US20030091463A1 - Unleaded solder alloy and electronic components using it - Google Patents
Unleaded solder alloy and electronic components using it Download PDFInfo
- Publication number
- US20030091463A1 US20030091463A1 US10/258,540 US25854002A US2003091463A1 US 20030091463 A1 US20030091463 A1 US 20030091463A1 US 25854002 A US25854002 A US 25854002A US 2003091463 A1 US2003091463 A1 US 2003091463A1
- Authority
- US
- United States
- Prior art keywords
- solder
- copper
- lead
- solder alloy
- tin
- 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.)
- Abandoned
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
- B23K35/0261—Rods, electrodes, wires
- B23K35/0266—Rods, electrodes, wires flux-cored
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/04—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing coils
- H01F41/10—Connecting leads to windings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/36—Electric or electronic devices
- B23K2101/38—Conductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2103/00—Materials to be soldered, welded or cut
- B23K2103/08—Non-ferrous metals or alloys
- B23K2103/12—Copper or alloys thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F27/00—Details of transformers or inductances, in general
- H01F27/28—Coils; Windings; Conductive connections
- H01F27/29—Terminals; Tapping arrangements for signal inductances
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12708—Sn-base component
- Y10T428/12715—Next to Group IB metal-base component
Definitions
- the present invention relates to a solder alloy that does not contain lead, namely lead-free solder alloy, and particularly to an electronic component using this lead-free solder alloy.
- tin (Sn)-lead (Pb) type solder alloy has often been used as solder for electrical connections within an electronic component or for connecting electronic components to a printed circuit boad.
- Japanese Patent No. 3036636 relates to a lead-free solder alloy for bonding electronic components to a printed circuit boad of an electronic device, and has part of a copper component of tin(Sn)-copper (Cu) alloy replaced by nickel (Ni) with the compositional ratio being Cu: 0.05-2.0 weight %, Ni: 0.001-2.0 weight % and the remainder being Sn.
- the purpose of this is to increase mechanical strength of the bonding sections.
- U.S. Pat. No. 4,758,407 proposes use of copper pipe and brass pipe as mains water pipe, in order to prevent lead and cadmium leaking into drinking water from lead pipes used in mains water pipes, and the invention of this patent relates to a solder alloy for welding these copper pipes and brass pipes to connecting joints in order to join them together for extension purposes.
- solder alloy The main component of this solder alloy is tin(Sn) or tin (Sn) and Antimony (Sb), and neither solder contains lead (Pb) or cadmium (Cd).
- the composition of the solder alloy having tin as a main component is Sn: 92.5-96.9 wt %, Cu:3.0-5.0 wt %, Ni: 0.1-0 2.0 wt %, Ag: 0.0-5.0 wt %.
- the composition of the solder alloy having tin/antimony as a main component is Sn: 87.0-92.9 wt %, Sb: 4.0-6.0 wt %, Cu: 3.0-5.0 wt %, Ni: 0.0-2.0 wt %, Ag: 0.0-5.0 wt %.
- the melting temperature of the solder alloy of Japanese Patent No. 3036636 is around 230° C., and this solder alloy, as mentioned above, is for bonding electronic components to conductive portions of a printed circuit boad , which means that the melting temperature (temperature at the time of reflow) is preferably as low as possible.
- the melting temperature of the solder alloy of U.S. Pat. No. 4,758,407 is from around 240° C. to around 330° C., but this solder alloy is used for welding together copper pipe or brass pipe or their joints used as water supply pipes in, for example, a domestic water heater, which means that when considering operability at the time of melting, the melting temperature of this alloy solder is preferably low.
- windings Inside the electronic components there are high frequency coils or transformers formed by winding linear or substantially belt-shaped electrical conductors (referred to below as windings). Wires that have an insulating coat formed by coating a copper core with enamel or urethane are used as these coil windings.
- each of a starting end and a finishing end of a winding are wrapped around electrode sections such as terminal pins provided in the bottom of a bobbin etc., followed by dipping the wrapped sections into solder liquid that has been heated to a high temperature.
- a method is generally used where the insulating coat of the windings is removed simultaneously with attaching the solder.
- solder erosion arises where copper that is the base material is dissolved in the solder liquid and made thinner. This copper erosion phenomenon is a major factor causing wire bursts in electronic components such as the above described coil.
- a first aspect of the present invention provides a lead-free solder alloy containing from 5.3 to 7.0 wt % copper (Cu), from 0.1 to less than 0.5 wt % nickel, and the remainder being tin (Sn).
- a second aspect of the present invention provides an electronic component, having a core formed from copper or an alloy containing copper that uses conductors having the cores coated with an insulating coat, the conductors, or the conductors and sites other than the electronic component provided with solder using a lead free solder alloy containing the above described 5.3 to 7.0 wt % copper (Cu) from 0.1 to less than 0.5 wt % nickel (Ni) and the remainder being tin (Sn), and in this way, open circuit faults caused by the copper erosion phenomenon of the above described electronic component are prevented.
- a third aspect of the present invention is basically the same as the second aspect of the invention, wherein at the time of attaching solder to the electronic component, the insulating coat of the conductors is reliably dissolved by setting the melting temperature of the lead-free solder to from 400° C. to 480° C.
- FIG. 1 is an explanatory drawing showing one example of a coil component.
- coils high frequency coils or transformers (hereafter referred to as coils) formed by winding linear. or substantially belt-shaped electrical conductors (referred to below as windings). Wires that have an insulating film formed by coating a copper core with enamel or urethane are used as these coil windings.
- FIG. 1 One example of a coil using wires that have an insulating film formed by coating a copper core with enamel or urethane as the coil windings is shown in FIG. 1.
- reference numeral 1 is a coil
- 2 is a bobbin, and in this embodiment they are integrally formed from ferrite core.
- Reference numeral 3 is winding material formed by coating a copper core with an insulating coat of enamel or urethane
- 4 is a winding section having the winding material 3 wound around a body section of the bobbin 2
- 5 is a terminal pin embedded in the bottom of the bobbin 2
- 6 , 6 are the starting end and finishing end lead out terminal of the winding material and electrically connected to the terminal pin 5 by being wrapped around.
- the terminal pin 5 is for electrically connecting the coil 1 to circuit conductors of a circuit substrate (not shown).
- An HCP wire having copper plating coated on the surface of a steel wire is commonly used as the terminal pin 5 .
- the inventor carried out experiments with coils using lead-free solder having copper added to tin, and it was not possible to completely remove enamel coating with a solder attachment temperature of less than 350° C.
- Table 1 contains measurement results showing a relationship between solder attachment temperature when enamel coated copper wire having a diameter of 0.4 mm is dipped in a molten solder liquid, and shows a relationship between the compositional content of the solder alloy and solder attachment temperature, extent of copper erosion, and the condition of the solder attachment surface.
- “extent of copper erosion” has the conductor diameter of the enamel coated copper wire before solder attachment (0.4 mm) as a reference, with a reduction of 10% being “large”, a reduction of from 5% to less than 10% being “medium”, and a reduction of from 0 to less than 5% being “small”.
- the added amount of nickel exceeds a specified range in a region where the copper content exceeds a specified amount, a copper-nickel precipitate floats in the molten solder, and since the precipitate adheres to the surface of the solder attachment regions, the solder attachment surface becomes microscopically uneven and ravaged, the thickness of the solder is not uniform, it is more likely that a bridge phenomenon or icicle phenomenon will occur, and wetting deteriorates. It was confirmed that it was easier for these phenomena to occur in a region where the melting temperature of the solder alloy is low.
- the HCP wire is copper plating coated on a surface of a steel wire, and is used as a terminal pin 5 of the coil of FIG. 1 or as terminal conductors of other electronic components.
- Table 2 shows the relationship between the number of times until the copper plate of the HCP wire is peeled away from the steel wire section, which is the undercoat, and the composition of the solder alloy and the temperature at the time of solder attachment, and shows that as the number of times increases, the degree of peeling of the copper plate decreases, in other words, the rate of copper erosion and the amount of copper erosion is reduced.
- the lead-free solder alloy of the present invention is not prone to copper erosion even in a region where solder attachment temperature is high, and it is possible to reduce the amount of copper lost due to the copper erosion.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
- Connections Effected By Soldering, Adhesion, Or Permanent Deformation (AREA)
- Details Of Resistors (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/237,918 US20060024194A1 (en) | 2001-02-27 | 2005-09-29 | Lead-free solder alloy and electronic component using this lead-free solder alloy |
US12/379,238 US20090173770A1 (en) | 2001-02-27 | 2009-02-17 | Lead-free solder alloy and electoronic component using this lead-free solder alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2001/001453 WO2002068146A1 (fr) | 2001-02-27 | 2001-02-27 | Alliage de brasage sans plomb et composants electriques l'utilisant |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/237,918 Division US20060024194A1 (en) | 2001-02-27 | 2005-09-29 | Lead-free solder alloy and electronic component using this lead-free solder alloy |
Publications (1)
Publication Number | Publication Date |
---|---|
US20030091463A1 true US20030091463A1 (en) | 2003-05-15 |
Family
ID=11737070
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US10/258,540 Abandoned US20030091463A1 (en) | 2001-02-27 | 2001-02-27 | Unleaded solder alloy and electronic components using it |
US11/237,918 Abandoned US20060024194A1 (en) | 2001-02-27 | 2005-09-29 | Lead-free solder alloy and electronic component using this lead-free solder alloy |
US12/379,238 Abandoned US20090173770A1 (en) | 2001-02-27 | 2009-02-17 | Lead-free solder alloy and electoronic component using this lead-free solder alloy |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/237,918 Abandoned US20060024194A1 (en) | 2001-02-27 | 2005-09-29 | Lead-free solder alloy and electronic component using this lead-free solder alloy |
US12/379,238 Abandoned US20090173770A1 (en) | 2001-02-27 | 2009-02-17 | Lead-free solder alloy and electoronic component using this lead-free solder alloy |
Country Status (9)
Country | Link |
---|---|
US (3) | US20030091463A1 (de) |
EP (1) | EP1275467B1 (de) |
JP (1) | JP4139686B2 (de) |
CN (1) | CN1240515C (de) |
AT (1) | ATE284294T1 (de) |
DE (1) | DE60107670T2 (de) |
HK (1) | HK1056523A1 (de) |
TW (1) | TW469297B (de) |
WO (1) | WO2002068146A1 (de) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090289102A1 (en) * | 2005-07-19 | 2009-11-26 | Nihon Superior Sha Co., Ltd. | SOLDER FREE FROM LEAD FOR ADDITIONAL SUPPLY AND METHOD OF REGULATING Cu CONCENTRATION AND Ni CONCENTRATION IN SOLDER BATH |
WO2014084242A1 (ja) * | 2012-11-30 | 2014-06-05 | 株式会社日本スペリア社 | 低融点ろう材 |
US20160016245A1 (en) * | 2013-03-18 | 2016-01-21 | Mitsubishi Materials Corporation | Method for manufacturing power module substrate |
US10199237B2 (en) | 2013-03-18 | 2019-02-05 | Mitsubishi Materials Corporation | Method for manufacturing bonded body and method for manufacturing power-module substrate |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7172726B2 (en) * | 2002-10-15 | 2007-02-06 | Senju Metal Industry Co., Ltd. | Lead-free solder |
WO2004105997A1 (en) * | 2003-05-28 | 2004-12-09 | Koninklijke Philips Electronics N.V. | Method for soldering to a copper comprising object using a lead-free solder alloy |
EP1924393A1 (de) * | 2005-08-24 | 2008-05-28 | Fry's Metals Inc. | Verringerung von gelenkversprödung in bleifreien lötprozessen |
CN100459325C (zh) * | 2006-09-27 | 2009-02-04 | 许晓华 | 铝漆包线与铜线的焊接方法 |
WO2009051181A1 (ja) * | 2007-10-19 | 2009-04-23 | Nihon Superior Sha Co., Ltd. | 無鉛はんだ合金 |
US8395051B2 (en) * | 2008-12-23 | 2013-03-12 | Intel Corporation | Doping of lead-free solder alloys and structures formed thereby |
CN101902007B (zh) * | 2009-06-01 | 2012-05-23 | 北京七六一通信雷达有限公司 | 多股励磁线端头处理方法 |
WO2014024271A1 (ja) * | 2012-08-08 | 2014-02-13 | 千住金属工業株式会社 | 高温鉛フリーはんだ合金 |
JPWO2015053114A1 (ja) * | 2013-10-10 | 2017-03-09 | 株式会社日本スペリア社 | 低融点ろう材 |
JP5842973B1 (ja) * | 2014-09-04 | 2016-01-13 | 千住金属工業株式会社 | 端子予備メッキ用鉛フリーはんだ合金及び電子部品 |
CN109702374B (zh) * | 2019-02-13 | 2021-02-09 | 南昌大学 | 一种Sn-Cu-Ni-In无铅钎料合金及其制备方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4643875A (en) * | 1985-07-24 | 1987-02-17 | Gte Products Corporation | Tin based ductile brazing alloys |
US4758407A (en) * | 1987-06-29 | 1988-07-19 | J.W. Harris Company | Pb-free, tin base solder composition |
US5102748A (en) * | 1991-05-03 | 1992-04-07 | Taracorp, Inc. | Non-leaded solders |
US5583483A (en) * | 1993-08-16 | 1996-12-10 | Mercedes-Benz Ag | Method for tire pressure warning |
US5817194A (en) * | 1996-11-14 | 1998-10-06 | Fukuda Metal Foil & Powder Co., Ltd. | Tin base soldering/brazing material |
US5939626A (en) * | 1996-09-25 | 1999-08-17 | Nippon Soken, Inc. | Tire pressure detecting device which compares driven and driving wheel speeds and acceleration wherein judgment is prohibited when slippage occurs |
US6450020B1 (en) * | 1999-08-30 | 2002-09-17 | Denso Corporation | Tire air pressure warning device |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01218794A (ja) * | 1988-02-29 | 1989-08-31 | Hitachi Ltd | 絶縁被覆銅線の接合用ろう材及びその接合方法 |
JPH06269983A (ja) * | 1993-03-18 | 1994-09-27 | Tokuriki Honten Co Ltd | Ag系はんだ |
JP3760586B2 (ja) * | 1997-09-05 | 2006-03-29 | 株式会社村田製作所 | 半田組成物 |
JP3829475B2 (ja) * | 1998-05-13 | 2006-10-04 | 株式会社村田製作所 | Cu系母材接合用のはんだ組成物 |
KR20010072364A (ko) * | 1999-06-11 | 2001-07-31 | 이즈하라 요조 | 무연 땜납 |
-
2001
- 2001-02-27 US US10/258,540 patent/US20030091463A1/en not_active Abandoned
- 2001-02-27 DE DE60107670T patent/DE60107670T2/de not_active Expired - Lifetime
- 2001-02-27 JP JP2002567493A patent/JP4139686B2/ja not_active Expired - Lifetime
- 2001-02-27 EP EP01906341A patent/EP1275467B1/de not_active Expired - Lifetime
- 2001-02-27 CN CNB018086993A patent/CN1240515C/zh not_active Expired - Lifetime
- 2001-02-27 WO PCT/JP2001/001453 patent/WO2002068146A1/ja active IP Right Grant
- 2001-02-27 AT AT01906341T patent/ATE284294T1/de not_active IP Right Cessation
- 2001-04-27 TW TW090110117A patent/TW469297B/zh not_active IP Right Cessation
-
2003
- 2003-12-09 HK HK03108928A patent/HK1056523A1/xx not_active IP Right Cessation
-
2005
- 2005-09-29 US US11/237,918 patent/US20060024194A1/en not_active Abandoned
-
2009
- 2009-02-17 US US12/379,238 patent/US20090173770A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4643875A (en) * | 1985-07-24 | 1987-02-17 | Gte Products Corporation | Tin based ductile brazing alloys |
US4758407A (en) * | 1987-06-29 | 1988-07-19 | J.W. Harris Company | Pb-free, tin base solder composition |
US5102748A (en) * | 1991-05-03 | 1992-04-07 | Taracorp, Inc. | Non-leaded solders |
US5583483A (en) * | 1993-08-16 | 1996-12-10 | Mercedes-Benz Ag | Method for tire pressure warning |
US5939626A (en) * | 1996-09-25 | 1999-08-17 | Nippon Soken, Inc. | Tire pressure detecting device which compares driven and driving wheel speeds and acceleration wherein judgment is prohibited when slippage occurs |
US5817194A (en) * | 1996-11-14 | 1998-10-06 | Fukuda Metal Foil & Powder Co., Ltd. | Tin base soldering/brazing material |
US6450020B1 (en) * | 1999-08-30 | 2002-09-17 | Denso Corporation | Tire air pressure warning device |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090289102A1 (en) * | 2005-07-19 | 2009-11-26 | Nihon Superior Sha Co., Ltd. | SOLDER FREE FROM LEAD FOR ADDITIONAL SUPPLY AND METHOD OF REGULATING Cu CONCENTRATION AND Ni CONCENTRATION IN SOLDER BATH |
US7861909B2 (en) * | 2005-07-19 | 2011-01-04 | Nihon Superior Sha Co., Ltd. | Replenished lead-free solder and a control method for copper density and nickel density in a solder dipping bath |
WO2014084242A1 (ja) * | 2012-11-30 | 2014-06-05 | 株式会社日本スペリア社 | 低融点ろう材 |
US20160016245A1 (en) * | 2013-03-18 | 2016-01-21 | Mitsubishi Materials Corporation | Method for manufacturing power module substrate |
US9833855B2 (en) * | 2013-03-18 | 2017-12-05 | Mitsubishi Materials Corporation | Method for manufacturing power module substrate |
US10199237B2 (en) | 2013-03-18 | 2019-02-05 | Mitsubishi Materials Corporation | Method for manufacturing bonded body and method for manufacturing power-module substrate |
Also Published As
Publication number | Publication date |
---|---|
CN1240515C (zh) | 2006-02-08 |
US20060024194A1 (en) | 2006-02-02 |
HK1056523A1 (en) | 2004-02-20 |
EP1275467A4 (de) | 2003-07-09 |
EP1275467B1 (de) | 2004-12-08 |
WO2002068146A1 (fr) | 2002-09-06 |
DE60107670D1 (de) | 2005-01-13 |
CN1426339A (zh) | 2003-06-25 |
JP4139686B2 (ja) | 2008-08-27 |
JPWO2002068146A1 (ja) | 2004-06-24 |
ATE284294T1 (de) | 2004-12-15 |
EP1275467A1 (de) | 2003-01-15 |
DE60107670T2 (de) | 2005-10-06 |
US20090173770A1 (en) | 2009-07-09 |
TW469297B (en) | 2001-12-21 |
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