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EP0870080B1 - Elektrisch leitende fasern - Google Patents

Elektrisch leitende fasern Download PDF

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Publication number
EP0870080B1
EP0870080B1 EP95944815A EP95944815A EP0870080B1 EP 0870080 B1 EP0870080 B1 EP 0870080B1 EP 95944815 A EP95944815 A EP 95944815A EP 95944815 A EP95944815 A EP 95944815A EP 0870080 B1 EP0870080 B1 EP 0870080B1
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EP
European Patent Office
Prior art keywords
polyaniline
fiber
solution
poly
ppd
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Expired - Lifetime
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EP95944815A
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English (en)
French (fr)
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EP0870080A1 (de
Inventor
Che-Hsiung Hsu
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
    • D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
    • 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
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides

Definitions

  • Sulfonic acid ring - substituted polyaniline is a "self-doped" conducting polymer, reported by Yue, Epstein and Mac Diarmid in Proc. Symposium on Electroresponsive Molecular and Polymeric Systems, Brookhaven National Laboratory, Oct. 1989, to have a conductivity of ⁇ 0.03 S/cm. without external doping. Synthesis of the material is also described in J.A.C.S. 1991, V.113, N.7 pp. 2665-2671 which shows a conductivity of ⁇ 0.1 S/cm measured on pressed pellets.
  • U.S. Patent Number 5,135,696 teaches a method to produce a polyaniline fiber, spun from isotropic solutions, which does not produce fibers having desirable mechanical properties.
  • U.S. Patent Number 5,248,554 teaches coating a p-aramid yarn with polyaniline by passing the p-aramid yarn through polyaniline/sulfuric acid both resulting in a surface coating of polyaniline.
  • EP-A-355518 teaches polymerizing aniline from a water solution while the solution is in contact with a fiber or film substrate. This process results in a polyaniline salt being self-adhered on the surface of the substrate.
  • Fibers of a blend of polyaniline and poly(p-phenylene terephthalamide) prepared from homogeneous solutions in concentrated sulfuric acid are described in Polymer Commun 31,275 (1990).
  • the fibers are said to have improved mechanical properties while retaining the conductivity of pure polyaniline.
  • concentration of poly(p-phenylene terephthalamide) in the spinning solution employed by the experimentors was below the onset of formation of lyotropic phase, thus, the fibers were spun from isotropic solutions.
  • Figure 1 is photomicrograph of transverse and longitudinal cross-sections of fibers of the invention at 1200X.
  • the present invention provides a high strength, high modulus, electrically conductive fiber consisting essentially of poly (p-phenylene terephthalarnide) and a sulfonic acid ring-substituted poly-anilene wherein the raio of sulphonated polyaniline to poly(p-phenylene terephthalamide) on a weight % basis is from 10/90 to 30/70, said fiber having an as-spun tenacity of at least 10 grams per denier (90 g per Tex) and a sulfur content of at least 9% by weight based on the weight of the sulfonated polyaniline.
  • Also encompassed by the present invention is a process for preparing the novel fiber which comprises forming a lyotropic solution of sulfonated polyaniline and poly (p-phenylene terephthalamide) in concentrated sulfuric acid (>100%) the ratio of sulfonated polyaniline to poly (p-phenylene terephthalamide) being from 10/90 to 30/70 on a weight % basis and the solution containing at least 15% by weight of total polymer content and extruding the solution through an air gap into a coagulating bath to form the fiber.
  • the spin dope employed in the process of the invention may be prepared by combining the polyaniline with a solution of poly (p-phenylene terephthalamide) (PPD-T) in concentrated sulfuric acid (>100%) at temperatures in excess of 45°C. Sulfonation of the polyaniline occurs under such conditions, with more rapid reaction taking place with increased temperature, sulfuric acid concentration and time.
  • PPD-T poly (p-phenylene terephthalamide)
  • concentrated sulfuric acid >100%
  • the particular method employed for sulfonation of the polyaniline is not critical. Methods of sulfonation are disclosed in the references mentioned in the "Background" section.
  • the sulfur content of the sulfonated polyaniline should be at least 9% by wt. for high conductivity.
  • the molecular weight of the polyaniline employed in the invention is not critical.
  • the PPD-T is used in its high molecular form, having an inherent viscosity of at least 5. In order to obtain the desirable high strength, a concentration of PPD-T is employed that provides a lyotropic solution as discussed in U.S. Patent No. 3,767,756. Spin solutions containing at least 15% by wt. of total polymer content, i.e., sulfonated polyaniline plus PPD-T, meet this requirement.
  • the ratio of sulfonated polyaniline to PPD-T in the spin solution and ultimately in the spun fiber has an important influence on fiber properties.
  • the sulfonated polyaniline should constitute at least 10 wt% of the polymer mixture to provide electrical conductivity of at least about 0.03 S/cm.
  • the sulfonated polyaniline should constitute from 20 to 30 wt% based on the polymer mixture.
  • fibers of the invention composed of this mixture exhibit a level of electrical conductivity far in excess of that of 100% sulfonated polyaniline. It is believed that the spinning process of this invention enhances the conductivity.
  • the fibers of the invention have good strength, an as-spun tenacity above 10 gpd, and a reasonable level of conductivity.
  • "as-spun” is meant that the fibers formed in the spinning step following take-up, have not been subjected to a drawing or heat-treating operation which changes the molecular order or arrangement of the polymer molecules. Washing and drying operations needed to remove solvents or impurities are permitted.
  • the conductivity of the fiber of the invention remains stable under conditions of use and the fiber requires no doping.
  • the sulfonated polyaniline is dispersed within the fiber as elongated amorphous structures aligned with the fiber axis. This may explain the high conductivity even at low levels of sulfonated polyaniline in the composite fiber.
  • Fiber specimen to be tested is about 1.5 cm long.
  • Room temperature curing silver paste is used for making four electrodes on fiber specimen.
  • the two inner voltage measuring electrodes are about 8 mm apart. Electrical current is applied to the two outer electrodes and the voltage corresponding to the known current is determined with an electrometer. Resistance is calculated based on Ohm's law.
  • Conductivity in S/cm is calculated by normalization based on fiber cross-section and the distance between the voltage electrodes. S corresponds to Siemen.
  • Tenacity/Elongation/Modulus (T/E/Mi) of single filaments at 1" (2.54 cm) gauge length are reported in grams per denier for T and Mi and in % for E.
  • the tensile test is determined according to ASTM 2101. Filament denier is determined according to ASTM D1577 using a vibroscope.
  • Fiber sample is first combusted with oxygen in a flask.
  • the generated SO 2 and SO 3 gases are absorbed in water.
  • Hydrogen peroxide is added to insure that all sulfur is converted to sulfate.
  • After boiling with platinum black to remove any excess H 2 O 2 the pH is adjusted.
  • the solution is then added with isopropanol in a 50/50 in ratio to water.
  • the solution is then titrated with a standardized BaCl 2 solution for determination of sulfate concentration. The amount of sulfur is determined based on the sulfate concentration.
  • This example illustrates air-gap spinning of polyaniline/poly(p-phenylene terephthalamide) solutions of high polymer concentration to form conductive fibers.
  • Polyaniline was prepared according to the following method.
  • a solution consisting of 134.3 g aniline, 194.4 g 37 wt% HCl solution and 1,350 g deionized water were placed in a two liter jacketed glass reaction vessel under a nitrogen atmosphere. The solution was stirred continuously using a 3 inch (7.62 cm) diameter twin-blade impeller.
  • a coolant supplied by a chilling unit, was circulated through the reaction vessel jacket to cool the aniline/HCl solution to -3°C.
  • An oxidant solution consisting of 155 g ammonium persulfate in 270 g water was added to the reaction vessel at a rate of 1.95 ml/min using a syringe pump.
  • the reaction mixture was stirred at about -3°C for 3.5 days.
  • the reactor contents were then filtered and the collected powder was washed by repetitively slurrying in water and filtering, followed by vacuum-drying prior to being neutralized by re-slurrying the powder in 0.15 M ammonium hydroxide solution twice for 24 hours each time.
  • the neutralized polymer was then dried before being washed twice with 1.5 liters of methanol followed by a final wash with acetone.
  • the polymer was dried and stored in a dry box until use.
  • the polymer has an inherent viscosity of 1.29 measured at 30°C as a 0.5 wt. % solution in H 2 SO 4 (96.7% conc.) and is not electrically conductive because neutralization with ammonium hydroxide converts the polyaniline from the conductive form (emeraldine salt) to the insulating base form.
  • a 17 wt% polyaniline/H 2 SO 4 solution was prepared by adding 10.2 g of the polyaniline (base form) prepared as described above to 49.8 g H 2 SO 4 (100.15%) which was in a nitrogen-purged glove bag and had been chilled in a pre-dried glass bottle using a dry ice/acetone bath located outside the glove bag. The mixture was stirred vigorously with a spatula while being chilled with the dry ice/acetone bath. The mixture was then transferred to a pre-dried twin cell having a cross-over plate for mixing (see Blades U.S. 3,767,756). The mixture was pushed back and forth through the cross-over plate for 2 hrs at approximately 45°C to obtain a homogeneous solution.
  • the solution in the twin cell was transferred to three pre-dried glass bottles in amounts of 3.32, 7.83, and 9.3 g.
  • the polyaniline solutions were mixed with poly(p-phenylene terephthalamide) (PPD-T) and concentrated sulfuric acid (>100%) to prepare 18.6 wt % spin dope solutions having weight ratios of polyaniline:PPD-T of 10:90, 20:80, and 30:70.
  • the 10:90 solution was prepared by mixing 3.32 g of the 17 wt % polyaniline solution with 0.81 g H 2 SO 4 (100.15 wt %) and 26.19 g of a 19.4 wt % solution of poly(p-phenylene terephthalamide) in H 2 SO 4 (>100%) at room temperature under nitrogen. The mixture was then stirred at about 65°C for 30 min and transferred to a 1 inch (2.54 cm) diameter twin cell where it was kept at 70°C for 30 minutes and further mixed at 65°C for 30 minutes by passing the mixture through a cross-over plate between cells to ensure homogeneity. The same procedure was used, adjusting the amounts of poly(p-phenylene terephthalamide) solution and polyaniline solution, to prepare spin dopes having polyaniline:PPD-T ratios of 20:80 and 30:70.
  • the spin dopes containing 18.6 wt % polymer were spun through an air gap according to the following procedure.
  • the spin dope solutions prepared above were transferred to one side of the twin cell and a filtration pack consisting of 200 and 325 mesh stainless steel screens and a dynalloy disc was inserted between the twin cell and a single-hole spinneret having a diameter of 3 mil (0.0762 mm) and a length of 9 mil (0.2286 mm).
  • the spinneret was located 0.25 inch (0.635 cm) above a one gallon (3.785 1) glass container of ice-chilled deionized water.
  • a threadline guide was placed 3 inches (7.62 cm) below the spinneret in the deionized water.
  • the threadline traveled an additional 8 inches (20.32 cm) in the water before being wound up on a bobbin which was partially immersed in a deionized water containing tray.
  • the extrusion pressure in pounds per square inch (psi) [kPa], spinneret temperature (same as spinning cell) and fiber wind-up speeds for the samples spun from the three polyaniline/PPD-T solutions are summarized in Table 1.
  • the continuous filament on each bobbin typically weighing less than 0.3 g, was immersed in 900 ml deionized water for one day immediately after the spinning. The water was changed three times with fresh deionized water during that period.
  • the filament samples were then dried and denier (D)[Tex]/tenacity(T)/elongation(E)/modulus (M), electrical conductivity and sulfur elemental analysis were measured.
  • the results in Table 1 show that the fibers are electrically conductive after extensive washing with deionized water. This was unexpected because doped polyaniline typically loses conductivity when contacted with aqueous solutions having a pH greater than about 4.
  • the fiber samples all contain sulfur which may be attributed to covalently bound sulfonic acid groups in the polyaniline at positions ortho to the imide groups. Due to the processing in concentrated H 2 SO 4 (>100%) at elevated temperatures, sulfonation of the polyaniline occurred in situ.
  • the sulfonic acid groups function as internal dopants to render the polyaniline polymer conductive. This hypothesis is supported by the fact that the sulfur is not readily removed as illustrated in Table 1 for samples 10 and 12. These two samples were immersed in 900 ml 0.1 M ammonium hydroxide for 4 hrs. The ammonium hydroxide-treated fibers were then washed extensively with deionized-water. After the neutralization and water washing, the two fiber samples contained 3.24 and 3.21 wt % sulfur. Since the sulfur is not removed by neutralization is evidence that it exists as sulfonated acid groups covalently bound to the polyaniline.
  • This example illustrates air-gap spinning of a 15.2 wt% polymer solution in H 2 SO 4 containing sulfonated polyaniline/PPD-T in a weight ratio of 30/70.
  • a 10 wt % polyaniline/H 2 SO 4 solution was prepared by mixing 8 g of the polyaniline prepared in Example 1 with 72 g H 2 SO 4 (100.15 %) while cooling with a dry ice/acetone mixture in a dry nitrogen atmosphere. The mixture was then transferred to a twin cell under nitrogen and mixed further at room temperature for two hours to obtain a homogeneous solution.
  • a 15.2 wt % spin dope was prepared by mixing 22.66 g of the 10 wt % polyaniline solution with 27.30 g of a 19.4 wt % solution of PPD-T/H 2 SO 4 (>100%) at 65°C in a twin cell under a dry nitrogen atmosphere. The mixture was further mixed at 65°C for one hour to obtain a homogeneous solution. The solution was then spun at 80°C, 340 psi (2344 kPa) extrusion pressure and 195 feet/min (59.44 m/min) wind-up speed using the procedure described in Example 1.
  • the filament After washing with deionized water, as described in Example 1, the filament has D/T/E/M of 2.0(0.222 Tex)/7.9(71.1 g/Tex)/4.1/265 (2385 g/Tex)and electrical conductivity of 0.09 S/cm. Comparing with samples 11 and 12 in Table 1, these results show that the 15.2 wt % polyaniline/PPD-T solution yields fiber having lower tensile strength, modulus and electrical conductivity than the 18.6 wt % solution.
  • This example illustrates air-gap spinning of a 13.2 wt % polymer solution in H 2 SO 4 containing sulfonated polyaniline/PPD-T in a weight ratio of 30/70.
  • a spin dope was prepared by mixing 5.91 g H 2 SO 4 (100.15% concentration), 21.91 g of a 19.4 wt % solution of PPD-T/H 2 SO 4 (>100%), and 18.16 g of the 10.0 wt % polyaniline/H 2 SO 4 solution prepared in Example 2 in a twin cell at room temperature for two hours. The twin cell was then heated to 45°C for additional mixing for one hour to obtain a homogeneous 13.2 wt % polyaniline/PPD-T (30/70) solution.
  • the solution was spun into a continuous filament at 70°C, 400 psi (27 58 kPa) extrusion pressure, and 195 feet/min (59.44 m/min) wind-up speed according to the procedure described in Example 1.
  • the filament After washing with deionized water, as described in Example 1, the filament has D/T/E/M of 3.4(0.378 Tex)/5.5 (49.5 g/Tex)/4.7/206(1854 g/Tex) and electrical conductivity of 0.03 S/cm.
  • This example illustrates air-gap spinning of sulfonated polyaniline/PPD-T solutions containing 18.6 wt % polymer to form conductive fibers.
  • Spinning solutions containing 18.6 wt % polymer in concentrated H 2 SO 4 and having polyaniline/PPD-T ratios of 10/90, 20/80, 30/70 and 40/60 were prepared according to the following procedure.
  • PPD-T (19.4 wt % in H 2 SO 4 ), polyaniline polymer (base form) prepared in Example 1, and sulfuric acid (100.15 wt %) were placed in a pre-dried glass bottle in amounts required to form solutions containing 18.6 wt % polymer and the desired polyaniline/PPD-T ratio.
  • the bottle was then placed in a nitrogen-purged oven at 70°C for one hour, after which the mixture eras stirred before transferring to a hot (70°C) twin cell.
  • the twin cell was heated in the nitrogen-purged oven at 70°C for one hour, after which the mixture was mixed through a cross-over plate for 1.5 hrs to obtain a homogeneous solution.
  • the polyaniline/PPD-T solutions were spun using the procedure described in Example 1.
  • the extrusion pressure, spinneret temperature, and wind-up speed for the individual spinning runs are summarized in Table 2.
  • the bobbins containing the continuous filaments were immersed in 900 ml deionized water for one day. The water was changed three times with fresh deionized water during that time. D/T/E/M, and electrical conductivity of the water-washed fibers are summarized in Table 2. Although the fibers were washed extensively with deionized water, they remained electrically conductive. The results in Table 2 also demonstrate that tensile strength and modulus decrease as the polyaniline/PPD-T ratio increases. The preferred ratio is 30/70 since the fibers have the highest conductivity and yet still have high strength and modulus.
  • X-ray photographs taken of fibers of each composition show that sulfonated polyaniline exists as amorphous polymer whereas PPD-T polymer chains are highly oriented with orientation angles in the range of 13.6 to 14.8.
  • Optical photographs (Fig. 1) of Item 1 of Table 2 show that PPD-T and sulfonated polyaniline are segregated.
  • Sulfonated polyaniline (1) is shown dispersed homogeneously in a matrix of PPD-T (2) in the transverse cross-section and as elongated striations aligned along the fiber axis, in the longitudinal cross-section. This may explain the high conductivity even at the 10/90 ratio.
  • the neutralized fiber was then washed in running deionized water for 6 hr, after which the fiber had reverted back to its original green color.
  • the fiber contained 1.82 wt % sulfur and had a conductivity of 0.07 S/cm. This result shows that the conductivity is not affected by the neutralization with ammonium hydroxide providing evidence that the sulfur exists as sulfonic acid groups covalently bound to polyaniline.
  • the ammonium hydroxide solutions were slightly purple in color following each immersion.
  • the neutralized fiber was then washed in running deionized water for 16 hr, after which it still had a sulfur content of 4.14 wt % and a conductivity of 0.3 S/cm.
  • This example as well as Example 5 illustrate that the polyaniline in the fibers is sulfonated and that the sulfonic acid groups are not readily extracted with basic solutions.
  • the ammonium hydroxide solutions were dark purple following each immersion.
  • some of the polyaniline in the fiber was extracted into the ammonium hydroxide solutions.
  • the neutralized fiber was washed extensively in running deionized water for 13 hrs.
  • the treated fiber had a sulfur content of 1.67 wt %, significantly lower than the sulfur content in the untreated fiber.
  • the conductivity decreased from 0.4 S/cm to 0.04 S/cm. This example suggests that a portion of the sulfonated polyaniline is extractable at polyaniline/PPD-T ratios significantly greater than 30/70.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Artificial Filaments (AREA)

Claims (2)

  1. Hochfeste, elektrisch leitende Hochmodulfaser, die im wesentlichen aus Poly(p-phenylenterephthalamid) und mit Sulfonsäure ringsubstituiertem Polyanilin besteht, wobei das Verhältnis von sulfoniertem Polyanilin zu Poly(p-phenylenterephthalamid) in Gew.-% gleich 10/90 bis 30/70 ist und die Faser eine Zugfestigkeit im gesponnenen Zustand von mindestens 10 Gramm pro Denier (90 g/Tex) und einen Schwefelgehalt von mindestens 9 Gew.-% aufweist, bezogen auf das Gewicht von Polyanilin.
  2. Verfahren zur Herstellung der Faser nach Anspruch 1, mit den folgenden Schritten:
    a. Herstellen einer Lösung von sulfoniertem Polyanilin mit einem Schwefelgehalt von mindestens 9 Gew.-% und Poly(p-phenylenterephthalamid) in konzentrierter Schwefelsäure, wobei das Verhältnis von sulfoniertem Polyanilin zu Poly(p-phenylenterephthalamid) in Gew.-% gleich 10/90 bis 30/70 ist, und wobei die Lösung mindestens 15 Gew.-% des gesamten Polymergehalts enthält, und
    b. Extrudieren der Lösung durch einen Luftspalt in ein Koagulationsbad zur Ausbildung der Faser.
EP95944815A 1995-12-18 1995-12-18 Elektrisch leitende fasern Expired - Lifetime EP0870080B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1995/016523 WO1997022740A1 (en) 1995-12-18 1995-12-18 Electrically conductive fibers

Publications (2)

Publication Number Publication Date
EP0870080A1 EP0870080A1 (de) 1998-10-14
EP0870080B1 true EP0870080B1 (de) 2000-03-08

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EP95944815A Expired - Lifetime EP0870080B1 (de) 1995-12-18 1995-12-18 Elektrisch leitende fasern

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EP (1) EP0870080B1 (de)
JP (1) JP3764485B2 (de)
KR (1) KR100393509B1 (de)
DE (1) DE69515531T2 (de)
WO (1) WO1997022740A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5911930A (en) * 1997-08-25 1999-06-15 Monsanto Company Solvent spinning of fibers containing an intrinsically conductive polymer
US6001475A (en) * 1998-10-20 1999-12-14 E. I. Du Pont De Nemours And Company Silver-containing poly(p-phenylene terephthalamide)/sulfonated polyaniline composite fibers
US6436236B1 (en) * 2001-03-05 2002-08-20 E. I. Du Pont De Nemours & Company Electrically-conductive para-aramid pulp
CN1323199C (zh) * 2005-12-05 2007-06-27 西安交通大学 一种导电高分子聚苯胺纳米纤维的制备方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR900003916A (ko) * 1988-08-03 1990-03-27 이.아이.듀 퐁 드 네모어 앤드 캄파니 전도성 제품
US5109070A (en) * 1989-10-19 1992-04-28 Ohio State University Research Foundation Compositions of insulating polymers and sulfonated polyaniline compositions and uses thereof
US5135696A (en) * 1989-10-19 1992-08-04 Ohio State University Research Foundation Process for forming fibers of sulfonated polyaniline compositions and uses thereof
US5248554A (en) * 1992-06-01 1993-09-28 E. I. Du Pont De Nemours And Company Process for impregnating filaments of p-aramid yarns with polyanilines

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Publication number Publication date
KR100393509B1 (ko) 2003-11-28
WO1997022740A1 (en) 1997-06-26
DE69515531T2 (de) 2000-08-10
EP0870080A1 (de) 1998-10-14
DE69515531D1 (de) 2000-04-13
JP3764485B2 (ja) 2006-04-05
JP2000502408A (ja) 2000-02-29
KR20000064439A (ko) 2000-11-06

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