CN1410605A - Preparation method of melt spinning polyurethane fiber thin denier filament - Google Patents
Preparation method of melt spinning polyurethane fiber thin denier filament Download PDFInfo
- Publication number
- CN1410605A CN1410605A CN 01126972 CN01126972A CN1410605A CN 1410605 A CN1410605 A CN 1410605A CN 01126972 CN01126972 CN 01126972 CN 01126972 A CN01126972 A CN 01126972A CN 1410605 A CN1410605 A CN 1410605A
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- polyether
- polyester
- crosslinking agent
- polyol
- thermoplastic
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Abstract
The method includes following steps. (1) With being added in the screw extruder, the thermoplastic polyurethane is melted and mixed. (2) The crosslinking agent is added in the metering section of the extruder or between the extruder and mixer. (3) The melted woven material through the nozzle plate is ejected, spun and wound. The invention solves the issue of the mating use between the thermoplastic polyurethane and the crosslinking agent and prevents the thermal degradationand the carbonization so as to obtain the product with excellent combination property.
Description
Technical field
The fine denier spandex continuous yarn preparation method that the present invention announced is meant the fiber number melt spun spandex long filament in 10-30 dawn scope for preparing fiber.
Background technology
In the prior art, melt spun spandex generally comprise two kinds of technologies:
The typical case of first kind of technology representative is a Japanese Kuraray company product, and its spun fine denier spandex silk elastic recovery rate is obviously on the low side.Simplified production technology on this technical face, but to thermoplastic polyurethane raw material heat endurance, hydrolytic stability and all very high to the accurate ratio requirement of raw material, and elastic recovery rate is not high.The clock that the typical case of second kind of technology is represented as Japan spins company, the fracture strength of melt spun spandex long filament was on the low side in it was spun, can adopt the low thermoplastic polyurethane of molecular weight and viscosity in this technology, can to a certain degree avoid raw material in spinning process, to degrade and the generation of phenomenon such as carbonization, but end-caps discharges micromolecular compound when deblocking, this influences the physical and mechanical property of gained fiber on the one hand, also causes environmental pollution on the other hand.
Summary of the invention
The object of the present invention is to provide a kind of method of fiber number melt spun spandex long filament in 10-30 dawn scope that can spinning fibre, elastic recovery rate height, the fracture strength of the long filament that it spins out are also high.
Technical scheme of the present invention is: a kind of preparation method of melt spinning polyurethane fiber thin denier filament, it comprises the steps:
(1). carrying out fusion, mixing in the analog thermoplastic polyurethane adding screw extruder;
(2). add a class crosslinking agent at the metering section of extruder or after going out extruder, before entering blender;
(3). the melt-spun material is through spinnerets ejection, spinning and coiling and molding;
Described thermoplastic polyurethane has three types: the first kind is the thermoplastic polyester type polyurethane, and second class is a thermoplastic polyether urethane, and the 3rd class is thermoplastic polyether-polyester mixed type polyurethane;
Described crosslinking agent is also to there being three types: the first kind is the polyether-type crosslinking agent, and second class is the polyester-type crosslinking agent, and the 3rd class is a polyether-polyester mixed type crosslinking agent;
The use that matches with described polyester-type crosslinking agent of described thermoplastic polyether urethane; Described thermoplastic polyester type polyurethane and the supporting use of described polyether-type crosslinking agent; Described thermoplastic polyether-polyester mixed type polyurethane and the supporting use of described polyether-polyester mixed type crosslinking agent;
Described polyether-type crosslinking agent is by polyether polyol, isocyanate reaction and get;
Described polyester-type crosslinking agent is by polyester polyol, isocyanate reaction and get;
Described polyether-polyester mixed type crosslinking agent is the polyols blend that is made of polyether polyol and polyester polyol, isocyanate reaction and get.
Of the present invention mainly is the supporting use problem that has solved thermoplastic polyurethane and crosslinking agent.Here comprise two aspect work, solved the situation that domestic portion of hot plastic polyurethane raw material is not furnished with crosslinking agent on the one hand, solve existing thermoplastic polyurethane on the other hand and cooperated not good problem with crosslinking agent, thereby solved silk poor heat stability that spins out or the difficult problem that fracture strength is low or elastic recovery rate is not high.The present invention spells out the Matching Relationship between ardent hope based polyurethane and the crosslinking agent.The starting point of the present invention's innovation is to optimize the dispersiveness of the hard segment domains of thermoplastic polyurethane.Be used by making between polyethers and polyester backbone particularly, reduced the dispersion size of the hard segment domains of thermoplastic polyurethane, strengthened that polarity interacts between the strand of microcell inside, improved the phase separation of hard segment domains, thereby the thermal degradation and the carbonization phenomenon that occur polymeric material when preventing to produce effectively, and successfully melt-spun goes out the fine denier spandex continuous yarn of excellent combination property.
Description of drawings
Accompanying drawing 1 is the flow chart of first kind of technology of the present invention (claiming one-step method again);
Accompanying drawing 2 is the flow chart of second kind of technology of the present invention (claiming blocking method again);
The specific embodiment
The thermoplastic polyurethane section is after cleaning, with the additive combination drying except that crosslinking agent, dried material adds in the screw extruder, fusion, mixing, at the metering section of extruder or after going out extruder and add quantitative crosslinking agent before entering blender, the melt-spun material sprays through spinnerets, and spun filament is stretched, cools off, oils, reels, and promptly gets the melt-spun fine denier spandex continuous yarn.Why successfully melt-spun of the present invention goes out fine denier spandex continuous yarn, is to be to have solved crosslinking agent and the supporting use problem of thermoplastic polyurethane.
The supporting use of described crosslinking agent and thermoplastic polyurethane is meant the supporting use that crosslinking agent chemical composition and thermoplastic polyurethane are formed.The main material of melt-spun fine denier spandex continuous yarn comprises three classes: thermoplastic polyester type polyurethane, thermoplastic polyether urethane and thermoplastic polyether-polyester mixed type polyurethane.Three kinds of crosslinking agents of the present invention refer to: polyester-type crosslinking agent, polyether-type crosslinking agent and polyether-polyester mixed type crosslinking agent.Thermoplastic polyether urethane and the supporting use of polyester-type crosslinking agent; Thermoplastic polyester type polyurethane and the supporting use of polyether-type crosslinking agent; Thermoplastic polyether-polyester mixed type polyurethane and the supporting use of polyether-polyester mixed type crosslinking agent.
Three kinds of crosslinking agents of the present invention are promptly: polyester-type crosslinking agent, polyether-type crosslinking agent and polyether-polyester mixed type crosslinking agent.So-called polyester-type crosslinking agent is again to be got by polyester polyol, isocyanates and chain extender reaction, wherein also can not have chain extender; The polyether-type crosslinking agent is to be got by polyether polyol, isocyanates and chain extender reaction, wherein also can not have chain extender; The polyols blend that polyether-polyester mixed type crosslinking agent is made of polyether polyol and polyester polyol, isocyanates and chain extender react and get, and wherein also can not have chain extender.
Polyester polyol of the present invention is meant and contains the base polymer ester group group and that contain two or more hydroxyls.It can carry out the esterifying polycondensation prepared in reaction by binary acid and dihydroxylic alcohols and polyalcohol under catalytic action such as acid or alkali or transistion metal compound and under 50-240 ℃, till esterification finishes.During batching, dihydroxylic alcohols and polyalcohol the mole dosage theoretical amount of esterification are fully omited many.The binary acid that is suitable for can be aliphatic and aromatic, as adipic acid, succinic acid, certain herbaceous plants with big flowers diacid, terephthalic acid (TPA), M-phthalic acid etc.The dihydroxylic alcohols, the polyalcohol that are suitable for can be respectively: ethylene glycol, 1, ammediol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol, glycerol, trimethylolpropane pentaerythrite and sucrose etc.Above-mentioned binary acid, dihydroxylic alcohols, multicomponent alcoholics compound can use separately, use also capable of being combined.Described polyester polyol also can comprise polycaprolactone polyol, polycarbonate polyol.Preferred polyester polyalcohol of the present invention be tetramethylene adipate be main chain and contain polyalcohols such as a small amount of neopentyl glycol, trimethylolpropane.The number-average molecular weight of polyester segment should be between 200-5000, more preferably between 500-2500.
Polyether polyol of the present invention is meant that a class contains the polymer ether group and that contain two or more hydroxyls, normally hydroxy compounds, amino-compound etc. are initiator, carry out the cyclic ether compounds ring-opening polymerization and make the polymer that polyalkylene oxide contains two or more hydroxyls under catalyst actions such as alkali metal hydroxide, metal alkyl compound, lewis acid.Used initiator is mainly glycerine, trimethylolpropane, pentaerythrite, xylitol, sucrose of propylene glycol, neopentyl glycol and a spot of polyfunctionality etc., cyclo other compounds mainly contains oxirane, expoxy propane, oxolane etc., above-mentioned cyclic ethers can use separately, use also capable of being combined.The number-average molecular weight of polymer then is controlled between the 200-5000, more preferably between 500-2500.Above-mentioned polyether polyol is the PolyTHF polyalcohol more preferably;
Polyether-polyester mixed type polyalcohol of the present invention is the block copolymer that contains ester group group and ether group roughly the same the time, contains two or more hydroxyls.Its preparation method still adopts conventional esterifying polycondensation technology to carry out.Binary acid, dihydroxylic alcohols and a spot of polyalcohol in temperature 50-240 ℃, 2-20 hour and under the catalyst action after the polycondensation, are carried out the esterifying polycondensation reaction with polyether polyol again, thereby make polyether-polyester mixed type polyalcohol.Wherein polyethers, polyester construction can be similar with above-mentioned polyether polyol, polyester polyol structure, and the number-average molecular weight of block copolymer then is controlled between the 200-5000, more preferably between 500-2500.Above-mentioned polyether-polyester mixed type polyalcohol is the polyalcohol of tetramethylene adipate and oxolane block copolymer more preferably.
The used isocyanates of crosslinking agent of the present invention can be aliphatic and aromatic isocyanate class, such as, hexamethylene diisocyanate, 4,4 ' methyl diphenylene diisocyanates, 3,3 '-two chloro-4,4 ' methyl diphenylene diisocyanate, 2,6 toluene di-isocyanate(TDI)s etc., these isocyanates can use separately, can also be used in combination.
The used chain extender of crosslinking agent of the present invention can be low molecular weight less than 400 diatomic alcohol compounds, for example, and propylene glycol, 1,4-butanediol, 1,6-hexylene glycol, 1, two (hydroxy ethoxy) benzene of 4-etc.These chain extenders can use separately, use also capable of being combined.
The polymer polyatomic alcohol of described crosslinking agent, chain extender and isocyanates mole quantitative relationship can be as follows:
The polymer polyatomic alcohol degree of functionality is N, and number-average molecular weight is M
1, its consumption is n
1Mole; The molecular weight of chain extender dihydroxylic alcohols is M
2, its consumption is n
2Mole; The molecular weight of isocyanates is M
3, its consumption is n
3Mole.If the degree of functionality of gained crosslinking agent is M
NCO, the weight percentage of isocyanates weight percentage and hard section calculates isocyanates weight percentage W respectively as follows
1For:
The weight percentage W of hard section
2For:
The degree of functionality M of the crosslinking agent that the present invention requires
NCOIn scope
2≤M
NCO≤ 10, more preferably at 3≤M
NCO≤ 6 the present invention require isocyanates weight percentage W
1In scope
1.0%≤W
1≤ 15.0%, more preferably at 3.0%≤W
1Hard section the weight percentage W that≤10.0% the present invention requires
2In scope
15%≤W
2≤ 70%, more preferably at 25%≤W
2The polymerization process for preparing of≤60% crosslinking agent of the present invention does not have specific (special) requirements, adopts conventional single still method synthetic.With above-mentioned a certain amount of polyester polyol or polyether polyol or polyether-polyester mixed type polyalcohol, vulcabond, chain extender (also can without chain extender) by a certain percentage, order adds, reaction time, temperature, vacuum, stir speed (S.S.) etc. all do not have specific (special) requirements, can be at 50-180 ℃, 30 minutes reaction time was undertaken by 5 hours.In addition, in the crosslinking agent preparation process, also can add a spot of heat stabilizer, antioxidant, lubricant etc.
Three kinds of crosslinking agents of the present invention and the corresponding supporting use of thermoplastic polyurethane, its consumption is relevant with the physical and mechanical property of desired fiber, and the consumption of crosslinking agent can be at 5-40 weight %, more preferably at 10-30 weight %.
Claims (6)
1. preparation method of melt spinning polyurethane fiber thin denier filament, it is characterized in that: it comprises the steps:
(1), carrying out fusion, mixing in the analog thermoplastic polyurethane adding screw extruder;
(2), at the metering section of extruder or after going out extruder, add a class crosslinking agent before entering blender;
(3), the melt-spun material is through spinnerets ejection, spinning and coiling and molding;
Described thermoplastic polyurethane has three types: the first kind is the thermoplastic polyester type polyurethane, and second class is a thermoplastic polyether urethane, and the 3rd class is thermoplastic polyether-polyester mixed type polyurethane;
Described crosslinking agent is also to there being three types: the first kind is the polyether-type crosslinking agent, and second class is the polyester-type crosslinking agent, and the 3rd class is a polyether-polyester mixed type crosslinking agent;
The use that matches with described polyester-type crosslinking agent of described thermoplastic polyether urethane; Described thermoplastic polyester type polyurethane and the supporting use of described polyether-type crosslinking agent; Described thermoplastic polyether-polyester mixed type polyurethane and the supporting use of described polyether-polyester mixed type crosslinking agent;
Described polyether-type crosslinking agent is by polyether polyol, isocyanate reaction and get;
Described polyester-type crosslinking agent is by polyester polyol, isocyanate reaction and get;
Described polyether-polyester mixed type crosslinking agent is the polyols blend that is made of polyether polyol and polyester polyol, isocyanate reaction and get.
2. preparation method of melt spinning polyurethane fiber thin denier filament according to claim 1 is characterized in that: described polyester polyol is meant the straight or branched that contains the ester group group and contains a base polymer of two or more hydroxyls; Described polyether polyol is meant that a class contains the polymer ether group and that contain two or more hydroxyls; Described polyether-polyester mixed type polyalcohol is the block copolymer that contains ester group group and ether group simultaneously, contains two or more hydroxyls.
3. preparation method of melt spinning polyurethane fiber thin denier filament according to claim 1 is characterized in that: described polyether-type crosslinking agent is to be reacted and got by polyether polyol, isocyanates, chain extender; Described polyester-type crosslinking agent is to be reacted and got by polyester polyol, isocyanates, chain extender; Described polyether-polyester mixed type crosslinking agent is to be reacted and got by polyols blend, isocyanates, chain extender that polyether polyol and polyester polyol constitute.
4. preparation method of melt spinning polyurethane fiber thin denier filament according to claim 2, it is characterized in that: described polyester polyol is by catalytic action by binary acid and dihydroxylic alcohols, polyalcohol, carrying out the esterifying polycondensation reaction under 50-240 ℃ temperature forms, the number-average molecular weight of polyester segment is between 200-5000, more preferably between 500-2500.
5. preparation method of melt spinning polyurethane fiber thin denier filament according to claim 2, it is characterized in that: described polyether polyol is to be carried out the cyclic ether compounds ring-opening polymerization and made the polymer that polyalkylene oxide contains two or more hydroxyls under catalyst action by hydroxy compounds, amino-compound, the number-average molecular weight of polymer is between 200-5000, more preferably between 500-2500.
6. preparation method of melt spinning polyurethane fiber thin denier filament according to claim 2, it is characterized in that: described polyether-polyester mixed type polyalcohol be by binary acid, dihydroxylic alcohols, polyalcohol after polycondensation under the catalyst action, carry out the esterifying polycondensation reaction with polyether polyol again, thereby make polyether-polyester mixed type polyalcohol, wherein, the number-average molecular weight of copolymer is between 200-5000, more preferably between 500-2500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011269723A CN1170017C (en) | 2001-10-09 | 2001-10-09 | Preparation method of melt spinning polyurethane fiber thin denier filament |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011269723A CN1170017C (en) | 2001-10-09 | 2001-10-09 | Preparation method of melt spinning polyurethane fiber thin denier filament |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1410605A true CN1410605A (en) | 2003-04-16 |
| CN1170017C CN1170017C (en) | 2004-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011269723A Expired - Fee Related CN1170017C (en) | 2001-10-09 | 2001-10-09 | Preparation method of melt spinning polyurethane fiber thin denier filament |
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Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005005697A1 (en) * | 2003-06-30 | 2005-01-20 | Noveon Ip Holdings Corp. | Melt spun monofilament or elastic tape and process |
| WO2005005509A1 (en) * | 2003-06-30 | 2005-01-20 | Noveon Ip Holdings Corp. | Melt spun polyether tpu fibers having mixed polyols and process |
| CN100537859C (en) * | 2003-07-16 | 2009-09-09 | 李绍光 | A kind of melt spinning method of making polyurethane elastomeric fiber |
| CN101255224B (en) * | 2008-04-09 | 2010-12-15 | 南通华盛高聚物科技发展有限公司 | Melt extrusion spandex cross-linking agent and production method |
| CN102011211A (en) * | 2010-12-02 | 2011-04-13 | 张家港市沃斯汀新材料研究所有限公司 | Method for preparing melt spun chlorine-resistance high resilient polyurethane fiber |
| CN102021673A (en) * | 2010-12-10 | 2011-04-20 | 太仓市金祥氨纶纤维有限公司 | Method for producing melt direct spinning superfine (4.6-5.5) denier high elastic modulus polyurethane fibers |
| CN103506966A (en) * | 2013-05-08 | 2014-01-15 | 河南星智发明电子科技有限公司 | Coated grinding wire producing method |
| CN103590137A (en) * | 2012-08-16 | 2014-02-19 | 南通华盛高聚物科技发展有限公司 | Preparation method of low melting point spandex fiber |
| CN104862809A (en) * | 2015-05-21 | 2015-08-26 | 苏州富莱克斯氨纶有限公司 | Preparation method of colored melt-spun spandex |
| CN104911723A (en) * | 2015-05-21 | 2015-09-16 | 苏州富莱克斯氨纶有限公司 | Bi-component spandex preparing technology |
| CN105696101A (en) * | 2009-06-25 | 2016-06-22 | 路博润高级材料公司 | High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers |
| CN107299410A (en) * | 2017-08-18 | 2017-10-27 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic chinlon filament |
| CN107299409A (en) * | 2017-08-18 | 2017-10-27 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic polyvinyl long filament |
| CN107299408A (en) * | 2017-08-18 | 2017-10-27 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of antibiotic spandex filament |
| CN107326471A (en) * | 2017-08-18 | 2017-11-07 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of antibacterial nylon long filament |
| CN107385552A (en) * | 2017-08-18 | 2017-11-24 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of antibacterial dacron long filament |
| CN107513777A (en) * | 2017-08-18 | 2017-12-26 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic polypropylene filament yarn |
| CN107513776A (en) * | 2017-08-18 | 2017-12-26 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic spandex filament |
| CN107557903A (en) * | 2017-08-25 | 2018-01-09 | 浩沙实业（福建）有限公司 | A kind of cold-resistant polyurethane fiber material of swimming suit |
| CN113789588A (en) * | 2021-10-14 | 2021-12-14 | 华峰化学股份有限公司 | Degradable melt-spun polyurethane elastic fiber |
-
2001
- 2001-10-09 CN CNB011269723A patent/CN1170017C/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005005697A1 (en) * | 2003-06-30 | 2005-01-20 | Noveon Ip Holdings Corp. | Melt spun monofilament or elastic tape and process |
| WO2005005509A1 (en) * | 2003-06-30 | 2005-01-20 | Noveon Ip Holdings Corp. | Melt spun polyether tpu fibers having mixed polyols and process |
| CN100523322C (en) * | 2003-06-30 | 2009-08-05 | 路博润高级材料公司 | Melt spun monofilament or elastic tape and process |
| US7763351B2 (en) | 2003-06-30 | 2010-07-27 | Lubrizol Advanced Materials, Inc. | Melt spun elastic tape and process |
| US7799255B2 (en) | 2003-06-30 | 2010-09-21 | Lubrizol Advanced Materials, Inc. | Melt spun elastic tape and process |
| US8148475B2 (en) | 2003-06-30 | 2012-04-03 | Lubrizol Advanced Materials, Inc. | Melt spun polyether TPU fibers having mixed polyols and process |
| CN100537859C (en) * | 2003-07-16 | 2009-09-09 | 李绍光 | A kind of melt spinning method of making polyurethane elastomeric fiber |
| CN101255224B (en) * | 2008-04-09 | 2010-12-15 | 南通华盛高聚物科技发展有限公司 | Melt extrusion spandex cross-linking agent and production method |
| CN105696101A (en) * | 2009-06-25 | 2016-06-22 | 路博润高级材料公司 | High Strength Fabrics Consisting Of Thin Gauge Constant Compression Elastic Fibers |
| CN102011211A (en) * | 2010-12-02 | 2011-04-13 | 张家港市沃斯汀新材料研究所有限公司 | Method for preparing melt spun chlorine-resistance high resilient polyurethane fiber |
| CN102011211B (en) * | 2010-12-02 | 2012-11-21 | 张家港市沃斯汀新材料研究所有限公司 | Method for preparing melt spun chlorine-resistance high resilient polyurethane fiber |
| CN102021673A (en) * | 2010-12-10 | 2011-04-20 | 太仓市金祥氨纶纤维有限公司 | Method for producing melt direct spinning superfine (4.6-5.5) denier high elastic modulus polyurethane fibers |
| CN103590137A (en) * | 2012-08-16 | 2014-02-19 | 南通华盛高聚物科技发展有限公司 | Preparation method of low melting point spandex fiber |
| CN103506966A (en) * | 2013-05-08 | 2014-01-15 | 河南星智发明电子科技有限公司 | Coated grinding wire producing method |
| CN104862809A (en) * | 2015-05-21 | 2015-08-26 | 苏州富莱克斯氨纶有限公司 | Preparation method of colored melt-spun spandex |
| CN104911723A (en) * | 2015-05-21 | 2015-09-16 | 苏州富莱克斯氨纶有限公司 | Bi-component spandex preparing technology |
| CN107299410A (en) * | 2017-08-18 | 2017-10-27 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic chinlon filament |
| CN107299409A (en) * | 2017-08-18 | 2017-10-27 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic polyvinyl long filament |
| CN107299408A (en) * | 2017-08-18 | 2017-10-27 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of antibiotic spandex filament |
| CN107326471A (en) * | 2017-08-18 | 2017-11-07 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of antibacterial nylon long filament |
| CN107385552A (en) * | 2017-08-18 | 2017-11-24 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of antibacterial dacron long filament |
| CN107513777A (en) * | 2017-08-18 | 2017-12-26 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic polypropylene filament yarn |
| CN107513776A (en) * | 2017-08-18 | 2017-12-26 | 太仓佩利斯高分子材料有限公司 | A kind of processing technology of long acting antibiotic spandex filament |
| CN107557903A (en) * | 2017-08-25 | 2018-01-09 | 浩沙实业（福建）有限公司 | A kind of cold-resistant polyurethane fiber material of swimming suit |
| CN113789588A (en) * | 2021-10-14 | 2021-12-14 | 华峰化学股份有限公司 | Degradable melt-spun polyurethane elastic fiber |
Also Published As
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|---|---|
| CN1170017C (en) | 2004-10-06 |
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