KR960022607A - 시클로올레핀 랜덤공중합체 제조방법 - Google Patents
시클로올레핀 랜덤공중합체 제조방법 Download PDFInfo
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- KR960022607A KR960022607A KR1019950061486A KR19950061486A KR960022607A KR 960022607 A KR960022607 A KR 960022607A KR 1019950061486 A KR1019950061486 A KR 1019950061486A KR 19950061486 A KR19950061486 A KR 19950061486A KR 960022607 A KR960022607 A KR 960022607A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract 8
- 150000001925 cycloalkenes Chemical class 0.000 title claims abstract 5
- 229920005604 random copolymer Polymers 0.000 title 1
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 24
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract 10
- 239000002904 solvent Substances 0.000 claims abstract 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract 8
- 229920001577 copolymer Polymers 0.000 claims abstract 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract 8
- 238000000034 method Methods 0.000 claims abstract 2
- 239000012046 mixed solvent Substances 0.000 claims abstract 2
- 239000004711 α-olefin Substances 0.000 claims abstract 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 6
- 229910052799 carbon Inorganic materials 0.000 claims 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims 4
- 239000003054 catalyst Substances 0.000 claims 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims 4
- 125000003545 alkoxy group Chemical group 0.000 claims 3
- 125000003118 aryl group Chemical group 0.000 claims 3
- 125000002950 monocyclic group Chemical group 0.000 claims 3
- 125000003367 polycyclic group Chemical group 0.000 claims 3
- 125000003342 alkenyl group Chemical group 0.000 claims 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 2
- 150000003623 transition metal compounds Chemical class 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 125000005741 alkyl alkenyl group Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 125000001118 alkylidene group Chemical group 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 125000005018 aryl alkenyl group Chemical group 0.000 claims 1
- 125000004104 aryloxy group Chemical group 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 229960003839 dienestrol Drugs 0.000 claims 1
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 1
- 125000004407 fluoroaryl group Chemical group 0.000 claims 1
- 229910052732 germanium Inorganic materials 0.000 claims 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 claims 1
- 229910052758 niobium Inorganic materials 0.000 claims 1
- 239000010955 niobium Substances 0.000 claims 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims 1
- -1 oxy compound Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910052715 tantalum Inorganic materials 0.000 claims 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims 1
- 229910052718 tin Inorganic materials 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
- 239000012968 metallocene catalyst Substances 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 abstract 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims (6)
- (1) (i) 수소수 2 이상의 α-올레핀과 (ii) 하기식(I) 및 (II)(식 (I)중에서 n은 0 또는 1이고, m은 0 또는 정의 정수이고, q는 0 또는 1이고, R1~R18및, Ra와 Rb는 각각 독립적으로 수소원자, 할로겐원자 또는 탄화수소기이고, R15~R12중 임의의 2개가 공동으로 각각 결합되어 있는 탄소원자를 포함하여 단환 또는 다환을 형성해도 좋고, 또 상기 단환 또는 다환이 2중결합을 갖고 있어도 좋고, 또 R15와 R16또는 R17과 R18이 알킬리덴기를 형성하고 있어도 좋다.)(식 (III)중에서 P 및 q는 0 또는 1이상의 정수이고, m과 n은 0, 1 또는 2이고, R1~R19는 각각 독립적으로 수소원자, 할로겐원자, 지방족탄화수소기 지환족탄화수소기, 방향족탄화수소 또는 알콕시기이고, R9및 R10이 결합되어 있는 탄소원자와, R13이 결합되어 있는 탄소원자 또는 R11이 결합되어 있는 탄소원자는 직접 또는 탄소원자수 1~3의 알킬렌기를 거쳐서 결합되어 있어도 좋고, 또 n=m=0인 경우 R15와 R12또는 R15와 R19는 공동으로 각각이 결합되어 있는 탄소원자를 포함하고 단환 또는 다환의 방향족환을 형성해도 좋다.)으로 표시되는 단량체로된 군에서 선택한 적어도 한 종의 시클로올레핀을 (2) (i) 하기식(III)(식 (III)중에서 M1은 티탄, 지르코늄, 하프늄, 바나듐, 니오븀 또는 탄탈륨이고, R1과 R2는 독림적으로 수소원자, 할로겐원자, 탄소원자수 1~10의 알킬, 탄소원자수 1~10의 알콕시기, 탄소원자수 6~10의 아릴기, 탄소원자수 6~10의 아릴옥시기, 탄소원자수 2~10의 알케닐기, 탄소원자수 7~40의 아릴알킬기, 탄소원자수 7~40의 알킬아릴기 또는 탄소원자수 8~40의 아릴알케닐기이고, R3및 R4는 독립적으로 중심금속 M1과 함께 샌드위치구조를 형성할 수 있는 시클6로 펜타디에닐 골격을 갖는 단핵 또는 다핵 탄화수소기이고, R5는 하기 2가 기중하나이다.) (상기 식에서 R6, R7및 R8은 각각 독립적으로 수소원자, 할로겐원자, 탄소원자수 1~10의 알킬기, 탄소원자수 1~10의 플루오로 알킬기, 탄소원자수 6∼10의 플루오로아릴기, 탄소원자수 6~10의 아릴기, 탄소원자수 10~10의 알콕시기, 탄소원자수 2∼10의 알케닐기, 탄소원자수 7~40의 아릴알킬기, 탄소원자수 7~40 알킬아릴기 또는 탄소원자수 8~40의 알킬알케닐기이고, R6와 R7또는 R6와 R8은 각각 공동으로 이들이 결합된 원자를 포함하여 환을 형성해도 좋고, M7는 규소, 게르마늄 또는 주석이다.)으로 표시되는 촉매성분(a)의 천이금속 화합물과, (ii) 유기알루미늄 옥시화합물 및 상기 천이금속 화합물과 반응하여 이온성 착체를 형성할 수 있는 화합물로부터 선택한 적어도 한 종류 촉매성분(b)으로부터 형성되는 촉매의 존재하에 (3) 용해도 파라미터 (δ값)가 7.7〔cal/cm3)1/2〕 이상인 탄화수소 용매(i)와, 용해도 파라미터(δ값)가 7.5〔cal/cm3)1/2〕 이하인 탄화수소용매(ii)로되고, 비율은 체적비((i)/(ii))가 99/1~50/50인 혼합 용매중에서 공중합하는 것을 특징으로 하는 시클로올레핀 공중합체 제조방법.
- 제1항에 있어서, 촉매의 형성을 위해서 촉매성분(c)으로서 유기알루미늄화합물을 더 사용하는 것이 특징인 시클로올레핀 공중합체 제조방법.
- 제1항에 있어서, 탄화수소용매 (i)와 탄화수소용매 (ii)의 체적비〔(i)/(ii)〕를 90/10~50/50으로 사용하는 것이 특징인 시클로올레핀 공중합체 제조방법.
- 제1항에 있어서, 탄화수소 용매(i)와 탄화수소 용매(ii)의 조합이 시클로헥산/헥산, 시클로헥산/헵탄, 시클로헥산/옥탄, 시클로헥산/데칸, 메틸시클로헥산/헥산, 메틸시클로헥산/헵탄, 메틸시클로헥산/옥탄 및 메틸시클로헥산/데칸중 어느 하나인 것이 특징이 시클로올레핀 공중합체 제조방법.
- 제1항에 있어서, 시클로올레핀과 공중합하는 α-올레핀이 에틸렌인 것이 특징인 시클로올레핀 공중합체 제조방법.
- 제5항에 있어서, 시클로올레핀이 노르보르넨인 것이 특징인 시클로올레핀 공중합체 제조방법.※ 참고사항:최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP94-328548 | 1994-12-28 | ||
JP32854894A JP3517471B2 (ja) | 1994-12-28 | 1994-12-28 | 環状オレフィン共重合体の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
KR960022607A true KR960022607A (ko) | 1996-07-18 |
KR100385199B1 KR100385199B1 (ko) | 2003-08-27 |
Family
ID=18211515
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019950061486A KR100385199B1 (ko) | 1994-12-28 | 1995-12-28 | 시클로올레핀랜덤공중합체제조방법 |
Country Status (8)
Country | Link |
---|---|
US (1) | US5650471A (ko) |
EP (1) | EP0719803B1 (ko) |
JP (1) | JP3517471B2 (ko) |
KR (1) | KR100385199B1 (ko) |
CN (1) | CN1102935C (ko) |
CA (1) | CA2166159A1 (ko) |
DE (1) | DE69520418T2 (ko) |
TW (1) | TW326452B (ko) |
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IT1275856B1 (it) * | 1995-03-03 | 1997-10-24 | Spherilene Srl | Composti metallocenici bis-fluorenilici, procedimento per la loro preparazione e loro utilizzo in catalizzatori per la polimerizzazione |
FI105196B (fi) * | 1995-05-08 | 2000-06-30 | Optatech Oy | Amorfiset olefiini-ko/terpolymeerit |
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KR20000048045A (ko) * | 1998-12-11 | 2000-07-25 | 고오사이 아끼오 | 공중합체, 이의 제조 방법 및 이의 성형품 |
EP1085025A1 (en) * | 1999-02-04 | 2001-03-21 | Idemitsu Petrochemical Co., Ltd. | Catalyst for olefin polymerization, process for producing the same, and process for producing olefin polymer |
US6288181B1 (en) * | 1999-03-30 | 2001-09-11 | Eastman Chemical Company | Process for producing polyolefins |
US6417301B1 (en) | 1999-06-07 | 2002-07-09 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
US6417299B1 (en) | 1999-06-07 | 2002-07-09 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
US6417298B1 (en) * | 1999-06-07 | 2002-07-09 | Eastman Chemical Company | Process for producing ethylene/olefin interpolymers |
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KR100626476B1 (ko) * | 1999-08-31 | 2006-09-20 | 이스트만 케미칼 컴파니 | 폴리올레핀의 제조방법 |
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US6613187B1 (en) | 1999-09-09 | 2003-09-02 | Baxter International Inc | Solvent bonding method for polyolefin materials |
US6590033B2 (en) | 1999-09-09 | 2003-07-08 | Baxter International Inc. | Cycloolefin blends and method for solvent bonding polyolefins |
US6497676B1 (en) | 2000-02-10 | 2002-12-24 | Baxter International | Method and apparatus for monitoring and controlling peritoneal dialysis therapy |
US6875719B2 (en) * | 2000-04-27 | 2005-04-05 | Industrial Technology Research Institute | Catalyst composition for preparing olefin polymers |
US6372848B1 (en) | 2000-10-10 | 2002-04-16 | Baxter International Inc. | Blend of ethylene and α-olefin copolymers obtained using a metallocene catalyst for fabricating medical films and tubings |
US20030125662A1 (en) | 2002-01-03 | 2003-07-03 | Tuan Bui | Method and apparatus for providing medical treatment therapy based on calculated demand |
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JP5588626B2 (ja) | 2008-08-04 | 2014-09-10 | 富士フイルム株式会社 | 光学フィルム、偏光板、光学補償フィルム、反射防止フィルムおよび液晶表示装置 |
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JPH0713084B2 (ja) * | 1985-03-26 | 1995-02-15 | 三井石油化学工業株式会社 | 環状オレフイン系共重合体の製法 |
US5003019A (en) * | 1987-03-02 | 1991-03-26 | Mitsui Petrochemical Industries, Ltd. | Cyclo-olefinic random copolymer, olefinic random copolymer, and process for producing cyclo-olefinic random copolymers |
DE3922546A1 (de) * | 1989-07-08 | 1991-01-17 | Hoechst Ag | Verfahren zur herstellung von cycloolefinpolymeren |
JP2781252B2 (ja) * | 1990-03-08 | 1998-07-30 | 三井化学株式会社 | 環状オレフィン系ランダム共重合体の製造方法 |
CA2070654C (en) * | 1990-10-05 | 2003-06-03 | Takuji Okamoto | Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers |
ATE223440T1 (de) * | 1991-03-09 | 2002-09-15 | Basell Polyolefine Gmbh | Metallocen und katalysator |
EP0597119B1 (en) * | 1992-05-26 | 2000-12-13 | Mitsui Chemicals, Inc. | Cycloolefin copolymer composition and production thereof |
DE59402624D1 (de) * | 1993-02-12 | 1997-06-12 | Hoechst Ag | Verfahren zur Herstellung von Cycloolefincopolymeren |
TW369545B (en) * | 1993-02-12 | 1999-09-11 | Hoechst Ag | Process for preparing cycloolefin copolymers |
TW312696B (ko) * | 1994-04-22 | 1997-08-11 | Mitsui Petroleum Chemicals Ind |
-
1994
- 1994-12-28 JP JP32854894A patent/JP3517471B2/ja not_active Expired - Fee Related
-
1995
- 1995-12-27 US US08/579,011 patent/US5650471A/en not_active Expired - Fee Related
- 1995-12-27 CA CA002166159A patent/CA2166159A1/en not_active Abandoned
- 1995-12-28 KR KR1019950061486A patent/KR100385199B1/ko not_active IP Right Cessation
- 1995-12-28 TW TW084114067A patent/TW326452B/zh not_active IP Right Cessation
- 1995-12-28 CN CN95119491A patent/CN1102935C/zh not_active Expired - Fee Related
- 1995-12-28 EP EP95120663A patent/EP0719803B1/en not_active Expired - Lifetime
- 1995-12-28 DE DE69520418T patent/DE69520418T2/de not_active Expired - Lifetime
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US5650471A (en) | 1997-07-22 |
CN1102935C (zh) | 2003-03-12 |
EP0719803A2 (en) | 1996-07-03 |
TW326452B (en) | 1998-02-11 |
JPH08183812A (ja) | 1996-07-16 |
CA2166159A1 (en) | 1996-06-29 |
KR100385199B1 (ko) | 2003-08-27 |
DE69520418T2 (de) | 2001-08-23 |
EP0719803A3 (en) | 1997-02-19 |
DE69520418D1 (de) | 2001-04-26 |
CN1131162A (zh) | 1996-09-18 |
JP3517471B2 (ja) | 2004-04-12 |
EP0719803B1 (en) | 2001-03-21 |
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