EP0601278B1 - Centrifuge de filage - Google Patents
Centrifuge de filage Download PDFInfo
- Publication number
- EP0601278B1 EP0601278B1 EP93112923A EP93112923A EP0601278B1 EP 0601278 B1 EP0601278 B1 EP 0601278B1 EP 93112923 A EP93112923 A EP 93112923A EP 93112923 A EP93112923 A EP 93112923A EP 0601278 B1 EP0601278 B1 EP 0601278B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- threads
- spinning rotor
- particles
- airflow
- spinning
- 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
- 238000009987 spinning Methods 0.000 title claims description 60
- 239000002245 particle Substances 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000155 melt Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007786 electrostatic charging Methods 0.000 claims description 2
- 239000004753 textile Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 description 15
- 239000004745 nonwoven fabric Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 235000012434 pretzels Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000011144 upstream manufacturing 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
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
Definitions
- the invention relates to a method with the features of the preamble of claim 1 for the production of a textile fabric.
- Such a method and an apparatus for carrying out the method are known from JP-A-52-18927.
- the threads emerging from the spinning rotor are passed through a chamber which is located radially outside the spinning rotor and is filled with particles.
- An air flow acts on the particles within the chamber in order to establish a connection with the threads emerging from the spinning rotor.
- JP-A-52-99324 Another method and an apparatus are known from JP-A-52-99324. With the help of a spinning rotor, the melt is converted into the form of threads which exit radially from nozzles of the spinning rotor. The exiting threads are coated with metallic particles by means of an air flow, the chambers in which the coating takes place and the air flow with which the particles are applied being assigned adjacent to the nozzles of the spinning rotor at a radial distance.
- Spunbonded processes enable the production of fine fiber nonwovens, which have different properties depending on the composition of the starting materials and the subsequent processing.
- a Polymer granules are usually melted in an extruder and conveyed under an excess pressure of up to 200 bar into a spinning rotor rotating at 3000 to 11000 rpm, which is electrically heated by heating elements.
- the threads emerging radially from the spinning rotor are then deflected and consolidated on a conveyor belt to form a flat structure and deposited.
- the invention has for its object to further develop a method such that filter elements made of nonwoven fabrics are provided with filter-effective charges even after a long period of use, that the distribution of particles on the threads is evened out and that the particles are simply applied to the threads in a hot gas stream can be brought in.
- This object is achieved in that the particles are sprinkled into the air flow before the air flow hits the threads and that the gas particle mixture through a boundary layer flow, which is generated on the surface of the spinning rotor by its rotation, to the still sticky threads on the Outlet openings is promoted. After leaving the spinning rotor, the threads are acted upon by a gas flow in a still sticky state, solid particles being sprinkled into the gas flow before they hit the threads.
- these particles consist of different materials.
- Barium titanate particles, for example, are dipoles that form agglomerates at room temperature and thus neutralize their charge.
- the particles are heated to temperatures above 120 ° C by means of the air flow, they lose their charge. In this state, the particles reach the still plastic fiber surface facing the air flow in a uniform distribution and stick to the fiber.
- This pretzel stick effect has the advantage that no separate adhesive is used which negatively influences the filter effect of the fabric. As the size of the applied particles increases, the filter effect of the nonwoven fabric is further improved.
- the threads are exposed to ionizing radiation immediately after their exposure to the particles. Due to the ionizing radiation, filter-effective charges form on the particle-loaded fibers, which remain effective even after long filter use.
- the threads can be continuously and progressively deposited on a carrier fleece.
- the suction box which can be arranged in a ring around the spinning rotor and also surrounds the carrier and cover material, ensures that the material webs are coated with the charge-carrying, particle-laden threads.
- the fabric sheets are then laminated by pairs of rollers and can be rolled up on a winding station.
- the invention relates to a device comprising a spinning rotor with outlet openings which can be rotated about its axis, the spinning rotor being associated with a second auxiliary means for continuously supplying a gas to the threads and a third auxiliary means for the continuous feeding of solid particles into the gas.
- a device for producing spunbonded nonwovens should be simple in construction, work reliably and largely maintenance-free and at the same time be able to process the most varied of starting products to form as many end products as possible.
- Centrifugal spinning devices are known and are explained in the documents EP 0 071 085 A1, EP 0 168 817 A2, DE 3 105 784 A1, DE 3 215 810 C2, DE 3 801 080 A1, US 4,277,436.
- the invention has for its object to further develop a method such that filter elements made of nonwoven fabrics are provided with filter-effective charges even after a long period of use, that the distribution of particles on the threads is evened out and that the particles are simply applied to the threads in a hot gas stream can be brought in.
- the second tool consists of an annular nozzle in front of the spinning rotor in the axial direction and that the ring nozzle has an exit direction facing the outer circumference of the spinning rotor, which, when the spinning rotor rotates, opens into the boundary layer flow on its surface, in that the third tool there is a particle store upstream of the spinning rotor in the axial direction and that the particle store has an outlet opening opening into the ring nozzle.
- the second and third tools are assigned to the spinning rotor axially so close that the hot gas particle mixture is conveyed to the still sticky threads at the outlet openings by the boundary layer flow which is generated on the circumference of the spinning rotor by its rotation.
- the spinning rotor In the axial direction, the spinning rotor is preceded by an annular nozzle which has an exit direction facing the outer circumference of the spinning rotor.
- the hot gas with the particles contained therein is conveyed to the still plastic threads by a boundary layer flow generated by the spinning rotor along the outer circumference of the spinning rotor.
- the particle store is also located in front of the spinning rotor in the axial direction and has an outlet opening that opens into the ring nozzle.
- This requirement of particle storage and ring nozzle proves to be particularly advantageous. It enables compact dimensions of the device and unproblematic introduction of the particles into the hot gas stream. Acting on the gas in the boundary layer flow with particles that are added outside of the ring nozzle is structurally significantly more complex and problematic because of the required uniform distribution of the particles over the circumference of the spinning rotor.
- the cross section of the outlet opening of the particle container is variable.
- the amount of particles supplied to the hot gas can thus be varied at any time without great effort.
- a wide range of particles can then be processed in terms of size and shape in the system.
- the spinning rotor according to claim 8 is radially enclosed by corona elements for the electrostatic charging of the threads, and the corona elements are axially adjacent to the radial plane of the outlet openings on both sides. As soon as the threads emerge from the spinning rotor, they are passed through a high-voltage field and their charge carriers align. Then there is a filter-effective charge on the threads, which remain effective even after long filter use.
- the claims 9 and 10 relate to the corona elements, which are ring-shaped according to claim 9, based on the spinning rotor, can be fixed according to claim 10. Due to the ring shape and the fixed storage, unbalance in the device is excluded even at high speeds of the spinning head. In addition, there are no rotating inertial forces in the case of stationary corona elements. Speed changes and corrections of the spinning rotor can be carried out faster and more precisely.
- the first aid can be moved parallel to the axis and is provided for the continuous collection of the threads emerging from the outlet opening.
- FIG. 1 shows the schematic arrangement of the device according to the invention.
- the covering material 15 see FIG. 3
- the upper part of the suction box 5 are not shown.
- the rotation of the spinning head 1 exerts a centrifugal force on the polymer melt in the spinning head 1.
- the melt accumulates on the inner circumference of the spinning head 1 in front of the nozzles 3 and is pressed into the open by the nozzles 3 as a function of the speed 4 of the spinning head 1 (and thus as a function of the centrifugal force) and the viscosity of the melt.
- the large number of still plastic threads 10 emerging from the nozzles 3 is greatly stretched by the braking effect of the air, the centrifugal force and the mass inertia.
- Carrier 14 and cover material 15 move past the nozzles 3 in the axial direction of the spinning head 1.
- the spinning head 1 is radially enclosed by the carrier 14 and cover material 15.
- the threads are progressively brought to rest on the carrier 14 and the covering fleece 15 after they have solidified.
- the two material webs coated with the fine fiber nonwoven 16 are laminated in the nip 6 and can be wound up by a winding station, not shown in the drawing.
- FIG. 2 shows a spinning head 1 with an at least one-row nozzle ring 7 and the drive shaft 2.
- a hot gas particle mixture 9 is applied to the rotating spinning rotor 1 through an annular nozzle 8, which is arranged in front of the spinning rotor 1 in the axial direction and has an outlet opening facing the outer circumference of the spinning rotor 1 blown.
- the rotating spinning rotor 1 generates a boundary layer flow on its surface, as a result of which the hot gas particle mixture 9 arrives at the still plastic threads 10 emerging from the nozzles 3.
- the particles of the hot gas particle mixture 9 stick to the surface of the threads 10.
- FIG. 3 shows the structure of the filter material according to the invention.
- a layer of fine-fiber nonwoven fabric 16 is embedded between a carrier 14 and cover material 15.
- the particles 17 are shown on the fine-fiber nonwoven fabric 16.
- the filter-effective charges, which remain effective even after prolonged use of the filter due to the dipole effect of the particles 17, are applied to the fine-fiber nonwoven 16, 17 which is loaded with particles.
- FIG 4 a fiber made of polymeric material is shown schematically on a greatly enlarged scale.
- the particles 17 located on the fiber surface bring about good usage properties over a long period of use.
- FIG. 5 shows a greatly enlarged detail from the fiber of FIG. 4.
- the particles 17, which are not arranged as agglomerates, but separately on the fiber surface, can be clearly seen.
- the particles 17 are firmly adhered to the surface of the fibers without impairing the effective filter surface.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Nonwoven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Filtering Materials (AREA)
- Spinning Or Twisting Of Yarns (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Claims (11)
- Procédé de fabrication d'une nappe textile, transformant en fils (10) la masse fondue d'une matière polymère à l'aide d'une centrifuge de filage (1), les fils (10) étant ensuite combinés et consolidés sous forme de nappe, les fils (10) encore collants étant admis dans un courant d'air à leur sortie de la centrifuge de filage (1), et des particules solides (17) étant répandues dans le courant d'air, caractérisé en ce que les particules (17) sont répandues dans le courant d'air, avant que le courant d'air n'ait atteint les fils (10) et en ce que le mélange particules-gaz (9) est transporté vers les fils encore collants (10), aux orifices de sortie, par un courant de couche limite produit à la surface de la centrifuge de filage (1) par sa rotation.
- Procédé selon la revendication 1, caractérisé en ce que en tant que particules (17), des dipôles formant des agglomérats à température ambiante, sont répandus dans le courant d'air.
- Procédé selon la revendication 2, caractérisé en ce que les dipôles sont chauffés par le courant d'air et atteignent au minimum une température de 120 °C.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que les fils (10) sont soumis à un rayonnement ionisant directement après leur mélange avec des particules (17).
- Procédé selon l'une des revendications 1 à 4, caractérisé en ce que les fils (10), après leur façonnage et leur consolidation, sont déposés en continu sur une nappe porteuse (14, 15).
- Dispositif d'utilisation d'un procédé selon l'une des revendications 1 à 5, comprenant une centrifuge de filage (1) pouvant être mise en rotation autour de son axe (2) et pourvue d'orifices de sortie, un deuxième dispositif auxiliaire étant associé de manière contigüe à la centrifuge de filage (1) pour l'amenée en continu de gaz sur les fils ainsi qu'un troisième dispositif auxiliaire pour l'introduction en continu de particules solides (17) dans le gaz, caractérisé en ce que le deuxième dispositif auxiliaire est constitué d'une tuyère annulaire (8) placée dans le sens axial avant la centrifuge de filage (1) et en ce que la tuyère annulaire (8) est pourvue d'un orifice de sortie orienté vers le périmètre extérieur de la centrifuge de filage et débouchant dans le courant de couche limite à la surface de la centrifuge de filage (1) en rotation, en ce que le troisième dispositif auxiliaire est constitué d'un réservoir de particules (18) placé dans le sens axial avant la centrifuge de filage (1) et en ce que le réservoir de particules (18) est pourvu d'un orifice de sortie débouchant dans la tuyère annulaire (8).
- Dispositif selon la revendication 6, caractérisé en ce que la section transversale de l'orifice de sortie du réservoir de particules (18) est modifiable.
- Dispositif selon l'une des revendications 4 à 7, caractérisé en ce que la centrifuge de filage (1) est radialement entourée d'éléments à effet corona (12, 13) pour la charge électrostatique des fils (10) et en ce que les éléments à effet corona (12, 13) sont associés de manière contigüe, des deux côtés en direction axiale, au plan radial des orifices de sortie.
- Dispositif selon la revendication 8, caractérisé en ce que les éléments à effet corona (12, 13) ont une forme annulaire.
- Dispositif selon l'une des revendications 8 à 9, caractérisé en ce que les éléments à effet corona (12,13) sont fixés de manière stationnaire par rapport à la centrifuge de filage (1).
- Dispositif selon l'une des revendications 6 à 10, caractérisé en ce que le premier dispositif auxiliaire est déplaçable parallèlement à l'axe (2) et est destiné à la collecte en continu des fils (10) provenant des orifices de sortie.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE4241514 | 1992-12-10 | ||
DE4241514A DE4241514C2 (de) | 1992-12-10 | 1992-12-10 | Verfahren zur Herstellung eines mit Dipolen beladenen Flächengebildes und Vorrichtung zur Durchführung des Verfahrens |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0601278A1 EP0601278A1 (fr) | 1994-06-15 |
EP0601278B1 true EP0601278B1 (fr) | 1997-10-15 |
Family
ID=6474813
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93112923A Expired - Lifetime EP0601278B1 (fr) | 1992-12-10 | 1993-08-12 | Centrifuge de filage |
Country Status (5)
Country | Link |
---|---|
US (1) | US5419794A (fr) |
EP (1) | EP0601278B1 (fr) |
JP (1) | JP2635924B2 (fr) |
DE (1) | DE4241514C2 (fr) |
ES (1) | ES2108793T3 (fr) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5637326A (en) * | 1995-12-04 | 1997-06-10 | Fuisz Technologies Ltd. | Apparatus for making chopped amorphous fibers with an air transport system |
US20070031607A1 (en) * | 2000-12-19 | 2007-02-08 | Alexander Dubson | Method and apparatus for coating medical implants |
DE10137161C5 (de) * | 2001-07-30 | 2009-04-09 | Mann+Hummel Innenraumfilter Gmbh & Co. Kg | Filterelement |
AU2003269345A1 (en) * | 2002-09-16 | 2004-04-30 | Triosyn Holding, Inc. | Electrostatically charged filter media incorporating an active agent |
BRPI0409518B1 (pt) * | 2003-04-03 | 2014-08-19 | Du Pont | Processo, aparelho de fiação rotacional e folha não tecida fibrosa |
WO2005099995A2 (fr) * | 2004-04-12 | 2005-10-27 | Polymer Group, Inc. | Procede de fabrication de substrats electroconducteurs |
CA2718895A1 (fr) * | 2008-03-17 | 2009-09-24 | The Board Of Regents Of The University Of Texas System | Filiere de creation de fibres superfines et utilisations correspondantes |
US8647541B2 (en) | 2011-02-07 | 2014-02-11 | Fiberio Technology Corporation | Apparatuses and methods for the simultaneous production of microfibers and nanofibers |
WO2012109240A2 (fr) * | 2011-02-07 | 2012-08-16 | Fiberio Technology Corporation | Dispositifs de fabrication de fibre clivée et procédés de fabrication de microfibres et de nanofibres |
DE102013007118A1 (de) * | 2013-04-25 | 2014-10-30 | Mann + Hummel Gmbh | Mehrlagiges Filterelement |
DE102014011443B4 (de) | 2014-08-07 | 2021-12-16 | Mann+Hummel Gmbh | Filtermedium, Filterelement und Wechselfilter zur Filterung von partikulären Verunreinigungen aus einer Flüssigkeit |
AU2018330936A1 (en) | 2017-09-08 | 2020-03-26 | Board Of Regents Of The University Of Texas System | Mechanoluminescence polymer doped fabrics and methods |
US11427937B2 (en) | 2019-02-20 | 2022-08-30 | The Board Of Regents Of The University Of Texas System | Handheld/portable apparatus for the production of microfibers, submicron fibers and nanofibers |
Family Cites Families (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3357807A (en) * | 1961-12-08 | 1967-12-12 | Owens Corning Fiberglass Corp | Method and apparatus for forming and processing continuous filaments |
FR1348800A (fr) * | 1962-02-19 | 1964-01-10 | Ici Ltd | Filaments modifiés |
US3174182A (en) * | 1962-06-22 | 1965-03-23 | Edward W O Shaughnessy | Spinning arrangement for spinning fibers from molten plastic or the like |
JPS5043218A (fr) * | 1973-08-28 | 1975-04-18 | ||
JPS5218927A (en) * | 1975-07-31 | 1977-02-12 | Matsushita Electric Works Ltd | Process for producing inorganic fibers coated with a protective coatin g |
JPS5299324A (en) * | 1976-02-14 | 1977-08-20 | Matsushita Electric Works Ltd | Apparatus for producing inorganic fibers |
US4215682A (en) * | 1978-02-06 | 1980-08-05 | Minnesota Mining And Manufacturing Company | Melt-blown fibrous electrets |
US4277436A (en) * | 1978-04-26 | 1981-07-07 | Owens-Corning Fiberglas Corporation | Method for forming filaments |
NL187915C (nl) * | 1981-02-16 | 1992-02-17 | Sten Halvor Harsem | Werkwijze voor het spinnen van vezels en inrichting voor het uitvoeren van deze werkwijze. |
CA1155619A (fr) * | 1981-02-19 | 1983-10-25 | Leif E. Stern | Methode de filature de fibres |
US4440700A (en) * | 1981-04-28 | 1984-04-03 | Polymer Processing Research Institute Ltd. | Process for collecting centrifugally ejected filaments |
DE3128872A1 (de) * | 1981-07-22 | 1983-02-10 | Basf Ag, 6700 Ludwigshafen | Verfahren zur reproduzierbaren herstellung von formteilchen unterschiedlicher geometrie aus polymerdispersionen, schmelzen oder loesungen |
US4790736A (en) * | 1984-07-20 | 1988-12-13 | John E. Benoit | Apparatus for centrifugal fiber spinning with pressure extrusion |
JPS6176363A (ja) * | 1984-08-09 | 1986-04-18 | 株式会社クラレ | 加硫ゴム製品の製造法 |
US4797318A (en) * | 1986-07-31 | 1989-01-10 | Kimberly-Clark Corporation | Active particle-containing nonwoven material, method of formation thereof, and uses thereof |
JPH0647479B2 (ja) * | 1986-12-16 | 1994-06-22 | 新日鐵化学株式会社 | 軽量な無機繊維の製造方法 |
DE3839956C2 (de) * | 1987-11-28 | 1998-07-02 | Toyo Boseki | Elektret-Folie und Verfahren zu ihrer Herstellung |
DE3801080A1 (de) * | 1988-01-16 | 1989-07-27 | Bayer Ag | Verfahren zur herstellung von feinstpolymerfasern |
US4865755A (en) * | 1988-05-03 | 1989-09-12 | Kimberly-Clark Corporation | Method for incorporating powdered detergent ingredients into a meltblown laundry detergent sheet |
US4904174A (en) * | 1988-09-15 | 1990-02-27 | Peter Moosmayer | Apparatus for electrically charging meltblown webs (B-001) |
DE4009351A1 (de) * | 1989-03-28 | 1990-10-04 | Nmi Naturwissenschaftl U Mediz | Verfahren und vorrichtung zur herstellung von keramischen und/oder metallischen fasern |
US5173356A (en) * | 1989-09-25 | 1992-12-22 | Amoco Corporation | Self-bonded fibrous nonwoven webs |
CA2027687C (fr) * | 1989-11-14 | 2002-12-31 | Douglas C. Sundet | Materiau de filtration et methode de fabrication connexe |
US5123949A (en) * | 1991-09-06 | 1992-06-23 | Manville Corporation | Method of introducing addivites to fibrous products |
-
1992
- 1992-12-10 DE DE4241514A patent/DE4241514C2/de not_active Expired - Fee Related
-
1993
- 1993-08-12 ES ES93112923T patent/ES2108793T3/es not_active Expired - Lifetime
- 1993-08-12 EP EP93112923A patent/EP0601278B1/fr not_active Expired - Lifetime
- 1993-12-08 JP JP5307992A patent/JP2635924B2/ja not_active Expired - Lifetime
- 1993-12-10 US US08/166,056 patent/US5419794A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
DE4241514A1 (de) | 1994-06-16 |
JPH06220761A (ja) | 1994-08-09 |
JP2635924B2 (ja) | 1997-07-30 |
ES2108793T3 (es) | 1998-01-01 |
US5419794A (en) | 1995-05-30 |
DE4241514C2 (de) | 1995-09-07 |
EP0601278A1 (fr) | 1994-06-15 |
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