EP1711279B1 - Ultraviolett-vernetzungseinrichtung unter kontrollierter atmosphäre - Google Patents

Ultraviolett-vernetzungseinrichtung unter kontrollierter atmosphäre Download PDF

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Publication number
EP1711279B1
EP1711279B1 EP05717683A EP05717683A EP1711279B1 EP 1711279 B1 EP1711279 B1 EP 1711279B1 EP 05717683 A EP05717683 A EP 05717683A EP 05717683 A EP05717683 A EP 05717683A EP 1711279 B1 EP1711279 B1 EP 1711279B1
Authority
EP
European Patent Office
Prior art keywords
channel
gas
chamber
labyrinth
components
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP05717683A
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English (en)
French (fr)
Other versions
EP1711279A1 (de
Inventor
François Coeuret
Géraldine Rames-Langlade
Andrea Spizzica
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Priority to PL05717683T priority Critical patent/PL1711279T3/pl
Priority to SI200530295T priority patent/SI1711279T1/sl
Publication of EP1711279A1 publication Critical patent/EP1711279A1/de
Application granted granted Critical
Publication of EP1711279B1 publication Critical patent/EP1711279B1/de
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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
    • 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
    • B05D3/04—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 exposure to gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B21/00—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects
    • F26B21/14—Arrangements or duct systems, e.g. in combination with pallet boxes, for supplying and controlling air or gases for drying solid materials or objects using gases or vapours other than air or steam, e.g. inert gases
    • 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
    • B05D3/04—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 exposure to gases
    • B05D3/0486—Operating the coating or treatment in a controlled atmosphere
    • 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
    • B05D3/06—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 exposure to radiation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B13/00—Machines and apparatus for drying fabrics, fibres, yarns, or other materials in long lengths, with progressive movement
    • F26B13/005—Seals, locks, e.g. gas barriers for web drying enclosures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F26—DRYING
    • F26B—DRYING SOLID MATERIALS OR OBJECTS BY REMOVING LIQUID THEREFROM
    • F26B3/00—Drying solid materials or objects by processes involving the application of heat
    • F26B3/28—Drying solid materials or objects by processes involving the application of heat by radiation, e.g. from the sun
    • 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
    • B05D3/06—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 exposure to radiation
    • B05D3/061—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 exposure to radiation using U.V.
    • B05D3/065—After-treatment
    • B05D3/067—Curing or cross-linking the coating
    • 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
    • B05D3/06—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 exposure to radiation
    • B05D3/068—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 exposure to radiation using ionising radiations (gamma, X, electrons)

Definitions

  • the invention relates to installations in which are carried out operations requiring control of the atmosphere inside an enclosure, and concerns in particular the field of crosslinking operations of a coating (for example an ink or a varnish ) by Ultra Violet radiation (“UV Curing” in the literature) or by electron beam (“Electron Beam” in the literature) in the presence of a controlled atmosphere, most often an inert gaseous mixture, for example based on nitrogen, CO2, argon etc ... or mixtures of such gases.
  • a coating for example an ink or a varnish
  • UV Curing Ultra Violet radiation
  • Electro Beam electron beam
  • transformation products capable of curing (cross-linking) by UV radiation or electron beams (EB), such as glues, protective varnishes, lacquers, inks and paints is largely widespread today in printing and surface varnishing.
  • EB electron beams
  • these products have technical advantages (rapid crosslinking, less material shrinkage, quality of the finished product and easy cleaning of printing plates) and ecological ( resins made of 100% dry matter and reduced energy consumption).
  • the crosslinking step to be industrially performed continuously 24/24, the enclosure that comprises one or more UV lamps is an open system. Therefore, the crosslinking mechanism that takes place in the zone irradiated by the UV lamp is made in atmospheric air.
  • This step is carried out industrially at scrolling speeds ranging from 10 to several hundreds of m / min depending on the application.
  • the formulation contains a photoinitiator (PA).
  • PA photoinitiator
  • This photoinitiator under the action of UV, generates free radicals (step a) which will initiate the radical polymerization reactions according to the different steps described in scheme 1 below.
  • the radicals (R *) react with the reactive functions (M) of the prepolymer and the diluent, and initiate the polymerization reaction (step b). Since the reactive functions are both contained in the prepolymer and the diluent, the propagation (step c) of the polymerization reaction develops in all three dimensions. In this way, the termination (step d) of the polymer chain leads to a highly crosslinked polymeric network (R (M) n ).
  • Oxygen can thus slow down or completely inhibit the radical polymerization reaction.
  • the inhibitory effect of oxygen is all the more marked as the thickness of the UV resin layers is thin.
  • a first solution consists in increasing the intensity of the UV lamps in order to increase the production of free radicals (according to reaction a, scheme 1). These radicals, produced in greater quantity, react with the oxygen present in the reaction zone and reduce the oxygen concentration of the chamber and thus the oxygen-inhibiting effect.
  • a second solution is to introduce into the formulation of high amounts of photoinitiators and molecules (synergists) whose role is to react with, and thus eliminate, the oxygen present in the reaction zone. Even if these products are more and more efficient, it is estimated that, in standard formulations, 80% of photoinitiators and synergists react with oxygen and thus serve to destroy it, the remaining 20% serve to ensure the crosslinking of resins. UV.
  • a third solution consists in removing the residual oxygen present in the reaction zone and replacing this oxygen with an inert gas such as nitrogen.
  • This solution requires modifying the enclosure, open system, where the crosslinking of the resin takes place and equip it with a device for operating under an inert controlled atmosphere.
  • the crosslinking of UV resins under a controlled nitrogen atmosphere has multiple advantages since the absence of oxygen in the UV zone makes it possible to increase the rate of crosslinking, to reduce the luminous intensity of the UV lamps or the number of UV lamps. used, reduce the amount of photoinitiators and synergists introduced into the formulation and reduce the formation of by-products (such as peroxides and hydroperoxides) while obtaining a very high quality finished product.
  • the document WO 0014468 proposed equipment that can operate with about 50 ppm of residual oxygen in the reaction zone, at speeds up to several hundred meters per minute.
  • This equipment is characterized by the presence of two gas injection blocks placed at the entrance and exit of the UV chamber.
  • Each of these blocks comprises two gas injection systems; the first injection, placed at the ends of the enclosure, has the function of opposing any entry of air into the enclosure and the second injection, placed towards the inside of the enclosure, has the function of filling the pregnant with nitrogen.
  • the first injection system is a slit oriented so that the flow of gas is directed towards the outside of the enclosure.
  • the second injection system is a tube having pores oriented so that the flow of gas is directed towards the interior of the enclosure.
  • the width of the slot and the orientation angles of the two injection systems are modifiable and depend on the operating conditions.
  • the gas flows required for a low residual oxygen concentration as a function of the speeds used are very high (even considerable).
  • the amount of nitrogen should be 140 normal m 3 / h for a concentration of less than 50 ppm.
  • the rejection of a high amount of nitrogen outside the UV chamber in the work area requires an efficient suction system to avoid the risk of asphyxiation by anoxia.
  • Each of the input and output devices is typically constituted (see figure 1 below, we can also refer to the figure 2 of said document WO 0240738 ) of three components positioned in series and successively seen by the treated substrate: a channel, a gas injection slot and a "labyrinth".
  • the concept of "labyrinth” is well detailed in this prior document, and relates in fact to a system of open grooves vis-à-vis the internal space (gap) of the input device (or output) concerned (in which circulates the substrate to be treated) and forming a labyrinth.
  • the channel separated from the gas injection slot by a partition, is open opposite the interior space of the input or output device concerned.
  • the gas (nitrogen) injected through the slot will allow to take off the boundary layer of entrained air on the surface of the film.
  • the labyrinth by creating an overpressure zone (high pressure drop) in the direction of travel of the film forces nitrogen to go upstream, that is to say in the channel. This phenomenon is favored by a lower pressure drop in the channel.
  • This turbulence in the channel creates a zone of low vacuum on the surface of the film that pulls the air boundary layer on the surface of the film. Then the flow of nitrogen in the channel becomes laminar and forms a piston effect which opposes the flow of air and pushes it back.
  • This equipment has shown remarkable efficiency since it allows a film surface treatment in the presence of an oxygen concentration not exceeding 50 ppm with acceptable nitrogen flow rates.
  • the tests consisted of measuring the oxygen concentration inside the chamber and about 0.8 mm from the roll surface by injecting about 1.4 normal l / m 2 of nitrogen in each input / output device, with a width of 700 mm moving at speeds between 50 and 250 m / min.
  • the results of the measurements show that the oxygen concentration is between 6000 and 8000 ppm depending on the speed used (these results are represented on the figure 4 below).
  • the use of higher nitrogen rates (3.25 Normal liters / m 2 in each input / output device) reduces this concentration to about 3000 ppm.
  • the present invention therefore seeks to provide a new Ultra Violet or electron beam crosslinking equipment, the design of which significantly reduces the oxygen concentration prevailing inside the enclosure.
  • the height of the channel is advantageously between 3 and 5 mm.
  • the device at the entrance of the enclosure has, one can think, a dual function: due to the pressure drop created by the inlet labyrinth, the injected nitrogen tends to move towards the inside of the cross-linking chamber (enclosure), and makes it possible to minimize very strongly the entry of air into this same enclosure.
  • the device at the outlet of the enclosure which makes it possible to direct nitrogen towards the interior of the enclosure and to limit the gas discharges to the outside.
  • the input device plays a primordial role, as regards the output device, if its presence could be obscured or at least simplified in its structure for certain applications. less demanding (as we will see below), its presence is highly recommended in order to work in optimal atmosphere conditions.
  • the present invention thus relates to a crosslinking installation of a coating such as an ink or a varnish by ultraviolet radiation or by electron beam, in the presence of a gaseous mixture with a controlled residual oxygen content, the installation comprising an enclosure which comprises one or more UV lamps or an accelerated electron source, necessary for carrying out the crosslinking operation, characterized in that it comprises an input device adjoining the enclosure comprising at least the three following components, seen successively by the scrolling product to be treated: a labyrinth system, means for injecting an inert gas by forming a gas knife and a channel.
  • a labyrinth system means for injecting an inert gas by forming a gas knife and a channel.
  • labyrinth relates to a system of open grooves vis-à-vis the inner space of the input or output device concerned and forming a labyrinth.
  • the figure 3 hereinafter relates the result of tests of implementation of an equipment according to the invention, comprising the input / output systems described in the context of the figure 2 , which consisted of measuring the oxygen content in the middle of the chamber, approximately 5 mm from the treated roll, for speeds of between 50 and 250 m / min and nitrogen injections in each of the inlet devices / output of about 1.4 to 3.25 Normals Liters / m 2 .
  • the abbreviation "NI / m 2 " used in the figures should be understood as actually referring to normal liters / m 2 of treated substrate).
  • the figure 5 allows us to visualize a comparison of the results obtained within the framework of the figure 3 with those obtained under the figure 4 .
  • the axis in ordinates represents the reduction (in%) of the oxygen content achieved thanks to the equipment according to the invention.
  • the reduction of the residual oxygen level in the chamber is at least 94% with the same nitrogen speed and flow rate parameters, it even reaches 98 to 99% in the case of the highest flow rates. high.
  • the device at the input of the speaker (represented in figure 6 ) has been modified, it consists here of five components. Successively: a channel, a (1st) gas injection slot, a labyrinth, a (2d) gas injection slot followed by another channel.
  • the speaker output device ( figure 7 ) is identical to that of the figure 2 as consisting of three successive components: a channel, a nitrogen injection slit followed by a labyrinth.
  • the orientation of the nitrogen injection slits relative to the roller is, for the embodiment shown, approximately 90 ° for the first slit of the input device and 45 ° for the 2d slit of the device. Entrance.
  • the width of the slots is respectively close to 0.2 mm for the first slot and 0.4 mm for the 2d slot.
  • the distance between the input device and the roller is close to 0.8 mm.
  • the orientation of the nitrogen injection slit of the exit device is about 90 ° to the roll and its width is about 0.3 mm.
  • the distance between the output device and the support roller is close to 0.8 mm.
  • the configuration illustrated by this embodiment allows a further improved efficiency in the separation of the air boundary layer located on the surface of the film (compared to the previously described configuration in connection with the figure 2 ), and therefore a better assurance that the air conveyed on the surface of the film will not penetrate into the treatment chamber.
  • Slots No. 1 and 2 correspond to those of the input device, while slot No. 3 corresponds to that of the output device.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Microbiology (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Coating Apparatus (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Supply, Installation And Extraction Of Printed Sheets Or Plates (AREA)

Claims (6)

  1. Einrichtung, in der ein Arbeitsvorgang zur Vernetzung eines Überzugs, wie einer Farbe oder eines Lacks, durch UV-Strahlung oder durch Elektronenstrahl im Vorhandensein eines Gasgemisches mit kontrolliertem Restgehalt an Sauerstoff durchgeführt wird, wobei die Einrichtung ein Gehäuse aufweist, das eine oder mehrere UV-Lampen oder eine Quelle beschleunigter Elektronen aufweist, die zur Durchführung des Arbeitsvorgangs der Vernetzung notwendig sind, dadurch gekennzeichnet, dass sie eine an das Gehäuse angrenzende Eingangsvorrichtung aufweist, die mindestens die drei folgenden Bauteile aufweist, mit denen das vorbeilaufende zu verarbeitende Produkt nacheinander zusammentrifft: ein Labyrinthsystem, Mittel zum Einpressen eines Inertgases unter Bildung eines Gasabschneiders und einen Kanal.
  2. Einrichtung nach Anspruch 1, dadurch gekennzeichnet, dass sie eine Ausgangsvorrichtung aufweist, die an das Gehäuse angrenzt und aus mindestens den drei folgenden Bauteilen besteht, mit denen das vorbeilaufende zu verarbeitende Produkt nacheinander zusammentrifft: einem Kanal ("Ausgangskanal"), Mitteln zum Einpressen eines Inertgases unter Bildung einem Gasabschneider und einem Mittel zum Erzeugen eines Druckverlusts, wie ein glattes Profil, und wobei die Distanz zwischen dem glatten Profil und der Fläche des Überzugs kleiner als die Höhe des Kanals ist.
  3. Einrichtung nach Anspruch 1, dadurch gekennzeichnet, dass sie eine Ausgangsvorrichtung aufweist, die an das Gehäuse angrenzt und aus mindestens den drei folgenden Bauteilen besteht, mit denen das vorbeilaufende zu verarbeitende Produkt nacheinander zusammentrifft: einem Kanal, Mitteln zum Einpressen eines Inertgases unter Bildung eines Gasabschneiders, und einem Labyrinthsystem.
  4. Einrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Eingangsvorrichtung mindestens die fünf folgenden Bauteile aufweist, mit denen das vorbeilaufende zu verarbeitende Produkt nacheinander zusammentrifft: einen Kanal, einen ersten Schlitz zum Einpressen von Gas, ein Labyrinth, einen zweiten Schlitz zum Einpressen von Gas, gefolgt von einem zweiten Kanal.
  5. Einrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass die Mittel zum Einpressen des Inertgases unter Bildung eines Gasabschneiders einen Schlitz zum Einpressen von Gas mit ebenen Wänden bilden, der in das Innere der jeweiligen Eingangs- oder Ausgangsvorrichtung einmündet.
  6. Einrichtung nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, dass das Verhältnis zwischen der Länge und der Höhe mindestens eines der Kanäle mindestens gleich 3, vorzugsweise mindestens gleich 6 ist.
EP05717683A 2004-01-28 2005-01-24 Ultraviolett-vernetzungseinrichtung unter kontrollierter atmosphäre Not-in-force EP1711279B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL05717683T PL1711279T3 (pl) 2004-01-28 2005-01-24 Urządzenie do sieciowania pod wpływem promieniowania ultrafioletowego w atmosferze kontrolowanej
SI200530295T SI1711279T1 (sl) 2004-01-28 2005-01-24 Naprava za ultravijolično zamreženje pod kontrolirano atmosfero

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0450155A FR2865418B1 (fr) 2004-01-28 2004-01-28 Equipement de reticulation ultraviolette sous atmosphere controlee
PCT/FR2005/050040 WO2005075111A1 (fr) 2004-01-28 2005-01-24 Equipement de reticulation ultraviolette sous atmosphere controlee

Publications (2)

Publication Number Publication Date
EP1711279A1 EP1711279A1 (de) 2006-10-18
EP1711279B1 true EP1711279B1 (de) 2008-04-16

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EP05717683A Not-in-force EP1711279B1 (de) 2004-01-28 2005-01-24 Ultraviolett-vernetzungseinrichtung unter kontrollierter atmosphäre

Country Status (15)

Country Link
US (1) US7806075B2 (de)
EP (1) EP1711279B1 (de)
JP (1) JP4763618B2 (de)
KR (1) KR101134861B1 (de)
CN (1) CN100591429C (de)
AT (1) ATE392270T1 (de)
CA (1) CA2552948C (de)
DE (1) DE602005006100T2 (de)
DK (1) DK1711279T3 (de)
ES (1) ES2306116T3 (de)
FR (1) FR2865418B1 (de)
PL (1) PL1711279T3 (de)
PT (1) PT1711279E (de)
SI (1) SI1711279T1 (de)
WO (1) WO2005075111A1 (de)

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DE102009048824A1 (de) 2009-10-09 2011-04-28 Linde Ag Vorrichtung zur Strahlungshärtung von Werkstücken

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DE102013005741B3 (de) 2013-04-05 2014-05-22 IOT - Innovative Oberflächentechnologien GmbH Vorrichtung zur Inertisierung bei UV-Bestrahlung in offenen Durchlaufanlagen
CN111299105A (zh) * 2020-02-19 2020-06-19 浙江晶通塑胶有限公司 一种超哑光地板的制备方法
JP2023025313A (ja) * 2021-08-10 2023-02-22 日本エア・リキード合同会社 紫外線硬化装置及び紫外線硬化方法
DE102022126294A1 (de) * 2022-10-11 2024-04-11 Maschinenfabrik Kaspar Walter Gmbh & Co Kg Vorrichtung und Verfahren zum Härten einer Polymerschicht auf einem zylindrischen Körper

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Also Published As

Publication number Publication date
PL1711279T3 (pl) 2008-09-30
KR20070008560A (ko) 2007-01-17
FR2865418A1 (fr) 2005-07-29
CA2552948A1 (fr) 2005-08-18
CA2552948C (fr) 2013-04-02
US7806075B2 (en) 2010-10-05
CN100591429C (zh) 2010-02-24
WO2005075111A1 (fr) 2005-08-18
JP4763618B2 (ja) 2011-08-31
DK1711279T3 (da) 2008-07-21
DE602005006100D1 (de) 2008-05-29
ES2306116T3 (es) 2008-11-01
PT1711279E (pt) 2008-07-04
FR2865418B1 (fr) 2006-03-03
ATE392270T1 (de) 2008-05-15
KR101134861B1 (ko) 2012-04-24
CN1913980A (zh) 2007-02-14
JP2007519519A (ja) 2007-07-19
SI1711279T1 (sl) 2008-08-31
EP1711279A1 (de) 2006-10-18
US20070109333A1 (en) 2007-05-17
DE602005006100T2 (de) 2009-05-07

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