WO2004087423A2 - Inkjet printhead having bubble chamber and heater offset from nozzle - Google Patents
Inkjet printhead having bubble chamber and heater offset from nozzle Download PDFInfo
- Publication number
- WO2004087423A2 WO2004087423A2 PCT/US2004/008852 US2004008852W WO2004087423A2 WO 2004087423 A2 WO2004087423 A2 WO 2004087423A2 US 2004008852 W US2004008852 W US 2004008852W WO 2004087423 A2 WO2004087423 A2 WO 2004087423A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- heater
- inkjet printhead
- bubble chamber
- orifice
- heater element
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14016—Structure of bubble jet print heads
- B41J2/14032—Structure of the pressure chamber
- B41J2/1404—Geometrical characteristics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14016—Structure of bubble jet print heads
- B41J2/14088—Structure of heating means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2/14016—Structure of bubble jet print heads
- B41J2002/14185—Structure of bubble jet print heads characterised by the position of the heater and the nozzle
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/14—Structure thereof only for on-demand ink jet heads
- B41J2002/14387—Front shooter
Definitions
- the present invention relates to inkjet printheads.
- it relates to an arrangement of a bubble chamber and heater element in a printhead having a substantial offset from an orifice or nozzle of a nozzle plate.
- inkjet printing is relatively well known.
- an image is produced by emitting ink drops from a printhead at precise moments such that they impact a print medium at a desired location.
- the printhead is supported by a movable print carriage within a device, such as an inkjet printer, and is caused to reciprocate relative to an advancing print medium and to emit ink drops at times pursuant to commands of a microprocessor or other controller.
- the timing of the ink drop emissions corresponds to a pattern of pixels of the image being printed.
- familiar devices incorporating inkjet technology include fax machines, all-in-ones, photo printers, and graphics plotters, to name a few.
- a conventional thermal inkjet printhead includes access to a local or remote supply of color or mono ink, a heater chip, a barrier layer, a nozzle or orifice plate attached or formed with the heater chip, and an input/output connector, such as a tape automated bond (TAB) circuit, for electrically connecting the heater chip to the printer during use.
- the heater chip typically includes a plurality of thin film resistors or heater elements fabricated by deposition, masking and etching techniques on a substrate such as silicon.
- a typical geometry of a heater element 10 and a bubble chamber 12 relative to an orifice 14 in a nozzle plate 15 includes a substantially centered and symmetrical relationship.
- a plumb line 28 originating from an orifice center 30 has no lateral offset from a heater center 32.
- the orifice center exists substantially equidistant from each corner of the bubble chamber.
- stagnant regions 22 of the bubble chamber 12 serve to trap air bubbles in ink 16 that flows into the bubble chamber (through ink channel 20 and ink via 18) during use. Over time, trapped bubbles accumulate and grow large enough to prevent heat transfer from the heater element to the ink which eventually stops operation. Accordingly, a need exists to prevent air bubble formation and accumulation in inkjet printheads.
- the invention teaches an inkjet printhead with a substantially rectangular heater element.
- the heater element has an aspect ratio of more than about 2.0. More preferably, it has an aspect ratio of more than about 2.5, 4.0 or 5.0 or greater.
- a bubble chamber substantially surrounds the heater element with a plurality of walls that reside substantially equidistant from a periphery of the heater element.
- a nozzle plate covers the bubble chamber and has an orifice axially extending through a thickness thereof. A center of the orifice originates a plumb line such that an offset distance exists from a center of the heater element in a range from about 6 to about 10 microns, for example.
- An ink flow channel through one of the bubble chamber walls has a primary direction of ink flow substantially paralleling a length dimension of the heater element.
- the bubble chamber and ink flow channel may exist in the nozzle plate, in a barrier layer or in a plurality of film layers that define a heater chip.
- Inkjet printheads and inkjet printers for housing the printheads are also disclosed.
- Figure la is a diagrammatic top view in accordance with the teachings of the prior art of an inkjet printhead bubble chamber and heater symmetrically centered relative to a nozzle;
- Figure lb is a partial side view of the inkjet printhead bubble chamber and heater of Figure la taken along line lb-lb;
- Figure 2a is a diagrammatic top view in accordance with the teachings of the present invention of an inkjet printhead bubble chamber and heater element offset relative to a nozzle;
- Figure 2b is a partial side view of the inkjet printhead bubble chamber and heater element of Figure 2a taken along line 2b-2b;
- Figure 3 is a perspective view in accordance with an alternative embodiment of the present invention of an inkjet printhead bubble chamber and heater element offset relative to a nozzle;
- Figure 4 is a perspective view in accordance with the teachings of the present invention of an inkjet printhead with a heater chip having a bubble chamber and heater element offset relative to a nozzle;
- Figure 5 is a perspective view in accordance with the teachings of the present invention of an inkjet printer for housing an inkjet printhead with a bubble chamber and heater element offset relative to a nozzle.
- an inkjet printhead bubble chamber and heater element having an offset from a nozzle or orifice of a nozzle plate is hereinafter described.
- a heater element 210 for heating ink in an inkjet printhead has a substantially rectangular shape defined by a length 1 and width w dimension.
- an aspect ratio of the length dimension to the width dimension is greater than about 2.0.
- the aspect ratio is greater than about 2.5.
- the length dimension is about 35.6 microns while the width dimension is about 13.2 microns.
- the aspect ratio is about 4.0.
- the length dimension is about 40 microns while the width dimension is about 10 microns.
- the aspect ratio is about 5.0 or greater.
- a bubble chamber 212 having a plurality of walls 214.
- the walls 214 rise above the heater element 210 to provide a chamber in which ink can become heated to form a bubble as is well know in the art.
- Each of the walls resides substantially equidistant from a periphery 216 of the heater element such that the heater element is substantially centered within the bubble chamber.
- the walls 214 of the bubble chamber are substantially perpendicular to one another and define length L and width W distances substantially paralleling the length and width dimensions of the heater element. In one embodiment, the length distance is about 42 microns while the width distance is about 31 microns.
- any, some or all of the comer regions 215 (two of the four labeled) of the bubble chamber have a chamfer cut 217. They may additionally include fillets or other.
- a nozzle plate 218 that attaches by epoxy or the like or is formed as one or more of a series of polymer layers or thin-film layers of a heater chip.
- the nozzle plate has a first surface 220 and a second surface 222 that define a thickness thereof. Axially extending through the nozzle plate from the second to the first surface is an orifice 224 for ejecting and projecting ink there through during use.
- the shape of the orifice comprises a frustum conical shape defined by sloping walls 226 having a large diameter opening 228 at one end thereof and a small diameter opening 230 at the other end thereof.
- openings 228 and 230 are shown superimposed in phantom.
- present day printheads have small diameter openings on the order of about 11 or 14 microns. In the future, it is expected that this dimension will gradually shrink as printing resolutions increase from 600 DPI (dots-per-inch) to 900 or 1200 DPI or more.
- the orifice 224 has an orifice center 232.
- a plumb line 234 originating from the orifice center has an offset distance O from a center 236 formed on a surface 238 of the heater element 210.
- the offset distance O is about 6 to about 10 micrometers in a straight line distance on the surface 238 of the heater and all within the periphery 216. In another embodiment, it is about 8.0 or 8.5 microns. In still another embodiment, it ranges from about 6 to about 18 microns.
- the maximum offset is calculated according to the formula Vi (f- (d + 2t)).
- this offset essentially translates prior art orifices from a central position above the heater element to a backside of the bubble chamber in a direction away from the ink via 240.
- stagnant regions (element 22, Figures la, lb) of the prior art become effectively eliminated.
- the formation and accumulation of air bubbles in a single bubble chamber over time becomes lessened or eliminated.
- first pass print tests of an inkjet printhead having these offsets revealed an increase of about 10 to 20% in population- wide functional test yields.
- an ink flow channel 250 having a long and short dimension of about 22 microns and 18 microns, respectively.
- Two substantially parallel walls 257, 259 define the ink flow channel and a primary direction of ink flow therein.
- the walls exist substantially perpendicular to a longitudinal extent of the ink via 240 and substantially parallel to the length dimension of the heater element.
- ink 258 flows through the ink channel in a primary direction substantially paralleling the length dimension 1 of the heater element on the surface 238 thereof.
- Ink is ejected through the orifice 224 in a direction substantially transverse to the primary direction. Further operation of the printhead will be described below.
- an individual heater element is one of many heater elements on a heater chip
- skilled artisans know the economy of scale achieved by fabricating the heater elements as thin film layers on a substrate through a series of growth layers, deposition layers, masking, patterning, photolithography, and or etching or other processing steps.
- the thin film layers include, but are not limited to: a base substrate (including any base semiconductor structure such as silicon- on-sapphire (SOS) technology, silicon-on-insulator (SOI) technology, thin film transistor (TFT) technology, doped and undoped semiconductors, epitaxial layers of silicon supported by a base semiconductor stracture, as well as other semiconductor structures known or hereinafter developed); a thermal barrier layer on the substrate; a heater or resistor layer on the thermal barrier layer; a conductor layer (bifurcated into positive and negative electrode sections, i.e., anodes and cathodes) on the resistor layer to heat the resistor layer through thermal conductivity during use; passivation layers, such as SiC and/or SiN; and a cavitation layer on the passivation layer(s).
- a base substrate including any base semiconductor structure such as silicon- on-sapphire (SOS) technology, silicon-on-insulator (SOI) technology, thin film transistor (TFT) technology, doped and und
- the heater element 310 is formed on a substrate 360 in the manner described.
- the bubble chamber 312 surrounds the heater element with a plurality of walls 314.
- a nozzle plate 318 has an orifice 334 cut therein and overlies the bubble chamber.
- a plumb line originating from a center of the orifice intersects a surface of the heater element at a position 334.
- a center 336 of the heater element is offset from position 334 in a straight line distance of about 6 to about 10 micrometers.
- Ink 358 flows into the bubble chamber during use through an ink channel 350 cut through one of the walls 314.
- either one or both of the bubble chamber and ink flow channel can be formed as a series of thin film or polymer layers or as part of a nozzle plate. They should also appreciate that the nozzle plate itself can be formed as a series of thin film or polymer layers or as a separate structure later aligned and fastened over the bubble chamber. All embodiments and variations are embraced herein.
- the layers become deposited by any variety of chemical vapor depositions (CVD), physical vapor depositions (PVD), epitaxy, ion beam deposition, evaporation, sputtering or other similarly known techniques.
- CVD techniques include low pressure (LP), atmospheric pressure (AP), plasma enhanced (PE), high density plasma (HDP) or other.
- Preferred etching techniques include, but are not limited to, any variety of wet or dry etches, reactive ion etches, deep reactive ion etches, etc.
- Preferred barrier layer or ink flow channel feature formation techniques include polymer layer deposition, followed by photolithographic and image development techniques; or laser ablation techniques applied to a polymer film.
- Preferred photolithography steps include, but are not limited to, exposure to ultraviolet or x-ray light sources, or other and photomasking includes clear-field or dark- field masks as those terms are well understood in the art.
- the substrate comprises a silicon wafer of p-type, 100 orientation, having a resistivity of 5-20 ohm/cm. Its beginning thickness is preferably, but not necessarily required, any one of 525 +/- 20 microns, 625 +/- 20 microns, or 625 +/- 15 microns with respective wafer diameters of 100 +/- 0.50 mm, 125 +/- 0.50 mm, and 150 +/- 0.50 mm.
- the thermal barrier layer overlying the substrate includes a silicon oxide layer mixed with a glass such as BPSG, PSG or PSOG with an exemplary thickness of about 0.5 to about 3 microns, especially 1.82 +/- 0.15 microns. This layer can be deposited or grown according to manufacturing preference.
- the heater element layer on the thermal barrier layer is about a 50-50% tantalum- aluminum composition layer of about 900 or 1000 angstroms thick.
- the resistor layer includes essentially pure or composition layers of any of the following: hafnium, Hf, tantalum, Ta, titanium, Ti, tungsten, W, hafnium-diboride, HfB 2 , Tantalum-nitride, Ta 2 N, TaAl(N,0), TaAISi, TaSiC, Ta/TaAl layered resistor, Ti(N,0), WSi(O) and the like.
- a conductor layer overlying portions of the heater layer includes an anode and a cathode.
- the conductor layer is about a 99.5 - 0.5% aluminum- copper composition of about 5000 +/- 10% angstroms thick.
- the conductor layer includes pure or compositions of aluminum with 2% copper and aluminum with 4% copper.
- a printhead of the present invention is shown generally as 101.
- the printhead 101 has a housing 121 formed of a body 161 and a lid 160. Although shown generally as a rectangular solid, the housing shape varies and depends upon the external device that carries or contains the printhead.
- the housing has at least one compartment, internal thereto, for holding an initial or refillable supply of ink and a structure, such as a foam insert, lung or other, maintains an appropriate backpressure therein during use.
- the internal compartment includes three chambers for containing three supplies of ink, especially cyan, magenta and yellow ink.
- the compartment may contain black ink, photo- ink and/or plurals of cyan, magenta or yellow ink. It will be appreciated that fluid connections (not shown) may exist to connect the compartment(s) to a remote source of ink.
- a portion 191 of a tape automated bond (TAB) circuit 201 adheres to one surface
- the two surfaces 181, 221 exist substantially perpendicularly to one another about an edge 231.
- the TAB circuit 201 has a plurality of input/output (I/O) connectors 241 fabricated thereon for electrically connecting a heater chip 251 to an external device, such as a printer, fax machine, copier, photo-printer, plotter, all-in-one, etc., during use.
- I/O input/output
- Pluralities of electrical conductors 261 exist on the TAB circuit 201 to electrically connect and short the I/O connectors 241 to the bond pads 281 of the heater chip 251 and various manufacturing techniques are known for facilitating such connections.
- Skilled artisans should appreciate that while eight I/O connectors 241, eight electrical conductors 261 and eight bond pads 281 are shown, any number are possible and the invention embraces all variations. The invention also embraces embodiments where the number of connectors, conductors and bond pads do not equal one another.
- the heater chip 251 contains at least one ink via 321 with a longitudinal extent (alternatively: ink via 240 with a longitudinal extent in Figures 2a, 2b) that fluidly connects the heater chip to a supply of ink internal to the housing.
- the heater chip 251 preferably attaches to the housing with any of a vaiiety of adhesives, epoxies, etc. well known in the art.
- the heater chip contains two columns of heater elements on either side of via 321. For simplicity in this crowded figure, dots or small circles depict the heater elements in the columns.
- a nozzle plate (218 or 318 Figures 2a, 2b or 3) with pluralities of orifices adheres over the heater chip such that the nozzle holes align with the heaters.
- the nozzle plate adheres to a (polymer) barrier layer which then adheres to the heater chip.
- an external device in the form of an inkjet printer contains the printhead 101 and is shown generally as 401.
- the printer 401 includes a carriage 421 having a plurality of slots 441 for containing one or more printheads.
- the carriage 421 is caused to reciprocate (via an output 591 of a controller 571) along a shaft 481 above a print zone 461 by a motive force supplied to a drive belt 501 as is well known in the art.
- the reciprocation of the carriage 421 is performed relative to a print medium, such as a sheet of paper 521, that is advanced in the printer 401 along a paper path from an input tray 541, through the print zone 461, to an output tray 561.
- the carriage 421 reciprocates in the Reciprocating Direction generally perpendicularly to the paper Advance Direction as shown by the arrows.
- Ink drops from the printheads ( Figure 4) are caused to be ejected from the heater chip at such times pursuant to commands of a printer microprocessor or other controller 571.
- the timing of the ink drop emissions corresponds to a pattern of pixels of the image being printed. Often times, such patterns are generated in devices electrically connected to the controller (via Ext. input) that are external to the printer such as a computer, a scanner, a camera, a visual display unit, a personal data assistant, or other.
- the heater element is uniquely addressed with a short pulse of current to rapidly heat a small volume of ink. This causes the ink to vaporize in the bubble chamber and to be ejected through an orifice of the nozzle plate towards the print medium.
- a control panel 581 having user selection interface 601 may also provide input 621 to the controller 571 to enable additional printer capabilities.
- the term inkjet printhead may in addition to thermal technology include piezoelectric technology, or other.
Landscapes
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Particle Formation And Scattering Control In Inkjet Printers (AREA)
- Ink Jet (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2004225950A AU2004225950B2 (en) | 2003-03-25 | 2004-03-23 | Inkjet printhead having bubble chamber and heater offset from nozzle |
EP04758222A EP1613474B1 (en) | 2003-03-25 | 2004-03-23 | Inkjet printhead having bubble chamber and heater offset from nozzle |
CA2520187A CA2520187C (en) | 2003-03-25 | 2004-03-23 | Inkjet printhead having bubble chamber and heater offset from nozzle |
BRPI0408772-0A BRPI0408772A (en) | 2003-03-25 | 2004-03-23 | inkjet printhead that has displaced bubble chamber and nozzle heater |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/396,657 US6761435B1 (en) | 2003-03-25 | 2003-03-25 | Inkjet printhead having bubble chamber and heater offset from nozzle |
US10/396,657 | 2003-03-25 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2004087423A2 true WO2004087423A2 (en) | 2004-10-14 |
WO2004087423A3 WO2004087423A3 (en) | 2006-06-01 |
Family
ID=32681832
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2004/008852 WO2004087423A2 (en) | 2003-03-25 | 2004-03-23 | Inkjet printhead having bubble chamber and heater offset from nozzle |
Country Status (8)
Country | Link |
---|---|
US (1) | US6761435B1 (en) |
EP (1) | EP1613474B1 (en) |
CN (1) | CN100421946C (en) |
AU (1) | AU2004225950B2 (en) |
BR (1) | BRPI0408772A (en) |
CA (1) | CA2520187C (en) |
TW (1) | TWI324964B (en) |
WO (1) | WO2004087423A2 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2160295A4 (en) * | 2007-06-19 | 2012-10-10 | Silverbrook Res Pty Ltd | Printhead with heaters offset from nozzles |
US20090027457A1 (en) * | 2007-07-25 | 2009-01-29 | Clark Garrett E | Fluid ejection device |
US7780271B2 (en) * | 2007-08-12 | 2010-08-24 | Silverbrook Research Pty Ltd | Printhead with heaters offset from nozzles |
JP5058719B2 (en) * | 2007-08-30 | 2012-10-24 | キヤノン株式会社 | Liquid discharge head and ink jet recording apparatus |
WO2009082391A1 (en) * | 2007-12-20 | 2009-07-02 | Hewlett-Packard Development Company, L.P. | Droplet generator |
US8328330B2 (en) * | 2008-06-03 | 2012-12-11 | Lexmark International, Inc. | Nozzle plate for improved post-bonding symmetry |
US8794745B2 (en) * | 2011-02-09 | 2014-08-05 | Canon Kabushiki Kaisha | Liquid ejection head and liquid ejection method |
JP5863336B2 (en) * | 2011-08-25 | 2016-02-16 | キヤノン株式会社 | Ink jet recording head and ink discharge method |
JP6271898B2 (en) * | 2013-07-29 | 2018-01-31 | キヤノン株式会社 | Liquid ejection head and recording apparatus |
RU2685037C1 (en) | 2015-09-04 | 2019-04-16 | Хьюлетт-Паккард Дивелопмент Компани, Л.П. | Replaceable cartridge with cover collector |
CN113059914B (en) * | 2021-03-25 | 2022-07-08 | 苏州印科杰特半导体科技有限公司 | Liquid jet flow passage |
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2003
- 2003-03-25 US US10/396,657 patent/US6761435B1/en not_active Expired - Lifetime
-
2004
- 2004-03-23 AU AU2004225950A patent/AU2004225950B2/en not_active Ceased
- 2004-03-23 EP EP04758222A patent/EP1613474B1/en not_active Expired - Lifetime
- 2004-03-23 CA CA2520187A patent/CA2520187C/en not_active Expired - Fee Related
- 2004-03-23 WO PCT/US2004/008852 patent/WO2004087423A2/en active Application Filing
- 2004-03-23 CN CNB2004800124352A patent/CN100421946C/en not_active Expired - Lifetime
- 2004-03-23 BR BRPI0408772-0A patent/BRPI0408772A/en not_active Application Discontinuation
- 2004-03-25 TW TW093108137A patent/TWI324964B/en not_active IP Right Cessation
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EP0758585A2 (en) | 1995-08-10 | 1997-02-19 | Fuji Xerox Co., Ltd. | Ink-jet recorder |
US6137052A (en) | 1996-11-11 | 2000-10-24 | Siemens Aktiengesellschaft | Shielded mounting rack for electrical printed circuit board assemblies provided with a spring conductive strip |
JP2002248769A (en) | 2001-02-23 | 2002-09-03 | Canon Inc | Ink jet recording head |
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Title |
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See also references of EP1613474A4 |
Also Published As
Publication number | Publication date |
---|---|
AU2004225950A1 (en) | 2004-10-14 |
US6761435B1 (en) | 2004-07-13 |
CA2520187C (en) | 2011-05-31 |
EP1613474A4 (en) | 2008-11-19 |
TWI324964B (en) | 2010-05-21 |
EP1613474B1 (en) | 2012-06-06 |
EP1613474A2 (en) | 2006-01-11 |
CA2520187A1 (en) | 2004-10-14 |
TW200520972A (en) | 2005-07-01 |
CN1863678A (en) | 2006-11-15 |
AU2004225950B2 (en) | 2010-04-08 |
WO2004087423A3 (en) | 2006-06-01 |
BRPI0408772A (en) | 2006-03-28 |
CN100421946C (en) | 2008-10-01 |
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