CN101495683A - A polyurethane elastic fiber with high heat settable property - Google Patents

A polyurethane elastic fiber with high heat settable property Download PDF

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Publication number
CN101495683A
CN101495683A CNA2007800277099A CN200780027709A CN101495683A CN 101495683 A CN101495683 A CN 101495683A CN A2007800277099 A CNA2007800277099 A CN A2007800277099A CN 200780027709 A CN200780027709 A CN 200780027709A CN 101495683 A CN101495683 A CN 101495683A
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China
Prior art keywords
polyurethane
chain extender
fabric
silk
prepolymer
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Granted
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CNA2007800277099A
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Chinese (zh)
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CN101495683B (en
Inventor
姜渊秀
徐升渊
晋中成
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Xiaoxing Tianxi (zhu)
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Hyosung Corp
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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/70Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2331/00Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
    • D10B2331/10Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyurethanes
    • DTEXTILES; PAPER
    • D10INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10BINDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00Physical properties
    • D10B2401/06Load-responsive characteristics
    • D10B2401/061Load-responsive characteristics elastic
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S528/00Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S528/906Fiber or elastomer prepared from an isocyanate reactant

Abstract

The present invention relates to a process for preparing polyurethane and polyurethane elastic yarns made therefrom, wherein an amount of 1,3-diaminopropane contained in a chain extender is 40 mol % or more based on the total chain extender and the chain extender further comprises at least one selected from a group consisting of ethylene diamine, 1,2- diaminopropane, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexandiamine and 1,4-cyclohexanediamine. The polyurethane elastic yarns show excellent heat settable property at low temperature and a fabric using the elastic yarns may be heat-set at low temperature to prevent edge curling and to improve fabric hand value of a knitted fabric.

Description

Polyurethane elastomeric fiber with high heat settability
Technical field
The elastic fabric that the present invention relates to a kind of method for producing polyurethanes and contain the elastic polyurethane silk that makes by this polyurethane, specifically, the present invention relates to the polyurethane for preparing by the diamine chain stretching agent that adds predetermined ratio and the elastic polyurethane silk that makes by this polyurethane, have excellent heat setting performance.
In particular, the present invention relates to a kind of knitted fabric, this knitted fabric is made of elastic fabric that has excellent heat setting performance at low temperatures and thermal sensitivity fiber (as nylon, silk, wool, polypropylene, artificial silk and polytrimethylene terephthalate).This knitted fabric can carry out heat setting at low temperatures, to prevent generation thermal degradation of thermal sensitivity fiber and knitted fabric generation crimping.
Background technology
Generally prepare polyurethane by the following method, described method is: make polyalcohol and excessive di-isocyanate reaction with the preparation prepolymer, this prepolymer is dissolved in the organic solvent, in resulting solution, add diamines or diol chain-extension agent then, and with chain terminating agent (as, monohydric alcohol and monoamine) react to form the polyurethane spinning solution, make polyurethane elastomeric fiber by dry spinning or wet spinning then.
Polyurethane fiber is characterised in that to have high elasticity, and is widely used in the multiple field.Along with the expansion of its purposes, more and more need to develop other character of polyurethane fiber.
Usually, in the last handling process after knitting polyurethane fiber is carried out heat setting under high temperature, and high temperature can cause thermal sensitivity fiber (as nylon, silk, wool, polypropylene, artificial silk and polytrimethylene terephthalate) that thermal degradation takes place.In order to prevent thermal degradation and to improve the feel value of fabric, need to develop the polyurethane fiber that carries out heat setting at low temperatures day by day.
In relevant prior art, people are devoted to improve the heat setting performance of polyurethane fiber always.For example, the open No.S63-53287 of Japan Patent, the open No.S63-53288 of Japan Patent, the open No.S43-639 of Japan Patent, the open No.H7-316922 of Japan Patent, the open No.2001-5854 of Korean Patent, the open No.2001-16788 of Korean Patent disclose the technology of the heat setting performance that is used to improve the elastic polyurethane silk.In addition, U.S. Patent No. 6,472,494, U.S. Patent No. 6,403, and 682, U.S. Patent No. 6,376,071, U.S. Patent No. 6,063, and 892, U.S. Patent No. 5,981,686, U.S. Patent No. 5,948, and 875 disclose the technology of the heat setting performance that is used to improve the elastic polyurethane silk.Yet because the thermal sensitivity fiber lacks the performance of heat setting at low temperatures, so it still can not be applied in the disclosed technology of prior art.
Summary of the invention
Technical problem
The objective of the invention is to prepare elastic polyurethane silk with excellent heat setting performance with suitable amine.According to the present invention, this elastic polyurethane silk carries out knitting with thermal sensitivity fiber (as nylon, cotton thread, silk, wool, polypropylene, artificial silk and polytrimethylene terephthalate).This knitted fabric heat setting at low temperatures improves the feel value of fabric then, and the knitted fabric that does not have crimping is provided to prevent the degraded of thermal sensitivity fiber generation fabric.
Technical scheme
According to embodiment preferred of the present invention, prepare elastic polyurethane silk with excellent heat setting performance and the elastic fabric that makes by this elastic polyurethane silk by following method, described method is: make polyalcohol and excessive di-isocyanate reaction with the preparation prepolymer, be dissolved in this prepolymer in the organic solvent and make resulting solution and chain extender reaction with preparation elastic polyurethane silk, contain in the wherein said chain extender 1, the amount of 3-diaminopropanes is 40 moles of % or more of this chain extender total amount.
According to another embodiment preferred of the present invention, a kind of method for preparing the elastic polyurethane silk is provided, wherein said chain extender also comprises and is selected from ethylenediamine, 1,2-diaminopropanes, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexamethylene diamine and 1, at least a material in the 4-cyclohexane diamine.
According to another embodiment preferred of the present invention, a kind of method that is used to prepare the elastic polyurethane silk is provided, wherein said prepolymer comprises the isocyanates of 1.56 weight % to the 4.29 weight % that account for this prepolymer total amount.
Beneficial effect
Compared with prior art, by using elastic polyurethane silk constructed in accordance, can carry out heat setting at low temperatures at knitting knitted fabric afterwards.Therefore, can prevent thermal sensitivity fiber generation thermal degradation, improve the feel value of fabric then.In addition, also prevent knitted fabric generation crimping.
Preferred forms of the present invention
Elastic polyurethane silk with excellent heat setting performance of the present invention hereinafter will be described.
Prepare employed block polyurethane among the present invention by the following method, described method is: make the reaction of organic diisocyanate and polymer diatomic alcohol with the preparation prepolymer, this prepolymer is dissolved in the organic solvent, then with diamines and monoamine reaction.
The example of employed organic diisocyanate can comprise among the present invention: be selected from diphenyl methane-4,4-vulcabond, 1,5-naphthalene diisocyanate, 1,4-phenylene diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate, 4, at least a material in 4 '-dicyclohexyl methyl hydride diisocyanate and the isophorone diisocyanate.
The example of the polymer diatomic alcohol that uses among the present invention can comprise polytetramethylene ether diol, polypropylene glycol ether and PCDL.Can use diamines as chain extender, described diamines is for being selected from ethylenediamine, 1,2-diaminopropanes, 1,6-hexamethylene diamine and 1, at least a material in the 3-diaminopropanes.Based on the total amount of chain extender, 1, the content of 3-diaminopropanes should be preferably 40 moles of % or more.If be lower than 40 moles of %, the heat setting performance of elastic polyurethane silk can significantly descend.
The example of the amine that being used to of using among the present invention controlled the molecular weight of polyurethane-urea and have a functional group can comprise diethylamine, monoethanolamine, dimethylamine etc.
In addition, in order to prevent that spandex from (for example ultraviolet ray and smog) under some environmental condition variable color and deterioration (may take place in the process in heat setting) taking place, and can be used in combination sterically hindered phenolic compounds, benzofuran ketonic compound, semicarbazide compound, benzotriazole cpd and poly-tertiary amine stabilizing agent in spinning solution.
Elastic polyurethane silk among the present invention can also comprise additive, as titanium dioxide and dolomol.
Implement mode of the present invention
The present invention may be better understood for example by hereinafter, enumerates these examples and be in order to explain the present invention, and should not be construed as limiting the invention.
As described in the following examples and Comparative Examples, make the heat setting performance of measuring the polyurethane silk with the following method and the edge-rolling of polyurethane fiber.
The evaluation of the heat setting performance of polyurethane silk
The silk thread with manufacturing stretches 100% (from 125mm to 250mm) in air after, it was descended xeothermic 1 minute at 170 ℃, then this silk thread is cooled to room temperature.Measure the length of silk thread, and calculate the heat setting performance according to following formula:
Heat setting performance (%)={ (heat setting length-initial length) }/(back length-initial length stretches) } * 100
The evaluation of edge-rolling
The spandex of heat setting at low temperatures is knitting with nylon, with the preparation circular knitted fabric.The length of side of drawing on knitted fabric is after the equilateral triangle of 5cm, cuts off leg-of-mutton two limits with scissors, and spray water is dry then in the above.After the drying, calculate the edge-rolling of knitted fabric according to following formula.
Edge-rolling (%)=(the leg-of-mutton area after crispaturaing/leg-of-mutton initial area) * 100
[embodiment 1]
Under nitrogen atmosphere, 80 ℃, stirring condition, with 550g diphenyl methane-4,4-vulcabond and 2328g polytetramethylene ether diol (mean molecule quantity is 1800) reaction 90 minutes is to prepare the polyurethane prepolymer that has isocyanates on its two end.This prepolymer is cooled to room temperature, adds the 4122g dimethylacetylamide and make its dissolving, with polyurethane preformed polymer solution.Subsequently, with 46.08g (0.622 mole) 1,3-diaminopropanes, 16.01g (0.266 mole) ethylenediamine and 5.2g diethylamine are dissolved in the 894g dimethylacetylamide, then it are added in the pre-polymer solution that is lower than 10 ℃, with the preparation polyurethane solutions.
Join solid additive in the solution can comprise the ethylenebis (oxygen ethylidene) of 1.5 weight % two-[3-(a 5-tertiary butyl-4-hydroxy-tolyl)-propionic ester], 0.5 weight % 5,7-di-t-butyl-3-(3, the 4-3,5-dimethylphenyl)-3H-benzofuran-2-ones, 1 weight % 1,1,1 ', 1 '-tetramethyl-4, poly-(the N of 4 '-(methylene-two-to phenylene) diaminourea, 1 weight %, N-diethyl-2-amino-ethyl methacrylate) and the titanium dioxide of 0.1 weight %, to make the polyurethane spinning solution.
Then with solution 250 ℃ of following dry spinnings, to make the elastic polyurethane silk of 40 DENIER.
Use resulting heat-set temperature low elastic polyurethane silk and nylon fiber, prepare circular knitted fabric by the round needle loom, the tube diameter of wherein said knitting machine is that 38 inches, needle gage (gauge) are 28 and have 120 thread-carriers (feeder).Preparation during knitted fabric employed nylon be the nylon of 70 DENIER, and with it with knitting by the elastic yarn of 40 DENIER of the inventive method manufacturing, and the content of elastic yarn is 8 weight % of fabric gross weight.
[embodiment 2]
Under nitrogen atmosphere, 80 ℃, stirring condition, with 550.2g diphenyl methane-4,4-vulcabond and 2328g polytetramethylene ether diol (mean molecule quantity is 1800) reaction 90 minutes is to prepare the polyurethane prepolymer that has isocyanates on its two end.This prepolymer is cooled to room temperature, adds the 4122g dimethylacetylamide and make its dissolving, to make polyurethane prepolymer solution.Subsequently, with 32.92g (0.444 mole) 1,3-diaminopropanes, 16.01g (0.2664 mole) ethylenediamine, 13.17g (0.1776 mole) 1,2-diaminopropanes and 5.2g diethylamine are dissolved in the 894g dimethylacetylamide, then it are added in the pre-polymer solution that is lower than 10 ℃ to make polyurethane solutions.Add the additive that has same composition with embodiment 1, and implement to prepare the process of silk thread and fabric according to the method among the embodiment 1.
[embodiment 3]
Under nitrogen atmosphere, 80 ℃, stirring condition, with 550.2g diphenyl methane-4,4-vulcabond and 2328g polytetramethylene ether diol (number-average molecular weight is 1800) reaction 90 minutes is to prepare the polyurethane prepolymer that has isocyanates on its two end.This prepolymer is cooled to room temperature, adds the 4122g dimethylacetylamide and make its dissolving, to make polyurethane prepolymer solution.Subsequently, with 65.83g (0.888 mole) 1,3-diaminopropanes and 5.2g diethylamine are dissolved in the 900g dimethylacetylamide, then it are added in the pre-polymer solution that is lower than 10 ℃, to make polyurethane solutions.
Add the additive that has same composition with embodiment 1, and implement to prepare the process of silk thread and fabric according to the method among the embodiment 1.
[embodiment 4 to 6 and Comparative Examples 1 to 3]
Carry out the process of embodiment 4 to 6 and Comparative Examples 1 to 3 according to the method among the embodiment 1, difference is that variation has taken place for the percentage by weight (weight %) of isocyanates as shown in table 1, the type and the molar percentage (mole %) of chain extender.
Table 1
The weight % of isocyanates The type of chain extender The ratio of chain extender Heat setting performance (%)
Embodiment 1 2.64 EDA/1,3-PDA 30/70 76
Embodiment 2 2.64 EDA/1,2-PDA/1,3-PDA 30/20/50 72
Embodiment 3 2.64 1,3-PDA 100 74
Embodiment 4 2.64 EDA/1,3-PDA 60/40 72
Embodiment 5 1.93 EDA/1,3-PDA 30/70 83
Embodiment 6 4.29 EDA/1,3-PDA 30/70 70
Comparative Examples 1 2.64 EDA/1,2-PDA 80/20 48
Comparative Examples 2 2.64 EDA/1,2-PDA 30/70 52
Comparative Examples 3 1.93 EDA/1,2-PDA 30/70 55
As shown in table 1, to account for 40 moles of % or higher by 1, the elastic polyurethane silk that the 3-diaminopropanes prepares as chain extender makes the heat setting performance improve.
[embodiment 7 to 10 and Comparative Examples 4 to 6]
Make the circular knitted fabric of embodiment 7 to 10 with the elastic yarn of preparation among nylon and the embodiment 1, make the circular knitted fabric of Comparative Examples 4 to 6 with the elastic yarn of manufacturing in nylon and the Comparative Examples 1.Then they are handled under the heat-setting condition shown in the table 2.Edge-rolling of gained fabric (%) and fabric feeling value are as shown in table 2.
Table 2
The preboarding temperature (℃) The finalization temperature (℃) Edge-rolling (%) The fabric feeling value
Embodiment 7 170 160 0 Excellent
Embodiment 8 175 160 0 Excellent
Embodiment 9 165 155 0 Excellent
Embodiment 10 N/A 175 0 Excellent
Comparative Examples 4 175 165 100 Excellent
Comparative Examples 5 190 180 0 Relatively poor
Comparative Examples 6 180 170 100 Excellent
As shown in table 2, in the process of the circular knitting nylon fabrics of preparation, with compare with the fabric of the prepared Comparative Examples 5 of the silk thread in the Comparative Examples 1, even with the fabric of the prepared embodiment 7 to 10 of the silk thread among the embodiment 1 crimping does not take place under the temperature that is lower than 20 ℃ of heat-set temperature yet.Simultaneously, though crimping does not take place in Comparative Examples 5 yet, owing at high temperature carry out heat setting, so its fabric feeling value is relatively poor.As shown in Table, use the fabric of spandex manufacturing in the lower heat setting process of temperature, can not cause the nylon thermal degradation, so this fabric can have excellent fabric feeling value.In addition, shown in embodiment 10, the process of preboarding can be omitted.
By being provided, exemplary embodiment specifically explained the present invention.Should be appreciated that those skilled in the art can change or revise these embodiments under the situation that does not deviate from scope and spirit of the present invention.Although invention has been described with reference to concrete exemplary, the present invention should not limited by these embodiments, and limited by appended claim.
Industrial applicibility
Elastic polyurethane silk of the present invention shows excellent heat setting performance at low temperatures. Therefore, crimping does not occur in the fabric that comprises the prepared elastic yarn of the present invention in the lower heat setting process of temperature, and this is so that the gained knitted fabric that can be used in a plurality of fields has excellent fabric feeling value.

Claims (4)

1. method for preparing elastic polyurethane silk with excellent heat setting performance, this method may further comprise the steps:
(a) make polyalcohol and excessive di-isocyanate reaction with the preparation prepolymer, (b) this prepolymer is dissolved in the organic solvent, and (c) make the reaction of resulting solution and chain extender with preparation elastic polyurethane silk, contain in the wherein said chain extender 1, the amount of 3-diaminopropanes accounts for 40 moles of % or more of this chain extender total amount.
2. the method for preparing the elastic polyurethane silk according to claim 1, wherein said chain extender also comprise and are selected from ethylenediamine, 1,2-diaminopropanes, 1,4-diaminobutane, 2,3-butanediamine, 1,5-pentanediamine, 1,6-hexamethylene diamine and 1, at least a material in the 4-cyclohexane diamine.
3. the method for preparing the elastic polyurethane silk according to claim 1 and 2 contains the isocyanates of 1.56 weight % to the 4.29 weight % that account for this prepolymer total amount in the wherein said prepolymer.
4. elastic fabric, it contains the elastic polyurethane silk that makes by the described method of claim 1.
CN2007800277099A 2006-07-31 2007-07-31 A polyurethane elastic fiber with high heat settable property Active CN101495683B (en)

Applications Claiming Priority (4)

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KR10-2006-0071869 2006-07-31
KR1020060071869 2006-07-31
KR1020060071869A KR100711644B1 (en) 2006-07-31 2006-07-31 A polyurethane elastic fiber with high heat settable property
PCT/KR2007/003689 WO2008016255A1 (en) 2006-07-31 2007-07-31 A polyurethane elastic fiber with high heat settable property

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103255500A (en) * 2013-05-30 2013-08-21 浙江华峰氨纶股份有限公司 Preparation method of polyurethane elastic fiber suitable for low-temperature setting
CN103498209A (en) * 2013-10-21 2014-01-08 浙江华峰氨纶股份有限公司 Manufacturing method of high-temperature-resistant and alkali-resistant polyurethane elastic fibers
CN105506777A (en) * 2016-01-26 2016-04-20 浙江华峰氨纶股份有限公司 Polyurethane elastic fiber easy to adhere and preparation method thereof
CN107663670A (en) * 2017-08-16 2018-02-06 东华大学 A kind of polyurethane elastomeric fiber and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BRPI0915235B1 (en) * 2008-10-17 2018-10-09 Invista Tech Sarl fibers, fabric and process for the preparation of a multi-component, spun-solution, fusible, elastic fiber

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US5000899A (en) * 1988-05-26 1991-03-19 E. I. Du Pont De Nemours And Company Spandex fiber with copolymer soft segment
US5644015A (en) * 1996-07-24 1997-07-01 Hyosung T & C Co., Ltd. Process of manufacturing improved polyurethane fiber polymer
US6468652B1 (en) * 1999-03-19 2002-10-22 Asahi Kasei Kabushiki Kaisha Elastic polyurethane-urea fiber and method for producing the same
AUPP991799A0 (en) 1999-04-23 1999-05-20 Cardiac Crc Nominees Pty Limited Siloxane-containing polyurethane-urea compositions
TW589421B (en) * 2000-04-26 2004-06-01 Du Pont Spandex with high heat-set efficiency
US6984708B2 (en) * 2002-10-04 2006-01-10 Invista North America S.A.R.L. Spandex of a particular composition and process for making same

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103255500A (en) * 2013-05-30 2013-08-21 浙江华峰氨纶股份有限公司 Preparation method of polyurethane elastic fiber suitable for low-temperature setting
CN103255500B (en) * 2013-05-30 2015-03-25 浙江华峰氨纶股份有限公司 Preparation method of polyurethane elastic fiber suitable for low-temperature setting
CN103498209A (en) * 2013-10-21 2014-01-08 浙江华峰氨纶股份有限公司 Manufacturing method of high-temperature-resistant and alkali-resistant polyurethane elastic fibers
CN103498209B (en) * 2013-10-21 2015-10-28 浙江华峰氨纶股份有限公司 There is the preparation method of high temperature resistant and alkaline-resisting polyurethane elastomeric fiber
CN105506777A (en) * 2016-01-26 2016-04-20 浙江华峰氨纶股份有限公司 Polyurethane elastic fiber easy to adhere and preparation method thereof
CN107663670A (en) * 2017-08-16 2018-02-06 东华大学 A kind of polyurethane elastomeric fiber and preparation method thereof

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WO2008016255A1 (en) 2008-02-07
KR100711644B1 (en) 2007-04-25

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Effective date of registration: 20181203

Address after: Seoul, South Kerean

Patentee after: Xiaoxing Tianxi (Zhu)

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Patentee before: Hyosung Corp.