EP1257368A2 - Verfahren zur herstellung farb- und/oder effektgebender mehrschichtlackierungen auf automobilkarosserien - Google Patents
Verfahren zur herstellung farb- und/oder effektgebender mehrschichtlackierungen auf automobilkarosserienInfo
- Publication number
- EP1257368A2 EP1257368A2 EP01905723A EP01905723A EP1257368A2 EP 1257368 A2 EP1257368 A2 EP 1257368A2 EP 01905723 A EP01905723 A EP 01905723A EP 01905723 A EP01905723 A EP 01905723A EP 1257368 A2 EP1257368 A2 EP 1257368A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrostatic
- filler
- application
- layer
- powder slurry
- 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
- 230000000694 effects Effects 0.000 title claims abstract description 13
- 239000003973 paint Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000002002 slurry Substances 0.000 claims abstract description 27
- 230000005855 radiation Effects 0.000 claims abstract description 24
- 238000005507 spraying Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims description 17
- 239000007921 spray Substances 0.000 claims description 17
- 238000010422 painting Methods 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 4
- 238000000889 atomisation Methods 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000002966 varnish Substances 0.000 claims 2
- 238000004040 coloring Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 25
- 238000001723 curing Methods 0.000 description 14
- 239000003595 mist Substances 0.000 description 10
- 239000004922 lacquer Substances 0.000 description 8
- 239000004924 water-based lacquer Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/534—Base coat plus clear coat type the first layer being let to dry at least partially before applying the second layer
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/53—Base coat plus clear coat type
- B05D7/536—Base coat plus clear coat type each layer being cured, at least partially, separately
-
- 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
- B05D3/0209—Multistage baking
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/574—Three layers or more the last layer being a clear coat at least some layers being let to dry at least partially before applying the next layer
-
- 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
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/57—Three layers or more the last layer being a clear coat
- B05D7/576—Three layers or more the last layer being a clear coat each layer being cured, at least partially, separately
Definitions
- the present invention relates to a new method for producing color and / or effect multi-layer coatings on automobile bodies, in which a powder slurry clearcoat is used.
- Powder clearcoat slurry only covered, but not resumed. After this
- Elevations or disturbances in the course of the course that are visible with a size of more than 0.5 ⁇ m. Since these elevations or course disorders are also present in particularly easily visible areas of the body, they are particularly eye-catching and give the impression of insufficient quality of the
- solventborne clearcoats because they have higher solids contents, so that the difference between the Solids content of the wet paint and the solids content of the spray mist is lower than in the case of powder slurry clearcoats.
- the solventborne clearcoats have a lower viscosity, which is why they spread better. This also makes the spray mist more flat.
- long solvents high-boiling organic solvents
- the object of the present invention is to develop a new process for the production of color and / or effect multi-layer coatings
- the new process has the effect that the wet powder slurry clearcoat layers located on the outer skin of the automobile body and applied by electrostatic painting can easily absorb the spray mist drops from the interior painting, thereby achieving a much better flow.
- the automobile bodies used in the method according to the invention usually have a cathodically deposited and thermally hardened electro-dip coating. However, they can also have a cathodically deposited electrodeposition coating which is not thermally hardened, but is merely dried or partially hardened.
- the electrodeposition coating or the electrodeposition coating layer can be covered with a filler which is cured either on its own or together with the electrodeposition coating layer (wet-on-wet method).
- the overlay with a filler takes place in particular in areas that are exposed to strong mechanical stress, such as stone chips.
- Patent Application Laid-Open JP 52-065534 A 2 Chemical Abstracts No. 87: 137427) or the patents US 4,375,498 A 1, US 4,537,926 A 1, US 4,761,212 A1, EP 0 529 335 A1, DE 41 25 459 A1, EP 0 595 186 A1, EP 0 074 634 A1, EP 0 505 445 A1, DE 42 35 778 A1, EP 0 646 420 A 1, EP 0 639 660 A 1, EP 0 817 648 A 1, DE 195 12 017 C l.
- EP 0 192 113 A 2 DE 41 26476 AI or WO 98/07794.
- suitable fillers in particular aqueous fillers, which are also referred to as stone chip protection primers or functional layers, for example from the patents US 4,537,926 A1, EP 0 529 335 A1, EP 0 595 186 A1, EP 0 639 660 A1, DE 44 38 504 A1, DE 43 37 961 A1, WO 89/10387, US 4,450,200 A1, US 4,614,683 A1 or WO 490/26827.
- fillers can, however, also be applied to the baked electro-dip coating and then pre-dried or partially thermally hardened. In this variant of the method according to the invention, they are then cured together with the water-based lacquer layers and powder slurry clear lacquer layers applied to the filler layers (extended wet-on-wet method).
- the paint finishes are coated with water-based paints.
- suitable waterborne basecoats in particular waterborne basecoats based on polyurethane, can be found in the patents EP 0 089 497 A1, EP 0 256 540 A1, EP 0 260 447 A1, EP 0 297 576 A1, WO 96/12747, EP 0 523 610 A 1, EP 0 228 003 A 1, EP 0 397 806 A 1, EP 0 574 417 A 1, EP 0 531 510 A 1, EP 0 581 211 A 1, EP 0 708 788 A 1, EP 0 593 454 A 1, DE-A-43 28 092 A1, EP 0 299 148 A1, EP 0 394737 A1, EP 0590484 A1, EP 0234362 A1, EP 0234361 A1, EP 0543817 A1, WO 95/14721, EP 0521928 A1, EP 0522420 A1, EP 05224
- the resulting water-based lacquer layers are usually not cured, but rather pre-dried or partially cured.
- aqueous powder slurry clearcoats are applied to the water-based lacquer layers, so that powder slurry clearcoat layers result.
- suitable powder slurry clearcoats are known from US Pat. No. 4,268,542 and patent applications DE 195 40 977 A1, DE 195 18 392 A1, DE 196 17 086 A1, DE-A-196 13 547, EP 0 652 264 A1, DE 196 18 657 A1, DE 196 52 813 A1, DE 196 17 086 A1 or DE-A-198 14 471 A1.
- the aqueous powder slurry clearcoats are applied by electrostatic painting of the exterior parts of the body, followed by pneumatic spraying (compressed air spraying) of the interior parts of the body.
- the electrostatic painting can be carried out by means of an electrostatic spray gap, an electrostatic spray bell or an electrostatic spray disk.
- electrostatic painting can be done by electrostatic assisted mechanical atomization. This is preferably carried out with the aid of electrostatic high-rotation disks or high-rotation bells.
- Pneumatic spraying or compressed air painting also has no special features in terms of method, but can be carried out by hand or with the aid of conventional and known painting machines or robots.
- Lacquer layers with the exception of the cathodically depositable electrodeposition lacquer layer, are used.
- the application is preferably carried out under illumination with visible light of a wavelength of more than 550 ⁇ m or with exclusion of light if the water-based lacquers and / or the powder slurry clearcoats are curable thermally and with actinic radiation. This avoids a material change or damage to the coating material to be used according to the invention and to the overspray.
- the coating materials to be used according to the invention are applied in a wet layer thickness such that, after they have hardened, coatings result in the layer thicknesses necessary and advantageous for their functions.
- a base coat they are 5 to 50, preferably 5 to 40, particularly preferably 5 to 30 and in particular 10 to 25 ⁇ m
- a clear coat they are 10 to 100, preferably 15 to 80, particularly preferably 20 to 75 and in particular 25 to 70 ⁇ m.
- the water-based lacquer coats are cured thermally or thermally and with actinic radiation together with the powder slurry clear lacquer coats and, if appropriate, the lacquer coats below or not fully cured.
- actinic radiation means electromagnetic radiation such as near infrared (NIR), visible light, UV light or X-rays, but especially UV light, or corpuscular radiation such as electron beams.
- NIR near infrared
- visible light visible light
- UV light UV light
- X-rays UV light
- corpuscular radiation such as electron beams.
- Curing can take place after a certain rest period or flash-off time. It can have a duration of 30 s to 2 h, preferably 1 min to 1 h and in particular 1 min to 45 min.
- the resting time is used, for example, for the course and degassing of the layers and for the evaporation of volatile constituents such as any solvent and / or water still present.
- a dose of 1,000 to 2,000, preferably 1,100 to 1,900, particularly preferably 1,200 to 1,800, very particularly preferably 1,300 to 1,700 and in particular 1,400 to 1,600 mJ / cm 2 is preferably used.
- this hardening can be supplemented with actinic radiation from other radiation sources.
- work is preferably carried out under an inert gas atmosphere. This can be ensured, for example, by supplying carbon dioxide and / or nitrogen directly to the surface of the clear lacquer layer.
- inert gas in order to avoid the formation of ozone.
- suitable radiation sources are flash lamps from VISIT, high or low mercury low-pressure vapor lamps, which may be doped with lead to open a radiation window up to 405 nm, or electron beam sources.
- Their arrangement is known in principle and can be adapted to the conditions of the workpiece and the process parameters.
- the areas (shadow areas) which are not directly accessible to radiation, such as cavities, folds and other undercuts due to construction can be combined with point, small area or all-round emitters, combined with an automatic movement device for irradiating cavities or Edges to be (partially) cured.
- the curing can take place in stages, i. H. by multiple exposure or exposure to actinic radiation. This can also take place alternately, i. that is, curing alternately with UV radiation and electron radiation.
- the thermal curing also has no special features in terms of method, but is carried out according to the customary and known methods such as heating in a forced air oven or irradiation with IR and / or oderIR lamps. As with curing with actinic radiation, thermal curing can also be carried out in stages. The thermal curing is advantageously carried out at temperatures from 90 ° C. to 180 ° C.
- thermal curing and curing with actinic radiation can be used simultaneously or in succession. Will the two If curing methods are used one after the other, thermal curing can be started, for example, and curing with actinic radiation can be ended. In other cases, it may prove advantageous to start with actinic radiation and end with it.
- the multi-layer color and / or effect coating resulting from the process according to the invention can also be coated with a layer of an organically modified ceramic material, as is commercially available, for example, under the Ormocer® brand.
- the color and / or effect multi-layer coatings produced in the process according to the invention have a particularly high gloss. Compared to the multi-layer paintwork produced in the usual and known manner, they have significantly less haze and little or no disruptive surface structures such as orange peel structures. They are therefore of particularly high optical quality. Since the other advantages of waterborne basecoats and powder slurry clearcoats are fully retained, they are of particularly high technical and economic value for users and their customers.
- Basecoat were coated and flashed off at room temperature for two minutes. Then the powder slurry clearcoat was in Wedge shape applied over the spray mist droplets and flashed off at room temperature for two minutes. Spray mist droplets and powder slurry clearcoat wedge were then predried at 40 ° C. for 10 minutes and then baked at 150 ° C. for 30 minutes.
- the ripple of the powder slurry clearcoats of the example and the comparative experiment was measured using the Wavescan method.
- a laser beam was directed onto the surface at an angle of 60 °, and the fluctuations of the reflected light in the so-called long wave range (0.6 to 10 mm; observation distance: 2.5 m) and in the so-called short wave range (0.1 to 0.6 mm; observation distance: 45 cm) with the help of a measuring device.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10008946A DE10008946C1 (de) | 2000-02-25 | 2000-02-25 | Verfahren zur Herstellung farb- und/oder effektgebender Mehrschichtlackierungen auf Automobilkarosserien |
| DE10008946 | 2000-02-25 | ||
| PCT/EP2001/001081 WO2001062401A2 (de) | 2000-02-25 | 2001-02-01 | Verfahren zur herstellung farb- und/oder effektgebender mehrschichtlackierungen auf automobilkarosserien |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1257368A2 true EP1257368A2 (de) | 2002-11-20 |
| EP1257368B1 EP1257368B1 (de) | 2007-10-31 |
Family
ID=7632431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP01905723A Expired - Lifetime EP1257368B1 (de) | 2000-02-25 | 2001-02-01 | Verfahren zur herstellung farb- und/oder effektgebender mehrschichtlackierungen auf automobilkarosserien |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US7504134B2 (de) |
| EP (1) | EP1257368B1 (de) |
| AT (1) | ATE376890T1 (de) |
| AU (1) | AU2001233731A1 (de) |
| BR (1) | BR0108686A (de) |
| CA (1) | CA2400621C (de) |
| DE (2) | DE10008946C1 (de) |
| MX (1) | MXPA02006950A (de) |
| WO (1) | WO2001062401A2 (de) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10220414B4 (de) * | 2002-05-08 | 2005-09-22 | Basf Coatings Ag | Verfahren zum Überlackieren farb- und/oder effektgebender Mehrschichtlackierungen |
| US20100183820A1 (en) * | 2009-01-16 | 2010-07-22 | Ford Global Technologies, Llc | Methods for curing uv-curable coatings |
| US9260117B2 (en) * | 2012-04-12 | 2016-02-16 | Trinity Industries, Inc. | Composite roof conversion |
Family Cites Families (65)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS534048A (en) | 1975-12-26 | 1978-01-14 | Dainippon Toryo Co Ltd | Method of forming multi-layer coating film |
| FR2489350A1 (fr) | 1980-09-02 | 1982-03-05 | Corona Peintures | Procede et composition pour le revetement multi-couches en mouille/mouille de surfaces electro-conductrices |
| US4419467A (en) | 1981-09-14 | 1983-12-06 | Ppg Industries, Inc. | Process for the preparation of cationic resins, aqueous, dispersions, thereof, and electrodeposition using the aqueous dispersions |
| FR2522284A1 (fr) * | 1982-02-26 | 1983-09-02 | Renault | Installation automatique pour peindre les interieurs de vehicules automobiles |
| DE3210051A1 (de) | 1982-03-19 | 1983-09-29 | Basf Farben + Fasern Ag, 2000 Hamburg | Wasserverduennbares ueberzugsmittel zur herstellung der basisschicht eines mehrschichtueberzuges |
| GB2125421B (en) * | 1982-08-17 | 1986-07-23 | Nippon Paint Co Ltd | Coating composition and coated article |
| US4537926A (en) | 1982-09-14 | 1985-08-27 | Grow Group, Inc. | Aqueous chip resistant coating composition |
| US4615779A (en) | 1985-02-07 | 1986-10-07 | Ppg Industries, Inc. | Cationic coating compositions for electrodeposition over rough steel |
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| DE3606512A1 (de) | 1986-02-28 | 1987-09-03 | Basf Lacke & Farben | Dispersionen von vernetzten polymermikroteilchen in waessrigen medien, verfahren zur herstellung dieser dispersionen und beschichtungszusammensetzungen, die diese dispersionen enthalten |
| DE3606513C2 (de) | 1986-02-28 | 1998-05-07 | Basf Coatings Ag | Dispersionen von vernetzten Polymermikroteilchen in wäßrigen Medien und Verfahren zur Herstellung dieser Dispersionen |
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| DE3813866A1 (de) | 1988-04-23 | 1989-11-02 | Basf Lacke & Farben | Wasserverduennbare einbrennlacke und ihre verwendung als fuellermaterial und steinschlagzwischengrund sowie verfahren zur lackierung von automobilkarosserien |
| DE3825278A1 (de) | 1988-07-26 | 1990-02-01 | Basf Lacke & Farben | Verfahren zur herstellung von mehrschichtigen, schuetzenden und/oder dekorativen ueberzuegen auf substratoberflaechen |
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| DE4224617A1 (de) | 1992-07-25 | 1994-01-27 | Herberts Gmbh | Wäßriges Überzugsmittel, Verfahren zu dessen Herstellung und dessen Verwendung bei Verfahren zur Mehrschichtlackierung |
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-
2000
- 2000-02-25 DE DE10008946A patent/DE10008946C1/de not_active Expired - Fee Related
-
2001
- 2001-02-01 AT AT01905723T patent/ATE376890T1/de not_active IP Right Cessation
- 2001-02-01 EP EP01905723A patent/EP1257368B1/de not_active Expired - Lifetime
- 2001-02-01 CA CA002400621A patent/CA2400621C/en not_active Expired - Fee Related
- 2001-02-01 MX MXPA02006950A patent/MXPA02006950A/es active IP Right Grant
- 2001-02-01 BR BR0108686-3A patent/BR0108686A/pt not_active Application Discontinuation
- 2001-02-01 DE DE50113194T patent/DE50113194D1/de not_active Expired - Lifetime
- 2001-02-01 AU AU2001233731A patent/AU2001233731A1/en not_active Abandoned
- 2001-02-01 US US10/181,793 patent/US7504134B2/en not_active Expired - Fee Related
- 2001-02-01 WO PCT/EP2001/001081 patent/WO2001062401A2/de not_active Ceased
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0162401A3 * |
Also Published As
| Publication number | Publication date |
|---|---|
| ATE376890T1 (de) | 2007-11-15 |
| WO2001062401A3 (de) | 2002-03-14 |
| CA2400621A1 (en) | 2001-08-30 |
| US20030108681A1 (en) | 2003-06-12 |
| DE10008946C1 (de) | 2001-10-18 |
| EP1257368B1 (de) | 2007-10-31 |
| US7504134B2 (en) | 2009-03-17 |
| AU2001233731A1 (en) | 2001-09-03 |
| WO2001062401A2 (de) | 2001-08-30 |
| DE50113194D1 (de) | 2007-12-13 |
| BR0108686A (pt) | 2002-11-12 |
| MXPA02006950A (es) | 2003-03-27 |
| CA2400621C (en) | 2008-01-15 |
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