JP5093972B2 - フルオロオレフィンの製造方法 - Google Patents
フルオロオレフィンの製造方法 Download PDFInfo
- Publication number
- JP5093972B2 JP5093972B2 JP2003530643A JP2003530643A JP5093972B2 JP 5093972 B2 JP5093972 B2 JP 5093972B2 JP 2003530643 A JP2003530643 A JP 2003530643A JP 2003530643 A JP2003530643 A JP 2003530643A JP 5093972 B2 JP5093972 B2 JP 5093972B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- crown
- ether
- group
- present
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
- C07C17/04—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated halogenated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US09/962,974 US6548719B1 (en) | 2001-09-25 | 2001-09-25 | Process for producing fluoroolefins |
| US09/962,974 | 2001-09-25 | ||
| PCT/US2002/030353 WO2003027051A1 (en) | 2001-09-25 | 2002-09-25 | Process for producing fluoroolefins |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012168476A Division JP2012233001A (ja) | 2001-09-25 | 2012-07-30 | フルオロオレフィンの製造方法 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005504097A JP2005504097A (ja) | 2005-02-10 |
| JP2005504097A5 JP2005504097A5 (enExample) | 2009-07-16 |
| JP5093972B2 true JP5093972B2 (ja) | 2012-12-12 |
Family
ID=25506573
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003530643A Expired - Fee Related JP5093972B2 (ja) | 2001-09-25 | 2002-09-25 | フルオロオレフィンの製造方法 |
| JP2012168476A Pending JP2012233001A (ja) | 2001-09-25 | 2012-07-30 | フルオロオレフィンの製造方法 |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012168476A Pending JP2012233001A (ja) | 2001-09-25 | 2012-07-30 | フルオロオレフィンの製造方法 |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US6548719B1 (enExample) |
| EP (1) | EP1430011B1 (enExample) |
| JP (2) | JP5093972B2 (enExample) |
| KR (1) | KR100883425B1 (enExample) |
| CN (1) | CN100473633C (enExample) |
| ES (1) | ES2504140T3 (enExample) |
| WO (1) | WO2003027051A1 (enExample) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012233001A (ja) * | 2001-09-25 | 2012-11-29 | Honeywell Internatl Inc | フルオロオレフィンの製造方法 |
Families Citing this family (107)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7279451B2 (en) * | 2002-10-25 | 2007-10-09 | Honeywell International Inc. | Compositions containing fluorine substituted olefins |
| US7230146B2 (en) * | 2003-10-27 | 2007-06-12 | Honeywell International Inc. | Process for producing fluoropropenes |
| US20040089839A1 (en) * | 2002-10-25 | 2004-05-13 | Honeywell International, Inc. | Fluorinated alkene refrigerant compositions |
| US8033120B2 (en) * | 2002-10-25 | 2011-10-11 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
| US7880040B2 (en) * | 2004-04-29 | 2011-02-01 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US9255046B2 (en) * | 2003-07-25 | 2016-02-09 | Honeywell International Inc. | Manufacturing process for HFO-1234ze |
| US7592494B2 (en) * | 2003-07-25 | 2009-09-22 | Honeywell International Inc. | Process for the manufacture of 1,3,3,3-tetrafluoropropene |
| US8530708B2 (en) * | 2003-07-25 | 2013-09-10 | Honeywell International Inc. | Processes for selective dehydrohalogenation of halogenated alkanes |
| US9499729B2 (en) * | 2006-06-26 | 2016-11-22 | Honeywell International Inc. | Compositions and methods containing fluorine substituted olefins |
| US9308199B2 (en) * | 2004-04-29 | 2016-04-12 | Honeywell International Inc. | Medicament formulations |
| US7655610B2 (en) * | 2004-04-29 | 2010-02-02 | Honeywell International Inc. | Blowing agent compositions comprising fluorinated olefins and carbon dioxide |
| CN1926778A (zh) * | 2004-02-27 | 2007-03-07 | 日本电气株式会社 | Cdma接收装置和方法 |
| US7951982B2 (en) * | 2004-04-29 | 2011-05-31 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| JP4864879B2 (ja) * | 2004-04-29 | 2012-02-01 | ハネウェル・インターナショナル・インコーポレーテッド | 1,3,3,3−テトラフルオロプロペンの合成方法 |
| CA2564991C (en) * | 2004-04-29 | 2013-03-19 | Honeywell International Inc. | Processes for synthesis of 1,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene |
| US7659434B2 (en) | 2004-04-29 | 2010-02-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US8084653B2 (en) | 2004-04-29 | 2011-12-27 | Honeywell International, Inc. | Method for producing fluorinated organic compounds |
| US7674939B2 (en) * | 2004-04-29 | 2010-03-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| CA2564897C (en) * | 2004-04-29 | 2012-11-27 | Honeywell International Inc. | Processes for synthesis of 1,3,3,3-tetrafluoropropene |
| US9102579B2 (en) | 2004-04-29 | 2015-08-11 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US9024092B2 (en) * | 2006-01-03 | 2015-05-05 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US8383867B2 (en) | 2004-04-29 | 2013-02-26 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US20060058428A1 (en) * | 2004-09-16 | 2006-03-16 | Honeywell International Inc. | Fluorinated compounds having epoxy and vinyl ether functional groups |
| US20060122301A1 (en) * | 2004-12-08 | 2006-06-08 | Honeywell International Inc. | Fluorinated divinyl ethers |
| US8574451B2 (en) * | 2005-06-24 | 2013-11-05 | Honeywell International Inc. | Trans-chloro-3,3,3-trifluoropropene for use in chiller applications |
| WO2007019358A2 (en) * | 2005-08-05 | 2007-02-15 | E. I. Du Pont De Nemours And Company | Process for the preparation of 1,3,3,3-tetrafluoropropene and/or 1,1,3,3,3-pentafluoropropene |
| US7423188B2 (en) | 2005-11-01 | 2008-09-09 | E. I. Du Pont De Nemours And Company | Azeotrope compositions comprising E-1,3,3,3-tetrafluoropropene and hydrogen fluoride and uses thereof |
| US7902410B2 (en) * | 2005-11-03 | 2011-03-08 | Honeywell International Inc. | Process for the manufacture of fluorinated alkanes |
| WO2007056149A1 (en) * | 2005-11-03 | 2007-05-18 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| US8766020B2 (en) * | 2008-07-31 | 2014-07-01 | Honeywell International Inc. | Process for producing 2,3,3,3-tetrafluoropropene |
| US7560602B2 (en) * | 2005-11-03 | 2009-07-14 | Honeywell International Inc. | Process for manufacture of fluorinated olefins |
| ES2400732T3 (es) * | 2005-11-03 | 2013-04-11 | Honeywell International Inc. | Método para la producción de compuestos orgánicos fluorados |
| EP3336074B1 (en) | 2006-01-03 | 2025-07-09 | Honeywell International Inc. | Method for producing fluorinated organic compounds |
| ES2392591T3 (es) * | 2006-03-31 | 2012-12-12 | E.I. Du Pont De Nemours And Company | Coproducción de hidrofluoroolefinas |
| EP2046704A2 (en) * | 2006-06-27 | 2009-04-15 | E.I. Du Pont De Nemours And Company | Tetrafluoropropene production processes |
| US7485760B2 (en) * | 2006-08-24 | 2009-02-03 | Honeywell International Inc. | Integrated HFC trans-1234ze manufacture process |
| US8067650B2 (en) * | 2006-08-24 | 2011-11-29 | Honeywell International Inc. | Process for the production of HFO trans-1234ze from HFC-245fa |
| EP2066604B1 (en) | 2006-09-05 | 2015-06-03 | E. I. du Pont de Nemours and Company | Dehydrofluorination process to manufacture hydrofluoroolefins |
| KR101394583B1 (ko) | 2006-10-03 | 2014-05-12 | 멕시켐 아만코 홀딩 에스.에이. 데 씨.브이. | 탄소수 3-6의 (하이드로)플루오로알켄의 생성을 위한 탈수소할로겐화 방법 |
| GB0806422D0 (en) * | 2008-04-09 | 2008-05-14 | Ineos Fluor Holdings Ltd | Process |
| US8013194B2 (en) | 2008-03-14 | 2011-09-06 | Honeywell International Inc. | Process for the manufacture of fluorinated olefins |
| GB0625214D0 (en) * | 2006-12-19 | 2007-01-24 | Ineos Fluor Holdings Ltd | Process |
| US7803890B2 (en) * | 2006-12-20 | 2010-09-28 | Honeywell International Inc. | Fluorocopolymers |
| US8063149B2 (en) * | 2006-12-20 | 2011-11-22 | Honeywell International Inc. | Fluorocopolymers blends |
| JP5380882B2 (ja) * | 2007-04-17 | 2014-01-08 | セントラル硝子株式会社 | 3,3,3−トリフルオロプロピンの製造方法 |
| US7700815B2 (en) * | 2007-09-28 | 2010-04-20 | Honeywell International Inc | Method for producing fluorinated organic compounds |
| US9079818B2 (en) * | 2007-10-15 | 2015-07-14 | Honeywell International Inc. | Process for synthesis of fluorinated olefins |
| US8710282B2 (en) | 2008-03-14 | 2014-04-29 | Honeywell International Inc. | Integrated process for the manufacture of fluorinated olefins |
| GB0806389D0 (en) | 2008-04-09 | 2008-05-14 | Ineos Fluor Holdings Ltd | Process |
| GB0806419D0 (en) * | 2008-04-09 | 2008-05-14 | Ineos Fluor Holdings Ltd | Process |
| CN102015956B (zh) | 2008-05-07 | 2014-06-11 | 纳幕尔杜邦公司 | 包含1,1,1,2,3-五氟丙烷或2,3,3,3-四氟丙烯的组合物 |
| GB0808836D0 (en) | 2008-05-15 | 2008-06-18 | Ineos Fluor Ltd | Process |
| FR2935701B1 (fr) * | 2008-09-11 | 2012-07-27 | Arkema France | Procede de preparation de composes fluores olefiniques |
| FR2935703B1 (fr) | 2008-09-11 | 2010-09-03 | Arkema France | Procede de preparation de composes fluores. |
| RU2011130904A (ru) | 2008-12-25 | 2013-01-27 | Асахи Гласс Компани, Лимитед | Способы получения 1,1-дихлор-2,3,3,3-тетрафторпропена и 2,3,3,3-тетрафторпропена |
| US8552227B2 (en) * | 2009-01-05 | 2013-10-08 | E I Du Pont De Nemours And Company | Preparation of hydrofluoroolefins by dehydrofluorination |
| FR2940968B1 (fr) | 2009-01-13 | 2012-12-14 | Arkema France | Procede de preparation de composes fluores olefiniques |
| JP5598333B2 (ja) * | 2009-01-19 | 2014-10-01 | 旭硝子株式会社 | 1,1−ジクロロ−2,2,3,3,3−ペンタフルオロプロパンの製造方法 |
| WO2010129844A1 (en) | 2009-05-08 | 2010-11-11 | E. I. Du Pont De Nemours And Company | Processes for reducing the amount of monofluoroacetate in hydrofluoroolefin production |
| FR2946338B1 (fr) | 2009-06-04 | 2012-12-28 | Arkema France | Procede de preparation de composes fluores olefiniques |
| FR2948360B1 (fr) | 2009-07-23 | 2011-08-05 | Arkema France | Procede de preparation de composes fluores olefiniques |
| US8129574B2 (en) | 2009-08-31 | 2012-03-06 | Honeywell International Inc. | Hydrogenation process for fluorocarbons |
| DK2474517T3 (en) * | 2009-08-31 | 2017-09-18 | Sumitomo Chemical Co | PROCEDURE FOR MANUFACTURING THE TRICHLOR-1 PROP |
| JP2013504658A (ja) | 2009-09-09 | 2013-02-07 | ハネウェル・インターナショナル・インコーポレーテッド | モノクロロトリフルオロプロペン化合物及び組成物並びにそれを用いる方法 |
| US7829748B1 (en) | 2009-09-21 | 2010-11-09 | Honeywell International Inc. | Process for the manufacture of 1,3,3,3-tetrafluoropropene |
| WO2011102538A2 (en) * | 2010-02-19 | 2011-08-25 | Daikin Industries, Ltd. | Process for producing 2-chloro-3,3,3-trifluoropropene |
| US8927791B2 (en) * | 2010-04-29 | 2015-01-06 | Honeywell International Inc. | Method for producing tetrafluoropropenes |
| US8901360B2 (en) | 2010-05-21 | 2014-12-02 | Honeywell International Inc. | Process for cis 1,1,1,4,4,4-hexafluoro-2-butene |
| TW201204686A (en) * | 2010-06-23 | 2012-02-01 | Asahi Glass Co Ltd | Process for preparation of 1,1-dichloro-2,2,3,3,3-penta- fluoropropane |
| EP2586762B1 (en) * | 2010-06-23 | 2019-08-07 | AGC Inc. | Production method for 1,1-dichloro-2,3,3,3-tetra-fluoropropene and 2,3,3,3-tetrafluoropropene |
| US8436217B2 (en) | 2011-04-25 | 2013-05-07 | Honeywell International Inc. | Integrated process to co-produce 1,1,1,3,3-pentafluoropropane, trans-1-chloro-3,3,3-trifluoropropene and trans-1,3,3,3-tetrafluoropropene |
| CN102887812A (zh) * | 2011-07-20 | 2013-01-23 | 中化蓝天集团有限公司 | 1,1,3,3,3-五氟丙烯的合成方法 |
| JPWO2013015201A1 (ja) * | 2011-07-22 | 2015-02-23 | 旭硝子株式会社 | 熱サイクル用作動媒体および熱サイクルシステム |
| JP5712894B2 (ja) * | 2011-10-14 | 2015-05-07 | セントラル硝子株式会社 | (z)−1−クロロ−3,3,3−トリフルオロプロペンの製造方法 |
| US8889924B2 (en) | 2012-02-14 | 2014-11-18 | Honeywell International Inc. | Process for the production of 1,3,3,3-tetrafluoropropene |
| US8829254B2 (en) | 2012-02-14 | 2014-09-09 | Honeywell International Inc. | Process for making 1,3,3,3-tetrafluoropropene |
| JP6107466B2 (ja) | 2012-06-28 | 2017-04-05 | セントラル硝子株式会社 | トランス−1,3,3,3−テトラフルオロプロペンの精製方法 |
| JP6107467B2 (ja) | 2012-06-29 | 2017-04-05 | セントラル硝子株式会社 | 1−クロロ−3,3,3−トリフルオロプロペンの製造方法 |
| JP6183370B2 (ja) * | 2012-09-21 | 2017-08-23 | セントラル硝子株式会社 | 1,2−ジクロロ−3,3,3−トリフルオロプロペンの製造方法 |
| EP2922809A1 (en) * | 2012-09-28 | 2015-09-30 | E. I. du Pont de Nemours and Company | Dehydrochlorination of chlorinated reactants to produce 1,1,1,4,4,4-hexafluoro-2-butyne |
| US9532567B2 (en) * | 2012-11-29 | 2017-01-03 | Honeywell International Inc. | Synthesis and use of trans-1,3,3,3-tetrafluoropropene/vinylidene fluoride copolymers |
| CN103880590B (zh) | 2012-12-19 | 2016-10-05 | 中化蓝天集团有限公司 | 一种制备1,3,3,3-四氟丙烯的工艺 |
| US8791309B2 (en) * | 2012-12-21 | 2014-07-29 | Honeywell International Inc. | Synthesis of 3,3,3-trifluoropropyne |
| US9289758B2 (en) | 2013-01-22 | 2016-03-22 | Axiall Ohio, Inc. | Processes for producing chlorinated hydrocarbons and methods for recovering polyvalent antimony catalysts therefrom |
| US8889930B2 (en) | 2013-01-22 | 2014-11-18 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons |
| US9216932B2 (en) * | 2013-05-20 | 2015-12-22 | Honeywell International Inc. | Dehalogenation of trans-1-chloro-3,3,3-trifluoropropene |
| US9139497B2 (en) | 2013-10-23 | 2015-09-22 | Axiall Ohio, Inc. | Process for producing chlorinated hydrocarbons in the presence of a polyvalent bismuth compound |
| KR20230031374A (ko) * | 2014-02-07 | 2023-03-07 | 더 케무어스 컴퍼니 에프씨, 엘엘씨 | Z-1,1,1,4,4,4-헥사플루오로-2-부텐의 생산을 위한 통합 공정 |
| JP6582569B2 (ja) * | 2014-07-28 | 2019-10-02 | セントラル硝子株式会社 | 2−クロロ−1,3,3,3−テトラフルオロプロペンの製造方法 |
| CN104177219B (zh) * | 2014-08-01 | 2018-02-13 | 巨化集团技术中心 | 一种制备1,3,3,3‑四氟丙烯的方法 |
| US9790150B2 (en) | 2014-08-12 | 2017-10-17 | The Chemours Company Fc, Llc | Processes for producing branched fluoroalkyl olefins |
| WO2016025288A1 (en) | 2014-08-14 | 2016-02-18 | The Chemours Company Fc, Llc | Process for the production of e-1,3,3,3-tetrafluoropropene (hfc-1234ze) by dehydrofluorinatiokl |
| US10093601B2 (en) | 2015-06-29 | 2018-10-09 | The Boeing Company | Fire retardant compounds |
| CN113968769A (zh) * | 2015-09-11 | 2022-01-25 | 科慕埃弗西有限公司 | 氢氯氟烃的脱卤化氢 |
| EP3395789B1 (en) * | 2015-12-25 | 2020-11-18 | AGC Inc. | Manufacturing method of 1-chloro-2,3,3,3-tetrafluoropropene |
| CN105837397A (zh) * | 2016-04-19 | 2016-08-10 | 四川西艾氟科技有限公司 | 一种全氟烷基乙烯的合成方法 |
| CN106892794B (zh) * | 2016-12-28 | 2019-10-15 | 西安近代化学研究所 | 一种制备反式-1,3,3,3-四氟丙烯的方法 |
| GB201701099D0 (en) * | 2017-01-23 | 2017-03-08 | Mexichem Fluor Sa De Cv | Process |
| US10611709B2 (en) * | 2017-09-11 | 2020-04-07 | The Chemours Company Fc, Llc | Liquid phase process for preparing (E)-1,1,1,4,4,4-hexafluorobut-2-ene |
| FR3076553B1 (fr) | 2018-01-08 | 2020-07-31 | Arkema France | Procede de purification du 1,1,1,2,3-pentafluoropropane et utilisation de celui-ci pour l'obtention de 2,3,3,3-tetrafluoropropene de haute purete. |
| JP6974221B2 (ja) * | 2018-03-14 | 2021-12-01 | 株式会社クレハ | アルケンの製造方法 |
| FR3077072B1 (fr) | 2019-01-22 | 2021-08-06 | Arkema France | Procédé de purification du 1,1,1,2,3-pentafluoropropane et utilisation de celui-ci pour l’obtention de 2,3,3,3-tétrafluoropropène de haute pureté |
| CN113527040B (zh) * | 2020-04-22 | 2023-09-01 | 浙江省化工研究院有限公司 | 一种卤代丙烯的制备方法 |
| WO2023171325A1 (ja) * | 2022-03-09 | 2023-09-14 | 株式会社クレハ | アルケンの製造方法 |
| WO2023171326A1 (ja) * | 2022-03-09 | 2023-09-14 | 株式会社クレハ | アルケンの製造方法 |
| WO2025160051A2 (en) * | 2024-01-22 | 2025-07-31 | The Chemours Company Fc, Llc | Catalytic process for preparation of hydrofluoro(ether)olefins |
| WO2025160052A1 (en) * | 2024-01-22 | 2025-07-31 | The Chemours Company Fc, Llc | Integrated process to make 1,1,1,2,2,5,5,6,6,6-decafluoro-3-hexene |
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| US4798818A (en) | 1987-11-27 | 1989-01-17 | Dow Corning Corporation | Catalyst composition and process for its preparation |
| ATE172953T1 (de) | 1993-07-29 | 1998-11-15 | Allied Signal Inc | Verfahren zur herstellung von 1,1,1,3,3 pentafluorpropan |
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| US6548719B1 (en) * | 2001-09-25 | 2003-04-15 | Honeywell International | Process for producing fluoroolefins |
-
2001
- 2001-09-25 US US09/962,974 patent/US6548719B1/en not_active Expired - Lifetime
-
2002
- 2002-09-25 CN CNB028232666A patent/CN100473633C/zh not_active Expired - Fee Related
- 2002-09-25 KR KR1020047004392A patent/KR100883425B1/ko not_active Expired - Fee Related
- 2002-09-25 WO PCT/US2002/030353 patent/WO2003027051A1/en not_active Ceased
- 2002-09-25 JP JP2003530643A patent/JP5093972B2/ja not_active Expired - Fee Related
- 2002-09-25 EP EP02773563.8A patent/EP1430011B1/en not_active Expired - Lifetime
- 2002-09-25 ES ES02773563.8T patent/ES2504140T3/es not_active Expired - Lifetime
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2012
- 2012-07-30 JP JP2012168476A patent/JP2012233001A/ja active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012233001A (ja) * | 2001-09-25 | 2012-11-29 | Honeywell Internatl Inc | フルオロオレフィンの製造方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US6548719B1 (en) | 2003-04-15 |
| CN1589248A (zh) | 2005-03-02 |
| EP1430011B1 (en) | 2014-07-23 |
| CN100473633C (zh) | 2009-04-01 |
| US20030060670A1 (en) | 2003-03-27 |
| ES2504140T3 (es) | 2014-10-08 |
| WO2003027051A1 (en) | 2003-04-03 |
| JP2012233001A (ja) | 2012-11-29 |
| EP1430011A1 (en) | 2004-06-23 |
| JP2005504097A (ja) | 2005-02-10 |
| KR20040044993A (ko) | 2004-05-31 |
| KR100883425B1 (ko) | 2009-02-12 |
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