EP0702732B1 - Spandex contenant du sulfate de baryum - Google Patents

Spandex contenant du sulfate de baryum Download PDF

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Publication number
EP0702732B1
EP0702732B1 EP94916808A EP94916808A EP0702732B1 EP 0702732 B1 EP0702732 B1 EP 0702732B1 EP 94916808 A EP94916808 A EP 94916808A EP 94916808 A EP94916808 A EP 94916808A EP 0702732 B1 EP0702732 B1 EP 0702732B1
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EP
European Patent Office
Prior art keywords
spandex
barium sulfate
range
particles
isoelectric point
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EP94916808A
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German (de)
English (en)
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EP0702732A1 (fr
Inventor
Howard Wayne Jacobson
Charles William Goodrich
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EIDP Inc
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EI Du Pont de Nemours and Co
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Classifications

    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • 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

Definitions

  • the present invention relates to spandex in which particles of barium sulfate are dispersed. More particularly, the invention concerns an improvement in such a spandex wherein the spandex has a roughened surface and the barium sulfate particles have a very low isoelectric point. The invention also concerns a process for producing such spandex. The presence of the barium sulphate particles of low isoelectric point in the spandex provides unexpected and advantageous reductions in the tackiness of the spandex and improvements in the process for producing the spandex.
  • Spandex is known to exhibit considerable tackiness compared to conventional non-elastomeric textile fibers.
  • the filaments tend to stick to various surfaces and to each other, especially when wound up on a bobbin. Tackiness can cause excessive unwinding tension (referred to hereinafter as “take-off tension”) as well as frequent, large transients in the tension as the spandex is unwound from the package. Excessive take-off tensions and transients can cause yarn breaks during handling, fabric defects and other manufacturing difficulties, especially in making of knit fabrics.
  • lubricating finishes are applied to spandex yarn and/or special agents are dispersed within the spandex.
  • lubricating finishes include (a) metallic soaps dispersed in textile oils, such as those disclosed by Yuk, United States Patent 3,039,895, and (b) polyalkylsiloxanes, such as those disclosed by Chandler, U.S. Patent 3,296,063.
  • the dispersion of certain metal soaps (e.g., stearates of calcium, magnesium or lithium) within the spandex for tackiness reduction is disclosed by Hanzel et al, U.S. Patent 4,296,174. Further reductions in the tackiness of the spandex would improve its handling characteristics, make its production more economical and enhance its utilization in various fabrics.
  • barium sulfate among many other inert inorganic materials, has been disclosed for use in spandex, by for example, Bell et al US-A-3 386 942 and Imai et al, US-A-4 525 420. Barium sulfate is available commercially in several forms, purities and grades. Applicant now has found that the tackiness characteristics of the spandex can be modified very favorably by dispersing in the spandex particular barium sulfate particles having specific isoelectric properties.
  • the present invention provides an improved spandex of the type that has a lubricating finish on its surface and barium sulfate particles dispersed within its volume.
  • the barium sulfate particles have an isoelectric point in the range of 0 to 4, preferably in the range of 0.5 to 3.
  • the barium sulfate particles amount to in the range of 0.3 to 5%, preferably 1 to 3%, of the weight of the spandex.
  • the spandex containing the barium sulfate has a surface roughness parameter (defined hereinafter) of at least 75, preferably in the range of 100 to 200.
  • the average pore size is in the range of 1 to 3 nm (10 to 30 Angstroms) and the BET surface area is in the range of 1 to 5 m 2 /g.
  • the spandex contains titanium dioxide particles amounting to in the range of 1 to 5% of the total weight of the spandex and the lubricating finish is a polysiloxane amounting to in the range of 1 to 6% by weight of the spandex.
  • the yarn is wound up on a cylindrical member to form a yarn supply package of low tackiness.
  • the invention also provides an improved process for dry-spinning spandex, wherein a solution of a segmented polyurethane polymer in an organic solvent is mixed with additives and then dry-spun into filaments.
  • the improvement comprises at least one additive being barium sulfate having an isoelectric point in the range of 0 to 4.
  • the term "spandex” has its usual definition; that is, a manufactured fiber in which the fiber-forming substance is a long chain synthetic polymer composed of at least 85% by weight of a segmented polyurethane.
  • the term "fiber” includes in its meaning staple fibers and continuous filaments.
  • the chemical composition of a polymer of the spandex also may be abbreviated as illustrated by the following example, in which a polyurethaneurea made from poly(tetramethyleneether)glycol (“PO4G”) having a number average molecular weight of 1800, methylene-bis (4-phenylisocyanate) ("MDI”) and a mixture of ethylene diamine (“EDA”) and 2-methyl-1,5-diaminopentane (“MPMD”) in a molar ratio of 90 to 10, is abbreviated as PO4G(1800):MDI:EDA/MPMD(90/10).
  • PO4G poly(tetramethyleneether)glycol
  • MDI methylene-bis (4-phenylisocyanate)
  • EDA ethylene diamine
  • MPMD 2-methyl-1,5-diaminopentane
  • colons are used to separate the monomers of the repeating units of the polymer, a slash (i.e., /) between the diamines indicates that the diamines are in a mixture and parenthetic numbers immediately following the glycol and diamine mixture respectively refer to the number average molecular weight of the glycol and the molar ratio of the diamines in the mixture.
  • a spandex has dispersed within its volume barium sulfate particles having an isoelectric point in the range of 0 to 4, preferably 1 to 2.5.
  • Conventional techniques are employed to add the particles to a polyurethane solution from which the spandex is to be dry spun.
  • the barium sulfate amounts to 0.3 to 5%, preferably 1 to 3%, of the total weight of the spandex.
  • the particles of barium sulfate may be coated with specific agents for special purposes.
  • the particles can be coated with antimicrobial compositions such as those disclosed by Jacobson et al in U.S. Patent 5,180,585.
  • the use of coatings on the barium sulfate does not detrimentally affect the spandex produced therewith, and such coated particles are intended to be included within the scope of the invention.
  • the barium sulfate particles suitable for use in the present invention are small.
  • the average size of the particles is typically in the range of 0.5 to 3 ⁇ m, with the largest particles (i.e., not more than 2% of the particle size distribution) being greater than 25 ⁇ m, preferably no greater than 15 ⁇ m.
  • polymers used for preparing spandex by dry spinning are suitable for the spandex of the present invention. These typically are prepared by known processes in which a polyether-based glycol or polyester based glycol is reacted with a diisocyanate to form an isocyanate-capped glycol which is then reacted with diamine chain extender to form the segmented polyurethane polymer.
  • the polymer is dissolved in an inert organic solvent, such as dimethylacetamide (DMAc), dimethylformamide, N-methyl pyrrolidone or the like.
  • DMAc dimethylacetamide
  • the pH of the polymer solution is in the range of 9 to 12.
  • the particles are very well dispersed within the solution and subsequently within the spandex.
  • the polymer solution is dry-spun in conventional equipment through orifices into a shaft. Heated inert gas passes through the shaft to assist solvent evaporation from the surface of the formed filament as the filament passes through the shaft. Filaments from multiple orifices are twisted together to form a multi-filament yarn. Lubricant can be deposited on the surface of the filaments by a conventional finish roll or by being co-spun with the filaments from the polymer solution. Thereafter, the thusly dry-spun filaments (i.e., spandex) are wound up on cylindrical member to form a yarn supply package (e.g., pirn, bobbin, cake).
  • a yarn supply package e.g., pirn, bobbin, cake
  • spandex filaments are quite tacky.
  • Polyether-based spandex usually is more tacky than polyester-based spandex.
  • Clear spandex, derived from polyether glycols is the tackiest.
  • spandex yarns are well known.
  • "LYCRA" spandex is manufactured and sold by E.I. du Pont de Nemours & Co.
  • about 0.4 to 0.7 kilogram of spandex yarn is wound up on the cylindrical tube of such yarn supply packages.
  • the polymer of the spandex of the invention can contain conventional agents that are added for specific purposes, such as antioxidants, thermal stabilizers, UV stabilizers, pigments, dyes, lubricating agents and the like. Such agents are usually added to the solution of the polymer and become incorporated into the filaments during the dry spinning step.
  • the barium sulfate additive in accordance with the present invention, can be incorporated into the filaments in the same manner as the other additives.
  • the concentration of barium sulfate is typically in the range of 0.3 to 5% by weight of the spandex polymer.
  • various types and grades of barium sulfate particles are known, such as barites or barytes ore, chemically pure barium sulfate, blanc fixe and the like, only barium sulfate having an isoelectric point in the range of 0 to 4 is suitable for use in the spandex of the invention.
  • Barium sulfate particles with an isoelectric point in the range of 1 to 2.5 are preferred.
  • the particular barium sulfate suited for use in the present invention represents a small fraction of all the barium sulfates that are available commercially.
  • Natural barium sulfate, the mined ore also known as “barite” or “barytes"
  • contains several colored impurities Some of these impurities can be removed by beneficiation of the ore through washing, tabling, jigging or floatation.
  • the mined barium sulfate contains various impurities, such barium sulfate often can be used directly for drilling muds, the largest known use for the ore.
  • Finely ground barite is used as a filler or extender for paints.
  • Barite for pigment usually is "bleached” by treatment with acid and often also with a reducing agent to remove colorizing compounds. Chemically pure barium sulfate is also available for chemical reaction purposes. Still another commercially available barium sulfate is precipitated barium sulfate, also known as blanc fixe. Blanc fixe, usually is prepared by mixing aqueous solutions of barium sulfide and sodium sulfate under controlled conditions in order to produce a precipitate of uniform particles of pigmentary fineness.
  • barium sulfate particles having an isoelectric point of no greater than about 4 e.g., some of the blanc fixe grades
  • These particular blanc fixe particles were unexpectedly better than all the others in reducing the tackiness of dry-spun spandex and in providing more efficient operation of the dry-spinning process.
  • the barium sulfate particles having isoelectric points in accordance with the invention were employed, the barium sulfate particles were well dispersed and did not form agglomerates in the polymer solution; screens and filters operated longer before needing shutdown and cleaning; and even more surprisingly, the solvent content of the filaments leaving the spin shaft was decreased.
  • spandex yarns containing barium sulfate particles of 0-4 isoelectric point when wound up into yarn supply packages, permitted satisfactory removal of all the yarn from the package.
  • conventional spandex yarn packages having no barium sulfate particles in the filaments usually cannot be totally removed from the package.
  • the portion of the wound-up yarn that is closest to the central cylindrical member of the yarn package usually can not be removed satisfactorily from the package, which results in about 6% of the total yarn in the package being wasted.
  • the following table lists the isoelectric point and particle size determined for a selected group of commercial barium sulfates.
  • the above-listed "Micro grade” and "F Grade” commercial blanc fixe from Sachtleben, each having an isoelectric point well below 4 are barium sulfates that are suitable for use in the present invention.
  • Isoelectric point determinations are made with conventional instruments.
  • the isoelectric point is defined as the concentration of hydrogen ions and other ions, usually expressed as a pH, at which the particles have no net charge and the zeta potential is zero.
  • the procedure is as follows. A 20-gram sample of barium sulfate powder in 200ml of a 0.001N potassium nitrate is titrated with 3M potassium hydroxide or 2M nitric acid (depending on whether acid or base is needed for the titration). Prior to the titration, the sample is thoroughly dispersed in the liquid by means of a sonic mixer, a Sonicator Model W-385, sold by Heat Systems-Ultrasonics Corp. of Farmingdale, New York.
  • the titration is performed with the sample being stirred constantly.
  • a potentiometric titration meter an ESA-8000 System Model MBS-8000, sold by Matec Applied Science, Inc. of Hopkinton, Mass., was employed for the titration.
  • a laser light scattering instrument is used to measure sizes of barium sulfate particles.
  • the instrument was a Micro-Trac FRA (full range analyzer), sold by Leeds & Northrup of St. Moscow, Fla. Sonically dispersed samples are employed. Each sample consists of 0.8 to 2.0 grams of the particles in 80 ml of deionized water which containes 10 drops of "Darvon C" dispersant, sold by R. T. Vanderbilt Chemical of Norwalk, Conn. At least three samples of each material are analyzed to obtain average particle size and particle size distributions.
  • R Surface roughness
  • A the BET surface area in square meters/gram and P is the average pore size in Angstrom (where 10 Angstroms equals 1 nm).
  • the surface area of spandex is determined from nitrogen adsorption measurements in accordance with the method of Brunauer, Emmet and Teller (BET). The measurements are made with a Model 2100 Surface Area and Pore Volume Analyzer sold by Micromeritics Instruments Corp. of Norcross, Georgia. To prepare the test samples, the filaments are conditioned for about 10 hours under a vacuum of about 0.025 mm of mercury while at a temperature of about 120°C.
  • the instrument automatically measures at least 21 points during each adsorption-desorption cycle. From these data, the BET surface area A, individual pore sizes, and average pore size, P, are calculated. The surface roughness parameter, R, of the spandex is then computed by the formula given above.
  • thermogravimetric analyzer To determine the temperatures at which silicone lubricating oil is released from a spandex surface, a thermogravimetric analyzer is employed to raise the temperature of spandex samples at a rate of 10°C per minute, with the sample being flushed by a 100-cc/min flow of nitrogen. The flushed gas is passed to a Fourier Transform Infrared Analyzer. The time at which the infrared analyzer detects the presence of silicone oil in the nitrogen gas is correlated with the temperature of the sample when the oil is evolved from the sample.
  • Over-end take-off tension a measure of the tackiness of a spandex yarn, is determined in accordance with the procedure disclosed in Hanzel et al, US-A-4 296 174, column 4, lines 20-45, with reference to Figure 6 of the patent, which disclosure is hereby incorporated by reference. In accordance with this technique, measurement is made of the average tension required to remove a 183-meter sample of spandex yarn from a supply package of the yarn at a delivery rate of 45.7 meters per minute.
  • Strength and elastic properties of the spandex are measured in accordance with the general method of ASTM D 2731-72. Three filaments, a 2-inch (5-cm) gauge length and a zero-to-300% elongation cycle are used for each of the measurements. The samples are cycled five times at an constant elongation rate of 800% per minute and then held at the 300% extension for half a minute after the fifth extension. "Load power” is reported herein in deciNewtons/tex and is the stress measured at a given extension during the first load cycle. "Unload Power” is reported herein in deciNewtons/tex and is the stress measured at a given extension during the fifth unload cycle. Percent elongation at break is measured on the sixth extension cycle.
  • Percent set also is measured on samples that have been subjected to five 0-300% elongation-and-relaxation cycles.
  • the polymer for the spandex is made from a capped glycol, which was the reaction product of PO4G and MDI prepared with a capping ratio (i.e., the molar ratio of MDI to PO4G) of 1.63 and having an NCO content of 2.40%.
  • the capped glycol is chain extended with a 90/10 diamine mixture of EDA/MPMD.
  • DEA is employed as a chain terminator.
  • the polymer is dissolved in DMAc to provide a solution having 36.8% solids.
  • Additives consisting of 1.5% "Cyanox"-1790 antioxidant, 2% “Methacrol”-2138, and 0.6% silicone oil (based on the weight of the polymer) are added to the solution.
  • the solution described in the preceding paragraph is dry spun into 4-coalesced-filament 44-dtex yarns (or 2-filament 22-dtex yarns) in a conventional apparatus.
  • the solution is metered through spinneret orifices into a spin shaft, in which the thusly spun solution forms filaments and DMAc solvent evaporates from the filament.
  • a cocurrent flow of nitrogen gas is supplied to the shaft at a temperature of 420°C, which results in a temperature of 220°C at the half-way point through the shaft.
  • the DMAc gas exits through a pipe in a side wall near the bottom of the shaft.
  • the filaments are false-twisted by jets at the bottom of the shaft to cause groups of filaments to coalesce into single threadlines.
  • a counter current flow of nitrogen which is supplied at 135°C near the bottom of the shaft, combines with the exiting DMAc.
  • the coalesced multi-filament threadlines exit through the bottom of the shaft.
  • a silicone oil finish lubricant is applied to the threadlines by a kiss roll applicator, to provide an add-on of about 3.5% based on the weight of the threadline. Unless indicated otherwise, the yarn is then wound up at a speed of about 840 meters per minute.
  • Barium sulfate is added to the polymer solution as follows. An 11.4% solution of polymer in DMAc is made by diluting 450 parts of polymer solution in 1000 parts of DMAc and then adding 1050 parts (by weight) of barium sulfate particles to the dilute solution while providing thorough mixing. The resulting slurry is then passed through a sandgrinder to break up any agglomerates that had possibly formed. The concentration of the barium sulfate in the slurry is 42%. The barium sulfate slurry is then metered to the polymer solution that already contains the other additives at a rate selected to provide a 1.5% concentration of barium sulfate in the polymer (based on total weight of polymer).
  • This example shows the effects of isoelectric point of the barium sulfate additive on the surface roughness of the spandex that is produced.
  • Seven 44-dtex samples are prepared by the above-described procedures. Two samples (Samples 1 and 2) are in accordance with the invention and five samples (Comparison Samples A, B, C, D and E) are outside the invention. All samples are prepared in the same manner, except as otherwise noted in Table 1, which summarizes some of the properties of the spandex thusly produced.
  • Samples 1 and 2 are prepared with Sachtleben Micro-grade blanc fixe. Comparison Sample A is prepared with Sachtleben N-Grade blanc fixe and Comparison Sample B, with Fisher Scientific certified pure barium sulfate. Comparison Samples C, D, and E are prepared with no barium sulfate additive; D is wound up at 640 meters/min and E, at 914 meters/min.
  • Samples identical to Sample 3 and Comparison Sample F are prepared except that corresponding Samples 4 and G are 2-filament 22-dtex spandex yarns.
  • the over-end take-off tension (OET) is measured for wound up yarns of Sample 4 and Comparison Sample G, immediately after spinning and then after 2 weeks, 4 weeks and 8 weeks of storage. Table III summarizes the results. Time after spinning and winding up, weeks OET, centiNewtons Sample G Sample 4 0 0.116 0.095 2 0.275 0.101 4 0.391 0.101 8 0.444 0.203 Note that the take-off tension of Comparison Sample G increases to about four times its initial value while that of Sample 4 of the invention only doubles its initial value. Note also that the take-off tension of fresh yarn of the invention is already about 20% lower than that of the comparison sample.
  • two bobbins of 44-dtex spandex yarns are made by the procedures of Example I, but with 2 weight percent of titanium dioxide dispersed therein, and then tested for over-end take-off tension after 8 weeks of room-temperature storage.
  • Sample 6 contains 1.5% of micro-grade barium sulfate and is of the invention.
  • Comparison Sample J contains no barium sulfate and is outside the invention.
  • the measured OET for Sample 6 of the invention was 0.141 centiNewtons versus 0.380 cN for Comparison for sample J.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Claims (6)

  1. Spandex amélioré ayant un apprêt lubrifiant à sa surface et des particules de sulfate de baryum dispersées dans son volume, l'amélioration comprenant, pour réduire l'adhérence du spandex, des particules de sulfate de baryum qui ont un point isoélectrique qui se situe dans la plage de 0 à 4.
  2. Spandex amélioré selon la revendication 1, dans lequel les particules de sulfate de baryum sont présentes à raison de 0,3 à 5% du poids du spandex et le point isoélectrique se situe dans la plage de 0,5 à 3.
  3. Spandex amélioré selon la revendication 1 ou 2, dans lequel le spandex a une taille moyenne de pores dans la plage de 1 à 3 nm (10 à 30 angströms) et une surface spécifique BET dans la plage de 1 à 5 m2/g.
  4. Spandex amélioré selon la revendication 3, dans lequel le spandex contient des particules de dioxyde de titane à raison de 1 à 5% du poids total du spandex et l'apprêt lubrifiant est un polysiloxane présent dans la plage de 1 à 6% en poids du spandex.
  5. Spandex amélioré selon la revendication 1 ou 2 enroulé sur un élément cylindrique pour former un paquet d'alimentation en fil de faible adhérence.
  6. Procédé amélioré de filage à sec de spandex, dans lequel une solution d'un polymère de polyuréthanne segmenté dans un solvant organique est mélangée à des additifs, puis filée à sec pour former des filaments, l'amélioration consistant en au moins un additif qui est du sulfate de baryum ayant un point isoélectrique dans la plage de 0 à 4.
EP94916808A 1993-06-11 1994-05-25 Spandex contenant du sulfate de baryum Expired - Lifetime EP0702732B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7570293A 1993-06-11 1993-06-11
US75702 1993-06-11
PCT/US1994/005713 WO1994029499A1 (fr) 1993-06-11 1994-05-25 Spandex contenant du sulfate de baryum

Publications (2)

Publication Number Publication Date
EP0702732A1 EP0702732A1 (fr) 1996-03-27
EP0702732B1 true EP0702732B1 (fr) 1998-08-26

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EP (1) EP0702732B1 (fr)
JP (1) JP3279569B2 (fr)
KR (1) KR100245846B1 (fr)
BR (1) BR9407074A (fr)
DE (1) DE69412824T2 (fr)
TW (1) TW316931B (fr)
WO (1) WO1994029499A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4973647A (en) * 1989-05-31 1990-11-27 E. I. Du Pont De Nemours And Company Fiber from polyether-based spandex
DE69527956D1 (de) * 1994-05-16 2002-10-02 Honeywell Int Inc Gefüllte schnittfeste faser
US5626960A (en) * 1995-09-07 1997-05-06 E. I. Du Pont De Nemours And Company Spandex containing a huntite and hydromagnesite additive
EP0907771B1 (fr) 1996-06-24 2003-02-12 E.I. Du Pont De Nemours And Company Films et fibres en polyurethane
KR100591206B1 (ko) * 2002-03-26 2006-06-19 주식회사 효성 기능성이 부여된 폴리우레탄 섬유의 제조방법
CN101157015B (zh) * 2002-06-12 2011-11-02 创普太克公司 包封的活性颗粒及其制备和使用方法
ATE362003T1 (de) * 2003-05-14 2007-06-15 Shikibo Ltd Verfahren zur herstellung von laserbeschriftbare fasern oder faserprodukte
JP5218940B2 (ja) * 2009-12-22 2013-06-26 東レ・オペロンテックス株式会社 ポリウレタン弾性糸およびその製造方法
ES2629283T3 (es) * 2012-06-18 2017-08-08 Rhodia Poliamida E Especialidades Ltda Composición polimérica que contiene cargas minerales, para mejorar la cicatrización de la piel
KR20160077301A (ko) 2014-12-22 2016-07-04 주식회사 효성 균일성과 작업성이 우수한 폴리우레탄우레아 탄성사의 제조방법

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Publication number Priority date Publication date Assignee Title
JPS5959912A (ja) * 1982-09-22 1984-04-05 Toyobo Co Ltd ポリウレタン弾性繊維の製造法
US5183614A (en) * 1989-01-26 1993-02-02 E. I. Du Pont De Nemours And Company Method for producing x-ray detectable spandex fibers

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JP3279569B2 (ja) 2002-04-30
WO1994029499A1 (fr) 1994-12-22
JPH08511585A (ja) 1996-12-03
DE69412824T2 (de) 1999-02-25
EP0702732A1 (fr) 1996-03-27
KR100245846B1 (ko) 2000-04-01
KR19990037960A (ko) 1999-06-05
TW316931B (fr) 1997-10-01
BR9407074A (pt) 1996-08-27
DE69412824D1 (de) 1998-10-01

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