WO2002086208A1 - Fibre elastique de type polyurethane, et procede de preparation de la fibre - Google Patents

Fibre elastique de type polyurethane, et procede de preparation de la fibre Download PDF

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Publication number
WO2002086208A1
WO2002086208A1 PCT/KR2002/000714 KR0200714W WO02086208A1 WO 2002086208 A1 WO2002086208 A1 WO 2002086208A1 KR 0200714 W KR0200714 W KR 0200714W WO 02086208 A1 WO02086208 A1 WO 02086208A1
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WO
WIPO (PCT)
Prior art keywords
elastic fiber
polyurethane elastic
producing
polymer
prepolymer
Prior art date
Application number
PCT/KR2002/000714
Other languages
English (en)
Inventor
Il-Cheon Kwon
Doo-Hyun Kim
Kyung-Hwan Ro
Original Assignee
Kolon Industries, Inc
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
Priority claimed from KR1020010020975A external-priority patent/KR100719044B1/ko
Priority claimed from KR1020010020976A external-priority patent/KR100646647B1/ko
Application filed by Kolon Industries, Inc filed Critical Kolon Industries, Inc
Priority to US10/475,011 priority Critical patent/US20040121149A1/en
Priority to JP2002583718A priority patent/JP2004526069A/ja
Priority to EP02718687A priority patent/EP1392898A4/fr
Publication of WO2002086208A1 publication Critical patent/WO2002086208A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber

Definitions

  • the present invention relates to a polyurethane elastic fiber and a process of preparing the same. More particularly, the present invention relates to a process of preparing a polyurethane elastic fiber, which improves the stability of polymer and has high-speed spinnablity, thereby remarkably reducing the generation of wave yarn. Further, the present invention relates to a polyurethane elastic fiber having excellent heat resistance, thermosetting efficiency and coherence between monofilaments.
  • Polyurethane polymer can be prepared by a one-staged polymerization, in which polyol with high molecular weight of 1, 600-2, OOOg/mol, diisocyanate with an excessive amount, and chain extender such as diol or diamine compound are simultaneously reacted.
  • polyurethane polymer can be prepared by a two-staged polymerization comprising two steps, a first step of that polyol with high molecular weight of 1, 600-2, OOOg/mol and diisocyanate with the excessive amount are prepolymerized, thereby preparing a prepolymer, and a second step of that a chain extender and a chain terminator such as diol or diamine compound are simultaneously reacted with inputted the prepolymer.
  • the two-staged polymerization Compared with the one-staged polymerization, the two-staged polymerization produces a more regular structure and has a lower possibility in a bridged bond, thereby easily regulating the degree of polymerization. Most of the polyurethane elastic fibers are now prepared by the two-staged polymerization.
  • the first stage of the two-staged polymerization i.e., the prepolymerization step
  • polyol with high molecular weight i.e., diol compound
  • diisocyanate with excessive amount are reacted and forms urethane bonds, thereby preparing a prepolymer, in which an isocyanate group is formed on both ends of polyol.
  • the molecular weight of polyol is approximately l,800g/mol, and the ratio of NCO/OH is about 1.5 to 1.8.
  • the aforementioned prepolymerization is performed at the temperature of approximately 60 to 90 ° C for 1 to 2 hours in a bulky condition without solvent. As the reaction temperature is higher, the reaction speed is also higher. If a solvent such as Dimethylacetamide (hereinafter, referred to as "DMAc”) or Dimethylformamide (hereinafter, referred to as "DMF”) is used, the reaction temperature is increased by the catalysis of the solvent. Thus, the reaction is finished at the temperature of 30 to 60 ° C within 10 to 20 minutes.
  • DMAc Dimethylacetamide
  • DMF Dimethylformamide
  • the second stage of the two-staged polymerization i.e., the chain extending step
  • the prepolymer and compound with active hydrogen in a low molecular weight such as ethylene diamine, propylene diamine, 1,4-butadiol are reacted, thereby increasing the degree of polymerization.
  • this compound is used as the chain extender.
  • the chain- extending step is faster than the preliminary step and is an exothermic reaction. Therefore, in order to uniformly form the reaction, a polar solvent such as DMAc or DMF is used.
  • BACKGROUND ART Korean Patent Publication No. 196651 discloses a method of preparing a polyurethane polymer, in which glycol and diisocyanate (reaction mole ratio: 1.5—1.64) are mixed in a static mixer at the temperature of 40— 50 ° C and reacted, thereby preparing a first polymer with non-reacted diisocyanate of 4 mole%. After then, the first polymer is reacted with chain extender comprising ethylene diamine 74 to 80 mol%, 1,2-diaminopropane 19 to 25 mol% and diethyltriamine 0.2 to 0.8 mol , thereby preparing the polyurethane polymer.
  • chain extender comprising ethylene diamine 74 to 80 mol%, 1,2-diaminopropane 19 to 25 mol% and diethyltriamine 0.2 to 0.8 mol , thereby preparing the polyurethane polymer.
  • the aforementioned prior art has many problems, as follows.
  • the temperature of 40 to 50 ° C is too broad not to uniformly mix glycol and diisocyanate.
  • the reaction of glycol and diisocyanate is very intensive. Therefore, at the temperature of more than 45 ° C , a large amount of glycol and diisocyanate are reacted before being uniformly mixed.
  • the supply temperature of glycol and diisocyanate In order to maintain the reaction temperature to be less than 42 ° C , the supply temperature of glycol and diisocyanate must be predetermined to be less than 42 "C prior to being putted in the static mixer. However, when the temperature is deviated from 43-44 ° C , impurity such as dimmer is rapidly increased within diisocyanate. Therefore, in order to maintain the reaction temperature to be less than 42 ° C , a heat exchanger must be installed prior to the static mixer or an external jacket is attached to the static mixer, thereby controlling the temperature. Compared with a method, in which glycol and diisocyanate are mixed at the same temperature as the storage temperature (43-4 ° C) of diisocyanate, this method is improper.
  • Japanese Laid-open Publication No. 4-100919 discloses a method, in which only ethylene diamine of 0.18 weight% is used as the chain extender, and triamine, tetramine, pentamine, and the like are added to the polymer prior to the spinning step.
  • problems of this method are that viscosity of the polymer is very unstable before spinning, and the spinnability is low. Further, this method improves the heat resistance but decreases the thermosetting efficiency.
  • the present invention has been made in view of the above problems, and it is an object of the present invention to provide a method of preparing a polyurethane elastic fiber, which improves the stability of viscosity of polymer and has an excellent spinnablity even in a high-speed spinning, thereby remarkably reducing the generation of wave yarn. Further, the present invention provides a polyurethane elastic fiber having excellent heat resistance, thermosetting efficiency and coherence between monofilaments.
  • a method of producing a polyurethane elastic fiber characterized in that a prepolymer is produced using a continuous polymerizing tube in a cylinder pipe comprising a static mixer, a heat raiser, a reactor, and a cooler, as follows, and the prepolymer is reacted with a chain extender/ a chain terminator to produce a polymer, and an additive is then added to the polymer. as follows — [a process of producing the prepolymer]
  • the present invention employs a continuous polymerizing tube with a mixing element formed in a Kenics type or a Sulzer type on its inside.
  • the continuous polymerizing tube is shaped in a cylinder pipe.
  • the continuous polymerizing tube comprises a static mixer, a heat raiser, a reactor, and a cooler.
  • the static mixer is designed so that the shear rate is more than 20sec -1 without the inner mixing element.
  • the heat raiser is designed so that the shear rate is more than 3sec _1 without the inner mixing element.
  • the reactor is designed so that the shear rate is more than O.lsec -1 without the inner mixing element.
  • polyol with high molecular weight and diisocyanate with excessive amount are mixed within the static mixer with the shear rate of more than 20sec -1 without the inner mixing element, and reacted within the heat raiser with the shear rate of more than 3sec -1 without the inner mixing element, and reacted within the reactor with the shear rate of more than O. lsec -1 without the inner mixing element, thereby preparing a first prepolymer.
  • polytetramethyleneetherglycol with the number average molecular weight of 1,700-3,000 and 4,4'-methylenediphenyldi- isocyanate which are generally used to produce a polymer for polyurethane elastic fiber, are used.
  • the mole ratio of diisocyanate per glycol is properly about 1.5-1.75.
  • the shear rate of the mixture for the prepolymer within the static mixer is more than 20sec -1 . If the shear rate is less than 20sec -1 , the monomers are not uniformly mixed, thereby forming much gel, and reducing the spinnability and the quality of the prepolymer.
  • the mixing temperature of the static mixer is controlled to be 43-44 ° C . If the mixing temperature is more than 45 ° C , the reaction is considerably processed prior to the uniform mixing, thereby forming gel of three-dimensional bridged bonds. Components of gel are accumulated within the static mixer or moved into a next step.
  • the replacement cycle of the static mixer is shortened or the quality of the prepolymer is deteriorated.
  • the gel influences the final spinning step, thereby reducing the spinnability, generating the wave yarn, and providing a bad effect to the physical property of the produced elastic fiber. If the mixing temperature is less than 43 ° C , since the mixing temperature is lower than the storage temperature of diisocyanate, additional equipment is required.
  • the shear rate within the heat raiser is very important to set the shear rate within the heat raiser to be more than 3sec -1 without the inner mixing element. If the shear rate is less than 3sec -1 , the heterogeneous reaction is increased and gel is increased within the prepolymer.
  • the raised temperature of the heat raiser and the final temperature of the raised prepolymer are also important factors. It is desired to prevent the rapid heat-raising and to set the final raised temperature of the heat raiser to be less than 90 ° C .
  • the reaction temperature of the prepolymer is more than 90 ° C , the side reaction is rapidly progressed, thereby increasing the possibility of generating the gel.
  • the reaction of glycol and diisocyanate is an exothermic reaction, the exothermic reaction must be controlled by well regulating the heat raising time.
  • the finally raised temperature of the prepolymer can be more than 90 ° C .
  • the equipment of the heat raiser is long with the same supplying amount of the raw material, thereby additionally installing the heat raiser.
  • the shear rate within the reactor is very important to set the shear rate within the reactor to be more than O.lsec -1 without the inner mixing element. If the shear rate is less than O.lsec -1 , the heterogeneous reaction generates the formation of the gel.
  • the prepolymer manufactured by the aforementioned process comprises gels with a diameter of less than 20um. Herein, the number of these gels is 600/g. The gels improve the processing property and the quality of the final product. The number of the gels within the prepolymer is measured by a Coulter Counter.
  • a chain extender and a chain terminator are added to and reacted with the prepolymer, thereby preparing the polyurethane polymer. More particularly, the prepolymer is solved by a N,N'- Dimethylacetamide (hereinafter, referred to as "DMAc") solvent, thereby forming a solution of the prepolymer. This solution is reacted with a N,N'-Dimethylacetamide solution (chain extender) comprising diamine and triamine, and a N,N'-Dimethylacetamide solution (chain terminator) comprising monoamine.
  • diamine used as the chain extender ethylene diamine or 1,2-diaminopropane may be used.
  • triamine diethyltriamine may be used.
  • chain extender solution a solution comprising ethylene diamine of 60-75 mol%, 1,2-diaminopropane of 24.9-39 mol , and diethyltriamine of less than 0.1 mol% may be used.
  • monoamine used as the chain terminator diethylamine may be used.
  • the chain extender of 96-98.5 equivalent% and the chain terminator of 4.5-7.0 equivalent% are used.
  • the chain extender solution and the chain terminator solution may be separately provided, or may be simultaneously provided.
  • the prepared polyurethane polymer (hereinafter, referred to as "final polymer”) has a concentration of 36-38.5 weight% according to the amount of N,N'-Dimethylacetamide solution for solving the prepolymer, and a number average molecular weight of 30,000-50,000.
  • the number average molecular weight can be measured by a- Gel Permeation Chromatography (GPC).
  • the polyurethane polymer and an additive are mixed within the static mixer without the inner mixing element at the condition of the shear rate of more than 0.13sec -1 , thereby forming a dope just before spinning.
  • the additive comprises triamine group compound.
  • the additive may be selected from triamine group compound, a conventional antioxidant, an anti-yellowing agent, an ultraviolet stabilizer, a dyeing improving agent, a dulling agent, or a spinning-enhancing agent. More preferably, as the triamine group compound, diethylenetriamine is used.
  • the bridged bonds are formed in high-speed spinning, thereby improving the heat resistance of the elastic fiber, preventing the precipitation due to re-agglutination of inorganic additives, and uniformly mixing the additive and the polymer.
  • the uniform mixture of the additive and the final polymer is very important. If the mixture of the additive and the final polymer is heterogeneous, components of the additive, which are not uniformly dispersed and the mixed, generates wave yarns from the spun elastic fiber, thereby cutting the yarn. Further, the coherence between the filaments is lowered, thereby causing the crack of the filament in a subsequent processing step, and deteriorating the processing property and the quality of the final processed fiber.
  • a static mixer shaped in a cylinder pipe is used.
  • the shear rate within the static mixer is more than 0.13sec -1 without the inner mixing element.
  • the storage temperature of the additive slurry mixed into the final polymer is very important. If the storage temperature of the additive slurry is more than 60 ° C , factors of the raise and the discontinuance of the viscosity of the slurry are larger than factors of the lowering of the precipitation speed due to micro brown motion, thereby promoting the re -agglutination and the precipitation speed of the additive slurry, deteriorating the quality of the additive slurry and promoting the clogging cycle of a filter for the additive. Therefore, the quality and the production of the final polymer are influenced.
  • the storage temperature of the additive slurry is less than 40 ° C , the relative viscosity of the additive slurry against the temperature is raised, thereby increasing the generation of the difference pressure and functioning as an unstable factor of the process. And, the micro brown motion is weak, thereby promoting the re- agglutination, improving the quality of the additive and shortening the clogging cycle of the filter. Therefore, it is preferable to maintain the storage temperature of the additive slurry to be ranged from 40 to 60 ° C .
  • a designated amount of the formed dope is pushed into a spinning tub with the temperature of 180 ⁇ 280 ° C using a gear pump. Thereby, the solvent included in the dope is evaporated, thus preparing the polyurethane elastic fiber.
  • This method is referred to as a dry spinning method.
  • the polymer As the final polymer (dope) comprising various additives is changed into a yarn state, the polymer is chemically changed via transamidation or aminolysis. By this chemical change, the dope is changed into the yarn state and its molecular weight is increased.
  • the number average molecular weight of the elastic fiber, which is prepared by the present invention is about 40,000—70,000.
  • the number average molecular weight of the elastic yarn can be also measured by the Gel Permeation Chromatography (GPC). It is proper to set the spinning speed of the present invention to be 800-1,200 m/sec.
  • the spinning dope produced by the present invention has low content of gel.
  • the additives are uniformly mixed/dispersed within the spinning dope. Therefore, the spinning dope has an excellent spinnability and remarkably reduces the generation of wave yarn.
  • a proper amount of triamine is used as the chain extender and the additive, thereby causing the three-dimensional bridged bonds, and improving the heat resistance, the thermosetting efficiency, and the coherence between the monofilaments.
  • the strength maintenance rate is more than 54%
  • the coherence between the monofilaments is more than 145mgf.
  • the number of gel particles of the prepolymer, the molecular weight of the final polymer and the elastic yarn, the stability of viscosity of the final polymer, the heat resistance, and the thermosetting efficiency of the final polymer are measured, as follows.
  • the prepolymer is solved in 1% LiCl DMAc electrolyte by a 0.5% concentration. Then, the number of gel particles of the prepolymer is measured by the Coulter Counter (Coulter's product in England)
  • the sample with a length of 10cm is elongated at the speed of 500%/30sec until 500%, and is then left for 1 minute. And, the sample is also relaxed. If the produced yarn has at least 2 knobs, which are curved or winds, within a length of 10cm, this yarn is judged as a wave yarn.
  • the judgment of the wave yarn is represented by the number of the wave yarns among 5,000 cheeses in percentage.
  • Length change rate(%) - ⁇ - — founded & z- -z — - — . ⁇
  • One strand of the monofilament is separated by a length of 5cm from the polyurethane elastic yarn comprising plural filaments.
  • One end of the separated monofilament and one ends of other combined monofilaments are attached to an Instrung provided with a rod cell of less than 1kg so that a contact point between the separated monofilament and the non- separated monofilaments is disposed on the center of a cage of 5cm, and then elongated at the speed of 1000%/min, thereby measuring the shear strength of the separated monofilament and the non- separated monofilaments.
  • a result is obtained by the average of the coherences, which are measured during elongation. Each sample are measured more than three times.
  • the continuous polymerizing tube comprises the static mixer with the shear rate of 20sec -1 without the inner mixing element, the heat raiser with the shear rate of 3sec -1 without the inner mixing element, the reactor with the shear rate of O.lsec -1 without the inner mixing element, and the cooler.
  • the static mixer was maintained at 43.5 °C
  • the end of the heat raiser was maintained at 89 °C
  • the reactor was maintained at 88 ° C .
  • Polytetramethyleneetherglycol and 4,4'-diphenyldiisocyanate were reacted for 110 minutes, thereby producing the prepolymer with isocyanate on both ends.
  • the prepolymer was cooled to 40 ° C, and 4,4' -dimethylacetamide was added, thereby producing a solution including the prepolymer of 45%.
  • N,N' -dimethylacetamide solution 98.5 equivalent%, which is used as the chain extender and comprises ethylene diamine of 59.9 mol%, 1,2-diaminopropane of 40 mol% and diethylenetriamine of 0.1 mol%, and N,N' -dimethylacetamide solution 6.5 equivalent%, which is used as the chain terminator and comprises diethylamine, thereby preparing the final polymer.
  • the produced final polymer has the number average molecular weight of is 31,000 and the viscosity of 2,200 poise at 40°C , and comprises solid of 38.5%.
  • the final polymer was uniformly mixed with the additive slurry comprising l,3,5-tris(4-t- buthyl-3-hydroxy-2,6-dimethylbenzene)-l,3,5-triazine-2,4,6- (lH,3H,5H)trion antioxidant of 1.2 weight%, l,l,l',l'-tetramethyl-4,4'- (methylene-di-p-phethylene)disemicarbazide waste gas stabilizer of 1.0 weight%, N-(4-etoxycarbonylphenyl)-N-methyl-N-phenylformamidine ultraviolet stabilizer of 1.5 weight%, titanium oxide of 2 weight%, blue pigment(ultra marine blue) of 0.01 weight%, and diethylenetriamine of 0.2 weight%, and being stored at 45 ° C within the static mixer with the shear rate of 0.13sec -1 without the inner mixing element, thereby producing the dope just before spinning.
  • the additive slurry comprising l,3,5-tri
  • the dope is spun using the spinning tub with the temperature distribution between 260-200 ° C by the dry spinning, thereby producing the polyurethane elastic yarn of 40 denier.
  • Table 1 shows the measured results of the number of gel particles of the prepolymer, the rate of climb of viscosity of the final product, the frequency of generating the wave yarn, the heat resistance and the thermosetting efficiency of the produced elastic yarn, and coherence between monofilaments.
  • the elastic fiber of the present invention has excellent heat resistance (strength maintenance rate), thermosetting and coherence between the monofilaments, thereby being effectively used as a yarn for clothes.
  • the present invention improves the stability of the polymer, has an excellent spinnability even in high-speed spinning, and remarkably reduces the generation of wave yarns.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Artificial Filaments (AREA)

Abstract

L'invention concerne une fibre élastique en polyuréthane, et un procédé de production de ladite fibre. Le procédé se caractérise en ce qu'un polyol de poids moléculaire élevé et un diisocyanate en quantité excessive sont mélangés dans un état de vitesse de cisaillement indiqué et prépolymérisés pour produire un prépolymère. Ce prépolymère est mis en réaction avec un allongeur de chaîne et le terminateur afin de produire un polymère. Un additif est ajouté au polymère et le polymère final est filé. Ce procédé de production de la fibre élastique en polyuréthane améliore la stabilité du polymère, présente une excellente filabilité, et diminue remarquablement la survenue de fils ondulés. La fibre élastique en polyuréthane de l'invention présente une excellente résistance à la chaleur, un thermodurcissement efficient et une force de cohérence entre les monofilaments.
PCT/KR2002/000714 2001-04-19 2002-04-19 Fibre elastique de type polyurethane, et procede de preparation de la fibre WO2002086208A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US10/475,011 US20040121149A1 (en) 2001-04-19 2002-04-19 Polyurethane type elastic fiber, and a process of preparing for the same
JP2002583718A JP2004526069A (ja) 2001-04-19 2002-04-19 ポリウレタン系弾性繊維およびその製造方法
EP02718687A EP1392898A4 (fr) 2001-04-19 2002-04-19 Fibre elastique de type polyurethane, et procede de preparation de la fibre

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR1020010020975A KR100719044B1 (ko) 2001-04-19 2001-04-19 폴리우레탄계 탄성섬유 및 그의 제조방법
KR2001/20975 2001-04-19
KR2001/20976 2001-04-19
KR1020010020976A KR100646647B1 (ko) 2001-04-19 2001-04-19 폴리우레탄계 탄성섬유의 제조방법

Publications (1)

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WO2002086208A1 true WO2002086208A1 (fr) 2002-10-31

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PCT/KR2002/000714 WO2002086208A1 (fr) 2001-04-19 2002-04-19 Fibre elastique de type polyurethane, et procede de preparation de la fibre

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US (1) US20040121149A1 (fr)
EP (1) EP1392898A4 (fr)
JP (1) JP2004526069A (fr)
CN (1) CN1270006C (fr)
WO (1) WO2002086208A1 (fr)

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US6916896B2 (en) 2003-05-05 2005-07-12 Invista North America S.A.R.L. High productivity spandex fiber process and product
US7838617B2 (en) 2003-05-05 2010-11-23 Invista North America S.àr.l. Dyeable spandex

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CN101809209B (zh) * 2007-06-22 2012-08-29 因维斯塔技术有限公司 聚氨酯弹性纱线及其制造方法
US9279197B2 (en) * 2010-01-14 2016-03-08 Invista North America S.A.R.L. Spandex with high uniformity
CN107289806A (zh) * 2017-06-22 2017-10-24 兰州蓝星纤维有限公司 一种碳纤维原丝纺前原液温度控制的装置及其方法

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CN1509352A (zh) 2004-06-30
EP1392898A4 (fr) 2007-08-29
US20040121149A1 (en) 2004-06-24
JP2004526069A (ja) 2004-08-26
EP1392898A1 (fr) 2004-03-03
CN1270006C (zh) 2006-08-16

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