass, such as drug bottles, for containers or pipes, such as coated container or Pipe for dairy farming, as a window or cover for displays, component of hi-fi, computing or telecommunications equipment, for dining or drinking utensils, baby bottles, windows, optical lenses, laboratory glassware, in particular borosilicate glasses.
• the advantages of the present invention are many:
• the present invention provides a substrate as well as methods for its production, wherein the advantages of the sol-gel technology can be used, ie it can be provided wet-chemically coated at low cost and low cost coated substrates.
• the substrates are not particularly limited, particularly preferred are glass and glass ceramics.
• the sol-gel technology can be used in unexpected ways to produce almost arbitrarily structured substrates, although low-viscosity solutions can be used. Nevertheless, sharp and non-running structures are preserved.
• the viscosity of the sol-gel solution can be adjusted in the desired manner, so that it is possible to work with low-viscosity as well as highly viscous sol-gel solutions, whereby the best results are achieved for the respective application.
• sol-gel solution For structured application of the sol-gel solution can be made of known application and printing methods, so that no special equipment must be designed and designed.
• the sol-gel method allows economic structuring of large areas, which can be used, inter alia, on aqueous systems, so that the applied structures release no toxic solvents, are completely inert and used safely indoors can be.
• sol-gel fabricated structures are also the frequently obtained good mechanical thermal and photochemical stability, room temperature capability and, if desired, high spectral transparency.
• Another advantage of such sol-gel layers is in most cases also that they are not a source of food for microorganisms, since they are completely toxicologically as well as biologically inert.
• the inorganic sol-gel structure to be produced in the cured state is a structure which is free of impurities. This is therefore also suitable for uses with food contact.
• sol-gel method used according to the invention it is possible to produce thin, glassy, optionally colored, functional layers in great variety and structure. It is possible to create tailor-made structures related to specific applications.
• Cooking surface made of a transparent glass ceramic with a displayable, colored underside coating
• a displayable underside coating has recesses in those areas of the hob where electronic display panels and LEDs are located.
• the electronic display elements are thus better recognizable on the cooking surface.
• the structuring of the coating is realized by first masking the hob at the desired locations with a resist.
• a sufficiently viscous and thixotropic lacquer eg Wepelan Abdecklack SD 2154 E from Peters, Abziehlack SD 2962 P from Peters or Abziehlack 80 2039 from Ferro
• Pigments and fillers are stirred into the binder by means of a stirrer with dissolver disk.
• the color is mixed with a further 43.0 g of n-propanol as the solvent.
• pigment-filled sol-gel color is applied over the entire surface, for example by means of the spraying or casting process on the substrate and dried for sufficient time in the air.

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• Application Of Or Painting With Fluid Materials (AREA)
• Laminated Bodies (AREA)
• Paints Or Removers (AREA)
• Surface Treatment Of Glass (AREA)

Applications Claiming Priority (2)

Publications (2)

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• 2005
  • 2005-08-03 DE DE102005036427A patent/DE102005036427A1/de not_active Ceased
• 2006
  • 2006-07-13 WO PCT/EP2006/006856 patent/WO2007014631A2/de active Application Filing
  • 2006-07-13 CN CN2006800275972A patent/CN101232952B/zh not_active Expired - Fee Related
  • 2006-07-13 EP EP20060776219 patent/EP1909971B1/de not_active Not-in-force
  • 2006-07-13 JP JP2008524388A patent/JP2009502490A/ja active Pending
  • 2006-07-13 ES ES06776219T patent/ES2349659T3/es active Active
  • 2006-07-13 DE DE200650008031 patent/DE502006008031D1/de active Active
  • 2006-07-13 AT AT06776219T patent/ATE483531T1/de active
• 2008
  • 2008-01-30 US US12/022,293 patent/US20080145625A1/en not_active Abandoned

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