EP0658221B1 - Verfahren zur herstellung cellulosischer fasern sowie vorrichtung zur durchführung des verfahrens - Google Patents
Verfahren zur herstellung cellulosischer fasern sowie vorrichtung zur durchführung des verfahrens Download PDFInfo
- Publication number
- EP0658221B1 EP0658221B1 EP94919458A EP94919458A EP0658221B1 EP 0658221 B1 EP0658221 B1 EP 0658221B1 EP 94919458 A EP94919458 A EP 94919458A EP 94919458 A EP94919458 A EP 94919458A EP 0658221 B1 EP0658221 B1 EP 0658221B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cellulose
- filaments
- gas stream
- solution
- laminar
- 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
Links
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 title claims description 20
- 229920002678 cellulose Polymers 0.000 claims abstract description 23
- 239000001913 cellulose Substances 0.000 claims abstract description 23
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- 238000009987 spinning Methods 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 20
- 239000000112 cooling gas Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims 3
- 238000001816 cooling Methods 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 description 13
- 238000007664 blowing Methods 0.000 description 7
- 150000003512 tertiary amines Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Images
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
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
Definitions
- the invention relates to a process for producing cellulosic fibers by forming a solution of cellulose in a tertiary amine oxide in the warm state into filaments, cooling the filaments and then introducing them into a precipitation bath in order to precipitate the dissolved cellulose, and a device for carrying out the process .
- tertiary amine oxides can dissolve cellulose and that cellulosic fibers can be obtained from these solutions by precipitation.
- a method for producing such solutions is known for example from EP-A - 0 356 419.
- a suspension of cellulose in an aqueous tertiary amine oxide is first prepared.
- the amine oxide contains up to 40% by mass of water.
- the aqueous cellulose suspension is heated and water is drawn off under reduced pressure until the cellulose dissolves.
- the process is carried out in a specially developed, evacuable stirring device.
- a method of the type mentioned at the outset is known from DE-A-28 30 685, according to which a solution of cellulose in a tertiary amine oxide is formed into filaments in a warm state, the filaments are cooled with air and then introduced into a precipitation bath in order to dissolve them To cut down cellulose. The surface of the spun threads is further wetted with water to reduce their tendency to stick to adjacent threads.
- This object is achieved in such a way that in a process for the production of cellulosic fibers in which a solution of cellulose in a tertiary amine oxide is formed into filaments in the warm state, the filaments are cooled and then introduced into a precipitation bath in order to precipitate the dissolved cellulose , the shaped solution is exposed to a substantially laminar gas flow for cooling prior to introduction into the coagulation bath.
- the invention is based on the knowledge that the textile properties of the fibers can be influenced by blowing with an inert gas, preferably air.
- the cooling process of the filament emerging from the spinneret affects not only the thread quality but also the stretching and elongation of the filaments. It has been shown according to the invention that fibers with uniform properties can be produced if the freshly extruded filaments are blown with a cooling gas stream which has as little turbulence as possible, that is to say is largely laminar. This leads to a decisive improvement in the spinning process.
- a preferred variant of the method according to the invention is that the laminar gas flow is directed essentially perpendicular to the filaments.
- the invention also relates to an apparatus for carrying out the method according to the invention, which comprises a supply for cooling gas and a spinneret with spinning holes, which are arranged essentially in a ring to form an annular filament array, and is characterized in that the supply for cooling gas in the center of the the arrangement of the spinning holes formed ring is provided and the feed is designed such that an essentially laminar gas flow hits the filaments and the filaments are cooled with a laminar gas flow.
- the supply for cooling gas has a supply nozzle and an impact plate for deflecting the gas flow, the impact plate being designed so that the gas flow remains as laminar as possible during the deflection.
- the invention further relates to the use of the device according to the invention for producing cellulosic fibers from a solution of cellulose in a tertiary amine oxide.
- FIG. 1 shows schematically the implementation of a dry / wet spinning process for producing cellulosic fibers according to the prior art
- FIG. 2a shows a preferred embodiment of the process according to the invention Show spinning device.
- FIG. 2b shows a section of FIG. 2a on an enlarged scale.
- 3 shows a device for comparison which does not have the features according to the invention.
- 1 denotes a heatable (heating not shown) spinneret, which via the feed line 2 with spinning mass 3, i.e. warm cellulose solution at a temperature of about 100 ° C, is charged.
- the pump 4 serves to meter the spinning mass and to set the pressure required for the extrusion.
- the thread structure extruded from the spinneret 1 via the spinning holes is designated by the reference number 5.
- the thread assembly 5 reaches the precipitation bath 6 via an air gap, which is defined by the distance of the spinneret 1 from the surface of the precipitation bath 6, is collected and drawn off via a deflection roller 7.
- the extruded thread bandage 5 is cooled with air, which is shown schematically in the figure with an arrow. A delay is achieved by pulling the thread assembly 5 over the roller 7 at a higher speed than it leaves the spinneret 1.
- Figure 2a shows in section an annular, heatable (heating not shown) spinneret 1 'and a blowing device consisting of a central, tubular feed 8 for cooling gas and a baffle plate 9 for deflecting the gas flow from the vertical to a substantially horizontal direction.
- the ring-shaped spinneret 1 ' is fed at a point not shown in the drawing with spinning mass 3' which is spun into a dense, ring-shaped thread structure 5 'which is blown from the inside with cooling gas.
- the direction of blowing is indicated in the figure by means of a dashed arrow.
- the cooling air thus emerges from a circular slot nozzle, which is formed by the baffle plate 9 and the counterpart 10.
- the blowing device shown in FIG. 2b can either form a structural unit together with the spinneret 1 'or represent a separate component on which the ring-shaped spinneret 1' rests.
- An insulation (not shown) is expediently provided between the blowing device and the spinneret in order to prevent heat transfer from the spinning mass to the cooling air.
- the circular outlet slot opens at a total opening angle of 22 22 ° after the gas flow has been deflected.
- the steadily increasing cross-section minimizes the flow resistance for the cooling gas.
- the small total opening angle prevents the cooling gas flow from coming off and enables the filaments to flow without turbulence.
- a preferred embodiment of the device according to the invention has an annular bead 11, which deflects the cooling gas stream that has passed through the thread structure slightly downward from the spinneret plane.
- a cellulose solution prepared in accordance with the process described in EP-A-0 356 419 was filtered and spun in hot condition in accordance with the process shown in FIG. 1, the spinning device being that shown in FIG. 2a and in the comparative example that shown in section in section Device was used. Both devices had the same inner diameter of the tubular feed 8 for cooling gas (44 mm) and the same diameter of the baffle plate 9 (104 mm). In the example (device according to the invention), the angles ⁇ and ⁇ were each 5 °; the total opening angle ⁇ was thus 10 °. The angle ⁇ was 5 °.
- the table shows the mass of cellulose solution spun per hour for the example and for the comparative example (kg / h), its composition (% by mass), its temperature (° C.) during spinning, the hole density (number of holes / mm) the spinneret, the diameter of the spinning holes ( ⁇ ), the nozzle warpage, the supply of cooling air (m3 / h), its temperature (° C), the temperature (° C) the internal cooling air discharged, the fiber distortion, the NMMO content of the precipitation bath (mass% NMMO) and the final titer of the fibers produced (dtex).
- TABLE example Comparative example Cellulose solution (kg / h) 27.6 27.6 Cellulose content (% mass) 15 15 Temp. D cellulose solution.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT0129193A AT399729B (de) | 1993-07-01 | 1993-07-01 | Verfahren zur herstellung cellulosischer fasern sowie vorrichtung zur durchführung des verfahrens und deren verwendung |
AT1291/93 | 1993-07-01 | ||
PCT/AT1994/000083 WO1995001470A1 (de) | 1993-07-01 | 1994-06-29 | Verfahren zur herstellung cellulosischer fasern sowie vorrichtung zur durchführung des verfahrens |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0658221A1 EP0658221A1 (de) | 1995-06-21 |
EP0658221B1 true EP0658221B1 (de) | 1996-02-07 |
Family
ID=3510712
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94919458A Expired - Lifetime EP0658221B1 (de) | 1993-07-01 | 1994-06-29 | Verfahren zur herstellung cellulosischer fasern sowie vorrichtung zur durchführung des verfahrens |
Country Status (26)
Country | Link |
---|---|
US (1) | US5698151A (ru) |
EP (1) | EP0658221B1 (ru) |
JP (1) | JPH08500863A (ru) |
KR (1) | KR0177261B1 (ru) |
CN (1) | CN1039039C (ru) |
AT (2) | AT399729B (ru) |
AU (1) | AU668485B2 (ru) |
BG (1) | BG62408B1 (ru) |
BR (1) | BR9405438A (ru) |
CA (1) | CA2141817C (ru) |
CZ (1) | CZ285848B6 (ru) |
DE (2) | DE59400112D1 (ru) |
DK (1) | DK0658221T3 (ru) |
ES (1) | ES2085186T3 (ru) |
GB (1) | GB2284382B (ru) |
GR (1) | GR3019295T3 (ru) |
HU (1) | HU214308B (ru) |
PL (1) | PL307724A1 (ru) |
RO (1) | RO113160B1 (ru) |
RU (1) | RU2120504C1 (ru) |
SI (1) | SI0658221T1 (ru) |
SK (1) | SK281292B6 (ru) |
TR (1) | TR28801A (ru) |
WO (1) | WO1995001470A1 (ru) |
YU (1) | YU48686B (ru) |
ZA (1) | ZA944766B (ru) |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MY115308A (en) * | 1993-05-24 | 2003-05-31 | Tencel Ltd | Spinning cell |
AT401271B (de) * | 1993-07-08 | 1996-07-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von cellulosefasern |
ATA239194A (de) * | 1994-12-22 | 1996-02-15 | Chemiefaser Lenzing Ag | Vorrichtung zur durchführung eines trocken-/nassspinnverfahrens |
GB9500387D0 (en) * | 1995-01-10 | 1995-03-01 | Courtaulds Fibres Ltd | Manufacture of extruded articles |
AT402741B (de) * | 1995-10-13 | 1997-08-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung cellulosischer fasern |
GB9607456D0 (en) * | 1996-04-10 | 1996-06-12 | Courtaulds Fibres Holdings Ltd | Spinning of filaments |
US6221487B1 (en) | 1996-08-23 | 2001-04-24 | The Weyerhauser Company | Lyocell fibers having enhanced CV properties |
US6235392B1 (en) | 1996-08-23 | 2001-05-22 | Weyerhaeuser Company | Lyocell fibers and process for their preparation |
DE19717257A1 (de) * | 1997-04-24 | 1998-10-29 | Akzo Nobel Nv | Verfahren zur Herstellung cellulosischer Formkörper |
AT405531B (de) | 1997-06-17 | 1999-09-27 | Chemiefaser Lenzing Ag | Verfahren zur herstellung cellulosischer fasern |
AT405948B (de) * | 1998-03-26 | 1999-12-27 | Chemiefaser Lenzing Ag | Spinndüse |
US6409883B1 (en) | 1999-04-16 | 2002-06-25 | Kimberly-Clark Worldwide, Inc. | Methods of making fiber bundles and fibrous structures |
DE10019660B4 (de) * | 2000-04-20 | 2004-04-29 | Zimmer Ag | Verfahren zum Verspinnen einer Spinnlösung und Spinnkopf |
TW577940B (en) * | 2001-08-11 | 2004-03-01 | Acordis Ag | Precipitating bath |
DE10206089A1 (de) | 2002-02-13 | 2002-08-14 | Zimmer Ag | Bersteinsatz |
DE10223268B4 (de) * | 2002-05-24 | 2006-06-01 | Zimmer Ag | Benetzungseinrichtung und Spinnanlage mit Benetzungseinrichtung |
DE102004024065A1 (de) * | 2004-05-13 | 2005-12-08 | Zimmer Ag | Verfahren zum Herstellen von Endlosformkörpern und Spinnkopf |
DE102005040000B4 (de) * | 2005-08-23 | 2010-04-01 | Lenzing Ag | Mehrfachspinndüsenanordnung und Verfahren mit Absaugung und Beblasung |
CN101845674B (zh) * | 2010-06-07 | 2011-09-28 | 扬州华美丙纶纺织有限公司 | 二层环吹风纤维喷丝头 |
EP2565303A1 (de) * | 2011-09-02 | 2013-03-06 | Aurotec GmbH | Extrusionsverfahren |
TWI667378B (zh) | 2014-01-03 | 2019-08-01 | 奧地利商蘭精股份有限公司 | 纖維素纖維 |
DE102016004715A1 (de) * | 2016-04-19 | 2017-10-19 | Oerlikon Textile Gmbh & Co. Kg | Vorrichtung zum Abkühlen einer ringförmigen extrudierten Filamentschar |
WO2017211798A1 (en) | 2016-06-07 | 2017-12-14 | Universität Regensburg | Process for the preparation of a cellulose product |
KR20180089049A (ko) | 2017-01-31 | 2018-08-08 | 조금숙 | 복합 발효에 의한 아로니아 차 및 그 제조방법 |
Family Cites Families (40)
Publication number | Priority date | Publication date | Assignee | Title |
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US2179181A (en) * | 1936-04-21 | 1939-11-07 | Soc Of Chemical Ind | Cellulose solutions and process of making same |
US2284028A (en) * | 1939-09-26 | 1942-05-26 | Ubbelohde Leo | Dry spinning process |
BE452577A (ru) * | 1942-10-06 | |||
GB807248A (en) * | 1957-01-15 | 1959-01-14 | Dow Chemical Co | Method for spinning polyolefines |
US3118012A (en) * | 1959-05-01 | 1964-01-14 | Du Pont | Melt spinning process |
GB957534A (en) * | 1962-01-18 | 1964-05-06 | British Nylon Spinners Ltd | Improvements in or relating to melt-spinning synthetic polymer filaments |
IL21472A (en) * | 1963-06-06 | 1968-02-26 | Monsanto Co | Wet-spinning of synthetic vinyl polymers |
US3299469A (en) * | 1964-11-18 | 1967-01-24 | Du Pont | Melt-spinning apparatus |
US3619452A (en) * | 1969-03-07 | 1971-11-09 | Allied Chem | Filament quenching apparatus and process |
DE2113327A1 (de) * | 1971-03-19 | 1972-10-12 | Reifenhaeuser Kg | Vorrichtung zur Herstellung von schmelzgesponnenen Fasern |
US3858386A (en) * | 1971-07-06 | 1975-01-07 | Fiber Industries Inc | Polyester yarn production |
US3969462A (en) * | 1971-07-06 | 1976-07-13 | Fiber Industries, Inc. | Polyester yarn production |
US4038357A (en) * | 1972-06-28 | 1977-07-26 | Imperial Chemical Industries Inc. | Manufacture of synthetic filaments |
US3996321A (en) * | 1974-11-26 | 1976-12-07 | E. I. Du Pont De Nemours And Company | Level control of dry-jet wet spinning process |
FR2372251A1 (fr) * | 1976-11-26 | 1978-06-23 | Rhone Poulenc Textile | Nouveau procede de filage ou mise en forme de solutions de cellulose et articles ainsi obtenus |
US4078034A (en) * | 1976-12-21 | 1978-03-07 | E. I. Du Pont De Nemours And Company | Air gage spinning process |
US4416698A (en) * | 1977-07-26 | 1983-11-22 | Akzona Incorporated | Shaped cellulose article prepared from a solution containing cellulose dissolved in a tertiary amine N-oxide solvent and a process for making the article |
US4144080A (en) * | 1977-07-26 | 1979-03-13 | Akzona Incorporated | Process for making amine oxide solution of cellulose |
ZA785535B (en) * | 1977-10-31 | 1979-09-26 | Akzona Inc | Process for surface treating cellulose products |
US4261943A (en) * | 1979-07-02 | 1981-04-14 | Akzona Incorporated | Process for surface treating cellulose products |
EP0040482B1 (en) * | 1980-05-13 | 1984-08-08 | Celanese Corporation | Process and apparatus for melt spinning filaments in which quench gas and finishing liquid are introduced to the filaments through the fibre pack and spinneret |
US4285646A (en) * | 1980-05-13 | 1981-08-25 | Fiber Industries, Inc. | Apparatus for quenching melt-spun filaments |
DE3162048D1 (en) * | 1980-10-21 | 1984-03-01 | Fiber Industries Inc | Process of, apparatus for, and filament guide for, producing melt-spun filaments |
US4340559A (en) * | 1980-10-31 | 1982-07-20 | E. I. Du Pont De Nemours And Company | Spinning process |
JPS57161113A (en) * | 1981-03-31 | 1982-10-04 | Nippon Ester Co Ltd | Melt spinning method |
US4713290A (en) * | 1982-09-30 | 1987-12-15 | Allied Corporation | High strength and modulus polyvinyl alcohol fibers and method of their preparation |
US4440711A (en) * | 1982-09-30 | 1984-04-03 | Allied Corporation | Method of preparing high strength and modulus polyvinyl alcohol fibers |
DE3406346C2 (de) * | 1983-02-25 | 1986-08-28 | Barmag Barmer Maschinenfabrik Ag, 5630 Remscheid | Schmelzspinnvorrichtung zur Erzeugung einer Schar von Filamentfäden |
DD218121A1 (de) * | 1983-10-17 | 1985-01-30 | Chemiefaser Komb Schwarza Wilh | Verfahren zur herstellung von formkoerpern aus celluloseloesungen |
JPS61119704A (ja) * | 1984-11-13 | 1986-06-06 | Mitsui Petrochem Ind Ltd | フイラメント集合体の冷却方法 |
CH673659A5 (ru) * | 1987-03-05 | 1990-03-30 | Inventa Ag | |
US4836507A (en) * | 1987-08-10 | 1989-06-06 | E. I. Du Pont De Nemours And Company | Aramid staple and pulp prepared by spinning |
US5094690A (en) * | 1988-08-16 | 1992-03-10 | Lenzing Aktiengesellschaft | Process and arrangement for preparing a solution of cellulose |
AT392972B (de) * | 1988-08-16 | 1991-07-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von loesungen von cellulose sowie einrichtung zur durchfuehrung des verfahrens |
DE4004798A1 (de) * | 1990-02-16 | 1991-08-22 | Akzo Gmbh | Verfahren und vorrichtung zur herstellung von formkoerpern |
AT395863B (de) * | 1991-01-09 | 1993-03-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung eines cellulosischen formkoerpers |
ATA53792A (de) * | 1992-03-17 | 1995-02-15 | Chemiefaser Lenzing Ag | Verfahren zur herstellung cellulosischer formkörper, vorrichtung zur durchführung des verfahrens sowie verwendung einer spinnvorrichtung |
MY115308A (en) * | 1993-05-24 | 2003-05-31 | Tencel Ltd | Spinning cell |
AT401271B (de) * | 1993-07-08 | 1996-07-25 | Chemiefaser Lenzing Ag | Verfahren zur herstellung von cellulosefasern |
AT402738B (de) * | 1993-07-28 | 1997-08-25 | Chemiefaser Lenzing Ag | Spinndüse |
-
1993
- 1993-07-01 AT AT0129193A patent/AT399729B/de not_active IP Right Cessation
-
1994
- 1994-03-14 US US08/214,953 patent/US5698151A/en not_active Expired - Lifetime
- 1994-06-27 YU YU40894A patent/YU48686B/sh unknown
- 1994-06-29 EP EP94919458A patent/EP0658221B1/de not_active Expired - Lifetime
- 1994-06-29 SK SK267-95A patent/SK281292B6/sk unknown
- 1994-06-29 AU AU70184/94A patent/AU668485B2/en not_active Ceased
- 1994-06-29 PL PL94307724A patent/PL307724A1/xx unknown
- 1994-06-29 CZ CZ95548A patent/CZ285848B6/cs not_active IP Right Cessation
- 1994-06-29 RO RO95-00301A patent/RO113160B1/ro unknown
- 1994-06-29 HU HU9500590A patent/HU214308B/hu not_active IP Right Cessation
- 1994-06-29 SI SI9430008T patent/SI0658221T1/xx unknown
- 1994-06-29 CN CN94190458A patent/CN1039039C/zh not_active Expired - Lifetime
- 1994-06-29 ES ES94919458T patent/ES2085186T3/es not_active Expired - Lifetime
- 1994-06-29 GB GB9503083A patent/GB2284382B/en not_active Revoked
- 1994-06-29 CA CA002141817A patent/CA2141817C/en not_active Expired - Fee Related
- 1994-06-29 DE DE59400112T patent/DE59400112D1/de not_active Expired - Fee Related
- 1994-06-29 WO PCT/AT1994/000083 patent/WO1995001470A1/de active IP Right Grant
- 1994-06-29 DE DE4494608T patent/DE4494608D2/de not_active Expired - Fee Related
- 1994-06-29 RU RU95109441A patent/RU2120504C1/ru not_active IP Right Cessation
- 1994-06-29 JP JP7503156A patent/JPH08500863A/ja active Pending
- 1994-06-29 KR KR1019950700768A patent/KR0177261B1/ko not_active IP Right Cessation
- 1994-06-29 DK DK94919458.3T patent/DK0658221T3/da active
- 1994-06-29 AT AT94919458T patent/ATE134003T1/de not_active IP Right Cessation
- 1994-06-29 BR BR9405438-0A patent/BR9405438A/pt not_active IP Right Cessation
- 1994-07-01 TR TR00678/94A patent/TR28801A/xx unknown
- 1994-07-01 ZA ZA944766A patent/ZA944766B/xx unknown
-
1995
- 1995-02-16 BG BG99434A patent/BG62408B1/bg unknown
-
1996
- 1996-03-13 GR GR960400699T patent/GR3019295T3/el unknown
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