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EP0819189B1 - Verfahren zur herstellung eines glasfaservliesstoffs und das so erhaltende produkt - Google Patents

Verfahren zur herstellung eines glasfaservliesstoffs und das so erhaltende produkt Download PDF

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Publication number
EP0819189B1
EP0819189B1 EP96942392A EP96942392A EP0819189B1 EP 0819189 B1 EP0819189 B1 EP 0819189B1 EP 96942392 A EP96942392 A EP 96942392A EP 96942392 A EP96942392 A EP 96942392A EP 0819189 B1 EP0819189 B1 EP 0819189B1
Authority
EP
European Patent Office
Prior art keywords
binder
mat
glass
sheet
threads
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
EP96942392A
Other languages
English (en)
French (fr)
Other versions
EP0819189A2 (de
Inventor
Michel Arpin
Fabrice Duchamp
Michel Mottet
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Adfors SAS
Original Assignee
Saint Gobain Vetrotex France SA
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 Saint Gobain Vetrotex France SA filed Critical Saint Gobain Vetrotex France SA
Publication of EP0819189A2 publication Critical patent/EP0819189A2/de
Application granted granted Critical
Publication of EP0819189B1 publication Critical patent/EP0819189B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H13/00—Other non-woven fabrics
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/002—Inorganic yarns or filaments
    • D04H3/004—Glass yarns or filaments
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4209—Inorganic fibres
    • D04H1/4218—Glass fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2934—Coating or impregnation contains vinyl polymer or copolymer
    • 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
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2992—Coated or impregnated glass fiber fabric

Definitions

  • the present invention relates to a method of manufacturing a mat consisting of glass threads and the resulting product.
  • mat is meant glass a product formed of glass strands (cut or continuous) whose filaments components remain linked together, thus distinguishing themselves from glass veils formed by the association of dispersed glass filaments.
  • the nature of the binder chosen is most often a function of its chemical compatibility with the resin system that the mat should reinforce.
  • the binder can be used in the form of powder, suspension, emulsion or solution.
  • the liquid with which it is associated is, increasingly more often water to avoid the difficulties that always presents the job organic solvents.
  • the application methods are also very varied.
  • the deposit of the binder in the form of a dry powder avoids the use of a liquid that will need to be removed later, it is difficult to remove distribute evenly within the mass of the mat.
  • the grains of binder sometimes remains in the composite reinforced by the mat, which gives an irregular surface finish.
  • the present invention relates to a manufacturing process allowing to obtain a mat of glass strands which has good cohesion and which is easily wetted by resins, in particular by resins in an aqueous medium, especially in aqueous solution, dispersion or suspension or by a mixture based on cement and water.
  • the present invention relates to a manufacturing process which allows distribute the binder evenly throughout the thickness of the mat.
  • the present invention also relates to a method of manufacturing a glass fiber mat which allows continuous recycling of the binder used.
  • a manufacturing process which consists in continuously deposit on a sheet of glass threads, distributed on a conveyor in motion, a binder whose viscosity during deposition is less than approximately 40 mPa.s, said binder being formed from an aqueous solution of alcohol (s) polyvinyl (s).
  • the polyvinyl alcohol (s) used in the context of the invention preferably have a degree of polymerization of less than about 1,000.
  • the binder is deposited on the sheet of glass strands in the form of a liquid tablecloth or curtain of liquid nets which fall transversely over the entire width of said layer of wires.
  • the binder thus deposited, and thanks to its relatively low viscosity, penetrates and crosses the entire ply of yarns distributing throughout the volume of said sheet.
  • the binder is retained for the essential on a large part of the contact points of the crossing wires.
  • the binder is deposited when its temperature is higher than approximately 10 ° C and most generally between 20 and 60 ° C.
  • the flow rate of binder thus deposited is in particular a function of the speed of the conveyor and the quantity of glass deposited per square meter on said conveyor. This binder flow rate is determined so as to obtain between approximately 3 and 15% by weight of binder in the dry matter state relative to the weight of glass.
  • the binder may be deposited, in part, on the surface of the sheet of yarn, upstream of the area where it is deposited in the form of nets or of a liquid tablecloth.
  • the binder can be, for example, sprayed upstream, this which has the effect of compacting the layer of thread slightly and moistening its layer surface, thus promoting the penetration of the binder deposited downstream.
  • a fraction of the binder thus deposited completely crosses the sheet of yarns and can be collected under the conveyor.
  • One of the advantages of the binder used is that it is stable over time even after being heated to a temperature above about 30 ° C, unlike binders whose composition contains at least one constituent which promotes its crosslinking.
  • the binder used in the context of the invention can thus be directly recycled, this which constitutes an economic advantage.
  • the layer of wires passes through an oven of in a manner known per se, then possibly in a grille.
  • the method according to the invention applies to the glass son mats obtained by all known means, whether continuous or indirect processes.
  • the first type of process is used to make masts of continuous glass. It consists, most often, of stretching a multiplicity of filaments from molten glass flowing from the orifices of several dies, combine these filaments at the rate of at least one thread per die and distribute mechanically the wires thus obtained on a conveyor moving below said channels.
  • the second type of process is generally used to manufacture the chopped glass strands. It consists in extracting from a multiplicity of continuous wire windings, to cut them simultaneously and to distribute them on a moving conveyor.
  • the second type of process can also be used to manufacture continuous yarn mats when the extraction of the yarns from their winding is immediately followed by their distribution on the conveyor.
  • the mat used can be reinforced with continuous glass strands arranged longitudinally over at least part of its width. This is particularly the case when the mat is intended to be associated with a cement-based mixture.
  • This mat is obtained, for example, by distributing simultaneously over the moving conveyor cut and continuous wires, the latter being extracts from a series of windings.
  • the average diameter of the filaments constituting the wires is between approximately 9 and 30 micrometers. when these are chopped strands the length of the said strands is generally greater than 20 millimeters.
  • This solution was obtained by dissolution in water brought to 80 ° C of a polyvinyl alcohol characterized by a degree of polymerization of 530 and a hydrolysis rate of 88%.
  • This polyvinyl alcohol is sold under the reference F 105 by the Company Lamberti. This solution is poured onto the sheet of wires at a rate schedule of 3 cubic meters. The excess solution is sucked under the conveyor and recycled.
  • the layer of wires thus treated then passes into a hot air oven at the interior of which it is subjected to a temperature of the order of 200 ° C. for about 50 seconds.
  • the layer of wires is calendered and cooled before being wound on a rotary mandrel.
  • the mat obtained has a binder content of 8% and has a mass area of 250 grams per square meter. Its cohesion is good as the shows its tensile strength which, measured according to ISO 3342 method, is on average 40 decanewtons. In comparison, a mat that has the same characteristics, but the binder rate is 4.5%, this binder being plasticized polyvinyl acetate, has a tensile strength, measured by the same method, less than 20 decanewtons.
  • the binder used in the present invention also offers the advantage to be partially dissolved in the presence of water.
  • the following test allows you to note: a series of samples of 100 x 125 millimeters are cut in the mat whose manufacturing process has been described previously. These samples are immersed in water at 20 ° C and subjected to a load of 100 grams. Partial elimination of the binder in water and the effect of the filler cause the mat to tear in two parts after an average time of 25 seconds. This time is very short for this kind of test. Indeed, the tearing of the mat bound with plasticized polyvinyl acetate, cited previously, intervenes, under the same conditions, only after a average time greater than 5 minutes.
  • Cement sheets are made using on the one hand a mixture based on cement and cut glass yarns called premix, other part of mast according to the invention or, for comparison, of a known mast.
  • the mat according to the invention has a surface mass of 120 grams per square meter, it consists of cut wires 50 millimeters in length, including the title is 38 tex and which consist of a multiplicity of filaments of a average diameter of 14 micrometers. Its binder rate is 10%.
  • the mat used for comparison has the same characteristics, apart from the binder rate, which is 4.5% and the binder itself, which is plasticized polyvinyl acetate.
  • the glass used to obtain these mats is an alkali-resistant glass marketed under the CEMFIL brand.
  • a first layer of mat is deposited at the bottom of a mold and covered with a layer of premix uniformly distributed by subjecting said mold to vibrations.
  • a second mat layer identical to the first is deposited on the premix, then applied against the premix using a roller to impregnate.
  • the plate thus formed is maintained for 24 hours in the mold, then stored in an enclosure maintained at 20 ° C in a atmosphere at 50% relative humidity.
  • MOR, LOP and EPS respectively denote the module of rupture, the limit of proportionality or elasticity and the deformation at the rupture during the bending test.
  • the percentage of reinforcement in the premix is 2% by weight per compared to the composite for the two kinds of plates, the percentage of reinforcement due to the mat itself being 1.4% for the plate reinforced by the mat according to the invention and for the plate reinforced with known mat.
  • association with resins in an aqueous medium can also be carried out by all means known to those skilled in the art.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Laminated Bodies (AREA)
  • Paper (AREA)
  • Glass Compositions (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (13)

  1. Verfahren zur Herstellung eines Glasfadenvlieses, gemäß welchem auf einer Bahn aus Glasfäden, die auf einem sich bewegenden Gurtförderer verteilt sind, ein Bindemittel kontinuierlich aufgebracht und diese Bahn anschließend in einem Ofen erhitzt und gegebenenfalls kalandriert wird, und welches darin besteht, auf der Glasfadenbahn ein aus einer wässrigen Lösung von Polyvinylalkohol/en gebildetes flüssiges Bindemittel aufzubringen, dessen Viskosität beim Abscheiden niedriger als etwa 40 Millipaecal·Sekunde ist.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Bindemittel in Form einer Flüssigkeitsbahn oder eines Schleiers aus flüssigen Strahlen, die auf die gesamte Breite der Glasfadenbahn treffen, aufgebracht wird.
  3. Verfahren nach Anspruch 2, dadurch gekennzeichnet, dass ein Teil des Bindemittels vor dem Bereich aufgebracht wird, in welchem es in Form einer Flüssigkeitsbahn oder eines Schleiers aus flüssigen Strahlen aufgebracht wird.
  4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass das Bindemittel zuvor durch Versprühen aufgebracht wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnete dass der Teil des Bindemittels, der durch die Glasfadenbahn hindurchgelangt ist, unter dem Gurtförderer zurückgewonnen und direkt zurückgeleitet wird.
  6. Glasfadenbahn, die mit einem Bindemittel überzogen ist, dadurch gekennzeichnet, dass sie aus Glasfäden gebildet ist, deren filamentförmige Bestandteile miteinander verbunden bleiben, und dass das Bindemittel ein aus einer wässrigen Lösung von Polyvinylalkohol/en gebildetes flüssiges Bindemittel ist, dessen Viskosität beim Abscheiden auf die Glasfadenbahn niedriger als etwa 40 Millipascal·Sekunde ist.
  7. Glasfadenbahn nach Anspruch 6, dadurch gekennzeichnet, dass ihr Bindemitcelgehalt etwa 3 bis 15 Gew.-% des Glasgewichts beträgt.
  8. Glasfadenvlies, das nach Erhitzen in einem Ofen und gegebenenfalls Kalandrieren einer Glasfadenbahn nach Anspruch 6 oder 7 erhalten ist, dadurch gekennzeichnet, dass es aus Glasfäden gebildet ist, die aus Glasfilamenten bestehen, die miteinander verbunden bleiben und deren mittlerer Durchmesser 9 bis 30 Mikrometer beträgt.
  9. Glasfadenvlies nach Anspruch 8, dadurch gekennzeichnet, dass es aus Kurzfäden gebildet ist, deren Länge mehr als etwa 20 Millimeter beträgt.
  10. Glasfadenvlies nach Anspruch 9, dadurch gekennzeichnet, dass es durch endlose Glasfäden verstärkt ist, die auf wenigstens einem Teil der Vliesbreite in Längsrichtung angeordnet sind.
  11. Glasfadenvlies nach Anspruch 8, dadurch gekennzeichnet, dass es aus Endlosfäden gebildet ist.
  12. Verwendung des Glasfadenvlieses nach einem der Ansprüche 8 bis 11, dadurch gekennzeichnet, dass es mit einem Gemisch verbunden wird, das Zement und Wasser als Grundlage hat und gegebenenfalls Glasfäden enthält, um anschließend ein Verbundmaterial herzustellen.
  13. Verwendung des Glasfadenvlieses nach den Ansprüchen 8 bis 11, dadurch gekennzeichnet, dass es mit einem Harz im wässrigen Medium verbunden wird, um anschließend durch Formgebung ein Verbundmaterial herzustellen.
EP96942392A 1995-12-12 1996-12-12 Verfahren zur herstellung eines glasfaservliesstoffs und das so erhaltende produkt Expired - Lifetime EP0819189B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR9515113A FR2742172B1 (fr) 1995-12-12 1995-12-12 Procede de fabrication d'un mat de verre et produit en resultant
FR9515113 1995-12-12
PCT/FR1996/001988 WO1997021861A2 (fr) 1995-12-12 1996-12-12 Procede de fabrication d'un mat de verre et produit en resultant

Publications (2)

Publication Number Publication Date
EP0819189A2 EP0819189A2 (de) 1998-01-21
EP0819189B1 true EP0819189B1 (de) 2003-02-05

Family

ID=9485698

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96942392A Expired - Lifetime EP0819189B1 (de) 1995-12-12 1996-12-12 Verfahren zur herstellung eines glasfaservliesstoffs und das so erhaltende produkt

Country Status (20)

Country Link
US (1) US6034006A (de)
EP (1) EP0819189B1 (de)
JP (1) JPH11500795A (de)
KR (1) KR100410713B1 (de)
CN (1) CN1083028C (de)
AR (1) AR005045A1 (de)
AT (1) ATE232247T1 (de)
BR (1) BR9607736A (de)
CA (1) CA2212921C (de)
CZ (1) CZ297438B6 (de)
DE (1) DE69626106D1 (de)
ES (1) ES2191780T3 (de)
FR (1) FR2742172B1 (de)
IN (1) IN191056B (de)
NO (1) NO973682L (de)
PL (1) PL186513B1 (de)
RU (1) RU2171322C2 (de)
SK (1) SK284976B6 (de)
TW (1) TW340833B (de)
WO (1) WO1997021861A2 (de)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2781819B1 (fr) * 1998-08-03 2000-09-22 Vetrotex France Sa Procede de fabrication de mats de fils continus
PL346134A1 (en) * 1999-06-24 2002-01-28 Paroc Group Oy Ab Method for manufacturing a binder and use thereof
JP2005520171A (ja) * 2001-04-10 2005-07-07 トランス　テック　ファーマ，インコーポレイテッド ドラッグディスカバリーに関する、プローブ、システム、および方法
FR2862987B1 (fr) 2003-11-28 2006-09-22 Saint Gobain Vetrotex Mat de verre aiguillette
US20070003703A1 (en) * 2005-03-07 2007-01-04 Seng Jocelyn M Method and apparatus for applying liquid compositions to fiber webs
US8080171B2 (en) * 2007-06-01 2011-12-20 Ocv Intellectual Capital, Llc Wet-laid chopped strand fiber mat for roofing mat
US7927459B2 (en) * 2007-09-17 2011-04-19 Ocv Intellectual Capital, Llc Methods for improving the tear strength of mats
KR101221286B1 (ko) * 2008-06-11 2013-01-10 (주)엘지하우시스 복합시트의 제조방법
CN102182014B (zh) * 2011-01-26 2014-03-12 武汉鑫友泰光电科技有限公司 一种石英纤维毡的配制方法
CN102505353A (zh) * 2011-11-02 2012-06-20 成都彩虹环保科技有限公司 具有加强层的无纺布
FR2994201B1 (fr) 2012-07-31 2014-08-08 Saint Gobain Isover Procede de cuisson d'un matelas continu de fibres minerales ou vegetales
US10208414B2 (en) * 2012-11-13 2019-02-19 Johns Manville Soy protein and carbohydrate containing binder compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL133247C (de) * 1967-05-18
NL135509C (de) * 1967-11-01 Gelder Zonen Papierfab Van
NL143717B (nl) * 1970-11-11 1974-10-15 Koninkl Papierfabrieken Van Ge Werkwijze voor het vervaardigen van een glasvezelvlies voor isolatieplaten en op deze wijze verkregen glasvezelvlies en isolatieplaat.
GB8400290D0 (en) * 1984-01-06 1984-02-08 Wiggins Teape Group Ltd Fibre reinforced plastics structures

Also Published As

Publication number Publication date
EP0819189A2 (de) 1998-01-21
SK284976B6 (sk) 2006-03-02
FR2742172B1 (fr) 1998-01-09
PL186513B1 (pl) 2004-01-30
WO1997021861A3 (fr) 1997-08-14
CN1083028C (zh) 2002-04-17
TW340833B (en) 1998-09-21
FR2742172A1 (fr) 1997-06-13
WO1997021861A2 (fr) 1997-06-19
CA2212921C (fr) 2004-07-27
ATE232247T1 (de) 2003-02-15
NO973682L (no) 1997-09-10
JPH11500795A (ja) 1999-01-19
DE69626106D1 (de) 2003-03-13
BR9607736A (pt) 1999-10-19
KR19980702060A (ko) 1998-07-15
CN1180389A (zh) 1998-04-29
AR005045A1 (es) 1999-04-07
IN191056B (de) 2003-09-13
NO973682D0 (no) 1997-08-11
PL321732A1 (en) 1997-12-22
SK107497A3 (en) 1998-03-04
CZ297438B6 (cs) 2006-12-13
CZ248897A3 (en) 1997-12-17
ES2191780T3 (es) 2003-09-16
US6034006A (en) 2000-03-07
RU2171322C2 (ru) 2001-07-27
KR100410713B1 (ko) 2004-03-30
CA2212921A1 (fr) 1997-06-19

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