EP1044293B1 - Textilfäden aus multifilamenten mit hohlquerschnitt, herstellungsverfahren und daraus hergestellte textil-flächengebilde - Google Patents

Textilfäden aus multifilamenten mit hohlquerschnitt, herstellungsverfahren und daraus hergestellte textil-flächengebilde Download PDF

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Publication number
EP1044293B1
EP1044293B1 EP98963617A EP98963617A EP1044293B1 EP 1044293 B1 EP1044293 B1 EP 1044293B1 EP 98963617 A EP98963617 A EP 98963617A EP 98963617 A EP98963617 A EP 98963617A EP 1044293 B1 EP1044293 B1 EP 1044293B1
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EP
European Patent Office
Prior art keywords
yarn
section
filaments
polyamide
cross
Prior art date
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Expired - Lifetime
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EP98963617A
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English (en)
French (fr)
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EP1044293A1 (de
Inventor
Vincent Pellerin
Walter Roggenstein
Uwe Schaffner
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Nylstar SA France
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Nylstar SA France
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Classifications

    • 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
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • 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
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • Y10T428/264—Up to 3 mils
    • Y10T428/265—1 mil or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/2964—Artificial fiber or filament
    • Y10T428/2967—Synthetic resin or polymer
    • Y10T428/2969—Polyamide, polyimide or polyester
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2973—Particular cross section
    • Y10T428/2975—Tubular or cellular

Definitions

  • the present invention relates to a multifilament textile yarn, the filaments or strands have a hollow section, a method of making this hollow wire, and the surfaces textiles obtained with such a yarn.
  • It relates more particularly to the manufacture of multifilament yarns comprising hollow filaments obtained by melt spinning of a composition in polyamide.
  • This patent describes the manufacture of polyamide 6 filaments obtained at a speed 700 m / min. The filaments are then subjected to stretching to obtain the desired title.
  • the spinning speed is very low compared to the process speeds current industrialists who are often above 3000 m / min.
  • the stretching step is often integrated into the spinning, without rework filament intermediate.
  • One of the aims of the present invention is to provide a multifilament textile yarn whose strands have a hollow section obtained by a spinning or spinning-drawing process which has the advantages of current industrial processes for spinning filaments with a full section, namely productivity. and regularity of the properties of the yarn by using a polyamide of V R similar to that of the polyamides used in the manufacture of textile yarns.
  • the invention provides a multifilament textile yarn of polyamide of title strand less than 10 dtex, and whose strands have a hollow section comprising a central empty area representing at least 5% of the total section area transverse of said strand, characterized in that the wire has a USTER coefficient (U%) less than 3% and a number of strands with cross-section in the shape of an arc of a circle less than 30% of the total number of hollow section strands.
  • U% USTER coefficient
  • hollow section strand must be understood all the strands or filaments obtained at from a die hole in the shape of an arc of a circle as will be described below.
  • the hollow strands are those whose cross section is shaped closed or open crown.
  • the multifilament yarn has a U% of less than 2%, preferably less than 1%.
  • the number of filaments in the shape of an arc of a circle is advantageously less than 20% of the total number of hollow section filaments, preferably less than 10%.
  • U% or USTER coefficient is representative of the regularity of a thread continued. Thus, this coefficient is determined by measuring the variations in the titer of a thread continuous on a USTER device (Zellweger).
  • the wire kept under a certain tension passes at a constant speed between the plates of a capacitor, the variation of the element dielectric formed by the wire due to the variation in mass of the wire causes a variation in capacitance of the capacitor which is translated into irregularity in the title of the wire.
  • the percentage of empty area in the section of filaments or strands is greater than 10%, preferably greater than 15% of the cross section of each strand.
  • this value is between 15 and 50%.
  • the multifilament yarn is obtained by spinning from a die of a polyamide-based composition having a relative viscosity V R greater than 40 and preferably between 40 and 55, advantageously between 40 and 50.
  • the relative viscosity V R of the polyamide is determined on an 8.4% solution of polymer in formic acid.
  • the polyamide suitable for the invention is chosen from the group comprising advantageously, polyamide 6, polyamide 66, mixtures of polyamides comprising at least 80% by weight of polyamide 66 or polyamide 6, the copolyamides comprising at least 80% by number of polyamide 66 or polyamide 6 units.
  • the yarn of the invention has excellent regularity, and the absence of filaments open or cross-sectional, i.e. not coalescing at the exit from die, avoids breakage and jamming problems in downstream treatments yarn such as texturing, dyeing, weaving or knitting, for example, as well as irregularities on textile surfaces.
  • the invention also relates to a method for manufacturing a wire. multifilament having the characteristics indicated above.
  • the process for manufacturing a polyamide multifilament yarn comprising filaments of hollow section consists in extruding a composition polyamide through at least one die comprising several die holes for forming filaments or strands, to converge at least a portion of said strands into a distant point of the die to form said multifilament thread, then return said thread to a coil characterized in that each die hole is constituted by a slot in shape of a circular arc whose ends are distant by a length at most equal to 5 times the average width of said slot opening at the exit face of the die, with cooling of the filaments at the outlet of the die and with a speed of wire winding greater than 3000 m / min., preferably greater than 3500 m / min.
  • the width of the slot forming a die hole on the die exit surface is advantageously between 0.05 mm and 0.12 mm.
  • the ends of the arc of a circle forming each die hole are symmetrical over at least 5% of the total length of said circular arc, preferably over at least 15% of this total length.
  • the channels are produced according to the usual techniques such as by EDM
  • the density of holes on a die is between 0.25 hole / cm 2 and 3 holes / cm 2 .
  • the wire leaving the die is cooled.
  • the distance from the start of cooling and the exit from the die is as short as possible technologically. So a cooling immediately at the outlet of the die can be difficult to implement because it can cause deposits of polymer on the surface of the die which have for consequently a break in the filaments.
  • the cooling is obtained by a cooling fluid chosen from the group comprising air, a non-oxidizing gas, or an inert gas such as nitrogen.
  • this fluid is not saturated with water vapor.
  • the cooling fluid is air or an inert gas.
  • the methods of treating the wires thus formed are those usually used for the production of polyamide textile threads.
  • sizes to improve the surface lubrication, modify its hydrophilic or hydrophobic properties can be applied.
  • these threads are subjected to a drawing either cold or hot, in the presence of water vapor or not.
  • This stretching is generally integrated into the process of spinning, that is to say made before the rewinding.
  • the strands can also be drawn in an independent drawing process spinning, by taking up the returned thread.
  • the polyamide yarn can then be relaxed before rewinding on a spool.
  • the multifilament yarns of the invention can be subjected to crimping, texturing according to the field of use.
  • these threads can be used as flat thread, twisted or textured thread, in the weaving processes such as warp or weft thread, for example.
  • the yarns of the invention are also used for the manufacture of surfaces knitted. Such textile surfaces woven or knitted with at least one thread of the invention are also objects of the invention.
  • the yarns according to the invention are obtained by spinning a composition comprising a polyamide PA 66 with a relative viscosity VR equal to 49 and a matting agent consisting with titanium oxide at a concentration by weight of 0.3%.
  • This composition is fed into a conventional spinning device comprising a die suitable for spinning hollow wire.
  • the die comprises 40 die holes (hole density equal to 0.8 hole / cm 2 ) having a profile 1 in an arc of an outside diameter equal to 1.5 mm.
  • the ends 1a, 1b of the arc of a circle are separated by a distance e equal to 0.15 mm.
  • the width I of the slot is regular in the example illustrated and is equal to 0.08 mm. However, this width may be different over the length of the slot without thereby departing from the scope of the invention and while respecting the characteristic of symmetry of the end parts of the slot as defined above.
  • the filament bundle is cooled at the outlet of the die by a flow of cooling supplied in a direction substantially perpendicular to the direction beam travel.
  • This power supply is placed at a distance of 30 mm from the die exit surface.
  • the coolant is air at a temperature of 22 ° C.
  • the flow of coolant is fed at a speed which does not cause disturbance in the scrolling of the bundle of filaments.
  • the filaments are then converged at a point 130 cm from the outlet of the sector.
  • a sizing composition is deposited on the yarn thus formed according to conventional methods and devices.
  • the wire is then wound up on a spool at a winding speed equal to 4500 m / min.
  • the yarn obtained has a total titer of 165 dtex and comprises 40 filaments (thread title 165F40).
  • FIG. 2 representing a cross-sectional view of the wire obtained shows the hollow crown-shaped section of the filaments.
  • the percentage of vacuum is more than 15%.
  • the number of filaments with a cross-section, i.e. whose ends have not coalesced at the outlet of the die is equal to zero in the illustrated example.
  • a fabric was produced with threads obtained by the process described above and 165F40.
  • the fabric is made on a lance loom and is subjected to a calendar.
  • the yarns according to the invention are obtained by spinning in a drawing and drawing process Integrated, of a composition comprising a polyamide PA 6 of relative viscosity VR equal to 50 and a matting agent consisting of titanium oxide at a concentration 0.4% by weight.
  • This composition is fed into a conventional spinning device comprising a die suitable for spinning hollow wire identical to that used in Example 1, but having 20 holes per die.
  • the filament bundle is cooled at the outlet of the die by a flow of cooling supplied in a direction substantially perpendicular to the direction beam travel.
  • This power supply is placed at a distance of 40 mm from the die exit surface.
  • the coolant is air at a temperature of 20 ° C.
  • the flow of coolant is fed at a speed which does not cause disturbance in the scrolling of the bundle of filaments.
  • the filaments are then converged at a point 130 cm from the outlet of the sector.
  • a sizing composition is deposited on the yarn thus formed according to conventional methods and devices.
  • the wire is then wound up on a spool at a winding speed equal to 4500 m / min.
  • the yarn obtained has a total titer of 78 dtex and includes 20 filaments (thread title 78F20).
  • the yarn obtained has a percentage of void greater than 15%.
  • Number of filaments with an arcuate section, i.e. the ends of which do not have coalesced at the outlet of the die is equal to zero.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Woven Fabrics (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Knitting Of Fabric (AREA)

Claims (23)

  1. Multifilamente Textilfäden aus Polyamid mit einem Fasertiter von unter 10 dtex, bei denen die Fasern mit hohlem Querschnitt eine zentrale Hohlraumfläche aufweisen, die mindestens 5 % der Gesamtfläche des Querschnitts der genannten Faser ausmacht, dadurch gekennzeichnet, daß der Faden einen USTER-Koeffizienten (U %) von unter 3 % und eine Anzahl von Fasern mit einem Querschnitt in Form eines Kreisbogens von unter 30 % der Gesamtanzahl der Fasern mit hohlem Querschnitt besitzt.
  2. Faden nach Anspruch 1, dadurch gekennzeichnet, daß er einen U % von unter 2 % aufweist.
  3. Faden nach Anspruch 2, dadurch gekennzeichnet, daß er einen U % von unter 1 % aufweist,
  4. Faden nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Anzahl der Fasern mit offenem Querschnitt oder mit einem Querschnitt in Form eines Kreisbogens unter 20 %, vorzugsweise unter 10 % beträgt, bezogen auf die Anzahl der Fasern mit hohlem Querschnitt.
  5. Faden nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Hohlraumfläche des hohlen Querschnitts einer Faser mindestens 10 % des Gesamtquerschnitts der genannten Faser ausmacht.
  6. Faden nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß sich das Polyamid in der Gruppe befindet, die umfaßt: Polyamid 6, Polyamid 66, Mischungen von Polyamiden, die mindestens 80 Gew.-% Polyamid 66 oder Polyamid 6, Copolyamide, bei denen zahlenmäßig mindestens 80 % Einheiten von Polyamid 66 oder Polyamid 6 sind, umfassen.
  7. Faden nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Polyamid eine relative Viskosität VR zwischen 40 und 55 besitzt.
  8. Faden nach Anspruch 7, dadurch gekennzeichnet, daß die Viskosität zwischen 40 und 50 liegt.
  9. Verfahren zur Herstellung eines multifilamenten Fadens aus Polyamid, der Fasern mit hohlem Querschnitt umfaßt, darin bestehend, eine Polyamid-Zusammensetzung durch mindestens eine Spinndüse mit mehreren Düsenöffnungen zu extrudieren, um Filamente oder Fasern zu bilden, mindestens einen Teil der genannten Fasern in einem von der Spinndüse entfernten Punkt zusammenzuführen, um den genannten multifilamenten Faden zu bilden, und anschließend den genannten Faden auf eine Rolle aufzuwickeln, dadurch gekennzeichnet, daß jede Düsenöffnung durch einen Spalt in Form eines Kreisbogens gebildet wird, dessen Enden in einer Länge von höchstens fünfmal der mittleren Ereite des genannten Spaltes, der in der Austrittsfläche der Düse mündet, voneinander entfernt sind, mit Abkühlung der Fasern am Austritt der Spinndüse und mit einer Aufwickelgeschwindigkeit des Fadens von über 3000 m/min.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, daß die Hohlraumfläche des Querschnitts von jeder Faser mindestens 5 % der Gesamtfläche des Querschnitts der Faser ausmacht.
  11. Verfahren nach Anspruch 10, dadurch gekennzeichnet, daß der Anteil der hohlen Fläche mindestens 10 % der Querschnittsfläche der Faser ausmacht.
  12. Verfahren nach einem der Ansprüche 9 bis 11, dadurch gekennzeichnet, daß die mittlere Breite des Spaltes zwischen 0,05 mm und 0,12 mm beträgt.
  13. Verfahren nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, daß das Fluid zum Kühlen der Fasern unter der Spinndüse aus der Gruppe gewählt wird, die Luft oder Inertgas umfaßt.
  14. Verfahren nach einem der Ansprüche 9 bis 12, dadurch gekennzeichnet, daß der Faden zahlenmäßig höchstens 30 % Fasern mit einem Querschnitt in Form eines Kreisbogens umfaßt, bezogen auf die Anzahl der Fasern mit geschlossenem hohlen Querschnitt.
  15. Verfahren nach einem der Ansprüche 9 bis 14, dadurch gekennzeichnet, daß der Faden einen USTER-Koeffizienten von unter 3 % aufweist.
  16. Verfahren nach einem der Ansprüche 9 bis 14, dadurch gekennzeichnet, daß die Enden des Kreisbogens, der jede Düsenöffnung bildet, auf mindestens 5 % der Länge des genannten Kreisbogens symmetrisch sind.
  17. Verfahren nach Anspruch 16, dadurch gekennzeichnet, daß die symmetrischen Enden von jedem der Kreisbögen eine Länge von mindestens 15 % der Gesamtlänge eines Kreisbogens besitzen.
  18. Verfahren nach einem der Ansprüche 9 bis 17, dadurch gekennzeichnet, daß das Polyamid eine relative Viskosität zwischen 40 und 55 besitzt.
  19. Verfahren nach Anspruch 18, dadurch gekennzeichnet, daß das Polyamid eine relative Viskosität zwischen 40 und 50 besitzt.
  20. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß das Polyamid aus der Gruppe gewählt wird, die umfaßt: Polyamid 6, Polyamid 66, Mischungen von Polyamiden, umfassend mindestens 80 Gew.-% Polyamid 66 oder Polyamid 6, Copolyamide, die zahlenmäßig mindestens 80 % Einheiten von Polyamid 66 oder Polyamid 6 umfassen.
  21. Verfahren nach einem der Ansprüche 9 bis 20, dadurch gekennzeichnet, daß der Faden vor seinem Aufwickeln einem Strecken unterzogen wird.
  22. Flache, texturierte oder gezwirnte Fäden, erhalten ausgehend von einem multifilamenten Faden nach einem der Ansprüche 1 bis 8.
  23. Gewebte oder gestrickte textile Fläche, erhalten ausgehend von mindestens einem Faden nach einem der Ansprüche 1 bis 8 oder 22.
EP98963617A 1997-12-29 1998-12-23 Textilfäden aus multifilamenten mit hohlquerschnitt, herstellungsverfahren und daraus hergestellte textil-flächengebilde Expired - Lifetime EP1044293B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9716833A FR2773178B1 (fr) 1997-12-29 1997-12-29 Fils textiles multifilamentaires a section creuse - procede de fabrication de ces fils, et surfaces textiles obtenues avec ces fils
FR9716833 1997-12-29
PCT/FR1998/002857 WO1999034040A1 (fr) 1997-12-29 1998-12-23 Fils textiles multifilamentaires a section creuse, procede de fabrication de ces fils, et surfaces textiles obtenues avec ces fils

Publications (2)

Publication Number Publication Date
EP1044293A1 EP1044293A1 (de) 2000-10-18
EP1044293B1 true EP1044293B1 (de) 2001-12-05

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EP98963617A Expired - Lifetime EP1044293B1 (de) 1997-12-29 1998-12-23 Textilfäden aus multifilamenten mit hohlquerschnitt, herstellungsverfahren und daraus hergestellte textil-flächengebilde

Country Status (18)

Country Link
US (1) US6565972B1 (de)
EP (1) EP1044293B1 (de)
JP (2) JP3920571B2 (de)
KR (1) KR100361197B1 (de)
CN (1) CN1193119C (de)
AT (1) ATE210211T1 (de)
AU (1) AU1882399A (de)
BR (1) BR9814531A (de)
CA (1) CA2316819C (de)
DE (1) DE69802841T2 (de)
DK (1) DK1044293T3 (de)
ES (1) ES2164469T3 (de)
FR (1) FR2773178B1 (de)
PL (1) PL186839B1 (de)
PT (1) PT1044293E (de)
RU (1) RU2194102C2 (de)
SK (1) SK285172B6 (de)
WO (1) WO1999034040A1 (de)

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Publication number Priority date Publication date Assignee Title
US6855425B2 (en) * 2000-07-10 2005-02-15 Invista North America S.A.R.L. Polymer filaments having profiled cross-section
DE202007005259U1 (de) * 2007-04-10 2007-06-28 X-Technology Swiss Gmbh Bekleidungsstück
EP2150643B1 (de) * 2007-05-10 2014-05-14 Kolon Industries, Inc Verfahren zur faserfaltung und daraus hergestelltes faserbündel
CN102418160A (zh) * 2011-08-09 2012-04-18 马海燕 大直径圆中空聚合物单丝及其生产方法
US9845068B2 (en) * 2011-12-07 2017-12-19 Asahi Kasei Fibers Corporation Synthetic fiber used for fabric
CN104178828A (zh) * 2013-05-23 2014-12-03 东丽纤维研究所（中国）有限公司 一种中空假捻加工丝及其布帛

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Publication number Priority date Publication date Assignee Title
IT589708A (de) * 1955-09-17
AR204352A1 (es) * 1974-04-03 1975-12-22 Du Pont Hilo polihexametilenadipamida sin estirar vaporizado y procedimiento para su obtencion
JPS5721510A (en) * 1980-07-08 1982-02-04 Toray Ind Inc Spinneret for hollow fiber
JPS58169507A (ja) * 1982-03-26 1983-10-06 Tanaka Kikinzoku Kogyo Kk 中空糸紡糸用口金
JPS61289110A (ja) * 1985-06-14 1986-12-19 Toray Ind Inc 中空糸用紡糸口金
DE4334004A1 (de) * 1993-10-06 1995-04-13 Hoechst Ag Aramidfasern hoher Festigkeit und hohen Titers, Verfahren zu deren Herstellung sowie deren Verwendung
US5439626A (en) * 1994-03-14 1995-08-08 E. I. Du Pont De Nemours And Company Process for making hollow nylon filaments

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JP3920571B2 (ja) 2007-05-30
RU2194102C2 (ru) 2002-12-10
CA2316819C (fr) 2003-04-22
SK285172B6 (sk) 2006-07-07
PT1044293E (pt) 2002-05-31
DK1044293T3 (da) 2002-03-04
US6565972B1 (en) 2003-05-20
PL341523A1 (en) 2001-04-23
CN1284140A (zh) 2001-02-14
DE69802841D1 (de) 2002-01-17
JP2002500281A (ja) 2002-01-08
CA2316819A1 (fr) 1999-07-08
CN1193119C (zh) 2005-03-16
PL186839B1 (pl) 2004-03-31
AU1882399A (en) 1999-07-19
FR2773178B1 (fr) 2000-04-21
KR20010033785A (ko) 2001-04-25
FR2773178A1 (fr) 1999-07-02
ATE210211T1 (de) 2001-12-15
EP1044293A1 (de) 2000-10-18
JP2004150009A (ja) 2004-05-27
BR9814531A (pt) 2001-11-13
WO1999034040A1 (fr) 1999-07-08
SK9892000A3 (en) 2001-02-12
KR100361197B1 (ko) 2002-11-22
ES2164469T3 (es) 2002-02-16
DE69802841T2 (de) 2002-06-20

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