JP2005516764A5 - - Google Patents
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- Publication number
- JP2005516764A5 JP2005516764A5 JP2003567552A JP2003567552A JP2005516764A5 JP 2005516764 A5 JP2005516764 A5 JP 2005516764A5 JP 2003567552 A JP2003567552 A JP 2003567552A JP 2003567552 A JP2003567552 A JP 2003567552A JP 2005516764 A5 JP2005516764 A5 JP 2005516764A5
- Authority
- JP
- Japan
- Prior art keywords
- ultrafiltration
- porous polymer
- halar
- microfiltration membrane
- membrane
- 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
- 239000012528 membrane Substances 0.000 claims description 76
- 229920000642 polymer Polymers 0.000 claims description 50
- 238000001471 micro-filtration Methods 0.000 claims description 47
- 238000000108 ultra-filtration Methods 0.000 claims description 47
- 229920001780 ECTFE Polymers 0.000 claims description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 24
- 239000011148 porous material Substances 0.000 claims description 23
- 239000012510 hollow fiber Substances 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 18
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 18
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 239000012530 fluid Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 230000002209 hydrophobic effect Effects 0.000 claims description 6
- 238000002386 leaching Methods 0.000 claims description 6
- -1 methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy Chemical group 0.000 claims description 6
- 238000002145 thermally induced phase separation Methods 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000010791 quenching Methods 0.000 claims description 3
- 231100000331 toxic Toxicity 0.000 claims description 3
- 230000002588 toxic effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 239000012633 leachable Substances 0.000 claims 13
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims 10
- 235000013773 glyceryl triacetate Nutrition 0.000 claims 5
- 229960002622 triacetin Drugs 0.000 claims 5
- 235000013769 triethyl citrate Nutrition 0.000 claims 5
- 239000003795 chemical substances by application Substances 0.000 claims 4
- 239000012071 phase Substances 0.000 claims 4
- 229910002012 Aerosil® Inorganic materials 0.000 claims 1
- 238000009826 distribution Methods 0.000 claims 1
- 229910021485 fumed silica Inorganic materials 0.000 claims 1
- 229910002011 hydrophilic fumed silica Inorganic materials 0.000 claims 1
- 229910003480 inorganic solid Inorganic materials 0.000 claims 1
- 239000007791 liquid phase Substances 0.000 claims 1
- 230000035699 permeability Effects 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000000835 fiber Substances 0.000 description 3
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AUPS0466A AUPS046602A0 (en) | 2002-02-12 | 2002-02-12 | Halar membranes |
| PCT/AU2003/000179 WO2003068374A1 (en) | 2002-02-12 | 2003-02-12 | Halar membranes |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2005516764A JP2005516764A (ja) | 2005-06-09 |
| JP2005516764A5 true JP2005516764A5 (cg-RX-API-DMAC7.html) | 2006-03-30 |
| JP4656839B2 JP4656839B2 (ja) | 2011-03-23 |
Family
ID=3834067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003567552A Expired - Fee Related JP4656839B2 (ja) | 2002-02-12 | 2003-02-12 | ヘイラー膜 |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1474222B1 (cg-RX-API-DMAC7.html) |
| JP (1) | JP4656839B2 (cg-RX-API-DMAC7.html) |
| KR (1) | KR100991596B1 (cg-RX-API-DMAC7.html) |
| CN (1) | CN100500272C (cg-RX-API-DMAC7.html) |
| AT (1) | ATE505260T1 (cg-RX-API-DMAC7.html) |
| AU (1) | AUPS046602A0 (cg-RX-API-DMAC7.html) |
| CA (2) | CA2733826C (cg-RX-API-DMAC7.html) |
| DE (1) | DE60336707D1 (cg-RX-API-DMAC7.html) |
| ES (1) | ES2364041T3 (cg-RX-API-DMAC7.html) |
| MY (1) | MY135608A (cg-RX-API-DMAC7.html) |
| NZ (1) | NZ535133A (cg-RX-API-DMAC7.html) |
| WO (1) | WO2003068374A1 (cg-RX-API-DMAC7.html) |
Families Citing this family (66)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69740003D1 (de) | 1996-12-20 | 2010-11-04 | Siemens Water Tech Corp | Reinigungsmethode |
| AUPR421501A0 (en) | 2001-04-04 | 2001-05-03 | U.S. Filter Wastewater Group, Inc. | Potting method |
| AUPR692401A0 (en) | 2001-08-09 | 2001-08-30 | U.S. Filter Wastewater Group, Inc. | Method of cleaning membrane modules |
| US7247238B2 (en) | 2002-02-12 | 2007-07-24 | Siemens Water Technologies Corp. | Poly(ethylene chlorotrifluoroethylene) membranes |
| AUPS300602A0 (en) | 2002-06-18 | 2002-07-11 | U.S. Filter Wastewater Group, Inc. | Methods of minimising the effect of integrity loss in hollow fibre membrane modules |
| US7938966B2 (en) | 2002-10-10 | 2011-05-10 | Siemens Water Technologies Corp. | Backwash method |
| AU2003903507A0 (en) | 2003-07-08 | 2003-07-24 | U. S. Filter Wastewater Group, Inc. | Membrane post-treatment |
| WO2005021140A1 (en) | 2003-08-29 | 2005-03-10 | U.S. Filter Wastewater Group, Inc. | Backwash |
| WO2005037917A1 (en) * | 2003-10-20 | 2005-04-28 | Zenon Environmental Inc. | System and method for synthesizing a polymer membrane |
| NZ546959A (en) | 2003-11-14 | 2008-03-28 | Siemens Water Tech Corp | Improved cleaning method for a porous membrane filtration module |
| WO2005092799A1 (en) | 2004-03-26 | 2005-10-06 | U.S. Filter Wastewater Group, Inc. | Process and apparatus for purifying impure water using microfiltration or ultrafiltration in combination with reverse osmosis |
| AU2005259830C1 (en) * | 2004-07-02 | 2011-07-21 | Evoqua Water Technologies Llc | Gas transfer membrane |
| CN102512986A (zh) * | 2004-07-02 | 2012-06-27 | 西门子工业公司 | 气体可透膜 |
| WO2006002479A1 (en) * | 2004-07-05 | 2006-01-12 | U.S. Filter Wastewater Group, Inc. | Hydrophilic membranes |
| CA2579168C (en) | 2004-09-07 | 2015-06-23 | Siemens Water Technologies Corp. | Membrane filtration with reduced volume cleaning step |
| AU2005284677B2 (en) | 2004-09-14 | 2010-12-23 | Evoqua Water Technologies Llc | Methods and apparatus for removing solids from a membrane module |
| US8377305B2 (en) | 2004-09-15 | 2013-02-19 | Siemens Industry, Inc. | Continuously variable aeration |
| JP2006088114A (ja) * | 2004-09-27 | 2006-04-06 | Asahi Kasei Chemicals Corp | 親水性多孔膜 |
| CA2591408C (en) | 2004-12-24 | 2015-07-21 | Siemens Water Technologies Corp. | Cleaning in membrane filtration systems |
| NZ555987A (en) | 2004-12-24 | 2009-08-28 | Siemens Water Tech Corp | Simple gas scouring method and apparatus |
| ITMI20050474A1 (it) | 2005-03-22 | 2006-09-23 | Solvay Solexis Spa | Polveri o manufatti aventi una idrofilicita'superficiale |
| JP2008539054A (ja) | 2005-04-29 | 2008-11-13 | シーメンス・ウォーター・テクノロジーズ・コーポレイション | 膜フィルターのための化学洗浄 |
| CN101287538B (zh) | 2005-08-22 | 2013-03-06 | 西门子工业公司 | 使用歧管以减少回洗的水过滤装置 |
| JP2009509731A (ja) * | 2005-09-27 | 2009-03-12 | シーメンス・ウォーター・テクノロジーズ・コーポレイション | 化学洗浄剤および濾過膜洗浄方法 |
| WO2008051546A2 (en) | 2006-10-24 | 2008-05-02 | Siemens Water Technologies Corp. | Infiltration/inflow control for membrane bioreactor |
| WO2008123972A1 (en) | 2007-04-02 | 2008-10-16 | Siemens Water Technologies Corp. | Improved infiltration/inflow control for membrane bioreactor |
| US9764288B2 (en) | 2007-04-04 | 2017-09-19 | Evoqua Water Technologies Llc | Membrane module protection |
| CA2688455C (en) | 2007-05-29 | 2019-12-03 | Evoqua Water Technologies Llc | Pulsed random two phase gas/liquid flow for cleaning membrane surfaces |
| KR101614520B1 (ko) | 2008-07-24 | 2016-04-21 | 에보쿠아 워터 테크놀로지스 엘엘씨 | 막 여과 모듈용 프레임 시스템 |
| CN102365125B (zh) | 2009-03-26 | 2015-07-08 | Bl科技公司 | 非编织的增强中空纤维膜 |
| AU2010101488B4 (en) | 2009-06-11 | 2013-05-02 | Evoqua Water Technologies Llc | Methods for cleaning a porous polymeric membrane and a kit for cleaning a porous polymeric membrane |
| JP5745510B2 (ja) | 2009-06-26 | 2015-07-08 | ビーエル・テクノロジーズ・インコーポレイテッド | 非編組式織物で強化された中空糸膜 |
| US10173177B2 (en) | 2009-08-03 | 2019-01-08 | Solvay Specialty Polymers Italy S.P.A. | Process for the preparation of ethylene/chlorotrifluoroethylene polymer membranes |
| JP5531667B2 (ja) * | 2010-02-22 | 2014-06-25 | Nok株式会社 | ポリフッ化ビニリデン多孔質膜の製造法 |
| ES2738898T3 (es) | 2010-04-30 | 2020-01-27 | Evoqua Water Tech Llc | Dispositivo de distribución de flujo de fluido |
| JP5636762B2 (ja) * | 2010-06-22 | 2014-12-10 | Nok株式会社 | 繊維強化多孔質膜の製造法 |
| JP5636761B2 (ja) * | 2010-06-22 | 2014-12-10 | Nok株式会社 | 繊維強化ポリフッ化ビニリデン多孔質膜の製造法 |
| AU2011302393B2 (en) | 2010-09-15 | 2016-09-08 | Bl Technologies, Inc. | Method to make a yarn-reinforced hollow fibre membranes around a soluble core |
| US9022224B2 (en) | 2010-09-24 | 2015-05-05 | Evoqua Water Technologies Llc | Fluid control manifold for membrane filtration system |
| US8529814B2 (en) | 2010-12-15 | 2013-09-10 | General Electric Company | Supported hollow fiber membrane |
| WO2012175416A1 (en) | 2011-06-23 | 2012-12-27 | Solvay Specialty Polymers Italy S.P.A. | Process for manufacturing porous membranes |
| SG11201401089PA (en) | 2011-09-30 | 2014-04-28 | Evoqua Water Technologies Llc | Improved manifold arrangement |
| AU2013200808B2 (en) | 2011-09-30 | 2014-11-06 | Evoqua Water Technologies Llc | Isolation valve |
| KR101284405B1 (ko) * | 2011-10-28 | 2013-07-09 | 웅진케미칼 주식회사 | 다공성 금속 중공사 여과재의 제조방법 |
| US9321014B2 (en) | 2011-12-16 | 2016-04-26 | Bl Technologies, Inc. | Hollow fiber membrane with compatible reinforcements |
| US9643129B2 (en) | 2011-12-22 | 2017-05-09 | Bl Technologies, Inc. | Non-braided, textile-reinforced hollow fiber membrane |
| US9022229B2 (en) | 2012-03-09 | 2015-05-05 | General Electric Company | Composite membrane with compatible support filaments |
| US8999454B2 (en) | 2012-03-22 | 2015-04-07 | General Electric Company | Device and process for producing a reinforced hollow fibre membrane |
| KR101414193B1 (ko) * | 2012-04-30 | 2014-07-02 | 도레이케미칼 주식회사 | 폴리에틸렌클로로트리플루오로에틸렌 (ectfe) 중공사막의 제조방법 |
| WO2014004645A1 (en) | 2012-06-28 | 2014-01-03 | Siemens Industry, Inc. | A potting method |
| US9227362B2 (en) | 2012-08-23 | 2016-01-05 | General Electric Company | Braid welding |
| EP2895257A1 (en) | 2012-09-14 | 2015-07-22 | Evoqua Water Technologies LLC | A polymer blend for membranes |
| AU2013324056B2 (en) | 2012-09-26 | 2017-11-16 | Evoqua Water Technologies Llc | Membrane securement device |
| US9962865B2 (en) | 2012-09-26 | 2018-05-08 | Evoqua Water Technologies Llc | Membrane potting methods |
| US9815027B2 (en) | 2012-09-27 | 2017-11-14 | Evoqua Water Technologies Llc | Gas scouring apparatus for immersed membranes |
| WO2015050764A1 (en) | 2013-10-02 | 2015-04-09 | Evoqua Water Technologies Llc | A method and device for repairing a membrane filtration module |
| WO2015051928A1 (en) * | 2013-10-11 | 2015-04-16 | Solvay Specialty Polymers Italy S.P.A. | Process for manufacturing fluoropolymer membranes |
| EP3322511B1 (en) | 2015-07-14 | 2022-09-07 | Rohm & Haas Electronic Materials Singapore Pte. Ltd | Aeration device for filtration system |
| JP6791945B2 (ja) * | 2016-03-09 | 2020-11-25 | 旭化成株式会社 | 多孔性中空糸膜及びその製造方法、並びにろ過方法 |
| JP7219032B2 (ja) * | 2017-09-01 | 2023-02-07 | 旭化成株式会社 | 分離層を含む多孔性中空糸膜の製造方法、多孔性中空糸膜、およびろ過方法 |
| WO2019045069A1 (ja) * | 2017-09-01 | 2019-03-07 | 旭化成株式会社 | 多孔性中空糸膜、多孔性中空糸膜の製造方法、およびろ過方法 |
| JP7185448B2 (ja) * | 2017-09-01 | 2022-12-07 | 旭化成株式会社 | 多孔性中空糸膜及びその製造方法、並びにろ過方法 |
| JP6839766B2 (ja) * | 2017-09-07 | 2021-03-10 | 旭化成株式会社 | 多孔質膜を用いたろ過方法 |
| CN110141981A (zh) * | 2019-05-28 | 2019-08-20 | 迈博瑞生物膜技术(南通)有限公司 | 一种亲水性乙烯-三氟氯乙烯共聚物中空膜的制备方法 |
| CN110141979A (zh) * | 2019-05-28 | 2019-08-20 | 迈博瑞生物膜技术(南通)有限公司 | 一种乙烯-三氟氯乙烯共聚物中空纤维多孔膜的制备方法 |
| CN117531377B (zh) * | 2024-01-09 | 2024-04-26 | 赛普(杭州)过滤科技有限公司 | 一种非对称高通量除病毒纤维素滤膜及其制备方法和应用 |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2732357A (en) * | 1949-11-25 | 1956-01-24 | Suspensions of polymeric chlorotri- | |
| US4247498A (en) * | 1976-08-30 | 1981-01-27 | Akzona Incorporated | Methods for making microporous products |
| JPS61233026A (ja) * | 1985-04-09 | 1986-10-17 | Asahi Chem Ind Co Ltd | 多孔膜の製造方法 |
| GB2168981B (en) * | 1984-12-27 | 1988-07-06 | Asahi Chemical Ind | Porous fluorine resin membrane and process for preparation thereof |
| US4670341A (en) * | 1985-05-17 | 1987-06-02 | W. R. Grace & Co. | Hollow fiber |
| DE3829766A1 (de) * | 1988-09-01 | 1990-03-22 | Akzo Gmbh | Verfahren zur herstellung von membranen |
| JPH04187224A (ja) * | 1990-11-20 | 1992-07-03 | Mitsubishi Rayon Co Ltd | フッ素系多孔質中空糸膜の製法 |
| JPH06142468A (ja) * | 1992-11-11 | 1994-05-24 | Dainippon Ink & Chem Inc | 細孔を有する表面親水性膜の製造方法 |
| RU2108144C1 (ru) * | 1992-11-16 | 1998-04-10 | Алтин Медикал, Инк. | Ацетатцеллюлозная полупроницаемая мембрана в виде полого волокна, способ изготовления половолоконной полупроницаемой ацетатцеллюлозной мембраны, гемодиализатор и прибор для обработки экстракорпоральной крови |
| US6096213A (en) * | 1998-08-14 | 2000-08-01 | 3M Innovative Properties Company | Puncture-resistant polyolefin membranes |
| JP2001087636A (ja) * | 1999-09-21 | 2001-04-03 | Asahi Kasei Corp | ポリエチレン製中空糸状多孔膜の製法 |
| ITMI20010421A1 (it) * | 2001-03-01 | 2002-09-02 | Ausimont Spa | Membrane porose semipermeabili di fluoropolimeri semicristallini |
-
2002
- 2002-02-12 AU AUPS0466A patent/AUPS046602A0/en not_active Abandoned
-
2003
- 2003-02-11 MY MYPI20030454A patent/MY135608A/en unknown
- 2003-02-12 AT AT03739399T patent/ATE505260T1/de not_active IP Right Cessation
- 2003-02-12 NZ NZ535133A patent/NZ535133A/en not_active IP Right Cessation
- 2003-02-12 EP EP03739399A patent/EP1474222B1/en not_active Expired - Lifetime
- 2003-02-12 JP JP2003567552A patent/JP4656839B2/ja not_active Expired - Fee Related
- 2003-02-12 ES ES03739399T patent/ES2364041T3/es not_active Expired - Lifetime
- 2003-02-12 WO PCT/AU2003/000179 patent/WO2003068374A1/en not_active Ceased
- 2003-02-12 CA CA2733826A patent/CA2733826C/en not_active Expired - Fee Related
- 2003-02-12 DE DE60336707T patent/DE60336707D1/de not_active Expired - Lifetime
- 2003-02-12 CN CNB03805101XA patent/CN100500272C/zh not_active Expired - Fee Related
- 2003-02-12 KR KR1020047012363A patent/KR100991596B1/ko not_active Expired - Fee Related
- 2003-02-12 CA CA2474625A patent/CA2474625C/en not_active Expired - Fee Related
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