EP1449186A2 - Laser-transfer film for permanently labeling components - Google Patents
Laser-transfer film for permanently labeling componentsInfo
- Publication number
- EP1449186A2 EP1449186A2 EP02781201A EP02781201A EP1449186A2 EP 1449186 A2 EP1449186 A2 EP 1449186A2 EP 02781201 A EP02781201 A EP 02781201A EP 02781201 A EP02781201 A EP 02781201A EP 1449186 A2 EP1449186 A2 EP 1449186A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- adhesive
- laser
- transfer film
- film according
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/007—Digital printing on surfaces other than ordinary paper on glass, ceramic, tiles, concrete, stones, etc.
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0041—Digital printing on surfaces other than ordinary paper
- B41M5/0052—Digital printing on surfaces other than ordinary paper by thermal printing
Definitions
- the invention relates to a laser transfer film for the permanent labeling of components from a carrier layer, an adhesive layer with a pigmented boundary layer being present on the lower side of the carrier layer.
- Technical labels are used to identify components on vehicles, machines, electrical and electronic devices, for example as type plates, as control labels for process sequences and as warranty and test labels.
- Labeling using laser labels and printed or lacquered metal signs is becoming increasingly important, especially in the automotive industry, especially for high-quality markings.
- information and notes such as tire pressure or type of fuel are placed on various components of the automobile for the later user.
- Important production data can also be transported via a laser label in the upstream production stages.
- the label can be labeled with a barcode.
- a suitable reading device enables an assembly team to read information about the model, color and special equipment directly on the production line using the barcode.
- Powerful controllable lasers for burning markings such as writing, coding and the like are common.
- the following requirements are placed on the material to be labeled or the material used for labeling:
- High temperature resistance should be given, for example up to over 200 ° C.
- labels When using flat, sharp blades, labels can be completely removed from the substrate.
- the bond between the adhesive and the substrate shows weaknesses, particularly on plastic substrates such as polyethylene or polypropylene.
- plastic substrates such as polyethylene or polypropylene.
- a special blade tool can be inserted under the label at a flat angle. Careful cutting movements make it possible to lift an edge, creating a so-called handle. In this way you create a point of attack that simplifies detachment.
- the object of the invention is to provide a laser transfer film which enables the rapid and precise labeling of any component, which meets the stated requirement of improved security against forgery, which cannot be removed without being destroyed even with the aid of a cutting tool, in particular high contrast, has high resolution, high temperature resistance and easy application.
- the invention relates to a laser transfer film for the permanent marking of components made from at least one carrier layer, an adhesive layer being at least partially present on the lower side of the carrier layer, a pigment layer which is at least partially applied to the carrier layer and / or adhesive layer contains laser-sensitive pigment.
- the basic structure of the layer containing the laser-sensitive pigments also consists of the adhesive of the adhesive layer, so that the first adhesive layer and the pigment layer form a single homogeneous layer. Only in the edge region of the homogeneous layer, specifically on the side facing away from the carrier layer, are the pigments distributed in a particularly narrow region of the homogeneous layer, accordingly forming a type of boundary layer.
- a second layer of adhesive is preferably applied to the pigment layer containing the laser-sensitive pigment.
- the second adhesive layer can be applied in the form of dots or by screen printing, optionally also as edge printing, so that the transfer film can be glued to the substrate in any manner.
- the thicknesses of the individual layers are preferably selected from the following areas:
- Backing layer (preferably PET) 12 ⁇ m to 240 ⁇ m, particularly 25 ⁇ m to 100 ⁇ m
- Adhesive (preferably acrylate) 5 ⁇ m to 45 ⁇ m, especially 10 ⁇ m to 25 ⁇ m
- the films which are to be used according to the invention must be transparent and / or translucent, at least they must be designed in such a way that absorption of the laser beam, which would lead to their destruction, is ruled out.
- the carrier material does not absorb light within the wavelength range from 530 to 1064 nm.
- films which are transparent in a further excellently designed variant of the invention, in particular monoaxially and biaxially stretched films based on polyolefins, then containing films based on stretched polyethylene or stretched copolymers Ethylene and / or polypropylene units, optionally also PVC films, films
- PET films in particular are ideally suited as carriers.
- Films based on stretched polyethylene or stretched copolymers containing ethylene and / or polypropylene units can also be used as carrier films according to the invention.
- Monoaxially stretched polypropylene is characterized by its very high tear strength and low elongation in the longitudinal direction.
- Monoaxially stretched films based on polypropylene are preferred for producing the labels according to the invention.
- Single-layer, biaxially or monoaxially stretched films and multilayer, biaxial or monoaxial films based on polypropylene, which have a sufficiently firm bond between the layers, are particularly preferred for the laser transfer films according to the invention, since delamination of the layers during use is disadvantageous.
- Films based on rigid PVC are used for the production of laser transfer films as well as films based on soft PVC.
- Foils based on rigid PVC are preferably used for the laser transfer foils according to the invention.
- Polyester-based films for example polyethylene terephthalate, are also known and can also be used to produce the transfer films according to the invention.
- Polyesters are polymers whose basic building blocks are held together by ester bonds (-CO-O-). According to their chemical structure, the so-called homopolyesters can be divided into two groups,
- the dihydroxy-dicarboxylic acid types (AA-BB polyester).
- the former are produced from only a single monomer, for example by polycondensation of an ⁇ -hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2, for example
- the latter is built up by polycondensation of two complementary monomers, for example a diol 3 and a dicarboxylic acid 4:
- Polyesters generally include polycarbonates (carbonic acid polyesters).
- PBT Polybutylene terephthalate
- PCDT poly (1,4-cyclohexanedimethylene terephthalate) e
- polyester can be more aromatic by using other aromatic ones
- Dicarboxylic acids for example isophthalic acid
- diol for example diol
- Mixtures in polycondensation vary widely in their properties and can be adapted to different areas of application.
- the laser transfer films according to the invention can contain a self-adhesive composition based on natural rubber, PUR, acrylates or styrene-isoprene-styrene block polymers.
- a commercially available pressure-sensitive adhesive based on PUR, acrylate or rubber is used as the self-adhesive.
- An acrylic hotmelt-based adhesive which has a K value of at least 20, in particular greater than 30, has been found to be particularly advantageous as an adhesive, and can be obtained by concentrating a solution of such a composition to form a system which can be processed as a hotmelt.
- the solution of the composition can contain 5 to 80% by weight, in particular 30 to 70% by weight, of solvent.
- solvents are preferably used, in particular low-boiling hydrocarbons, ketones, alcohols and / or esters.
- Benzoin derivatives for example benzoin acrylate or benzoin methacrylate, acrylic acid or methacrylic acid esters, can be polymerized into the adhesive composition based on hot-melt acrylate.
- benzoin derivatives are described in EP 0 578 151 A1.
- the acrylic hot melt adhesive can also be chemically cross-linked.
- copolymers of (meth) acrylic acid and its esters with 1 to 25 carbon atoms, maleic, fumaric and / or itaconic acid and / or their esters, substituted (meth) acrylamides, maleic anhydride and other vinyl compounds are used as self-adhesive compositions , such as vinyl esters, especially vinyl acetate, vinyl alcohols and / or vinyl ethers.
- the residual solvent content should be less than 1% by weight.
- An adhesive that is particularly suitable is a low molecular weight
- Acrylic hotmelt PSA such as those under the name acResin UV or Acronal
- an adhesive which consists of the group of natural rubbers or synthetic rubbers or of any blend of natural rubbers and / or synthetic rubbers, the natural rubber or natural rubbers basically having all available qualities such as crepe, RSS, ADS -, TSR or CV types, depending on the required level of purity and viscosity, and the synthetic rubber or synthetic rubbers from the group of randomly copolymerized styrene-butadiene rubbers (SBR), butadiene rubbers (BR), synthetic polyisoprene ( IR), the butyl rubbers (IIR), the halogenated butyl rubbers (XIIR), the acrylate rubbers (ACM), the ethylene-vinyl acetate copolymers (EVA) and the polyurethanes and / or their blends can be selected.
- SBR randomly copolymerized styrene-butadiene rubbers
- BR butadiene rubbers
- synthetic polyisoprene IR
- IIR butyl rubbers
- thermoplastic elastomers can preferably be added to the rubbers in a weight fraction of 10 to 50% by weight, based on the total elastomer fraction.
- SIS styrene-isoprene-styrene
- SBS styrene-butadiene-styrene
- coal tar resins are the coumarone indene resins.
- hydrocarbon resins are obtained by polymerizing the unsaturated compounds that can be isolated from the raw materials.
- hydrocarbon resins are also polymers with a correspondingly low molar mass which are accessible by polymerizing monomers such as styrene or by polycondensation (certain formaldehyde resins).
- Hydrocarbon resins are products with a softening range that varies within a wide range from ⁇ 0 ° C (liquid hydrocarbon resins at 20 ° C) to> 200 ° C and a density of approx. 0.9 to 1.2 g / cm 3 .
- Rosin is a natural resin that is obtained from the raw resin of conifers. There are three types of rosin: balsam resin as a distillation residue from turpentine oil, root resin as an extract from coniferous rhizomes and tall resin, the distillation residue from tall oil. Balsam resin is of greatest importance in terms of quantity.
- Rosin is a brittle, transparent product from red to brown in color. It is insoluble in water, but soluble in many organic solvents such as (chlorinated) aliphatic and aromatic hydrocarbons, esters, ethers and ketones as well as in vegetable and mineral oils.
- the softening point of rosin is in the range of approx. 70 to 80 ° C.
- Rosin is a mixture of approx. 90% resin acids and 10% neutral substances (fatty acid esters, terpene alcohols and hydrocarbons).
- the most important rosin resin acids are unsaturated carboxylic acids of the gross formula C20H30O2, abietic, neoabietic, levopimaric, pimaric, isopimaric and palustric acids, in addition to hydrogenated and dehydrated abietic acid. The proportions of these acids vary depending on the
- plasticizing substances can be used as plasticizers. These include paraffinic and naphthenic oils, (functionalized) oligomers such as oligobutadienes, isoprene, liquid nitrile rubbers, liquid terpene resins, vegetable and animal oils and fats, phthalates, functionalized acrylates.
- thermally induced chemical crosslinking all known thermally activable chemical crosslinkers are accelerated sulfur or
- Phenolic resin or diisocyanate crosslinking systems with the corresponding activators, epoxidized polyester and acrylate resins and their combinations can be used.
- the crosslinking agents are preferably activated at temperatures above 50 ° C., in particular at temperatures from 100 ° C. to 160 ° C., very particularly preferably at temperatures from 110 ° C. to 140 ° C.
- the crosslinkers can also be thermally excited by IR rays or high-energy alternating fields.
- the adhesives that are to be used according to the invention should be transparent and / or translucent, at least they must be designed in such a way that absorption of the laser beam, which would lead to their destruction, is excluded.
- the adhesive does not absorb any light within the wavelength range from 530 to 1064 nm.
- the laser-sensitive pigment is preferably applied to the first adhesive layer in the form of a solvent suspension, for example an isopropanol suspension.
- the first layer of adhesive is particularly dissolved on the surface, so that the pigment can become embedded in the edge region of the adhesive layer, namely the boundary layer, by swelling of the adhesive polymer matrix, while the Solvent evaporates.
- the boundary layer forms the pigment layer containing the laser-sensitive pigment.
- the boundary layer has in particular a thickness of 2 ⁇ m to 5 ⁇ m.
- Suitable additives are, in particular, color pigments and metal salts.
- pigments from Firm TherMark are used, for example TherMark 120-30F, which are metal oxides, for example molybdenum trioxide.
- TherMark 120-30F which are metal oxides, for example molybdenum trioxide.
- Mixtures of several pigments or mixtures of pigments and glass particles, as are available from Merck, can also be used, which can lead to a sintering process.
- the additive can be used in addition to the additive titanium dioxide.
- additives are the suspension for forming the layer (as described for example in DE G 81 30 861) in particular in the order of a few parts per thousand to a maximum of 10 percent, preferably in amounts of 0.1 to 10 wt .-%, in particular 0 , 5 to 6 wt .-% based on the total weight of the layer, admixed, and very particularly advantageously in concentrations of 0.5 wt .-%, 1 wt .-%, and 2.5 wt .-% and 4 wt .-%.
- various pigments from Merck for example the pearl luster pigments EM 143220 and BR 3-01 are excellently suitable and the TherMark pigments ® 120-30 F (black).
- the laser beam penetrates through the carrier layer and the adhesive layer and strikes the pigment.
- the energy is absorbed and a sublimation process occurs in which the pigment is transferred to the substrate and forms a permanent and permanent bond with the substrate. Sharp, high-contrast labels and markings are obtained.
- the known direct and indirect application methods are suitable for applying the adhesive to the carrier material and for applying the layer containing the laser-sensitive pigment.
- the Accugravur, the doctor blade, the roller doctor blade, the RCC, the Super are mentioned
- Acrylic hot melts can be applied to the carriers mentioned in addition to the standard application methods such as direct coating from nozzles, over rollers, etc. also apply in the transfer process as disclosed in DE 43 24 748 C2.
- the adhesive is first applied to an endless, anti-adhesive webbing and then transferred to the backing in a laminating station - if necessary using pressure and temperature to improve the mass anchoring.
- the adhesive and the layer containing the laser-sensitive pigment can be screen-dotted by means of screen printing (DE 42 37 252 C2), whereby the dots of adhesive can also have different sizes and / or different distributions (EP 0 353 972 B1), by gravure printing (DE 43 08 649 C2) webs connected in the longitudinal and transverse directions, by raster printing or by flexographic printing.
- Both layers can preferably be in the form of a spherical cap by screen printing or else be applied in another pattern such as grids, strips, zigzag lines and, for example, also by gravure printing. It can also be sprayed on, for example, which results in a more or less irregular order image.
- these are applied in the form of polygeometric domes.
- the domes can have different shapes. Flattened hemispheres are preferred. Furthermore, it is also possible to print other shapes and patterns on the carrier material, for example a printed image in the form of alphanumeric character combinations or patterns such as grids, stripes, further cumulative calottes and zigzag lines.
- a possible indirect method for producing a carrier coated with an adhesive layer is disclosed in DE 40 32776 A1.
- a flowable adhesive composition is applied to an intermediate carrier, which has the following properties: it has a corrugated, pleated, fissured or furrowed surface that can be seen under the light or electron microscope, the adhesive composition is easily removable from its surface, it is essentially impermeable to air, b ) the microscopic air or solvent inclusions that arise after the coating of the intermediate carrier between the adhesive mass and the intermediate carrier are expanded by increasing the temperature until the surface of the adhesive mass bursts, and c) the adhesive mass is then transferred from the intermediate carrier to the final carrier.
- the base body for the intermediate carrier can be selected from all common materials for such purposes. Woven webbing made of glass fiber, polyester, polyamide or Nomex®, a fiber material from DuPont, is particularly advantageous. But also rubber blankets, plastic straps and the like have proven to be cheap. If fabric tapes are selected, it is favorable to use tapes which are already provided with an essentially unstructured plastic surface coating. This latter coating promotes the adhesion and uniformity of the actual surface coating on the base body.
- This surface of the intermediate carrier is advantageously coated with an anti-adhesive layer, for example made of cross-linked silicone rubber or fluoropolymers such as Teflon®.
- the laser transfer film according to the invention shows excellent properties, in particular much better than the transfer films which have laser sensitivity
- Adhesive property winding around adhesive
- in the transfer of the pigments into or onto the component is strongly influenced.
- the film according to the invention does not show the negative effects on paints and plastic plates (PP) due to the pigmented boundary layer with the bonding component, but does show permanent marking on the component.
- the film according to the invention can also be used excellently on rough surfaces, for example on ceramic bases from Osram fuses or generally on glass.
- the label can be applied to the component and lasered. After labeling, it is pulled off. The process is finished.
- the laser transfer film according to the invention can be used as an endless roll, in the form of an Archimedean spiral, which is usually wound around a cardboard tube, and as a die-cut Label are presented.
- the latter can have any shape, perfectly adapted to the particular application.
- Figure 1 shows the structure of a film according to the invention in the form of a
- Figure 2 shows the structure of a film according to the invention in the form of a
- Figure 3 shows the process of labeling a component
- FIG. 1 the structure of a film according to the invention is shown in the form of a label.
- the film is composed of the carrier layer 1, the first adhesive layer 2, which is applied to the entire surface of the carrier material 1, and the layer 3 containing the laser-sensitive pigment. Layer 3 is also applied over the entire surface.
- FIG. 2 shows the structure of a film according to the invention in the form of a label, a second adhesive layer 4 being additionally applied. This adhesive layer has only been partially applied in the form of individual domes.
- FIG. 3 discloses the process of labeling a component 5 using the film according to the invention.
- the laser transfer film preferably in the form of a label
- Adhesion and fixation of the label is achieved.
- the inscription is then carried out using a laser, which is indicated by the red cylinder.
Landscapes
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Decoration By Transfer Pictures (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10152073A DE10152073A1 (en) | 2001-10-25 | 2001-10-25 | Laser transfer film for permanent marking of components |
DE10152073 | 2001-10-25 | ||
PCT/EP2002/011023 WO2003035411A2 (en) | 2001-10-25 | 2002-10-02 | Laser-transfer film for permanently labeling components |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1449186A2 true EP1449186A2 (en) | 2004-08-25 |
EP1449186B1 EP1449186B1 (en) | 2011-08-31 |
Family
ID=7703301
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP02781201A Expired - Lifetime EP1449186B1 (en) | 2001-10-25 | 2002-10-02 | Laser-transfer film for permanently labeling components |
Country Status (7)
Country | Link |
---|---|
US (1) | US6764803B2 (en) |
EP (1) | EP1449186B1 (en) |
AT (1) | ATE522898T1 (en) |
AU (1) | AU2002349320A1 (en) |
DE (1) | DE10152073A1 (en) |
ES (1) | ES2370814T3 (en) |
WO (1) | WO2003035411A2 (en) |
Families Citing this family (24)
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DE19909723C5 (en) * | 1999-03-05 | 2004-04-15 | Daimlerchrysler Ag | Security adhesive foil as identification carrier |
DE10156852A1 (en) * | 2001-11-20 | 2003-05-28 | Giesecke & Devrient Gmbh | Object, especially valuable and security document has security marker with emitter layer for stimulated optical emission and periodic modulation, especially height modulation |
DE10213111A1 (en) * | 2002-03-23 | 2003-10-02 | Tesa Ag | Multi-layer laser transfer film for permanent marking of components |
DE10351951A1 (en) * | 2003-11-07 | 2005-06-09 | Continental Aktiengesellschaft | Tire and method for marking a tire |
US6855474B1 (en) * | 2004-05-03 | 2005-02-15 | Kodak Polychrome Graphics Llc | Laser thermal color donors with improved aging characteristics |
US20080317979A1 (en) * | 2004-07-22 | 2008-12-25 | Masahiko Itakura | Laser Weldable Label and Shaped Composite Article Therewith |
DE102004038774A1 (en) * | 2004-08-09 | 2006-02-23 | Tesa Ag | Laser film of an at least single-layer carrier layer of a transparent film, which is coated on one side with a self-adhesive |
US20070054130A1 (en) * | 2005-08-31 | 2007-03-08 | Illinois Tool Works, Inc. | Security laser printing film |
KR20080073750A (en) * | 2005-11-22 | 2008-08-11 | 메르크 파텐트 게엠베하 | Process for a thermal transfer of a liquid crystal film using a transfer element |
DE202006013892U1 (en) * | 2006-09-05 | 2008-01-10 | Herma Gmbh | bonding |
DE102007048193A1 (en) * | 2007-10-08 | 2009-04-09 | Tesa Scribos Gmbh | Sticker for sticking on an object |
DE102008025583A1 (en) | 2008-01-11 | 2009-07-16 | Tesa Ag | Pigment layer and method for permanent labeling of a substrate by means of high-energy radiation |
US20090181313A1 (en) * | 2008-01-14 | 2009-07-16 | Tesa Ag | Pigment layer and method especially for a durable inscription of glass using a high energy radiation |
DE102008025582A1 (en) | 2008-01-11 | 2009-07-16 | Tesa Ag | Process for the production of titanium carbide |
US8182633B2 (en) * | 2008-04-29 | 2012-05-22 | Samsung Electronics Co., Ltd. | Method of fabricating a flexible display device |
DE102009029903A1 (en) | 2009-06-19 | 2010-12-23 | Tesa Se | Method for applying permanently processed label on e.g. plate, involves loading laser transferring film with partially provided pigment layer and supporting layer by using laser, where pigment layer includes laser-sensitive pigment |
DE102014015119B4 (en) | 2014-10-10 | 2024-07-25 | Ralph Domnick | Coating film, layer structure, and method for coating a substrate |
CN106297544A (en) * | 2015-05-21 | 2017-01-04 | 联想(北京)有限公司 | Electronic product and the method forming mark on electronic product |
DE102015013927A1 (en) | 2015-10-28 | 2017-05-04 | Murrplastik Systemtechnik Gmbh | labeling unit |
DE102018120815A1 (en) * | 2018-04-23 | 2019-10-24 | bentlage - proprint GmbH | Method for producing a laser-modified decal or heat transfer |
IT201800006206A1 (en) * | 2018-06-11 | 2019-12-11 | TIRE FOR VEHICLE WHEELS | |
JP6454048B1 (en) * | 2018-07-26 | 2019-01-16 | 株式会社アイエヌジー | Image transfer sheet, image transfer sheet manufacturing method, and image transfer method |
EP3759746B1 (en) * | 2019-01-28 | 2021-09-08 | Wacker Chemie AG | Method for applying at least one silicone layer by laser transfer printing |
EP3924191A1 (en) | 2019-02-15 | 2021-12-22 | Lacotra GmbH | Method for transferring colored markings onto plastic surfaces |
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-
2001
- 2001-10-25 DE DE10152073A patent/DE10152073A1/en not_active Withdrawn
- 2001-11-20 US US09/988,510 patent/US6764803B2/en not_active Expired - Lifetime
-
2002
- 2002-10-02 ES ES02781201T patent/ES2370814T3/en not_active Expired - Lifetime
- 2002-10-02 EP EP02781201A patent/EP1449186B1/en not_active Expired - Lifetime
- 2002-10-02 WO PCT/EP2002/011023 patent/WO2003035411A2/en not_active Application Discontinuation
- 2002-10-02 AU AU2002349320A patent/AU2002349320A1/en not_active Abandoned
- 2002-10-02 AT AT02781201T patent/ATE522898T1/en active
Non-Patent Citations (1)
Title |
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See references of WO03035411A2 * |
Also Published As
Publication number | Publication date |
---|---|
ATE522898T1 (en) | 2011-09-15 |
US6764803B2 (en) | 2004-07-20 |
AU2002349320A1 (en) | 2003-05-06 |
WO2003035411A3 (en) | 2003-10-23 |
US20030104309A1 (en) | 2003-06-05 |
WO2003035411A2 (en) | 2003-05-01 |
DE10152073A1 (en) | 2003-05-08 |
ES2370814T3 (en) | 2011-12-23 |
EP1449186B1 (en) | 2011-08-31 |
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