EP1216319B1 - Absorbierender stoff - Google Patents

Absorbierender stoff Download PDF

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Publication number
EP1216319B1
EP1216319B1 EP00960844A EP00960844A EP1216319B1 EP 1216319 B1 EP1216319 B1 EP 1216319B1 EP 00960844 A EP00960844 A EP 00960844A EP 00960844 A EP00960844 A EP 00960844A EP 1216319 B1 EP1216319 B1 EP 1216319B1
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EP
European Patent Office
Prior art keywords
yarn
gel
fabric
forming
reinforcing
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
Application number
EP00960844A
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English (en)
French (fr)
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EP1216319A1 (de
Inventor
John Overton Hudson
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BHK Holding Ltd
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BHK Holding Ltd
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Filing date
Publication date
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Publication of EP1216319A1 publication Critical patent/EP1216319A1/de
Application granted granted Critical
Publication of EP1216319B1 publication Critical patent/EP1216319B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/10—Patterned fabrics or articles
    • D04B1/12—Patterned fabrics or articles characterised by thread material
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D3/00—Woven fabrics characterised by their shape
    • D03D3/02—Tubular fabrics
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/10—Patterned fabrics or articles
    • D04B1/12—Patterned fabrics or articles characterised by thread material
    • D04B1/123—Patterned fabrics or articles characterised by thread material with laid-in unlooped yarn, e.g. fleece fabrics
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2201/00—Cellulose-based fibres, e.g. vegetable fibres
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2403/00—Details of fabric structure established in the fabric forming process
    • D10B2403/01—Surface features
    • D10B2403/011—Dissimilar front and back faces
    • D10B2403/0114—Dissimilar front and back faces with one or more yarns appearing predominantly on one face, e.g. plated or paralleled yarns
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2509/00—Medical; Hygiene
    • D10B2509/02—Bandages, dressings or absorbent pads
    • D10B2509/022—Wound dressings

Definitions

  • the present invention pertains to fabrics that are capable of absorbing a relatively large quantity of a fluid. Certain embodiments of such fabrics are particularly useful for the control of bleeding.
  • fibrous materials including yarns, which gel when wet and which absorb body fluids.
  • Such materials are used as swabs during surgery, as hemostatic agents and wound dressings.
  • the problem with such materials is that they tend to become weak when wet. Structures formed from these materials tend to break or lose integrity upon absorption of blood or body fluids.
  • collagen oxidized cellulose
  • calcium alginate oxidized cellulose
  • hemostatic gelatin oxidized cellulose
  • Such materials will be referred to generically herein as gel-forming materials and yarns made therefrom as gel-forming yarns.
  • CMC sodium carboxymethylcellulose
  • staple fibre forms of which are used in non-woven fabrics that are commonly used in post-trauma and post-surgical situations as wound dressings.
  • CMC gels upon contact with water, blood or body fluids, and swells to absorb such materials.
  • CMC also facilitates blood clotting while absorbing any exude and is, therefore, hemostatic.
  • CMC is hydroscopic so it does not readily dry into clotted blood, and therefore can be removed easily without causing re-bleeding. If it does dry, it can be easily re-gelled by wetting with water or saline solution.
  • a composite structure, incorporating gel-forming fibres and conventional textile fibres, is disclosed in international patent application, WO 98/46818.
  • the materials described in WO 98/46818 as gel-forming fibres are essentially the same as those which are useful, in yarn form, in the present invention.
  • the gel-forming fibres are said to be "laid-in" to a knitted fabric. Applicant believes, however, that a knitted structure as disclosed there would, to a significant degree, lose its physical integrity upon gelling of the gel-forming fibres and would not be suitable in an application in which the fabric is stretched when the gel forming fibres are gelled.
  • the present invention provides a composite knit, woven or braided fabric comprised of a combination of gel-forming yarn and reinforcing yarn, wherein the reinforcing yarn is knit, woven or braided such that the fabric is capable of retaining its structural integrity independent of the gel-forming yarn.
  • the gel-forming yarn is composed of a hemostatic material such as sodium carboxymethylcellulose (CMC).
  • CMC sodium carboxymethylcellulose
  • the reinforcing yarn is a thin strong synthetic material, such as nylon.
  • the gel-forming yarn may follow the same yarn path as some or all of the reinforcing yarn courses.
  • the gel-forming yarn may also follow a different path by which it is laid in or interwoven with the reinforcing yarn.
  • the fabric may be made by weaving, knitting or braiding a composite fabric comprised of reinforcing yarn and a gel-forming yarn such as oxidized cellulose or CMC.
  • a fabric may be made by weaving, knitting or braiding, with a reinforcing yarn, a cellulosic yarn, the woven, knit or braided structure being such that the structural integrity of the fabric is dependent on the reinforcing yarn only, and then converting the cellulosic yarn therein to oxidized cellulose or sodium carboxymethylcellulose.
  • This conversion process is conventional and requires only that the reinforcing yarn be resistant to chemical attack in the conversion process.
  • the cellulosic yarn thus converted is in fact gel-forming, highly absorptive and may be hemostatic.
  • the resultant fluid absorbing fabric is stretchable, to the degree the reinforcing yarn and/or the structure of the fabric is stretchable. Such a fabric retains its structural integrity even when stretched and when the gel-forming yarn has absorbed water or blood or body fluid and formed a gel therewith.
  • This conversion process may be useful also with unreinforced knitted, woven or braided cellulosic fabric, that is cellulosic fabrics without reinforcing yarn, and to non-woven structures comprised of precursors of gel-forming fibres or yarns.
  • Still another form of reinforced gel-forming absorbent fabric may be made by forming the fabric or other structure with a composite yarn, the yarn itself comprising a composite or combination of gel-forming fibre (or a precursor thereof, convertible as described above) with a reinforcing fibre.
  • a composite yarn may comprise a yarn spun from a combination of such fibres or a core spun yarn, wherein the core fibre is a continuous strand of a reinforcing filament, or filaments, made of a material such as nylon.
  • the present invention in one embodiment, comprises a composite fabric, which retains its structural integrity while absorbing a large quantity of fluid, and particularly to such a fabric useful for the control of bleeding.
  • a composite fabric which retains its structural integrity while absorbing a large quantity of fluid, and particularly to such a fabric useful for the control of bleeding.
  • One application for such a fabric is in an expandable hemostatic device for the control of bleeding in body cavities, as disclosed and claimed in a separate patent application of partial common inventorship herewith, U.S. Application Serial No. 09/406/166, filed September 27, 1999.
  • hemostatic refers to a material that retards or prevents bleeding. Some gel-forming materials, such as CMC, are hemostatic.
  • reinforcing yarn refers to a yarn that has greater tensile strength in a wet phase than a gel-forming yarn with which it is combined.
  • the word "yarn,” as used herein, refers to an indefinite length of material suitable for weaving, knitting or braiding, typically comprised of one or more continuous strands of material or a multiplicity of relatively short length fibres spun into a fibre bundle of indefinite length, or some combination of continuous strands and spun fibres.
  • Gel-forming materials or yarns typically soften to form a gel or partially dissolve when brought into contact with a suitable liquid such as blood. Such a material absorbs liquid and will absorb many times its own weight. Certain gel-forming materials are referred to as hemostatic because they tend to cause blood to clot while absorbing any exudate. Hemostatic, gel-forming materials, such as CMC, are particularly useful for medical purposes wherein the absorption of body fluids is important. Such materials are also used during surgery, or other medical procedures, as hemostatic agents and wound dressings.
  • the composite fabric of the present invention comprises a reinforcing yarn woven, knitted or braided with a gel-forming yarn.
  • the reinforcing yarn is a relatively strong synthetic material, with which the gel-forming yarn is placed side by side during the weaving, knitting or braiding of the gel-forming and reinforcing yarns into a woven, knitted or braided fabric.
  • all or less than all of the yarn courses of the reinforcing yarn may be accompanied by gel-forming yarn.
  • still other yarn courses or picks of the woven or knitted fabric may comprise gel-forming yarn only, so long as the network of woven or knitted reinforcing yarn retains its structural integrity independent of the gel-forming yarn.
  • CMC a preferred gel-forming material in the present invention
  • a cellulosic yarn suitable for the present invention is a Lyocell yarn. It is available from Spinneroff Streif AG, Zurichstrasse 170, Uathal, Switzerland. Lyocell is a solvent spun cellulose, produced from the natural cellulose in wood pulp by dissolution of the pulp in a solvent and then extruding the solution through a multiple-hole die, called a spinneret, to form a yarn comprised of a plurality of continuous strands. The solvent is vaporized in the process, leaving a continuous multi-filament yarn composed of pure cellulose.
  • the filaments in such a yarn may be chopped into staple form and spun into a yarn in a way similar to that used in processing cotton fibre.
  • such an unconverted cellulose yarn is readily woven, knit or braided into a precursor fabric, from which the fabric of the present invention is made by conversion of the cellulose to sodium carboxymethylcellulose or to oxidized cellulose, in accordance with well-known techniques.
  • the conversion factor In the conversion of cellulose to sodium carboxymethylcellulose, less than all of the cellulose building blocks may be converted to the sodium carboxymethylcellulose form and the degree of this conversion will dictate the degree to which a resultant CMC yarn will absorb water and form a gel therewith. This proportion is sometimes referred to as the conversion factor. While the present invention is not limited to sodium carboxymethylcellulose of any particular conversion factor, such materials with a conversion factor of 50 to 70% are preferred in the fabric of the present invention.
  • Oxidized cellulose which is conventionally used in knitted form as a hemostatic agent during surgery, may also be used in the reinforced fabric of the present invention and may also be converted (oxidized) after cellulosic yarn is first woven, knit or braided into a precursor fabric.
  • hemostatic material useful in the present invention, is calcium alginate, which is a material derived from seaweed, and, in matted fibre form, is also used as a wound dressing.
  • Other fibrous polysaccharides, with similar chemistry and properties to CMC, may also be used.
  • Combinations of different gel-forming agents may be used within the scope of the present invention. Such combinations may be made by forming a yarn from different gel-forming or hemostatic fibres and/or by weaving, knitting or braiding combinations of different gel-forming yarns.
  • the reinforcing yarn must be non-reactive with the reactants and the products of the process of converting the cellulosic material into the gel-forming, chemically modified form thereof.
  • each of the multiple yarn end feeds to a weaving loom, knitting machine or braiding machine may comprise, in effect, two yarn ends, fed in parallel, one the gel-forming yarn (or a precursor yarn suitable for subsequent conversion to a gel-forming yarn), and one the reinforcing yarn.
  • the knit fabric product would include, as shown in Figure 1, a thin reinforcing yarn 2, combined in all yarn courses with a thicker (but weaker) yarn 1, which is either a gel-forming fibre or is convertible to a gel-forming yarn (i.e. a gel-forming yarn precursor).
  • Gel-forming yarn courses may be omitted, depending on the relative degree of strength and absorptive capacity desired.
  • Shown in Figure 2 is another knit fabric of the present invention. Reinforcing yarns 3 are knit so as to provide structural integrity to the fabric, while gel-forming (or precursor to gel-forming) yarns 4 are inlaid therewith. The inlaying of gel-forming yarns 4 is such that even if the gel-forming yarns 4 are fully dissolved, the network of reinforcing yarns will maintain the structural integrity of the fabric.
  • Knit forms of the composite fabric of this invention have some inherent stretchability.
  • still more stretchability may be provided.
  • the reinforcing yarn itself may be stretchable so that the fabric itself is more stretchable. This is particularly useful when the fabric is intended for disposition around a balloon-expanding device, as described in the above-referenced co-pending U.S. patent application.
  • a tubular fabric is preferred.
  • one particularly effective use for the fabric of the present invention is as a hemostatic shroud covering an expansible device, adapted for disposition in a body cavity or passageway, such as a nasal passageway, to control bleeding therein, as disclosed in the above-referenced U.S. Patent Application Serial No. 09/406,166, filed September 27, 1999.
  • an exemplary fabric made for use in a nasal hemostatic device, comprises a knit construction, as illustrated in Figure 1, knitted into a tubular form in accordance with well-known methods.
  • a gel forming precursor yarn (12 tex lyocell spun yarn is knit together with a reinforcing yarn comprised of 17 decitex 3 filament nylon.
  • the fabric structure is a plain weft, knitted in circular form with 36 needles.
  • the loop length is 5 mm and the weight of the finished fabric is 1.6 grams per metre (wet relaxed and dried to normal moisture regain).
  • the reinforcing yarn comprises about 12%, by weight, of this fabric before conversion of the Lyocell to CMC and about 11% after that conversion.
  • the conversion of the Lyocell in this exemplary fabric is accomplished by methods well known in the art.
  • nylon reinforcing yarn used in this embodiment would not be considered stretchable, the fabric structure itself is stretchable and deformable, that is it will expand in diameter at the expense of its length.
  • the present invention also includes the process of making a gel-forming or hemostatic structure, including a matted fibre or laid-in knit structure, as disclosed in the above-referenced WO 98/46818, by first forming the structure with gel-forming fibre precursors, such as cellulose fibre or yarn, and then converting the structure to the gel-forming state thereof, namely oxidized cellulose or CMC.
  • a gel-forming or hemostatic structure including a matted fibre or laid-in knit structure, as disclosed in the above-referenced WO 98/46818
  • Still other composites and fabrics within the scope of this invention comprise a composite yarn, the structure of which includes both reinforcing fibres, such as nylon, and gel-forming fibres (or precursors thereof).
  • the most elementary method of combining two different fibres within one yarn is to simply spin the yarn from a mixture of the two fibres in staple form. However, this may lead to an overly weakened yarn once the gelling has taken place.
  • a preferred example of such a composite yarn is a core spun yarn, that is a yarn wherein staple fibres are spun around a preformed yarn.
  • This preformed yarn may be another spun yarn, or, more commonly, a continuous filament yarn.
  • This preformed yarn may comprise a reinforcing material, such as nylon.
  • Gel-forming, or precursors of gel-forming, fibres comprise a second component of the final yarn product.
  • the gel-forming fibres therein (converted from precursor materials either prior to or after spinning) provide absorptive and hemostatic capacity to the yarn and the reinforcing fibres or central filament of the preformed yarn provide strength.
  • Such a yarn may be woven, knit or otherwise incorporated into a fabric or other structure, wherein fluid or blood absorption are important.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Materials For Medical Uses (AREA)
  • Woven Fabrics (AREA)
  • Knitting Of Fabric (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (20)

  1. Ein zusammengesetzter gestrickter, gewirkter, gewebter oder geflochtener Stoff, der folgende Merkmale aufweist:
    ein Garn (1, 4), das entweder gelbildend ist oder ein Zwischengarn aufweist, welches geeignet ist, in ein gelbildendes Garn umgewandelt zu werden; das gelbildende Garn oder das Zwischengarn (1, 4) mit einem verstärkenden Garn (2, 3) verwebt, verstrickt oder verflochten ist, wobei das verstrickte, verwebte oder verflochtene verstärkende Garn (2, 3) ein Netzwerk bildet, das die physikalische Intaktheit des Stoffes unabhängig von dem gelbildenden Garn oder dem Zwischengarn bereitstellt.
  2. Der Stoff nach Anspruch 1, dadurch gekennzeichnet, dass das gelbildende Zwischengarn (1, 4) ein Cellulosegarn ist.
  3. Der Stoff nach Anspruch 1, dadurch gekennzeichnet, dass das gelbildende Zwischengarn (1, 4) Natriumcarboximethylcellulose aufweist.
  4. Der Stoff nach Anspruch 1, dadurch gekennzeichnet, dass das gelbildende Zwischengarn (1, 4) aus der Gruppe Natriumcarboximethylcellulose, Oxicellulose und Kalziumalginat ausgewählt ist.
  5. Der Stoff nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das verstärkende Garn (2, 3) ein endloses Monofilamentgarn oder ein Multifilamentgarn aus Nylon ist.
  6. Der Stoff nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass er ein oder mehrere, bei Kontakt mit Flüssigkeit gelbildende Garne (1, 4) und ein oder mehrere verstärkende Garne (2, 3) aufweist, wobei das verstärkende Garn (2, 3) eine größere Zugfestigkeit als das gelbildende Garn in feuchtem Zustand aufweist und der Stoff Blut und Körperflüssigkeiten absorbierend ausgebildet ist.
  7. Ein Verfahren zur Herstellung eines zusammengesetzten Stoffes aus einer Kombination eines gelbildenden Garns (1, 4) und eines verstärkenden Garns (2, 3) mit folgenden Verfahrensschritten:
    Weben, Stricken, Wirken oder Flechten des gelbildenden Garns (1, 4) und des verstärkenden Garns (2, 3),
       wobei mindestens ein Garn (1, 4) mit blutstillenden Eigenschaften und mindestens ein Garn (2, 3) mit einer höheren Zugfestigkeit als das blutstillende Garn in feuchtem Zustand eingesetzt wird und das Garn (2, 3) mit der höheren Zugfestigkeit gewebt, gewirkt, gestrickt oder geflochten wird, sodass es die strukturelle Intaktheit des Stoffes unabhängig von dem blutstillenden Garn (1, 4) erbringt.
  8. Das Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Garn (1, 4) mit den blutstillenden Eigenschaften zu Cellulosegarn umgewandelt wird.
  9. Das Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das umgewandelte Cellulosegarn (1, 4) Natriumcarboximethylcellulose ist, welches aus einem Cellulose enthaltenden Zwischengarn nach dem Weben, Stricken, Wirken oder Flechten umgewandelt wird.
  10. Das Verfahren nach Anspruch 8, dadurch gekennzeichnet, dass das Cellulosegarn (1, 4) unter Bereitstellung oxidierter Cellulosefasern oxidiert wird.
  11. Das Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass das Cellulosegarn (1, 4) nach dem Weben, Stricken, Wirken oder Flechten oxidiert wird.
  12. Das Verfahren nach Anspruch 7, dadurch gekennzeichnet, dass das Cellulosegarn (1, 4) mit den blutstillenden Eigenschaften Kalziumalginat ist.
  13. Ein Zwischenstoff, der zur Umwandlung in einen gewebten, gestrickten, gewirkten oder geflochtenen Stoff nach einem der Ansprüche 1 bis 6 geeignet ist, dadurch gekennzeichnet, dass der Zwischenstoff ein Netzwerk aus gewebten, gestrickten, gewirkten oder geflochtenen Garnen, die geeignet sind, die strukturelle Intaktheit in Anwesenheit von Flüssigkeit bereitzustellen, und in Kombination damit aus einem Zwischengarn (1, 4), das zur Umwandlung in ein gelbildendes Garn (1, 4) geeignet ist, aufweist, wobei das gelbildende Garn (1, 4) die Eigenschaft hat, die Flüssigkeit unter Gelbildung zu absorbieren.
  14. Ein Verfahren zur Herstellung eines Stoffes nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass zuerst eine Struktur aus einem Material mit Fasern, die chemisch in ein gelbildendes absorbierendes Material (1, 4) umwandelbar sind, erstellt wird und dann dieses Material in seine gelbildende absorbierende Form umgewandelt wird.
  15. Ein Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass das Material (1, 4) des Zwischenstoffs ein Cellulosegarn ist.
  16. Ein Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass das umgewandelte Material (1, 4) CMC ist.
  17. Ein Verfahren nach einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, dass die Endstruktur ein gestrickter oder gewirkter Stoff ist.
  18. Ein Verfahren nach einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, dass die Endstruktur ein gewebter Stoff ist.
  19. Ein Verfahren nach einem der Ansprüche 14 bis 16, dadurch gekennzeichnet, dass die Endstruktur ein geflochtener Stoff ist.
  20. Eine Struktur nach einem der Ansprüche 17, 18 oder 19, dadurch gekennzeichnet, dass der Stoff Schlauchform aufweist.
EP00960844A 1999-09-27 2000-09-19 Absorbierender stoff Expired - Lifetime EP1216319B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US40649099A 1999-09-27 1999-09-27
US406490 1999-09-27
US61203800A 2000-07-07 2000-07-07
US612038 2000-07-07
PCT/GB2000/003586 WO2001023653A1 (en) 1999-09-27 2000-09-19 Absorptive fabric

Publications (2)

Publication Number Publication Date
EP1216319A1 EP1216319A1 (de) 2002-06-26
EP1216319B1 true EP1216319B1 (de) 2004-04-07

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EP00960844A Expired - Lifetime EP1216319B1 (de) 1999-09-27 2000-09-19 Absorbierender stoff

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EP (1) EP1216319B1 (de)
JP (1) JP2003510475A (de)
CN (1) CN1214141C (de)
AT (1) ATE263858T1 (de)
AU (1) AU771967B2 (de)
CA (1) CA2384689C (de)
DE (1) DE60009727T2 (de)
ES (1) ES2222231T3 (de)
WO (1) WO2001023653A1 (de)

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AU7301300A (en) 2001-04-30
JP2003510475A (ja) 2003-03-18
ATE263858T1 (de) 2004-04-15
ES2222231T3 (es) 2005-02-01
WO2001023653A1 (en) 2001-04-05
AU771967B2 (en) 2004-04-08
CA2384689C (en) 2009-05-12
CA2384689A1 (en) 2001-04-05
CN1214141C (zh) 2005-08-10
CN1376221A (zh) 2002-10-23
EP1216319A1 (de) 2002-06-26
DE60009727D1 (de) 2004-05-13
DE60009727T2 (de) 2004-08-12

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