WO1995021881A1 - A process for preparing copolyesters - Google Patents
A process for preparing copolyesters Download PDFInfo
- Publication number
- WO1995021881A1 WO1995021881A1 PCT/US1995/000940 US9500940W WO9521881A1 WO 1995021881 A1 WO1995021881 A1 WO 1995021881A1 US 9500940 W US9500940 W US 9500940W WO 9521881 A1 WO9521881 A1 WO 9521881A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- diol
- terephthalate
- copolyester
- containing compound
- temperature
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/84—Boron, aluminium, gallium, indium, thallium, rare-earth metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Definitions
- the present invention relates to a process for preparing copolyesters which involves two steps.
- the first step is a diol interchange step
- the second step is a polycondensation step. More specifically, the process involves (I) reacting in the presence of a polycondensation catalyst a dihydroxy terephthalate- containing compound having the formula:
- n is 1 to 10 and at least 99% of the endgroups are ethylene glycol moieties; and 0.01 to 10 moles, based on moles of the dihydroxy terephthalate-containing compound, of a diol, and (II) polycondensing the reaction product of Step (I) to form a copolyester while excess diol is removed until desired molecular weight is obtained.
- This process does not include a transesterification of a dialkyl ester reaction or an esterification reaction which are usually used to produce copolyesters.
- this process allows for polyethylene terephthalate and copolyesters prepared therefrom to be produced on an integrated production line.
- Copolyesters are widely used as extrusion and injection—molding resins for the fabrication of various articles for household or industrial use, including appliance parts, containers and auto parts.
- a majority of the copolyesters are composed of polyethylene terephthalate (PET) modified with other diols and/or dicarboxylic acid esters.
- Copolyesters are usually prepared according to copolyester forming conditions well known in the art. For example, a mixture of one or more aromatic dicarboxylic acids or ester forming derivatives thereof, and one or more diols is heated in the presence of esterification and/or transesterification catalysts at temperatures in the range of 150°C to 250°C, in an inert atmosphere.
- the by—product water or alcohol is removed.
- the dicarboxylic acid or dialkyl derivative thereof is esterified or transesterified with the diol(s) at atmospheric pressure and at a temperature at the lower end of the specified range. Polycondensation then is effected by increasing the temperature and lowering the pressure while excess diol is removed from the mixture. .
- U.S. Pat. Nos. 5,124,435 and 5,095,089 disclose poly(ethylene/1,4—cyclohexylenedimethylene terephthalate copolyesters (PETG) prepared by an esterification reaction or ester exchange reaction and a polycondensation reaction.
- Acetates of such metals as Zn, Mn, and Mg were employed as catalysts for the transesterification reaction of dimethylterephthalate (DMT)
- oxides of such metals as Sb and Ge were used for the polycondensation of bis—2—hydroxyethyl terephthalate.
- an alkali metal salt such as potassium carbonate or sodium acetate is incorporated into the catalyst formulation as a color stabilizer or masking agent to mask the yellow color generated during processing.
- U.S. Pat. Nos. 2,578,660, 3,074,913, and 3,377,320 disclose polyesters prepared using an ester—interchange catalyst and a germanium compound as a polycondensation catalyst.
- the patents suggest that the use of germanium compounds as polycondensation catalysts produce polyesters which are free from color without deleteriously affecting the rate of polycondensation.
- the process of the present invention has eliminated the transesterification of a dialkyl ester reaction and the esterification reaction in the production of copolyesters.
- the copolyesters produced by the process of the present invention are clear and colorless, and thus, do not require the addition of color stabilizers or masking agents.
- Another object of the present invention is to provide a process for preparing clear and colorless copolyesters without adding a color stabilizer or masking agent.
- a process for preparing a copolyester comprising the steps of: (I) reacting in the presence of a polycondensation catalyst under an inert atmosphere at a temperature of 150°C to 250°C for 0.01 to 8 hours
- n is 1 to 10 and at least 99% of the endgroups are ethylene glycol moieties; and (B) 0.005 to 10 moles, per mole of the dihydroxy terephthalate-containing compound, of a diol selected from the group consisting of cycloaliphatic diols having 6 to 20 carbon atoms, aliphatic diols having 2 to 20 carbon atoms and combinations thereof; and (II) polycondensing the reaction product of Step (I) to form a copolyester at a temperature in the range of 175°C to 325°C under reduced pressure while excess diol is removed until desired molecular weight is obtained.
- the process of the present invention involves two steps: 1) a diol interchange step, and 2) a polycondensation step.
- the first step involves adding a dihydroxy terephthalate-containing compound.
- the dihydroxy terephthalate-containing compound has the formula:
- n is 1 to 10, preferably, n is 1 to 5. More preferably, n is 1 and the dihydroxy terephthalate-containing compound is bis—2-hydroxyethyl terephthalate (BHET) .
- BHET bis—2-hydroxyethyl terephthalate
- Examples of higher order oligo eric dihydroxy terephthalate- containing compounds include:
- any type of oligomeric species must have greater than 99% of the total endgroups as ethylene glycol moieties.
- the dihydroxy terephthalate-containing compound can be a blend of monomer, dimer, trimer, etc.
- Non—functional ester or free—acid end groups will serve to limit the molecular weight, of the resulting copolyester.
- Non—functional methyl ester end—groups could be present when the dihydroxy terephthalate-containing compound is manufactured from a DMT/EG feed and free—acid end—groups could result from a TPA/EG feed.
- a dihydroxy terephthalate-containing compound from either process is suitable for this process, however, it is a requirement that less than 1%, preferably less than 0.1% of the total end groups can be non—hydroxyl—bearing ester or free—acid.
- the dihydroxy terephthalate-containing compound may contain residual catalyst, although a catalyst—free material is preferred.
- Component (B) is a diol including cycloaliphatic diols having 6 to 20 carbon atoms, aliphatic diols having 2 to 20 carbon atoms or combinations thereof.
- diols are: ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,4—cyclohexanedimethanol, 2,2,4,4—tetramethyl—1,3— cyclobutanediol, propane—1,3—diol, butane—1,4—diol, pentane—1,5—diol, hexane—1,6-diol, 2,2—dimethyl—1,3— —propanediol, 1,10—decanediol, 2,2,4,4—tetramethyl—1,3— —cyclobutanediol, 3— ethylpentanediol—(2,4) , 2—methyl— pentanediol
- the copolyester may be prepared from one or more of the above diols.
- the diol is 1,4—cyclohexanedimethanol (CHDM) or 2,2,4,4—tetramethyl—1,3—cyclobutanediol (TMCBD) . More preferably, the diol is 1,4—cyclohexanedimethanol (CHDM) or 2,2,4,4—tetramethyl—1,3—cyclobutanediol (TMCBD) . More preferably, the diol is 1,4—cyclohexanedimethanol (CHDM) or 2,2,4,4—tetramethyl—1,3—cyclobutanediol (TMCBD) . More preferably, the diol is 1,4—cyclohexanedimethanol (CHDM) or 2,2,4,4—tetramethyl—1,3—cyclobutanediol (TMCBD) . More preferably, the diol is 1,4—cyclohe
- 1,4 cyclohexanedimethanol.
- the cis and trans isomeric ratio of 1,4—cyclohexanedimethanol is not an important consideration for the process of this invention. It is to be recognized that certain diol combinations may be excluded due to physical and chemical process limitations. For example, a diol that has a boiling point below the minimum diol interchange temperature or a diol that is poorly reactive to the diol interchange process.
- the amount of diol added in the diol interchange step. Step (I) to yield a specific amount of said diol in the copolymer is highly dependent on the overall process conditions, such as reaction times, temperatures, catalyst type and level, and monomer distribution. At lower levels of diol incorporation, the same ratio of diol in the copolyester as was initially added in the feed can be obtained with a very short diol interchange time. At higher levels of diol incorporation, it is necessary to factor an increasing molar excess into the feed mix or lengthen the diol interchange time/temperature or a combination of both to achieve a particular copolyester composition. A specific diol will have a particular interchange reaction profile.
- 1,4—cyclohexane ⁇ dimethanol can be nearly quantitatively incorporated into a copolyester at molar substitution levels less than 50 mole%, while 2,2,4,4-tetramethyl-l,3— cyclobutanediol is incorporated at less than 66% of added diol at molar substitution levels up to 50 mole%.
- the diol interchange step. Step (I) is conducted in the presence of a polycondensation catalyst under an inert atmosphere at a temperature of 150°C to 250°C for 0.01 to 8 hours, preferably 180°C to 230°C for 0.1 to 4 hours.
- the molar amount of added diol in the feed may be varied from 0.005 to 10, preferably 0.005 to 3. Stirring or appropriate conditions are employed to ensure sufficient heat transfer and surface renewal for the reaction mixture.
- Polycondensation catalysts and the amounts used in polycondensation reactions are known in the art.
- 25 to 500 ppm of a polycondensation catalyst is used. More preferably, 50 to 300 ppm.
- Examples of polycondensation catalysts useful in the process of the present invention include: suitable germanium compounds, suitable tin compounds, suitable gallium compounds, suitable titanium compounds, and suitable antimony compounds. Although a large number of catalysts could facilitate both steps of the reaction, germanium compounds are most preferred since germanium compounds yield copolyesters of high molecular weight, low color, and good clarity. A variety of tetravalent germanium species are suitable, however, germanium(IV)—oxide is preferred.
- the concentration of germanium metal may vary from 25 to 500 ppm, preferably 50 to 300 ppm.
- Addition of the polycondensation catalyst to the reaction mixture may be as a solution or neat. For example, it is convenient to employ a solution of the germanium compound in ethylene glycol.
- Step II of the present invention is a polycondensation step which is performed under reduced pressure at a temperature of 175°C to 325°C, preferably 250°C to 300°C, and more preferably 270°C to 290°C for 0.1 to 6 hours, preferably 0.25 to 2 hours. Stirring or appropriate conditions are employed to ensure sufficient heat transfer and surface renewal for the reaction mixture.
- the copolyester is semi—crystalline then the copolyester may optionally be post reacted in the solid state by heating the solid copolyester to a temperature below the melting temperature of the copolyester in a vacuum or in a stream of inert gas. It is to be understood that the copolyesters of this invention contain substantially equal molar proportions of acid equivalents (100 mole%) to hydr ⁇ xy equivalents (100 mole%) . Thus, the copolyesters will have a total of acid and hydroxyl equivalents equal to 200 mole percent.
- the copolyesters have an inherent viscosity of 0.4 to 1.2 dl/g.
- the copolyesters have an inherent viscosity of 0.5 to 1.0 dl/g.
- copolyesters produced by the process of the present invention serve as excellent starting materials for the production of moldings of all types by compression, extrusion or injection molding.
- Specific applications include various packaging applications such as thermoformed or injection molded trays, lids and cups; injection stretch blow—molded bottles, film and sheet; extrusion blow— olded bottles and multilayer articles.
- package contents include, but are not limited to, food, beverages, and cosmetics.
- I.V. Inherent viscosity
- the temperature of the bath was raised to 285°C and the inert purge was replaced with a vacuum of 0.5 mm of Hg. After 180 minutes under reduced pressure, the viscosity of the polymer melt prevented any further increase in molecular weight and reaction was terminated.
- the flask was removed from the metal bath and the vacuum was replaced with nitrogen. Upon cooling to room temperature, the polymer was removed from the flask and ground to pass a 3 mm screen.
- Example I The apparatus and procedure set forth in Example I was used. The following amounts of reactants were initially charged to the flask: 127 grams (0.5 moles) BHET, 43.2 grams (0.3 moles) CHDM, and 4.76 mL of a 0.96% (w/v) solution of dibutyltin diacetate in n—butanol.
- the diol interchange step, Step I was conducted at 210°C for one hour, followed by the polycondensation or polymerization stage, Step II, which was performed at 0.7 mm of Hg for 25 minutes at 285°C.
- the diol composition consisted of 55 mole% CHDM, 44 mole% EG, and 1 mole% DEG.
- the inherent viscosity was determined to be 0.77 dl/g and a second run Tg of 86°C was recorded.
- the polymer had a yellow appearance.
- Example I The apparatus and procedure set forth in Example I was used. The following amounts of reactants were initially charged to the flask: 97 grams (0.5 moles) DMT, 56 grams (0.90 moles) EG, 22.4 grams (0.16 moles) CHDM, and 6.17 mL of a 0.53% (w/v) solution of germanium oxide in EG. Transesterification was conducted for one hour at 210°C and one hour at 230°C under a nitrogen purge. The temperature was raised to 275°C and a vacuum was applied. After 50 minutes nearly all of the reactor contents had distilled over into the receiver which indicated no molecular weight increase, and thus, no reaction had occurred.
- Example II The apparatus and procedure set forth in Example I was used. The following amounts of reactants were initially charged to the flask: 127 grams (0.5 moles)
- NMR analysis revealed the diol composition to be 75 mole% EG, 24 mole% TMCBD, and 1 mole% DEG.
- the inherent viscosity was determined to be 0.78 dl/g and a second run Tg of 97°C was recorded.
- Example I The apparatus and procedure set forth in Example I was used. The following amounts of reactants were initially charged to the flask: 127 grams (0.5 moles) BHET, 25.2 grams (0.175 moles) CHDM, and 300 ppm, by weight as the element based on grams of theoretical polymer yield, of germanium in the form of germanium dioxide.
- the diol interchange step, Step I was conducted at 210°C for two hours, followed by the polycondensation or polymerization stage, Step II, which was performed at less than 0.5 mm of Hg for 90 minutes at 280°C.
- the diol composition consisted of 33 mole% CHDM, 65 mole% EG, and 2 mole% DEG.
- the inherent viscosity was determined to be 0.81 dl/g and a second run Tg of 80°C was determined by DSC.
- Example I The apparatus and procedure set forth in Example I was used. The following amounts of reactants were initially charged to the flask: 127 grams (0.5 moles) BHET, 25.2 grams (0.175 moles) CHDM, and 100 ppm of titanium.
- the diol interchange step, Step I was conducted at 210°C for two hours, followed by the polycondensation or polymerization stage, Step II, which was performed at less than 0.5 mm of Hg for 2 hours at 280°C.
- the diol composition consisted of 33 mole% CHDM, 65 mole% EG, and 2 mole% DEG. The inherent viscosity was determined to be 0.92 dl/g and a second run Tg of 81°C was determined by DSC.
- Example V The color analysis results from Example V indicate that the use of a germanium compound as the polycondensation catalyst in the process of the present invention where 1,4—cyclohexanedimethanol is used as the diol, component (B) , produces a colorless copolyester.
- Example VI The color analysis results from Example VI indicate that the use of a titanium compound as the polycondensation catalyst where 1,4—cyclohexanedimethanol is used as the diol, produces a yellow copolyester. It is important to note that the level of whiteness or. Rd value for
- Examples V and VI are the same, however, the measure of tint or the a and b values for Example V is much closer to zero than the a and b values of Example VI.
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Abstract
Description
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX9603264A MX9603264A (en) | 1994-02-09 | 1995-01-30 | A process for preparing copolyesters. |
DE69512767T DE69512767T2 (en) | 1994-02-09 | 1995-01-30 | METHOD FOR PRODUCING COPOLYESTERS |
KR1019960704313A KR100322431B1 (en) | 1994-02-09 | 1995-01-30 | Manufacturing method of copolyester |
EP95909315A EP0743963B1 (en) | 1994-02-09 | 1995-01-30 | A process for preparing copolyesters |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/194,368 US5378796A (en) | 1994-02-09 | 1994-02-09 | Process for preparing copolyesters |
US08/194,368 | 1994-02-09 |
Publications (1)
Publication Number | Publication Date |
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WO1995021881A1 true WO1995021881A1 (en) | 1995-08-17 |
Family
ID=22717321
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1995/000940 WO1995021881A1 (en) | 1994-02-09 | 1995-01-30 | A process for preparing copolyesters |
Country Status (9)
Country | Link |
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US (1) | US5378796A (en) |
EP (1) | EP0743963B1 (en) |
KR (1) | KR100322431B1 (en) |
AT (1) | ATE185576T1 (en) |
CA (1) | CA2181054A1 (en) |
DE (1) | DE69512767T2 (en) |
MX (1) | MX9603264A (en) |
TW (1) | TW264489B (en) |
WO (1) | WO1995021881A1 (en) |
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US7179869B2 (en) * | 2004-03-22 | 2007-02-20 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyester resins |
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WO1996026245A1 (en) * | 1995-02-23 | 1996-08-29 | Kanegafuchi Kagaku Kogyo Kabushiki Kaisha | Polyethylene terephthalate resin composition |
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US9828461B2 (en) | 2012-03-01 | 2017-11-28 | Sabic Global Technologies B.V. | Poly(alkylene co-adipate terephthalate) prepared from recycled polyethylene terephthalate having low impurity levels |
US8901243B2 (en) | 2012-03-30 | 2014-12-02 | Saudi Basic Industries Corporation | Biodegradable aliphatic-aromatic copolyesters, methods of manufacture, and articles thereof |
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JPS4927592A (en) * | 1972-07-10 | 1974-03-12 | ||
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GB1486409A (en) * | 1973-11-06 | 1977-09-21 | Agfa Gevaert | Process for the preparation of high-molecular weight polyesters |
US4940772A (en) * | 1988-07-28 | 1990-07-10 | Nippon Ester Co., Ltd. | Process for producing flame resistant polyester |
WO1990007535A1 (en) * | 1988-12-28 | 1990-07-12 | Mitsubishi Rayon Co., Ltd. | Polyester copolymer |
KR930006046B1 (en) * | 1988-12-28 | 1993-07-03 | 미쓰비시 레이욘 가부시키가이샤 | Polyester copolymer |
DE69214686T2 (en) * | 1991-02-28 | 1997-06-05 | Agfa Gevaert Nv | Process for the production of polyesters with improved thermo-oxidative stability |
-
1994
- 1994-02-09 US US08/194,368 patent/US5378796A/en not_active Expired - Lifetime
- 1994-11-17 TW TW083110669A patent/TW264489B/zh active
-
1995
- 1995-01-30 CA CA002181054A patent/CA2181054A1/en not_active Abandoned
- 1995-01-30 MX MX9603264A patent/MX9603264A/en unknown
- 1995-01-30 WO PCT/US1995/000940 patent/WO1995021881A1/en active IP Right Grant
- 1995-01-30 DE DE69512767T patent/DE69512767T2/en not_active Expired - Lifetime
- 1995-01-30 AT AT95909315T patent/ATE185576T1/en active
- 1995-01-30 EP EP95909315A patent/EP0743963B1/en not_active Expired - Lifetime
- 1995-01-30 KR KR1019960704313A patent/KR100322431B1/en active IP Right Grant
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JPS4927592A (en) * | 1972-07-10 | 1974-03-12 | ||
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Title |
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CHEMICAL ABSTRACTS, vol. 78, no. 14, 9 April 1973, Columbus, Ohio, US; abstract no. 85079r, MATSUZAWA KATSUTO ET AL.: "Purifying bis(2-hydroxyethyl) terephthalate oligomers." page 20; * |
DATABASE WPI Week 2574, Derwent World Patents Index; AN 74-45941v * |
T. BALAKRISHNAN ET AL.: "Preparation and Study of Terephthalate Copolyester of Ethylene Glycol and Butane-1,4-diol.", POLYMER BULLETIN, vol. 5, no. 3/4, HEIDELBERG DE, pages 187 - 194 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1535945A1 (en) * | 2003-11-27 | 2005-06-01 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyester resins |
US7183362B2 (en) | 2003-11-27 | 2007-02-27 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyester resins |
CN100445312C (en) * | 2003-11-27 | 2008-12-24 | 三菱瓦斯化学株式会社 | Process for producing polyester resins |
KR101152087B1 (en) * | 2003-11-27 | 2012-06-11 | 미츠비시 가스 가가쿠 가부시키가이샤 | Process for producing polyester resins |
US7179869B2 (en) * | 2004-03-22 | 2007-02-20 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyester resins |
Also Published As
Publication number | Publication date |
---|---|
MX9603264A (en) | 1997-03-29 |
TW264489B (en) | 1995-12-01 |
US5378796A (en) | 1995-01-03 |
EP0743963B1 (en) | 1999-10-13 |
KR970701219A (en) | 1997-03-17 |
EP0743963A1 (en) | 1996-11-27 |
DE69512767D1 (en) | 1999-11-18 |
DE69512767T2 (en) | 2000-03-23 |
ATE185576T1 (en) | 1999-10-15 |
KR100322431B1 (en) | 2002-06-24 |
CA2181054A1 (en) | 1995-08-17 |
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