WO2002086203A1 - Dispositif et procede de fonte et de centrifugation - Google Patents

Dispositif et procede de fonte et de centrifugation Download PDF

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Publication number
WO2002086203A1
WO2002086203A1 PCT/JP2002/003738 JP0203738W WO02086203A1 WO 2002086203 A1 WO2002086203 A1 WO 2002086203A1 JP 0203738 W JP0203738 W JP 0203738W WO 02086203 A1 WO02086203 A1 WO 02086203A1
Authority
WO
WIPO (PCT)
Prior art keywords
cylinder
polymer material
melt
biodegradable polymer
spinning
Prior art date
Application number
PCT/JP2002/003738
Other languages
English (en)
Japanese (ja)
Inventor
Keiji Igaki
Hideki Yamane
Original Assignee
Kabushikikaisha Igaki Iryo Sekkei
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Kabushikikaisha Igaki Iryo Sekkei filed Critical Kabushikikaisha Igaki Iryo Sekkei
Priority to AU2002249597A priority Critical patent/AU2002249597B2/en
Priority to JP2002583713A priority patent/JP3898131B2/ja
Priority to EP02718587A priority patent/EP1310585B1/fr
Priority to DK02718587T priority patent/DK1310585T3/da
Priority to CA2412825A priority patent/CA2412825C/fr
Priority to KR1020027017021A priority patent/KR100780401B1/ko
Priority to DE60222848T priority patent/DE60222848T2/de
Publication of WO2002086203A1 publication Critical patent/WO2002086203A1/fr

Links

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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/04—Melting filament-forming substances
    • 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
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/06—Feeding liquid to the spinning head
    • 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

Definitions

  • the present invention relates to a method of melt-spinning a medical material implanted in a living body, for example, a yarn made of a biodegradable polymer material forming a stent implanted in a living body vessel.
  • the present invention relates to a melt spinning apparatus and a melt spinning method.
  • BACKGROUND ART Conventionally, when a stenosis occurs in a blood vessel of a living body, particularly a blood vessel such as an artery, a balloon attached near the distal end of a catheter is inserted into the stenosis and the balloon is expanded.
  • Percutaneous angioplasty which is a procedure to secure blood flow by expanding the stenosis, is performed.
  • a stent having a tubular shape is implanted in a portion where percutaneous angioplasty has been performed.
  • This stent is inserted into a blood vessel with its diameter reduced, then expanded and implanted into the blood vessel, thereby supporting the blood vessel from inside and preventing restenosis from occurring in the blood vessel. It is a thing.
  • a stent formed of a metal such as stainless steel or a Ti—Ni alloy is used.
  • the main purpose of implanting a stent in a blood vessel is to prevent acute coronary occlusion and reduce the frequency of restenosis.
  • the inventor of the present invention has disclosed a stent (Japanese Patent No. 2842493) made of a knitted fabric obtained by knitting a biodegradable polymer yarn into a tubular shape, and bending a biodegradable polymer yarn in a zigzag shape.
  • a stent wound in a tubular shape in a non-woven, non-woven state has been proposed.
  • a stent using a biodegradable polymer thread can be easily bent and deformed, it can be easily transported in a bent blood vessel and implanted at a target position.
  • biodegradable polymer materials which are high-molecular materials, have different decomposition-absorption characteristics and different mechanical characteristics depending on the molecular weight.
  • biodegradable polymer materials such as polylactic acid (PLLA)
  • PLLA polylactic acid
  • the decrease in molecular weight varies depending on the degree of thermal decomposition. Therefore, when the same biodegradable polymer material is melt-spun, if the heating time for the molten polymer material is not uniform, the average molecular weight of the spun yarn becomes uneven. Yarns with non-uniform average molecular weights have partially different degradation / absorption properties and mechanical properties.
  • an object of the present invention is to provide a yarn having uniform mechanical characteristics, uniform strength and uniform decomposition and absorption characteristics, that is, a yarn having a uniform average molecular weight can be spun, It is an object of the present invention to provide a spinning apparatus and a spinning method capable of spinning a yarn as a constituent material suitable for an elastic stent.
  • the present invention relates to a melt-spinning apparatus for melt-spinning a medical material implanted in a living body, for example, a thread made of a biodegradable polymer material forming a stent implanted in a vessel of a living body.
  • a screw provided with at least one spiral groove on a peripheral surface that is rotatably driven by a rotary drive mechanism coaxially with the cylinder, in a vertically installed cylinder to which the biodegradable polymer material is supplied;
  • the biodegradable polymer material fed into the cylinder and melted by the rotation of the screw is spun by vertically discharging from the discharge port of a nozzle coaxially mounted on the tip of the cylinder. .
  • the biodegradable polymer material melted by the screw is vertically sent out from the nozzle while being sent vertically, and spinning is performed. Stasis-Prevents the generation of non-uniform vortices and spins yarns with a uniform average molecular weight.
  • the melt spinning apparatus is capable of controlling the temperature independently in parallel with the cylinder in the axial direction on the outer peripheral side of the cylinder constituting the melting mechanism for melting the biodegradable polymer material.
  • a plurality of heating mechanisms are provided to control the molten state of the biodegradable polymer material charged into one cylinder.
  • the nozzle that discharges the molten biodegradable polymer material is controlled at a constant temperature by a heating mechanism.
  • the temperature of the molten biodegradable polymer material discharged from the nozzle can be controlled to be constant.
  • the present invention provides a melting mechanism provided with a screw provided in a vertically installed cylinder coaxially with the cylinder and provided with a spiral groove on a peripheral surface which is rotationally driven by a rotary driving mechanism.
  • the biodegradable polymer material is melted, and the melted biodegradable polymer material is vertically transferred from the discharge port of the nozzle provided coaxially with the cylinder. And spinning is performed.
  • the filament having a uniform average molecular weight is spun by the spinning method using the melt spinning device described above.
  • FIG. 1 is a side view showing a melt spinning apparatus according to the present invention.
  • FIG. 2 is a sectional view showing a cylinder and a screw of the melting mechanism.
  • FIG. 3 is a plan view showing a flow resistance plate attached to the distal end side of the cylinder c.
  • FIG. 4 is a cross-sectional view showing a discharge section provided at the distal end of the melting mechanism.
  • FIG. 5 is a cross-sectional view showing a supply unit for supplying the polymer material to the melting mechanism.
  • C FIG. 6 is a side view showing a screw disposed in one cylinder constituting the melting mechanism.
  • FIG. 7 is a side view showing a supply control mechanism provided between the melting mechanism and the discharge unit.
  • FIG. 8 is a cross-sectional view showing a set of gears that constitute the melting mechanism.
  • the melt spinning device according to the present invention is a vertical type in which a melt spinning machine is installed vertically.
  • the melt-spinning apparatus shown in FIG. 1 has a base plate 2 installed horizontally on an installation surface, and is supported by a support 3 vertically installed on the pace plate 2 via a support member 3a.
  • Machine 1 is provided.
  • the melt spinning machine 1 includes a melting mechanism 4 supported in parallel with a vertically installed column 3, and a discharge section for discharging the polymer material melted by the melting mechanism 4. 5, a supply section 6 for supplying the polymer material to the melting mechanism 4, and a rotation drive mechanism 7 for rotating a screw 16 constituting the melting mechanism 4.
  • the melting mechanism 4 of the melt spinning machine 1 includes a cylindrical cylinder 8 as shown in FIG.
  • a screw 16 is provided coaxially with the cylinder 8. The screw 16 presses the polymer material charged into the cylinder 8 and pushes the polymer material toward the tip of the cylinder 8 while promoting melting.
  • a plurality of heating sections 9 are arranged on the outer peripheral side of the cylinder 8 in parallel in the axial direction of the cylinder 8. These heating units 9 are controlled independently of each other, so that the temperature in the axial direction of the cylinder 8 can be controlled in multiple stages.
  • a connecting member 21 for connecting a discharge portion 5 for discharging the polymer material melted by the melting mechanism 4 to the cylinder 8 is attached to a tip side of the cylinder 8.
  • the connecting member 21 is formed in a ring shape, and at the center thereof, as shown in FIG. 3, a flow resistance plate 22 having a plurality of through holes 22 a parallel to the axial direction of the screw 16. Is attached.
  • the melted polymer material supplied from the tip of the cylinder 8 by the rotation of the screw 16 is given flow resistance when passing through the flow resistance plate 22 and is pressurized. It is pushed to the 5 side.
  • the through-holes 2 2 a provided in the flow resistance plate 22 are used to control the supply amount and supply speed of the molten polymer material supplied from the tip of the cylinder 8 by the rotation of the screw 16, as well as the viscosity resistance of the polymer material.
  • the number of holes and the number of holes to be provided are appropriately changed accordingly.
  • the flow resistance plate 22 may have any shape as long as the rotation of the screw 16 imparts flow resistance to the molten polymer material supplied from the tip of the cylinder 8 and pressurizes the polymer material. You may.
  • the discharge part 5 attached to the distal end side of the cylinder 8 via the connecting member 21 includes a sprue bush 11 connected to the connecting member 21 attached to the distal end side of the cylinder 8, And a nozzle 10 attached to the tip side of the sprue pipe 11.
  • Nozzle 10 is sprued through mounting member 12 It is fixed to the tip of shoe 11. Note that the nozzle 10 and the mounting member 12 may be formed integrally.
  • the sprue mesh 11 constituting the discharge section 5 functions to supply the molten polymer material supplied from the cylinder 8 to the nozzle 10 in a constant amount in a stable state, as shown in FIG.
  • the flow passage 1 la is formed at the center so as to be coaxial with the cylinder 8. That is, the flow passage 11a and the cylinder 8 are arranged vertically with their axes P i aligned.
  • the flow passage 11 a is formed in a gradually tapered shape from the vertically arranged cylinder 18 toward the nozzle 10, so that the molten polymer material supplied from the cylinder 8 stays or vortexes. This makes it possible to continuously supply the ink to the nozzle 10 in a stable state by a constant amount without causing the generation.
  • the nozzle 10 is provided with a discharge port 10 a for discharging the molten polymer material supplied from the sprue bush 11.
  • the discharge port 10a controls the diameter of the yarn to be spun, and is formed to have an appropriate diameter according to the thickness of the yarn to be spun.
  • the discharge port 10a is also formed so as to be coaxial with the flow passage 11a. That is, the discharge port 10 a and the flow passage 11 a are provided so as to be vertical and coaxial with the cylinder 8.
  • the nozzle 10 has a diameter of the discharge port 10a! By preparing a plurality of yarns having different ⁇ and replacing them appropriately, a yarn having a different thickness can be spun.
  • a heating unit 13 for controlling the temperature of the discharge unit 5 is provided on the outer peripheral side of the discharge unit 5.
  • the heating unit 13 controls the temperature of the polymer material discharged from the nozzle 10 by controlling the temperature of the discharge unit 5.
  • the supply unit 6 for supplying the polymer material to be melted to the melting mechanism 4 includes a hopper 14 for charging the polymer material into the cylinder 18 and a mounting unit 6a for the cylinder 8. I have.
  • a temperature control section 15 for controlling the temperature of the supply section 6 is provided on the outer peripheral side of the mounting section 6a.
  • the temperature controller 15 is for controlling the temperature of the polymer material supplied to the hopper 14 to a constant temperature, and is constituted by heating and cooling means.
  • the melting mechanism 4 will be described more specifically.
  • the screw 16 having a single spiral groove 17 formed on the peripheral surface is disposed coaxially in the cylinder 8.
  • the screw 16 is driven to rotate by a rotation drive mechanism 7 connected to the base end side.
  • the screw 16 is driven to rotate, the polymer material injected into the cylinder 8 and melted by the heating of the heating unit 9 is sent out to the tip side of the cylinder 8 by the rotation of the spiral groove 17.
  • the spiral grooves formed in the screw used in the commonly used melt spinning machine are formed at a pitch substantially equal to the diameter of the screw.
  • the spiral groove 17 is formed with a pitch Tp that is 1/2 of the diameter Sr of the screw 16.
  • the melt spinning apparatus is provided with a supply control mechanism 18 for controlling the supply amount of the polymer material in a molten state to be supplied to the discharge section 5 between the fusion mechanism 4 and the discharge section 5. It may be.
  • the supply control mechanism 18 for example, the one shown in FIG. 7 can be used.
  • the supply control mechanism 18 shown in FIG. 7 includes a pressure detecting means 19 for measuring the pressure of the polymer material in a molten state which is extruded from the melting mechanism 4 and flows through the flow passage 18 a, and a melted polymer. And a set of gears 20 for sending the material to the discharge section 5.
  • the supply control mechanism 18 detects the pressure of the polymer material flowing through the flow passage 18 a by the pressure detection means 19.
  • the pressure of the polymer material flowing through the flow passage 18a is made constant.
  • the pressure of the polymer material flowing through the flow passage 18a is made constant.
  • the temperature of the polymer material flowing through the flow passage 18 a where the heating section 23 is provided is set to a predetermined temperature. Is controlled.
  • the present invention is to melt spin a thread made of a biodegradable polymer material used to form a stent to be implanted in a living body.
  • a biodegradable polymer material is used as the polymer material to be melt-spun here.
  • biodegradable polymer materials include polylactic acid (PLA), polyglycolic acid (PGA), polyglactin (polyglycolic acid-polylactic acid copolymer), polydioxanone, polyglyconate (trimethylene carbonate-glycolide). Polymer), a copolymer of polylactic acid and ⁇ -caprolactone, and the like are used.
  • a pellet-shaped polymer material Pp is charged into a paper 14 of a supply unit 6.
  • the polymer material charged into the hopper 14 is supplied to the cylinder 8 of the melting mechanism 4.
  • the polymer material supplied to the hopper 14 In order for the polymer material supplied to the hopper 14 to be promptly supplied into the spiral groove 17 formed in the screw 16 rotating in the cylinder 8, it is necessary to be in a solid state. That is, the polymer material supplied to the cylinder 8 needs to be controlled to a melting point (Tm) or a softening point or lower. Further, the polymer material supplied to the cylinder 8 needs to be melted immediately after being supplied to the cylinder 18 in order to shorten the melting time in the melting mechanism 4. Therefore, the temperature control section 15 provided in the supply section 6 controls the polymer material supplied from the hopper 14 to a temperature at which the polymer material can be immediately melted while maintaining a solid state.
  • Tm melting point
  • the temperature control section 15 provided in the supply section 6 controls the polymer material supplied from the hopper 14 to a temperature at which the polymer material can be immediately melted while maintaining a solid state.
  • the polymer material supplied to the cylinder 18 via the hopper 14 is introduced into the spiral groove 17 of the screw 16 which is rotationally driven by the rotary drive mechanism 7, and is provided on the outer peripheral portion of the cylinder 8. While being heated by the heating unit 9, it is pushed out to the tip end side of the cylinder 8.
  • the polymer material being extruded is controlled by the plurality of heating units 9 to a temperature not higher than the thermal decomposition temperature at which the polymer material does not deteriorate. By controlling the temperature of the polymer material to a temperature equal to or lower than the thermal decomposition temperature, the polymer material is reliably extruded from the tip of the cylinder 8 while maintaining a molten state without being deteriorated.
  • the polymer material extruded to the tip of the cylinder 8 while maintaining the molten state is uniformly pressurized in each through-hole 22 a by being provided with flow resistance by the flow resistance plate 22. It is supplied to the discharge unit 5.
  • the through-holes 22 a formed in the flow resistance plate 22 allow the polymer material to stay or spread. Since it is formed vertically so as not to generate swirls and vortices, it can be sent to the discharge section 5 while maintaining a uniform molecular weight distribution.
  • the molten polymer material extruded from the cylinder 8 of the melting mechanism 4 is supplied to the supply control mechanism.
  • the pressure is controlled to be constant by 18, the flow rate sent to the discharge section 5 is controlled, and the pressure is reliably sent to the discharge section 5 at a constant flow rate.
  • the polymer material supplied to the supply control mechanism 18 is heated by the heating section 23 provided on the outer periphery of the supply control mechanism 18 so that the molten state is reliably maintained and the discharge section 5 is maintained. Will be sent to Also in this case, the heating unit 23 controls the heating to a temperature lower than the thermal decomposition temperature so as not to deteriorate the polymer material.
  • the polymer material in the molten state sent from the melting mechanism 4 or the supply control mechanism 18 to the discharge section 5 is heated by the heating section 23 to a temperature lower than the thermal decomposition temperature in the sprue bush 11.
  • the discharge section 5 since the discharge section 5 has a vertical flow path between the sprue bush 11 and the nozzle 10, the discharge section 5 is circulated without generating stagnation or eddy in the flowing polymer material.
  • the polymer material maintained in the molten state is supplied to the nozzle 10 through the vertical flow path, and can be discharged from the nozzle 10 while maintaining a uniform molecular weight distribution.
  • a yarn made of a polymer material having a uniform molecular weight distribution can be spun.
  • the melt-spinning apparatus and the melt-spinning method according to the present invention prevent the biodegradable polymer material from staying, preventing non-uniform overflow, and having a uniform average molecular weight.
  • Yarn can be spun.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Materials For Medical Uses (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Inorganic Fibers (AREA)

Abstract

L'invention concerne un dispositif de fonte et de centrifugation capable de fondre et de centrifuger un matériau polymère biodégradable. Ce dispositif est caractérisé en ce que le matériau polymère biodégradable est fondu au moyen d'un mécanisme de fonte (4) comprenant une vis (16) logée dans un cylindre disposé de manière verticale (8) et étant coaxiale avec celui- ci (8), la vis (16) étant entraînée de manière rotative par un mécanisme d'entraînement rotatif (7), ainsi qu'une rainure hélicoïdale (17) d'au moins une rangée formée au niveau de la surface périphérique de celle-ci, et en ce que le matériau polymère biodégradable fondu est déchargé de manière verticale à partir de l'orifice de sortie d'une buse (10) disposée de manière coaxiale avec le cylindre (8), aux fins de centrifugation.
PCT/JP2002/003738 2001-04-18 2002-04-15 Dispositif et procede de fonte et de centrifugation WO2002086203A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AU2002249597A AU2002249597B2 (en) 2001-04-18 2002-04-15 Melting and spinning device and melting and spinning method
JP2002583713A JP3898131B2 (ja) 2001-04-18 2002-04-15 溶融紡糸装置及び溶融紡糸方法
EP02718587A EP1310585B1 (fr) 2001-04-18 2002-04-15 Dispositif et procede de fonte et de centrifugation
DK02718587T DK1310585T3 (da) 2001-04-18 2002-04-15 Fremgangsmåde og apparat til smeltespinding
CA2412825A CA2412825C (fr) 2001-04-18 2002-04-15 Dispositif et procede de fonte et de centrifugation
KR1020027017021A KR100780401B1 (ko) 2001-04-18 2002-04-15 용융 방사 장치 및 용융 방사 방법
DE60222848T DE60222848T2 (de) 2001-04-18 2002-04-15 Verfahren und vorrichtung zum schmelzspinnen

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-119964 2001-04-18
JP2001119964 2001-04-18

Publications (1)

Publication Number Publication Date
WO2002086203A1 true WO2002086203A1 (fr) 2002-10-31

Family

ID=18970088

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2002/003738 WO2002086203A1 (fr) 2001-04-18 2002-04-15 Dispositif et procede de fonte et de centrifugation

Country Status (13)

Country Link
US (1) US20030173702A1 (fr)
EP (1) EP1310585B1 (fr)
JP (1) JP3898131B2 (fr)
KR (1) KR100780401B1 (fr)
CN (1) CN1461361A (fr)
AT (1) ATE375411T1 (fr)
AU (1) AU2002249597B2 (fr)
CA (1) CA2412825C (fr)
DE (1) DE60222848T2 (fr)
DK (1) DK1310585T3 (fr)
ES (1) ES2295334T3 (fr)
PT (1) PT1310585E (fr)
WO (1) WO2002086203A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7794494B2 (en) 2002-10-11 2010-09-14 Boston Scientific Scimed, Inc. Implantable medical devices
CA2532548A1 (fr) * 2003-07-18 2005-02-03 Boston Scientific Limited Dispositifs medicaux
DE102010012845A1 (de) * 2010-03-25 2011-09-29 Carl Freudenberg Kg Durch Rotationsspinnverfahren hergestellte Mehrkomponentenfasern
KR102242444B1 (ko) * 2019-06-11 2021-04-21 울산대학교 산학협력단 다공성 보형물 생성 방법 및 장치
KR102168655B1 (ko) * 2019-11-06 2020-10-21 한국섬유개발연구원 생분해성 이종소재 복합 시스-코어 필라멘트 제조방법 및 이를 통해 제조된 생분해성 이종소재 복합 시스-코어 필라멘트
CN111647958B (zh) * 2020-05-29 2022-04-15 中鸿纳米纤维技术丹阳有限公司 一种聚乙醇酸喷丝组件

Citations (3)

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JPS4414711Y1 (fr) * 1964-04-14 1969-06-23
US3737506A (en) * 1970-04-03 1973-06-05 Viscose Suisse Soc D Process and apparatus for continuous extrusion of highly-viscous melts
WO1992015342A1 (fr) * 1991-03-08 1992-09-17 Keiji Igaki Extenseur pour vaisseaux, structure de maintien de l'extenseur et dispositif de montage de ce dernier

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US3344218A (en) * 1967-09-26 Retreatment of synthetic fibres
FR1028274A (fr) * 1950-11-23 1953-05-20 Dow Chemical Co Perfectionnements apportés aux fibres bouclées ou frisées
DE2431871C3 (de) 1974-07-03 1978-10-12 Akzo Gmbh, 5600 Wuppertal Verfahren und Düsenplatte zur Herstellung einer elastischen Mattenbahn
US4347207A (en) * 1981-01-27 1982-08-31 Kling-Tecs, Inc. Method of extruding polypropylene yarn
US4950735A (en) * 1988-07-26 1990-08-21 Sharpoint L.P. Biodegradable polyamides
US5166278A (en) * 1990-04-17 1992-11-24 E. I. Du Pont De Nemours And Company Process for modifying polyamide dyeability using co-fed polyamide flake
US6719935B2 (en) * 2001-01-05 2004-04-13 Howmedica Osteonics Corp. Process for forming bioabsorbable implants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4414711Y1 (fr) * 1964-04-14 1969-06-23
US3737506A (en) * 1970-04-03 1973-06-05 Viscose Suisse Soc D Process and apparatus for continuous extrusion of highly-viscous melts
WO1992015342A1 (fr) * 1991-03-08 1992-09-17 Keiji Igaki Extenseur pour vaisseaux, structure de maintien de l'extenseur et dispositif de montage de ce dernier

Also Published As

Publication number Publication date
ES2295334T3 (es) 2008-04-16
KR100780401B1 (ko) 2007-11-28
EP1310585B1 (fr) 2007-10-10
DE60222848D1 (de) 2007-11-22
CA2412825C (fr) 2010-09-14
EP1310585A4 (fr) 2006-07-12
DK1310585T3 (da) 2008-01-02
AU2002249597B2 (en) 2007-02-15
EP1310585A1 (fr) 2003-05-14
PT1310585E (pt) 2007-10-25
KR20030011898A (ko) 2003-02-11
JPWO2002086203A1 (ja) 2004-08-12
JP3898131B2 (ja) 2007-03-28
CN1461361A (zh) 2003-12-10
ATE375411T1 (de) 2007-10-15
CA2412825A1 (fr) 2002-12-13
US20030173702A1 (en) 2003-09-18
DE60222848T2 (de) 2008-07-17

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