KR940018180A - 엘라스토머 조성물의 가공 방법 - Google Patents
엘라스토머 조성물의 가공 방법 Download PDFInfo
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- KR940018180A KR940018180A KR1019940001256A KR19940001256A KR940018180A KR 940018180 A KR940018180 A KR 940018180A KR 1019940001256 A KR1019940001256 A KR 1019940001256A KR 19940001256 A KR19940001256 A KR 19940001256A KR 940018180 A KR940018180 A KR 940018180A
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- mixing
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- elastomeric material
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000000203 mixture Substances 0.000 title claims abstract 22
- 229920001971 elastomer Polymers 0.000 title claims 4
- 239000000806 elastomer Substances 0.000 title claims 4
- 239000012744 reinforcing agent Substances 0.000 claims abstract 14
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract 8
- 239000000463 material Substances 0.000 claims abstract 6
- 239000013536 elastomeric material Substances 0.000 claims 14
- 230000002787 reinforcement Effects 0.000 claims 5
- 238000001816 cooling Methods 0.000 claims 3
- 229920000642 polymer Polymers 0.000 claims 3
- 238000010008 shearing Methods 0.000 claims 2
- 239000004614 Process Aid Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 238000010586 diagram Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/285—Feeding the extrusion material to the extruder
- B29C48/297—Feeding the extrusion material to the extruder at several locations, e.g. using several hoppers or using a separate additive feeding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2791/00—Shaping characteristics in general
- B29C2791/001—Shaping in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/15—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/41—Intermeshing counter-rotating screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/425—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders using three or more screws
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2021/00—Use of unspecified rubbers as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
본 발명은 중합체 재료, 보강제, 가공조제 및 가황제의 혼합물을 형성시키므로써 엘라스토머 조성물을 제조하는 방법에 관한 것이다. 본 발명의 방법은 연속적이며, 가해진 총 에너지가 제1작동 온도 범위를 유발시키는 공간으로 한정된 제1혼합 영역에 따라 중합체 재료를 혼합하는 반복되는 연속적인 단계들을 포함한다. 제1영역의 혼합물은 연속적으로 제2혼합 영역에 통과시키고 동시에 보강제 및 가공조제를 첨가하여 함께 혼합하는데, 이때 제2혼합 영역은 가해진 총 에너지가 제2작동 온도 범위를 유발시키는 공간으로 한정된다. 이어서 제2영역의 혼합물은 연속적으로 제3혼합 영역에 통과시키고 동시에 가황제를 첨가하여 함께 혼합하는데, 이때 제2혼합 영역은 가해진 총 에너지가 제3작동 온도 범위를 유발시키는 공간으로 한정된다. 상기 제3영역의 혼합물은 연속적으로 전달 영역을 통과하여 엘라스토머 조성물의 형태로 압출시킨다. 이때, 상기 제2 및 제3작동 온도 범위는 제1작동 온도 범위보다 낮다.
Description
본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음
제1도는 본 발명의 방법의 연속적인 단계식 처리를 도시한 공정도이다. 제2도는 본 발명의 방법에 사용하기에 적합한 전형적인 2축 압출기(twin-screw extruder)의 횡단면도이다.
Claims (12)
- 엘라스토머 재료, 보강제, 가공조제 및 가황제를 혼합시키므로써 엘라스토머 조성물을 제조하는 방법에 있어서, 엘라스토머 재료를 전단하고, 제1작동 온도 범위의 온도까지 가열함과 동시에, 최소한 일부의 보강제의 혼합을 촉진시키기에 충분하게 엘라스토머 재료의 점성도를 감소시키는 단계; 상기 가열된 엘라스토머 재료의 온도보다 더 낮은 온도를 가진 보강제의 최소한 일부를 첨가하는 단계; 및 상기 저온의 보강제를 상기 가열되고 점성도가 저하된 엘라스토머 재료와 혼합합과 동시에 (1)저온 보강제에 이해 엘라스토머 재료를 냉각시키고 (2)상기 가열된 엘라스토머 재료의 온도보다 낮은 제1작동 온도 범위의 온도를 가진, 엘라스토머 재료와 보강제의 혼합물을 형성시키는 단계를 연속적으로 포함하는 것을 특징으로 하는 방법.
- 제1항에 있어서, 상기 혼합 단계 이후에, 상기 가열된 엘라스토머 재료의 온도보다 낮은 온도를 가진 가공조제의 최소한 일부를 별도로 첨가해서 혼합하여 상기 고온의 엘라스토머 재료의 냉각을 도모하고, 상기 엘라스토머 재료의 가열된 온도보다 낮은 제2작동 온도 범위의 온도를 가진, 엘라스토머 재료, 보강제 및 가공조제의 혼합물을 형성시키는 단계를 추가로 포함하는 방법.
- 제2항에 있어서, 가황제를 별도로 첨가해서 함께 혼합시켜 제3작동 온도 범위의 온도를 가진, 엘라스토머 재료, 보강제, 가공조제 및 가황제의 혼합물을 형성시키는 연속되는 단계를 추가로 포함하는 방법.
- 제2항에 있어서, 상기 엘라스토머 재료, 보강제 및 가공조제의 혼합물의 온도보다 낮은 온도를 가진 보강제의 제2분량을 별도로 첨가해서 혼합하며, 상기 가열된 엘라스토머 재료의 온도보다 낮은 온도를 가진 가공조제의 제2분량을 별도로 첨가해서 혼합하는 연속되는 단계들을 추가로 포함하는 방법.
- 제4항에 있어서, 혼합물을 엘라스토머 복합체로서 방출시키는 연속되는 단계를 추가로 포함하는 방법.
- 제3항에 있어서, 상기 제1작동 온도 범위가 약130-220℃이고, 상기 제2작동 온도 범위는 약110-160℃이며, 상기 제3작동 온도 범위는 약115-150℃인 것을 특징으로 하는 방법.
- 제3항에 있어서, 제1항의 가공 단계들에 가해진 총 에너지가 약 5.4×105내지 1.1×106J/kg이며, 제2항의 가공 단계들에 가해진 총 에너지가 약 4.3×104내지 7.2×104J/kg이며, 제3항의 가공 단계들에 가해진 총 에너지가 약 3.6×104내지 1.1× 105J/kg인 것을 특징으로 하는 방법.
- 제1항에 있어서, 전단을 제한하고 상기 중합체 재료의 탈중합화를 방지하는 것을 포함함을 특징으로 하는 방법.
- 제3항에 있어서, 상기 혼합물의 부피%가 제1항의 가공 단계, 제2항의 가공 단계 및 제3항의 가공 단계 전체에 걸쳐 거의 동일하게 유지되는 것을 특징으로 하는 방법.
- 제3항에 있어서, 상기 전단 단계에 앞서, 30 중량%이하의 보강제를 엘라스토머와 혼합하는 단계를 포함하고, 상기 제1작동 온도 범위를 약 130-220℃로 유지시키고, 상기 제2작동 온도 범위를 약 110-160℃로 유지시키며, 상기 제3작동 온도 범위를 약 115-150℃로 유지시키는 것을 특징으로 하는 방법.
- 제3항에 있어서, 상기 전단 단계에 앞서, 엘라스토머에 제1중합체 및 제2엘라스토머로 이루어진 군중에서 선택된 중합체를 첨가하는 단계를 포함하는 것을 특징으로 하는 방법.
- 세장형의 2축 압출기를 사용하여 엘라스토머 조성물을 제조하는 방법으로서, 중합체 재료, 보강제, 가공조제 및 가황제를 포함하는 조성물의 성분들을 연속되는 단계식-첨가 방식으로 5개 이상의 연속적으로 연결된 혼합 영역을 가진 상기 압출기의 길이를 따라 혼합하는 것을 포함하되, 상기 압출기의 제1혼합 영역에 따라 상기 중합체 재료를 첨가해서 혼합함과 동시에 전단 및 가열하고, 보강제의 최소한 일부를 혼합하는 것을 촉진시키기에 충분하게 상기 압출기의 제1혼합 영역을 따라 중합체 재료의 점성도를 감소시키는 단계; 상기 압출기의 제2혼합 영역을 따라 상기 가열된 중합체에 최소한 일부의 보강제와 가공조제를 별도로 연속해서 첨가함과 동시에 상기 보강제 및 가공조제에 의해 엘라스토머 재료를 냉각시키는 단계; 상기 압출기의 제3혼합 영역을 따라 상기 부분적인 성분 혼합물에 제2분량의 냉각용 보강제와 가공조제를 별도로 연속해서 첨가함과 동시에 상기 보강제 및 가공조제에 의해 상기 성분 혼합물을 냉각시키는 단계; 상기 압출기의 제4혼합 영역에 따라 상기 부분적인 성분 혼합물에 가황제를 첨가해서 혼합하는 단계; 및 상기 압출기의 제5영역을 통해 상기 혼합물을 이동시켜서 상기 혼합물을 상기 엘라스토머 조성물의 형태로 압출시키는 단계를 포함하는 방법.※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US08/010,126 | 1993-01-29 | ||
US08/010,126 US5374387A (en) | 1993-01-29 | 1993-01-29 | Process for processing elastomeric compositions |
Publications (2)
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KR940018180A true KR940018180A (ko) | 1994-08-16 |
KR0121859B1 KR0121859B1 (ko) | 1997-11-13 |
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KR1019940001256A KR0121859B1 (ko) | 1993-01-29 | 1994-01-25 | 엘라스토머 조성물의 가공방법 |
Country Status (9)
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US (2) | US5374387A (ko) |
EP (1) | EP0611078B1 (ko) |
JP (1) | JP2686592B2 (ko) |
KR (1) | KR0121859B1 (ko) |
AT (1) | ATE169553T1 (ko) |
BR (1) | BR9400340A (ko) |
CA (1) | CA2114364A1 (ko) |
DE (1) | DE69412299T2 (ko) |
ES (1) | ES2120567T3 (ko) |
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-
1993
- 1993-01-29 US US08/010,126 patent/US5374387A/en not_active Expired - Lifetime
-
1994
- 1994-01-25 KR KR1019940001256A patent/KR0121859B1/ko not_active IP Right Cessation
- 1994-01-26 BR BR9400340A patent/BR9400340A/pt not_active IP Right Cessation
- 1994-01-27 CA CA002114364A patent/CA2114364A1/en not_active Abandoned
- 1994-01-27 JP JP6024713A patent/JP2686592B2/ja not_active Expired - Fee Related
- 1994-01-31 AT AT94300693T patent/ATE169553T1/de not_active IP Right Cessation
- 1994-01-31 EP EP94300693A patent/EP0611078B1/en not_active Expired - Lifetime
- 1994-01-31 DE DE69412299T patent/DE69412299T2/de not_active Expired - Fee Related
- 1994-01-31 ES ES94300693T patent/ES2120567T3/es not_active Expired - Lifetime
- 1994-11-15 US US08/339,969 patent/US5597235A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0611078B1 (en) | 1998-08-12 |
JPH06240153A (ja) | 1994-08-30 |
DE69412299T2 (de) | 1999-01-07 |
EP0611078A1 (en) | 1994-08-17 |
ES2120567T3 (es) | 1998-11-01 |
DE69412299D1 (de) | 1998-09-17 |
US5374387A (en) | 1994-12-20 |
US5597235A (en) | 1997-01-28 |
BR9400340A (pt) | 1994-08-02 |
CA2114364A1 (en) | 1994-07-30 |
JP2686592B2 (ja) | 1997-12-08 |
KR0121859B1 (ko) | 1997-11-13 |
ATE169553T1 (de) | 1998-08-15 |
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