EP0752020B1 - Verfahren und vorrichtung zum abkühlen schmelzgesponnener filamente - Google Patents
Verfahren und vorrichtung zum abkühlen schmelzgesponnener filamente Download PDFInfo
- Publication number
- EP0752020B1 EP0752020B1 EP96900839A EP96900839A EP0752020B1 EP 0752020 B1 EP0752020 B1 EP 0752020B1 EP 96900839 A EP96900839 A EP 96900839A EP 96900839 A EP96900839 A EP 96900839A EP 0752020 B1 EP0752020 B1 EP 0752020B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- foam
- filaments
- vessel
- liquid
- level
- 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.)
- Expired - Lifetime
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Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
Definitions
- the invention relates to a method for cooling melt-spun Filaments made of thread-forming polymers and a Device for performing the method.
- Filament yarns and staple fibers made of thread-forming polymers such as Polyesters, polyamides or polyolefins are commonly used produced by the melt spinning process.
- a polymer melt is fed to a spinning pump, which melt through the spinnerets in the so-called spinning beam promotes.
- Those from the nozzles in the form of liquid filaments escaping melt solidifies in a cooling shaft.
- a preparation is carried out at the same time, i.e. Humidification and anti-static treatment and the like before the filaments go through another process be fed.
- the cooling of those emerging from the spinneret liquid filaments is of great influence the titer uniformity (Uster value) and the textile technology Properties of fibers and threads in the end product.
- Air cooling has the advantage that the air is low Exerts friction on the emerging filaments and therefore no unwanted stretching occurs.
- the disadvantage is, however low cooling effect of the air, so that a long cooling distance is required.
- a long cooling section also means a slow cooling.
- a slow cooling favors the crystallite formation in the thread, which is the result of the subsequent stretching Causing problems.
- a high throughput (g / min / hole) or thicker single filaments require one especially long cooling distance, because the cooling speed is low. Thus, as already mentioned above, there is this Spun material particularly the risk of crystallite formation.
- the cooling usually takes place by blowing the filaments crosswise.
- the air flow must be low in turbulence and the same Have speed across the chute width so every filament experiences exactly the same cooling in time and place.
- Perforated sheets or screen mesh in connection with honeycomb rectifiers are used to meet the required flow conditions to create. Also can be about the height of the cooling shaft if necessary, a speed profile can be provided. Despite this partly elaborate measures will be taken at high Number of filaments per surface no uniform cooling of all Single filaments guaranteed. From filament to filament arises a transverse temperature gradient, so that the number of rows of holes arranged one behind the other in the air flow is limited.
- the object of the present invention is to provide a method create, which the cooling of the emerging from the nozzles Spinning melt improved by means of foam and thus also that Spinning thicker filaments at high speed allows without crystallite formation in these filaments comes, which adversely affects the subsequent stretching / texturing process influenced.
- This task is characterized by the features of the claim 1 and the device claim 10 solved.
- Spinning nozzles 2 from which the filaments F emerge, are arranged on a spinning beam 1.
- these filaments F Before these filaments F, which leave the nozzles 2 in liquid form, can be fed to any further processing, they have to be solidified by cooling, for example to wind them up into bobbins or to deposit them in bundles in cans. They therefore pass through a so-called cooling section SK, on which the threads are guided freely without touching themselves or other objects and are cooled from the usual melting temperature of approximately 300 ° C. to a limit temperature t g , which is approximately 70 ° C. . Only when this limit temperature t g is reached or fallen below, the filaments F may have contact. 3 shows the temperature t of the spinning material in ° C.
- the line t g indicates the temperature to which the spinning material must have cooled at least before each contact (limit temperature).
- the cooling conditions are shown, for example, for a polyester POY monofilament with a titer of 22-35 dtex by curve A. The cooling takes place as usual with air, which has an intrinsic temperature corresponding to the room temperature of about 20 ° C. The course of the cooling shows that with this type of cooling and a production speed of 3600 m / min, the limit temperature of approximately 70 ° C. is only reached after a cooling section SA of approximately 3.5 m. Only at this distance from the nozzle have the filaments achieved such strength through cooling that they may be in contact with each other or with thread guide elements or the like.
- Curves B and C show the cooling conditions for foam with different volume fractions of liquid. It follows that in the case of a foam with a liquid volume fraction of 5% under the same conditions as for curve A, the cooling distance is shortened to approximately 1.1 to 1.2 m in order to reach the limit temperature t g . If the volume fraction is higher, the cooling distance is further shortened, since the heat transfer also increases greatly depending on the volume fraction of liquid in the foam. For example, curve C shows the cooling process for a foam with about 10% liquid volume. The cooling section SK is reduced to the section SC, which is less than 1 m, in order to reach the limit temperature.
- FIG. 3 shows the entire cooling process from the exit from the spinnerets to the preparation for the next treatment process.
- the air gap S between the nozzle plate 2 and the foam container 3 a relatively flat course of the temperature decrease can be seen first.
- the cooling curve is considerably steeper than if the cooling were only carried out by air and thus reaches the limit temperature t g after a short distance.
- the distance S can be very small be, e.g. only 1 - 2 cm. Its size depends on the Filament thickness and production speed. After the Filaments F emerge in liquid form from the nozzles 3 some solidification is necessary before going into the foam immerse yourself. This solidification occurs with fine filaments much faster than with coarser titles, where this Distance from the foam depending on the production speed can be up to 1.5 m.
- the foam container 3 is supported by a frame 32 and has a wide inlet opening 31 at its upper end so that the filaments F cannot touch the walls of the foam container 3, while a narrow opening 35 is provided at its lower end through which the Filaments F leave the foam container. Due to the widening cross section of the foam container 3, the flow rate of the foam is reduced and the regression and separation of the liquid is promoted and the spinning material passed through the foam in countercurrent is wetted and cooled intensively. Since the filaments F largely fill this narrow opening 35 and thus contact contacts occur, the limit temperature t g must be reached with certainty up to this point. As can be seen from Figure 3, this also determines the overall height of the foam container 3.
- the air supply 51 At the lower end, close to the outlet opening 35, there is a Foam generator 5 arranged, the air supply 51 and has a liquid supply 52 and the foam immediately supplies in the lower part of the foam container 3. While the foam by the continuous foam generation upwards increases, the filaments F countercurrently from top to bottom passed down through the foam container 3 and occur at the Exit opening 35 from the foam container 3 to then to be sent to another processing process.
- the rising foam is controlled by a sensor 4, which, if necessary, the fill level via Level controller 41 regulates.
- the edge of the upper entry opening 35 of the foam container 3 is designed as an overflow, so that re-forming liquid, if necessary, over the Edge can run off.
- the overflowing liquid as well as in Foam container 3 resulting from regression and down draining liquid is collected in a drip pan 33 and returned to the circulation pump 7 via drain lines 36.
- the foam generator 5 is continuously fed by the Circulation pump 7, which is also the circuit of the returned liquid caused by the foam container 3.
- the metering pump 72 water is added to this cycle to the extent that foam generation and cooling of the filaments F liquid is consumed.
- a second pump 71 removes the liquid Preparation oil added.
- the circulation pump then does both 7 pumped through a mixer 6 and thereby to the Prepared liquid that the foam generator 5 on the Line 52 is supplied.
- In the foam generator 5 is by Feed 51 air added to the liquid and so the foam generated, which is delivered in the lower part of the foam container 3 becomes.
- the foam container 3 When piecing, the foam container 3 is initially empty. From the filaments F emerging from the nozzle 2 fall down into the Foam container 3 and are inserted into the outlet opening 35. For this purpose, a flap 34 is used, which covers the lower part of the Foam container 3 makes accessible. After filament insertion F the flap 34 is closed again and foam is added.
- the sensor 4 controls the rising foam and regulates the motor 42, which controls the metering pump, via a controller 41 72 drives for the water supply. Through the over the Sensor 4 controlled level in the foam container 3 is thus also determines the cooling section SK, which the filaments at Need to go through the foam.
- the bubble bath is used at the same time to Apply the preparation solution to the filaments F.
- the system therefore also includes the required one Preparation device. Below the foam container 3, the emerging filaments through two electrodes 8 scanned. With a resistance measurement the constancy of the preparation pad is measured and if necessary through a target / actual value comparison in the concentration controller 81 and a frequency converter 82, the motor 83 for drives the metering pump 71 for the preparation oil.
- the foam container is something designed differently than in Figure 1.
- the foam container 30 is as rectangular or cylindrical shaft formed on the itself in continuation of its external form, but separated through a joint 38, the foam generator 50, 50 ', connects.
- the narrow outlet opening 35 of the foam container 3 is here in the foam generator 50, 50 ', so that the foam container 3 open at the parting line 38 in full cross section is.
- the foam generator consists of two half-shells 50, 50 ' are movable apart in the horizontal direction along the Parting line 38. This makes the lower part for piecing of the foam container 30 accessible so that the falling Filaments F captured and in yarn guides for further processing can be inserted. If this has happened, they will the two half-shells 50, 50 'of the foam generator are reassembled, so that they enclose the filaments F and the Foam container 30 is closed except for the outlet opening 35 for filaments F.
- Each of the two half-shells 50, 50 ' is independent Foam generator designed and both to an air supply 51st as well as connected to a liquid supply 52.
- This Supply lines are expediently elastic to the two half-shells 50, 50 'to be able to move apart.
- sintered metal candles 53 through which the air is fed into the liquid.
- the sintered metal candles 53 can also for the air supply over a plate or some other form of sintered metal manufactured body are supplied.
- a plate or some other form of sintered metal manufactured body are supplied.
- sintered material By using sintered material an exceptionally good treatment of the liquid with gas, preferably air to foam.
- you can other fine-pored elements for the gas supply in the Liquid can be used, such as strainers, nozzle plates and Like ..
- the liquid level 54 in the foam generator 50, 50 ' is controlled by a level limiter 37 to a to guarantee even foam production.
- the easiest The type of such a sensor 37 is shown in FIG represented an overflow. Instead of the overflow 37 a probe can also be provided which monitors the fluid supply controls each.
- the foam generated in this way increases up into the foam container 30, while the filaments F in Counter current flow through the foam container 30 and through the Leave outlet opening 35.
- the upper part of the foam container 30 is in the same way designed as in the described embodiment according to the figure 1.
- the edge of the opening 31 is designed as an overflow, so that regressive liquid collect and over can drain this edge to catch again and the Circuit to be fed again for foam generation.
- the sensor 4 regulates the level of the foam within of container 30, however, additional may be required Take measures to ensure that the foam level is even and thus all filaments F through the same cooling section SB go through the foam.
- a device for smoothing the foam level can also have a device for smoothing the foam level be provided.
- a suction channel 21 is provided, which is such a foam mountain transported away or the formation of such a foam mountain prevented by a slight air flow.
- the distance S to the nozzle plate 2 is much smaller here shown as in Figure 1. As mentioned above, this is Distance depending on the filament speed and the titer the filaments F. However, a certain distance S must be maintained as the foam should not touch the nozzle plate 2, to undesirably cool the foam avoid. Such a device 21 for smoothing the Foam level makes a certain distance from the nozzle plate required.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Treatment Of Fiber Materials (AREA)
Description
- Figur 1 -
- schematisch eine Anlage zum Spinnen von schmelzgesponnenen Filamenten aus fadenbildenden Polymeren, wobei die Teile der Anlage, die für die Erfindung unwesentlich sind, weggelassen wurden.
- Figur 2 -
- eine andere Ausführungsform der Schaumanlage
- Figur 3 -
- eine graphische Darstellung des Abkühlungsvorganges gemäß dem Stand der Technik und gemäß der Erfindung
- Spinnbalken
- 1
- Düsenplatte
- 2
- Luftkanal
- 21
- Schaumbehälter
- 3, 30
- Eintrittsöffnung
- 31
- Gestell
- 32
- Auffangwanne
- 33
- Klappe
- 34
- Austrittsöffnung
- 35
- Ablauf
- 36
- Füllstandsbegrenzer
- 37
- Trennfuge
- 38
- Füllstandsfühler
- 4
- Schaumerzeuger
- 5; 50, 50'
- Luftzufuhr
- 51
- Kühlflüssigkeitszufuhr
- 52
- Sinterkerzen
- 53
- Flüssigkeitsspiegel
- 54
- Mischer
- 6
- Umwälzpumpe
- 7
- Dosierpumpe Präp.Öl
- 71
- Dosierpumpe Wasser
- 72
- Antriebsmotoren
- 42, 83
- Elektroden
- 8
- Konzentrationsregler
- 81
- Frequenzwandler
- R2
- Kühlstrecke
- SK
- Luftspalt
- S
- Grenztemperatur
- tG
- Kühlstrecken zum Erreichen Grenztemperatur
- SA, SB, SC
- Filamente
- F
Claims (24)
- Verfahren zum Abkühlen schmelzgesponnener Filamente aus fadenbildenden Polymeren, bei welchem die Schmelze aus Spinndüsen in Form von flüssigen Filamenten austritt und diese Filamente danach einer Zone zugeführt werden, in welcher das Spinngut zur Kühlung einem Medium ausgesetzt wird, das als Schaum aufbereitet ist, und das aus den Spinndüsen (2) austretende Spinngut in der Kühlzone im Gegenstrom durch diesen Schaum geleitet wird, bevor das Spinngut einem weiteren Prozeß zugeführt wird, dadurch gekennzeichnet, daß das aus der Spinndüse (2) austretende Spinngut (F) nach einer möglichst kurzen, freien Strecke (S) mit dem Schaum in Berührung gebracht wird, so daß das Spinngut (F) eine gewisse Erstarrung erreicht hat, bevor es in den Schaum eintritt.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß der Schaum in einem Schaumerzeuger (5; 50, 50') bereitet und von diesem unmittelbar in einen Behälter (3) geleitet wird, durch den das Spinngut (F) geführt wird.
- Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß der Schaumbehälter (3) auf einem bestimmten Füllstandsniveau gehalten wird.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß eine Glättung des Schaumspiegels erfolgt.
- Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß die Glättung durch eine über den Schaumspiegel geleitete Luftströmung erfolgt.
- Verfahren nach anspruch 5, dadurch gekennzeichnet, daß über den Schaumspiegel eine Saugluftströmung geleitet wird.
- Verfahren naqch einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Schaumerzeugung kontinuierlich erfolgt und die bei Zerfall des Schaumes entstehende Flüssigkeit aufgefangen und zur Schaumerzeugung zurückgeführt wird.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Strömungsgeschwindigkeit des Schaumes zum Eintritt der Filamente in den Behälter hin verringert wird.
- Verfahren nach einem oder mehreren der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß der Schaum vorzugsweise aus etwa 5 bis 10% Volumenanteilen Flüssigkeit bereitet ist.
- Vorrichtung zum Abkühlen schmelzgesponnener Filamente mittels eines Schaumbades, wobei eine Polymerschmelze aus in einem Spinnbalken (1) angeordneten Spinndüsen (2) in Form von flüssigen Filamenten (F) austritt und durch eine Kühlzone geleitet wird, bevor die Filamente (F) einem weiteren Prozeß zugeführt werden, und in der Kühlzone ein Schaumbehälter (3) angeordnet ist, durch den die Filamente (F) zur Abkühlung hindurchgeleitet werden, dadurch gekennzeichnet, daß Mittel vorgesehen sind, um eine möglichst kurze freie Strecke (S) zwischen den Spinndüsen (2) und dem Schaumspiegel im Schaumbehälter (3) einzuhalten, so daß das Spinngut (F) eine gewisse Erstarrung erreicht hat, bevor es in den Schaum eintritt.
- Vorrichtung nach Anspruch 10, dadurch gekennzeichnet, daß dem Schaumbehälter (3) ein Schaumerzeuger (5, 50, 50') unmittelbar zugeordnet ist.
- Vorrichtung nach Anspruch 11, dadurch gekennzeichnet, daß der Schaumerzeuger (5; 50, 50') am unteren Ende des Schaumbehälters (3) angeordnet ist.
- Vorrichtung nach Anspruch 12, dadurch gekennzeichnet, daß der Schaumerzeuger (5; 50, 50') unmittelbar in den Schaumbehälter (3) mündet.
- Vorrichtung nach einem oder mehreren der Ansprüche 11 bis 13, dadurch gekennzeichnet, daß der Schaumerzeuger (5; 50, 50') in Fortsetzung des Schaumbehälters (3) an dessen unteren Ende angeordnet ist.
- Vorrichtung nach einem oder mehreren der Ansprüche 11 bis 14, dadurch gekennzeichnet, daß der Schaumerzeuger (5; 50, 50') an eine Flüssigkeitszufuhr (52) und an eine Luftzufuhr (51) angeschlossen ist.
- Vorrichtung nach Anspruch 14, dadurch gekennzeichnet, daß der Schaumerzeuger aus zwei Halbschalen (50, 50') besteht, die in radialer Richtung auseinanderschwenkbar sind, so daß die von den Halbschalen (50, 50') umgebene, aus dem Schaumbehälter (3) austretenden Filamente (F) freigegeben werden.
- Vorrichtung nach Anspruch 16, dadurch gekennzeichnet, daß die Halbschalen (50, 50') jeweils einen in sich geschlossenen Flüssigkeitsbehälter aufweisen, in welchem Lufteinführungselemente (53) angeordnet sind.
- Vorrichtung nach einem oder mehreren der Ansprüche 11 bis 17, dadurch gekennzeichnet, daß die Lufteinführungselemente (53) aus Sintermaterial bestehen.
- Vorrichtung nach Anspruch 18, dadurch gekennzeichnet, daß die Lufteinführungselemente (53) als Sintermetallkerzen ausgebildet sind.
- Vorrichtung nach einem oder mehreren der Ansprüche 11 bis 19, dadurch gekennzeichnet, daß der Schaumerzeuger (50, 50') einen Füllstandsbegrenzer (37) für die Flüssigkeit aufweist.
- Vorrichtung nach Anspruch 20, dadurch gekennzeichnet, daß der Füllstandsbegrenzer (37) als Überlauf ausgebildet ist.
- Vorrichtung nach einem oder mehreren der Ansprüche 11 bis 21, dadurch gekennzeichnet, daß der Schaumbehälter (3) an seinem oberen Ende eine weite Eintrittsöffnung (31) für die Filamente (F) aufweist, sodaß die Filamente (F) die Wandungen des Schaumbehälters (3) nicht berühren, und an seinem unteren Ende eine enge Austrittsöffnung (35) aufweist, die weitgehend von den Filamenten (F) ausgefüllt wird, und der Querschnitt des Schaumbehälters (3) sich in Richtung der Schaumströmumg erweitert.
- Vorrichtung nach einem oder mehreren der Ansprüche 11 bis 22, dadurch gekennzeichnet, daß an der Eintrittsseite (31) des Schaumbehälters (3) eine Vorrichtung zur Glättung des Schaumspiegels angeordnet ist.
- Vorrichtung nach Anspruch 23, dadurch gekennzeichnet, daß die Vorrichtung zur Glättung des Schaumspiegels aus einem Absaugkanal (21) besteht.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19501826 | 1995-01-21 | ||
DE19501826A DE19501826A1 (de) | 1995-01-21 | 1995-01-21 | Verfahren und Vorrichtung zum Abkühlen schmelzgesponnener Filamente |
PCT/DE1996/000089 WO1996022409A1 (de) | 1995-01-21 | 1996-01-17 | Verfahren und vorrichtung zum abkühlen schmelzgesponnener filamente |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0752020A1 EP0752020A1 (de) | 1997-01-08 |
EP0752020B1 true EP0752020B1 (de) | 2000-05-24 |
Family
ID=7752034
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96900839A Expired - Lifetime EP0752020B1 (de) | 1995-01-21 | 1996-01-17 | Verfahren und vorrichtung zum abkühlen schmelzgesponnener filamente |
Country Status (6)
Country | Link |
---|---|
US (1) | US5766533A (de) |
EP (1) | EP0752020B1 (de) |
JP (1) | JPH10501589A (de) |
AT (1) | ATE193338T1 (de) |
DE (2) | DE19501826A1 (de) |
WO (1) | WO1996022409A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7517494B2 (en) * | 2003-04-30 | 2009-04-14 | Hewlett-Packard Development Company, L.P. | Test tray and test system for determining response of a biological sample |
US7329723B2 (en) * | 2003-09-18 | 2008-02-12 | Eastman Chemical Company | Thermal crystallization of polyester pellets in liquid |
CA2482056A1 (en) | 2003-10-10 | 2005-04-10 | Eastman Chemical Company | Thermal crystallization of a molten polyester polymer in a fluid |
US8079158B2 (en) * | 2004-09-02 | 2011-12-20 | Grupo Petrotemex, S.A. De C.V. | Process for separating and drying thermoplastic particles under high pressure |
US20060047102A1 (en) * | 2004-09-02 | 2006-03-02 | Stephen Weinhold | Spheroidal polyester polymer particles |
US7875184B2 (en) * | 2005-09-22 | 2011-01-25 | Eastman Chemical Company | Crystallized pellet/liquid separator |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU386034A1 (ru) * | 1971-04-23 | 1973-06-14 | Способ получения термопластичных волокон | |
US4425293A (en) * | 1982-03-18 | 1984-01-10 | E. I. Du Pont De Nemours And Company | Preparation of amorphous ultra-high-speed-spun polyethylene terephthalate yarn for texturing |
JPS60134011A (ja) * | 1983-12-22 | 1985-07-17 | Toray Ind Inc | 熱可塑性重合体の溶融紡糸方法および装置 |
DE3409450A1 (de) * | 1984-03-15 | 1985-09-26 | Bayer Ag, 5090 Leverkusen | Verfahren und vorrichtung zur umlenkung von monofilen in einem kuehlbad |
DE3623748A1 (de) * | 1986-07-14 | 1988-02-18 | Groebe Anneliese Dr | Schnellgesponnene polyethylenterephthalatfaeden mit neuartigem eigenschaftsprofil, verfahren zu ihrer herstellung und ihre verwendung |
DE3901518A1 (de) * | 1989-01-20 | 1990-07-26 | Fleissner Maschf Ag | Verfahren zum kuehlen von aus spinnduesen austretenden filamenten |
US5268133A (en) * | 1990-05-18 | 1993-12-07 | North Carolina State University | Melt spinning of ultra-oriented crystalline filaments |
JPH06330403A (ja) * | 1993-05-25 | 1994-11-29 | Teijin Ltd | 油剤付与方法 |
-
1995
- 1995-01-21 DE DE19501826A patent/DE19501826A1/de not_active Withdrawn
-
1996
- 1996-01-17 US US08/716,408 patent/US5766533A/en not_active Expired - Fee Related
- 1996-01-17 DE DE59605282T patent/DE59605282D1/de not_active Expired - Fee Related
- 1996-01-17 AT AT96900839T patent/ATE193338T1/de not_active IP Right Cessation
- 1996-01-17 JP JP8521974A patent/JPH10501589A/ja active Pending
- 1996-01-17 EP EP96900839A patent/EP0752020B1/de not_active Expired - Lifetime
- 1996-01-17 WO PCT/DE1996/000089 patent/WO1996022409A1/de active IP Right Grant
Also Published As
Publication number | Publication date |
---|---|
WO1996022409A1 (de) | 1996-07-25 |
DE19501826A1 (de) | 1996-07-25 |
US5766533A (en) | 1998-06-16 |
ATE193338T1 (de) | 2000-06-15 |
DE59605282D1 (de) | 2000-06-29 |
EP0752020A1 (de) | 1997-01-08 |
JPH10501589A (ja) | 1998-02-10 |
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