JP2001139603A5 - - Google Patents
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- Publication number
- JP2001139603A5 JP2001139603A5 JP1999322369A JP32236999A JP2001139603A5 JP 2001139603 A5 JP2001139603 A5 JP 2001139603A5 JP 1999322369 A JP1999322369 A JP 1999322369A JP 32236999 A JP32236999 A JP 32236999A JP 2001139603 A5 JP2001139603 A5 JP 2001139603A5
- Authority
- JP
- Japan
- Prior art keywords
- group
- butadiene
- conjugated diene
- component
- compound
- 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 150000001993 dienes Chemical class 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 229920001971 elastomer Polymers 0.000 description 9
- 229910001507 metal halide Inorganic materials 0.000 description 9
- 150000005309 metal halides Chemical class 0.000 description 9
- 239000005060 rubber Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 8
- 229910052779 Neodymium Inorganic materials 0.000 description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- -1 vinyl compound Chemical class 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- XPUJOEOXHUYRPJ-UHFFFAOYSA-N 2,4-ditert-butyl-4-methylcyclohexa-1,5-dien-1-ol Chemical compound CC(C)(C)C1=C(O)C=CC(C)(C(C)(C)C)C1 XPUJOEOXHUYRPJ-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 150000007527 lewis bases Chemical class 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000002909 rare earth metal compounds Chemical class 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZZDXWFSIHDBOLS-UHFFFAOYSA-K cerium(3+);octanoate Chemical compound [Ce+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O ZZDXWFSIHDBOLS-UHFFFAOYSA-K 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000012721 stereospecific polymerization Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32236999A JP4332690B2 (ja) | 1999-11-12 | 1999-11-12 | ゴム組成物 |
| EP00309937A EP1099710B1 (en) | 1999-11-12 | 2000-11-09 | Modified conjugated diene polymer and rubber composition comprising it |
| DE60017528T DE60017528T2 (de) | 1999-11-12 | 2000-11-09 | Modifiziertes Polymer eines konjugierten Diens und dieses enthaltende Kautschukzusammensetzung |
| ES00309937T ES2234532T3 (es) | 1999-11-12 | 2000-11-09 | Polimero dienico conjugado modificado y composicion de caucho que lo comprende. |
| US10/253,933 US6747085B2 (en) | 1999-11-12 | 2002-09-25 | Conjugated diene polymer and rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32236999A JP4332690B2 (ja) | 1999-11-12 | 1999-11-12 | ゴム組成物 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2001139603A JP2001139603A (ja) | 2001-05-22 |
| JP2001139603A5 true JP2001139603A5 (https=) | 2006-04-13 |
| JP4332690B2 JP4332690B2 (ja) | 2009-09-16 |
Family
ID=18142886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32236999A Expired - Fee Related JP4332690B2 (ja) | 1999-11-12 | 1999-11-12 | ゴム組成物 |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6747085B2 (https=) |
| EP (1) | EP1099710B1 (https=) |
| JP (1) | JP4332690B2 (https=) |
| DE (1) | DE60017528T2 (https=) |
| ES (1) | ES2234532T3 (https=) |
Families Citing this family (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002284932A (ja) * | 2001-03-26 | 2002-10-03 | Asahi Kasei Corp | 防振ゴム組成物 |
| CA2351957A1 (en) * | 2001-06-29 | 2002-12-29 | Akhtar Osman | Process for the preparation of diene polymers |
| JP4963535B2 (ja) * | 2001-09-28 | 2012-06-27 | 株式会社ブリヂストン | ベルトコンベアのベルト用ゴム組成物、ベルト及びベルトコンベア |
| DE60313721T2 (de) | 2002-12-04 | 2008-01-17 | Sumitomo Rubber Industries Ltd., Kobe | Kautschukzusammensetzung für Reifenlaufflächen, sowie damit hergestellte Luftreifen |
| KR100746054B1 (ko) * | 2003-10-29 | 2007-08-03 | 아사히 가세이 케미칼즈 가부시키가이샤 | 신발용 고무 조성물 |
| US7351776B2 (en) * | 2004-03-02 | 2008-04-01 | Bridgestone Corporation | Bulk polymerization process |
| ES2334510T3 (es) * | 2004-04-27 | 2010-03-11 | Bridgestone Corporation | Procedimiento de fabricacion de una composicion de neumatico con refuerzo de silice mejorado. |
| ITMI20042022A1 (it) * | 2004-10-25 | 2005-01-25 | Polimeri Europa Spa | Processo per la preparazione di polibutadiene a basso grado di ramificazione |
| JP2006188571A (ja) * | 2005-01-04 | 2006-07-20 | Sumitomo Rubber Ind Ltd | ゴム組成物およびそれからなるタイヤ |
| JP4827424B2 (ja) * | 2005-03-17 | 2011-11-30 | 株式会社ブリヂストン | ゴム組成物及びこれを用いた空気入りタイヤ |
| JP4827423B2 (ja) * | 2005-03-17 | 2011-11-30 | 株式会社ブリヂストン | ゴム組成物及びこれを用いた空気入りタイヤ |
| FR2886937B1 (fr) * | 2005-06-14 | 2007-08-10 | Michelin Soc Tech | Procede de preparation d'un elastomere dienique, tel qu'un polybutadiene |
| JP5214886B2 (ja) * | 2007-01-12 | 2013-06-19 | 東洋ゴム工業株式会社 | 空気入りタイヤ |
| WO2009132514A1 (zh) | 2008-04-29 | 2009-11-05 | 中国科学院长春应用化学研究所 | 异戊二烯或丁二烯顺1,4-聚合双组分催化体系及聚合方法 |
| JP2010163590A (ja) | 2008-12-19 | 2010-07-29 | Ube Ind Ltd | 共役ジエン重合体の製造方法、ポリブタジエンおよびそれを用いたゴム組成物 |
| JP4538533B1 (ja) * | 2009-04-03 | 2010-09-08 | 住友ゴム工業株式会社 | タイヤコード被覆用ゴム組成物及び空気入りタイヤ |
| CN102365306B (zh) * | 2009-04-07 | 2014-04-02 | 住友橡胶工业株式会社 | 含极性基的共聚物、橡胶组合物以及无防滑钉轮胎 |
| JP2011068911A (ja) * | 2010-12-22 | 2011-04-07 | Sumitomo Rubber Ind Ltd | ゴム組成物およびそれからなるタイヤ |
| ITMI20111198A1 (it) * | 2011-06-29 | 2012-12-30 | Polimeri Europa Spa | "procedimento per la preparazione di copolimeri di 1,3-butadiene e stirene e loro impiego in composizioni elastomeriche vulcanizzabili" |
| RU2559057C1 (ru) * | 2011-08-22 | 2015-08-10 | Бриджстоун Корпорейшн | Способ получения полимера |
| JP5972433B1 (ja) * | 2015-07-21 | 2016-08-17 | 古河電気工業株式会社 | 電子デバイス封止用硬化性吸湿性樹脂組成物、樹脂硬化物および電子デバイス |
| JP5996053B1 (ja) * | 2015-07-21 | 2016-09-21 | 古河電気工業株式会社 | 電子デバイス封止用硬化性吸湿性樹脂組成物、樹脂硬化物、電子デバイス、樹脂硬化物の製造方法および電子デバイスの製造方法 |
| EP3781625A4 (en) | 2018-05-04 | 2022-01-05 | Bridgestone Americas Tire Operations, LLC | RUBBER COMPOSITION FOR TIRE TREAD |
| JP2021523261A (ja) | 2018-05-04 | 2021-09-02 | ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー | タイヤトレッドゴム組成物 |
| JP2021523959A (ja) | 2018-05-04 | 2021-09-09 | ブリヂストン アメリカズ タイヤ オペレーションズ、 エルエルシー | タイヤトレッドゴム組成物 |
| EP3788101A4 (en) | 2018-05-04 | 2022-01-12 | Bridgestone Americas Tire Operations, LLC | RUBBER COMPOSITION FOR TIRE TREAD |
| EP3976709A1 (en) | 2019-05-29 | 2022-04-06 | Bridgestone Americas Tire Operations, LLC | Tire tread rubber composition and related methods |
| US12325797B2 (en) | 2019-05-29 | 2025-06-10 | Bridgestone Americas Tire Operations, Llc | Tire tread rubber composition and related methods |
| WO2020243311A1 (en) | 2019-05-29 | 2020-12-03 | Bridgestone Americas Tire Operations, Llc | Tire tread rubber composition and related methods |
| US11584808B2 (en) | 2019-12-30 | 2023-02-21 | Bridgestone Corporation | Polymerization catalyst composition and method of employing same |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS621404A (ja) | 1985-06-27 | 1987-01-07 | Mitsubishi Rayon Co Ltd | 多層複合中空繊維状膜及びその製造法 |
| JPS6364444A (ja) | 1986-09-04 | 1988-03-22 | Nec Corp | デ−タ伝送方式 |
| US5064910A (en) | 1986-09-05 | 1991-11-12 | Japan Synthetic Rubber Co., Ltd. | Preparation of conjugated diene polymers modified with an organo-tin or germanium halide |
| JPS6416244A (en) | 1987-07-08 | 1989-01-19 | Tamagawa Seiki Co Ltd | Step motor |
| JPH042601A (ja) | 1990-04-18 | 1992-01-07 | Matsushita Electric Ind Co Ltd | 水素吸蔵合金の選別方法 |
| JPH06211916A (ja) | 1993-01-18 | 1994-08-02 | Asahi Chem Ind Co Ltd | 複合触媒および重合方法 |
| JPH06306113A (ja) | 1993-04-21 | 1994-11-01 | Asahi Chem Ind Co Ltd | 共役ジエン類の重合方法 |
| CA2118778A1 (en) | 1993-09-20 | 1995-03-21 | Jean-Claude Joseph Marie Kihn | Tire with silica reinforced tread |
| FR2710651B1 (fr) | 1993-10-01 | 1995-10-27 | Commissariat Energie Atomique | Composition de polymères équivalente au tissu biologique, utilisation de cette composition dans la fabrication d'un compteur proportionnel équivalent au tissu biologique et compteur ainsi fabriqué. |
| JPH0873515A (ja) | 1994-07-08 | 1996-03-19 | Ube Ind Ltd | 共役ジオレフィンの重合法 |
| JP3763490B2 (ja) | 1996-07-19 | 2006-04-05 | 株式会社サトー | 台紙なしラベルの粘着活性装置 |
| DE69815172T2 (de) * | 1997-03-05 | 2004-07-01 | Jsr Corp. | Verfahren zur Herstellung von konjugierten Dien-Polymeren |
| JP4489194B2 (ja) * | 1997-03-05 | 2010-06-23 | Jsr株式会社 | 共役ジエン系重合体の製造方法 |
| US6255416B1 (en) | 1998-05-13 | 2001-07-03 | Jsr Corporation | Method of producing conjugated diene polymers |
| KR100344230B1 (ko) | 1999-10-13 | 2002-07-24 | 금호석유화학 주식회사 | 산소분자를 이용한 하이드록시 고 1,4-시스 폴리부타디엔의 제조방법 |
-
1999
- 1999-11-12 JP JP32236999A patent/JP4332690B2/ja not_active Expired - Fee Related
-
2000
- 2000-11-09 DE DE60017528T patent/DE60017528T2/de not_active Expired - Lifetime
- 2000-11-09 EP EP00309937A patent/EP1099710B1/en not_active Expired - Lifetime
- 2000-11-09 ES ES00309937T patent/ES2234532T3/es not_active Expired - Lifetime
-
2002
- 2002-09-25 US US10/253,933 patent/US6747085B2/en not_active Expired - Lifetime
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