EP1423559B1 - Verfahren zur reformierung von verbundfasern und verwendungen - Google Patents

Verfahren zur reformierung von verbundfasern und verwendungen Download PDF

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Publication number
EP1423559B1
EP1423559B1 EP02772485A EP02772485A EP1423559B1 EP 1423559 B1 EP1423559 B1 EP 1423559B1 EP 02772485 A EP02772485 A EP 02772485A EP 02772485 A EP02772485 A EP 02772485A EP 1423559 B1 EP1423559 B1 EP 1423559B1
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EP
European Patent Office
Prior art keywords
polymer
process according
fibre
solvent
fiber
Prior art date
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Expired - Lifetime
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EP02772485A
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English (en)
French (fr)
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EP1423559A1 (de
Inventor
Philippe Poulin
Brigitte Vigolo
Pascale Launois
Patrick Bernier
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Centre National de la Recherche Scientifique CNRS
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Centre National de la Recherche Scientifique CNRS
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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/14—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated alcohols, e.g. polyvinyl alcohol, or of their acetals or ketals
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • 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
    • Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
    • Y10T428/2924—Composite
    • 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
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • 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
    • Y10T428/2929—Bicomponent, conjugate, composite or collateral fibers or filaments [i.e., coextruded sheath-core or side-by-side type]
    • Y10T428/2931—Fibers or filaments nonconcentric [e.g., side-by-side or eccentric, etc.]

Definitions

  • the present invention generally relates to the after-treatment of composite fibers and in particular to a novel process for reforming composite fibers comprising colloidal particles and at least one binder and / or bridging polymer, the use of the process and the fibers reformed obtained by said process.
  • colloidal particles is intended to mean particles defined according to IUPAC international standards as being particles whose size is between a few nanometers and a few micrometers.
  • the entanglement can be modified by more or less twisting the fiber and, as in the case of conventional polymeric fibers, the orientation of the particles must be able to be modified by pulling on the fiber, which can be produced, for example, by an extrusion process.
  • these alignments or orientations are obtained hot. Indeed, at high temperature, the fiber becomes deformable and the more mobile polymer chains can then be oriented by the traction exerted on the fibers.
  • the invention therefore proposes to remedy these drawbacks by providing a process for reforming composite fibers comprising colloidal particles and at least one binder and / or bridging polymer of an implementation particularly simple, requiring little or no energy, preserving the integrity of all components of the fiber and not requiring the installation of a particular equipment.
  • these composite fibers comprising colloidal particles and at least one binder and / or bridging polymer could perfectly be treated "cold” or at room temperature or even slightly at room temperature by the use of simple means of deformation of said bridging polymer and / or binder.
  • cold reforming at ambient temperature or at a temperature slightly above ambient temperature, it is meant any treatment of the fibers applied in said process at a temperature ranging from 0 ° C. to a temperature slightly above ambient, this being generally considered as being of the order of 20 to 25 ° C. Higher temperatures are advantageously between 25 ° C and 50 ° C.
  • said means for deforming said polymer are constituted by a plasticizer addition.
  • Another possibility of deformation of these polymers consists of an immersion of said fiber in a solvent or a mixture of solvents such that the reciprocal solubility of said polymer in said solvent or said mixture of solvents determines the optimization of said applied mechanical stresses.
  • said solvent is chosen from among the solvents in which the polymer is soluble or partially soluble.
  • the fiber is then softened by partial solubilization of the polymer and thus becomes easily malleable and transformable.
  • said solvent is chosen from solvents in which the polymer is insoluble or practically insoluble.
  • one of the advantages of the process according to the invention is that the solvation of a composite fiber comprising particles and at least one binder and / or bridging polymer allows the particles to move relative to one another without destroying the cohesion of the binder and / or bridging polymer due to the bridging forces existing between the polymer and the particles.
  • a conventional fiber consisting of particles in a polymer matrix subjected to the process according to the invention would lead to the complete dissolution of the polymer and thus to destruction of the fiber.
  • the process may be carried out by selecting as solvent all volume and / or weight mixtures of at least one solvent in which the polymer is soluble or partially soluble and at least one solvent in which the polymer is insoluble. or practically insoluble.
  • said solvent may contain at least one crosslinking agent.
  • crosslinking agent since said polymer may be particularly soluble in certain solvents, the addition of a crosslinking agent will lead to the curing of said polymer while avoiding slipping without reorientation of said colloidal particles which may occur if said polymer is made too plastic since the polymer does not play the role of matrix here but is by definition binder and / or bridging between the particles. There is then a stiffening of said polymer which then allows a better transmission of the mechanical stresses applied to the fiber and by incidence to the colloidal particles whose reorientation is desired within said fiber.
  • crosslinking agents will, of course, be chosen according to the nature of said polymer and that of said solvent. They may for example be salts or organic compounds.
  • the solvents used for carrying out the process according to the invention will be chosen from water, acetone, ethers, dimethylformamide, tetrahydrofuran, chloroform, toluene and ethanol. and / or aqueous solutions whose pH and / or concentrations of any solutes are controlled.
  • said polymer will be chosen from the polymers adsorbing on said colloidal particles.
  • the binder and / or bridging polymers according to the invention will be chosen from polyvinylalcohol, the flocculant polymers commonly used in the liquid effluent depollution industry, such as polyacrylamides, which are neutral polymers, acrylamide copolymers and acrylic acid, which are negatively charged, copolymers of acrylamide and cationic monomer, which are positively charged, the inorganic polymers based on aluminum, and / or natural polymers such as chitosan, guar and / or starch.
  • polyacrylamides which are neutral polymers
  • acrylamide copolymers and acrylic acid which are negatively charged
  • copolymers of acrylamide and cationic monomer which are positively charged
  • the inorganic polymers based on aluminum and / or natural polymers such as chitosan, guar and / or starch.
  • said polymer is polyvinylalcohol (PVA), commonly used in the synthesis of composite fibers comprising particles and at least one binder and / or bridging polymer.
  • PVA polyvinylalcohol
  • said polymer is polyvinyl alcohol with a molar mass of between 10,000 and 200,000.
  • an example of a choice of solvents may be the following: water, in which the PVA is soluble, acetone in which the PVA is insoluble or a mixture of water and acetone in which the PVA will have a controlled solubility.
  • borates will be an example of crosslinking agents that can be used when the fiber is immersed in water.
  • the colloidal particles will be chosen from carbon nanotubes, sulphide of tungsten, boron nitride, clay platelets, cellulose whiskers and / or silicon carbide whiskers.
  • the method may comprise additional steps of extracting said fiber from the solvent and / or drying said fiber so as to obtain a fiber free of any plasticizer and / or any trace of solvent.
  • These operations can advantageously be carried out in a known manner, such as, for example, drying in an oven at a temperature slightly below the boiling point of the solvent.
  • the method which is the subject of the invention may be used to manufacture fibers having an orientation of said particles composing said fiber mainly in the direction of the main axis of said fiber.
  • the method which is the subject of the invention may also be used to manufacture fibers having an increased length and / or a reduced diameter with respect to the original fiber.
  • the method which is the subject of the invention may be used to manufacture densified and / or refined fibers with respect to the original fiber.
  • carbon nanotube fibers are used so as to prove the efficiency and advantages of the process according to the invention.
  • This method comprises homogeneously dispersing nanotubes in a liquid medium.
  • the dispersion can be carried out in water using surfactants which adsorb at the interface of the nanotubes.
  • the nanotubes can be recondensed in the form of a ribbon or prefibre by injecting the dispersion into another liquid which causes the destabilization of the nanotubes.
  • This liquid may be for example a solution of polymers.
  • the flows involved can be modified to promote alignment of the nanotubes in the pre-fiber or ribbon. In addition, flow rates and flow rates also control the section of prefibers or ribbons.
  • pre-fibers or ribbons thus formed may then be washed or not by rinses which make it possible to desorb certain adsorbed species (in particular polymer or surfactants).
  • Pre-fibers or ribbons can be continuously produced and extracted from their solvent to be dried. We then obtain dry fibers and easily manipulated carbon nanotubes.
  • Drying in the initial manufacture of the fiber induces significant modifications that disturb the alignment of the carbon nanotubes and, regardless of the method for obtaining these fibers, they have little difference in orientation of the nanotubes of carbon.
  • the fiber is solvated in a given solvent to subject it to twists and / or pulls.
  • a polymer fiber can be oriented by simple extrusion or hot stretching. If the fiber contains particles such as carbon nanotubes or whiskers, they also orient themselves. The polymer then plays the role of matrix and it is the deformation of this support which causes the modifications of structures of the fiber.
  • the colloidal particles are directly connected to each other.
  • the cohesion of the structure no longer comes from the polymer itself, but directly from the particles which are bound by a bridging polymer.
  • the structure of the fiber can be modified by pulling or twisting, if the binder polymer is plastic, or made deformable by solvation.
  • such an implementation is carried out at ambient temperature by simply quenching the fiber in water or in another solvent having a certain affinity for the PVA.
  • the ribbon is then rinsed with pure water several times and extracted with water to form a dry thread.
  • water is qualified as a good solvent and acetone as a bad solvent.
  • the other important parameters correspond to the characteristics of the fibers and carbon nanotubes. As is known in the textile industry, for example, these parameters are critical for the final properties of a yarn composed of smaller fibers.
  • the problem here is identical insofar as the wire consists of carbon nanotubes.
  • the structural modifications are characterized by elongation measurements and by X-ray diffraction experiments which quantitatively give the average orientation of the carbon nanotubes.
  • the fibers thus obtained are then immersed in a solvent and subjected to tractions which are expressed in: kilogram (grams). Tractions are performed by hanging well defined masses to the fibers. The fibers are then extracted from the solvent and thus allowed to dry under tension. The dry fibers are recovered and their structure is characterized.
  • the carbon nanotubes in the fibers are organized into bundles and form a hexagonal network perpendicular to the axis of the fiber.
  • the alignment of the bundles of carbon nanotubes with respect to the axis of the fiber can be characterized by the total width at half height (FWHM) of the constant wave vector angular dispersion over a Bragg peak of the hexagonal network. (Gaussian adjustment) or by the value of the intensity diffracted along the axis of the fiber, that is to say by carbon nanotubes perpendicular to this axis.
  • the predominant role of the binder and / or bridging polymer is thus particularly emphasized in obtaining optimized mechanical properties for the solvated fiber.
  • it is the strong adsorption of the polymer on the particles and the important bridging which is carried out on the particles which is involved here.
  • the solvated fibers withstand strong twisting without breaking, up to more than a hundred turns per centimeter.
  • the carbon nanotube fibers are thus deformable and reformable by a simple cold treatment. These deformations, and the implementation of the method which is the subject of the invention make it possible to control the arrangement of the nanotubes by the combination of the numerous variable variable parameters such as torsion, tension, the quality of the solvent, the nature and the mass of the polymer. and the geometric characteristics of the fibers and ribbons used for reforming.
  • a fiber directly resulting from its manufacture will have a minimum FWHM of 80 °, whereas after reforming according to an implementation of the process according to the invention, the fiber will have a FWHM of less than 80 ° and thus an angular dispersion of between + 40 ° and -40 °.
  • the physical properties of the composite fibers comprising colloidal particles and at least one binder and / or bridging polymer are thus significantly improved. They become more efficient for all the applications they can be designed for, such as making high cables. resistance, light conductors, chemical detectors, force sensors and mechanical or sonic stress, electromechanical actuators and artificial muscles, the development of composite materials, nanocomposites, electrodes and microelectrodes for example.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Chemical Treatment Of Fibers During Manufacturing Processes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Claims (16)

  1. Verfahren zum Reforming einer Kompositfaser, die kolloidale Teilchen und mindestens ein bindendes und/oder brückenbildendes Polymer enthält, wobei besagtes Verfahren folgendes umfasst :
    - Mittel zur Verformung des besagten Polymers der besagten Faser bei Temperaturen zwischen 0°C und 50°C, besagte Mittel zur Verformung des besagten Polymers umfassen einen Schritt der Zugabe eines Weichmachers oder einen Schritt des Eintauchens der besagten Faser in ein Lösungsmittel oder eine Mischung aus Lösungsmitteln, die unter Wasser, Aceton, den Ether, Dimethylformamid, Tetrahydrofuran, Chloroform, Toluol, Ethanol gewählt werden; und
    - Mittel zur Anwendung mechanischer Spannungen auf besagte Faser, wobei die besagten mechanischen Spannungen Drehungen und/oder Zug sind.
  2. Verfahren gemäß Anspruch 1, wobei das besagte Lösungsmittel unter Lösungsmitteln gewählt wird, in denen das Polymer löslich oder teilweise löslich ist.
  3. Verfahren gemäß Anspruch 1, wobei das besagte Lösungsmittel unter Lösungsmitteln gewählt wird, in denen das Polymer unlöslich oder praktisch unlöslich ist.
  4. Verfahren gemäß Anspruch 1, wobei das besagte Lösungsmittel unter Mischungen gewählt wird, die mindestens ein in Anspruch 2 definiertes Lösungsmittel und ein in Anspruch 3 definiertes Lösungsmittel enthalten.
  5. Verfahren gemäß einem beliebigen der Ansprüche 1 bis 4, wobei das besagte Lösungsmittel zumindest ein Vernetzungsmittel enthält.
  6. Verfahren gemäß einem beliebigen der Ansprüche 1 bis 5, wobei das besagte Polymer ein Polymer ist, das auf besagten kolloidalen Teilchen adsorbiert wird.
  7. Verfahren gemäß Anspruch 6, wobei das Polymer unter Polyvinylalkohol, flockenden gewöhnlich in der flüssige Verschmutzungen kontrollierenden Industrie verwendeten Polymeren, wie Polyacrylamide, die neutrale Polymere sind, Mischpolymeren aus Acrylamid und Acrylsäure, die negativ geladen sind, Mischpolymeren aus Acrylamid und kationischen Monomeren, die positiv geladen sind, anorganischen Polymeren auf Aluminiumbasis, und/oder natürlichen Polymeren wie Chitosan, Guar und/oder Stärke gewählt wird.
  8. Verfahren gemäß Anspruch 7, wobei das besagte Polymer ein Polyvinylalkohol mit einer Molarmasse zwischen 10 000 und 200 000 ist.
  9. Verfahren gemäß Anspruch 8, wobei das Lösungsmittel unter Wasser, Aceton oder einer Mischung aus Wasser und Aceton gewählt wird.
  10. Verfahren gemäß einem beliebigen der Ansprüche 1 bis 9, wobei die Teilchen unter Kohlenstoffnanoröhren, Wolframsulfid, Bornitrid, Lehmplättchen, Zellulose-Whisker und/oder Siliciumcarbid-Whisker gewählt werden.
  11. Verfahren gemäß einem beliebigen der Ansprüche 1 bis 10, das zusätzliche Schritte zur Extraktion besagter Faser und/oder der Trocknung der besagten Faser umfasst.
  12. Verwendung des Verfahrens gemäß einem beliebigen der Ansprüche 1 bis 11 zur Herstellung von Fasern mit einer Orientierung besagter Teilchen, die besagte Faser größtenteils bilden, in Richtung der Hauptachse der besagten Faser.
  13. Verwendung des Verfahrens gemäß einem beliebigen der Ansprüche 1 bis 11, zur Herstellung von Fasern mit einer erhöhten Länge und/oder einem reduzierten Durchmesser in Bezug auf die ursprüngliche Faser.
  14. Verwendung des Verfahrens gemäß einem beliebigen der Ansprüche 1 bis 11, zur Herstellung dichterer und/oder feinerer Fasern im Bezug auf die ursprüngliche Faser.
  15. Kompositfaser, die kolloidale Teilchen und mindestens ein bindendes und/oder brückenbildendes Polymer enthält, wobei die FWHM besagter Faser unter 80° liegt und die kolloidalen Teilchen direkt miteinander verbunden sind.
  16. Faser gemäß Anspruch 15, wobei die Winkeldispersion besagter Teilchen zwischen +40° und -40° beträgt.
EP02772485A 2001-08-08 2002-08-05 Verfahren zur reformierung von verbundfasern und verwendungen Expired - Lifetime EP1423559B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0110611A FR2828500B1 (fr) 2001-08-08 2001-08-08 Procede de reformage de fibres composites et applications
FR0110611 2001-08-08
PCT/FR2002/002804 WO2003014431A1 (fr) 2001-08-08 2002-08-05 Procede de reformage de fibres composites et applications

Publications (2)

Publication Number Publication Date
EP1423559A1 EP1423559A1 (de) 2004-06-02
EP1423559B1 true EP1423559B1 (de) 2011-03-16

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US (1) US7288317B2 (de)
EP (1) EP1423559B1 (de)
JP (1) JP4518792B2 (de)
KR (1) KR100933537B1 (de)
CN (1) CN1309882C (de)
AT (1) ATE502139T1 (de)
AU (1) AU2002337253B2 (de)
BR (1) BR0211727B1 (de)
CA (1) CA2457367C (de)
DE (1) DE60239471D1 (de)
ES (1) ES2365726T3 (de)
FR (1) FR2828500B1 (de)
HU (1) HU229645B1 (de)
NO (1) NO333728B1 (de)
NZ (1) NZ530823A (de)
WO (1) WO2003014431A1 (de)

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CA2457367A1 (fr) 2003-02-20
NZ530823A (en) 2008-03-28
FR2828500A1 (fr) 2003-02-14
NO333728B1 (no) 2013-09-02
NO20040548L (no) 2004-03-26
CN1589340A (zh) 2005-03-02
DE60239471D1 (de) 2011-04-28
FR2828500B1 (fr) 2004-08-27
US20040177451A1 (en) 2004-09-16
AU2002337253B2 (en) 2007-04-26
HUP0501027A2 (en) 2006-01-30
EP1423559A1 (de) 2004-06-02
BR0211727A (pt) 2004-09-21
US7288317B2 (en) 2007-10-30
KR20040026706A (ko) 2004-03-31
HUP0501027A3 (en) 2007-08-28
JP4518792B2 (ja) 2010-08-04
JP2005526186A (ja) 2005-09-02
CA2457367C (fr) 2011-01-11
KR100933537B1 (ko) 2009-12-23
BR0211727B1 (pt) 2013-09-10
ATE502139T1 (de) 2011-04-15
ES2365726T3 (es) 2011-10-10
HU229645B1 (hu) 2014-03-28
CN1309882C (zh) 2007-04-11
WO2003014431A1 (fr) 2003-02-20

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