US20170114477A1 - System for industrial yarn production from composite polyethylene naphthalate material - Google Patents
System for industrial yarn production from composite polyethylene naphthalate material Download PDFInfo
- Publication number
- US20170114477A1 US20170114477A1 US15/301,414 US201515301414A US2017114477A1 US 20170114477 A1 US20170114477 A1 US 20170114477A1 US 201515301414 A US201515301414 A US 201515301414A US 2017114477 A1 US2017114477 A1 US 2017114477A1
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- US
- United States
- Prior art keywords
- mixture
- polyethylene naphthalate
- primary
- raw
- yarn production
- Prior art date
- Legal status (The legal status 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 status listed.)
- Abandoned
Links
- 239000011112 polyethylene naphthalate Substances 0.000 title claims abstract description 43
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 title claims description 39
- 239000002131 composite material Substances 0.000 title claims description 23
- -1 polyethylene naphthalate Polymers 0.000 title claims description 23
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 31
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims description 39
- 239000002245 particle Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 13
- 238000007865 diluting Methods 0.000 claims description 10
- 229920002959 polymer blend Polymers 0.000 claims description 10
- 239000011164 primary particle Substances 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010622 cold drawing Methods 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 230000002040 relaxant effect Effects 0.000 claims 1
- 239000004744 fabric Substances 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000007787 solid Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 241000254043 Melolonthinae Species 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D13/00—Complete machines for producing artificial threads
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
Definitions
- the present invention relates a system for industrial polyester yarn production, in which the mechanical properties of the yarn (tenacity, modulus, dimensional stability) are improved with additive, in order to be used in industrial fabric production.
- Liquid Crystal Polymers which can be used as reinforcing phase in different polymeric materials, are high performance resins with a unique structure comprising long, hard, rod like high oriented molecules. Rod-like molecules orient themselves in the flow direction during injection or extrusion molding.
- LCP The parts molded in LCP exhibit very high dimensional stability even if they are heated up to 200-250° C. Melting temperature of some LCP classes can reach up to 300° C. LCP can generally be used as an additive in many fields depending on its properties. Electronic and electrical components, fuel and gas barrier structures and sensors can be given as example for these fields.
- the objective of the present invention is to provide a system for liquid crystal polymer added industrial polyester yarn production.
- Another objective of the present invention is to provide a system for industrial yarn production wherein polyethylene naphthalate is used as polymer.
- a further objective of the present invention is to provide a system for industrial yarn production with improved tensile strength and elastic modulus.
- FIG. 1 is the schematic view of the inventive system for yarn production.
- FIG. 1 The components shown in FIG. 1 are each given with reference numerals as follows:
- the inventive system for composite polyethylene naphthalate industrial yarn production system ( 1 ) essentially comprises
- Raw mixture forming unit ( 1 ) present in inventive system ( 1 ) comprises
- PEN:LCP ratio of the mixture prepared in raw particle loading unit ( 21 ) is 60:40 by weight.
- the raw material which is prepared in this ratio and solidified in cooling unit ( 23 melted and blended in twin screw extruder ( 22 ) is become as particles.
- Primary mixture forming unit ( 3 ) comprises
- the raw mixture particles prepared in raw mixture forming unit ( 2 ) are sent to primary molten forming unit ( 3 ), and the polymer particles diluted with pure PEN are produced here.
- the PEN:LCP raw mixture is mixed with PEN till the LCP ratio becomes 1-3% by weight in particle loading and diluting unit ( 31 ). At the process is preferably carried out at 260-300° C.
- the molecular weight of the blended polymer particles that are obtained are increased at the outlet of primary mixture forming unit ( 3 ), and their internal viscosity (IV) is increased above 1 dL/g at 240-250° C. with solid state polymerization, which takes 12-24 hours.
- the purpose here is to increase molecular weight to obtain a polymer suitable for yarn drawing by decreasing the degradation and chain movement dining extrusion. %Clystallinity increase is above 100% with solid state polymerization.
- the particles obtained at primary mixture forming unit ( 3 ) with increased IV via solid state polymerization are dried in vacuum furnace for at least 24 hours at 120-140° C., and loaded to primary particle loading unit ( 4 ) under nitrogen atmosphere at 120° C.
- the humidity value of the blended and solid state polymerized particles should be under 60 ppm before loading to extruder ( 32 ).
- the primary polymer mixture coming out of primary mixture forming unit ( 3 ) is transferred to primary particle loading unit ( 4 ), and dried here at 100-120° C. and sent to extruder ( 5 ) which is heated to 290-320° C.
- PEN-LCP polymer mixture comprising 1-3% LCP by weight is become filaments via spinneret at the exit of extruder ( 5 ).
- the length/diameter ratio of the spinneret used at extruder exit ( 5 ) is 2-5, the hole diameter is 1 mm.
- the jet velocity of the material from extruder ( 5 ) is 6-7 m/min, the residence time of the material in the extruder is 11-12 minutes.
- the throughput here is adjusted as 6-7 g/min.
- the PEN-LCP filament coining out of extruder ( 5 ) is transferred to cooling unit ( 6 ) preferably treated with cooling water.
- the length of the cooling unit is 70 cm and its temperature is 80-95° C.
- the distance between extruder ( 5 ) and cooling unit ( 6 ) is adjusted as maximum 10 cm.
- the yarn coining out of cooling unit ( 6 ) first comes to primary roller ( 71 ) and it is sent to secondary roller ( 72 ) from here.
- the temperature of primary roller ( 71 ) is between 100-140° C.
- the temperature of secondary roller ( 72 ) is between 140-160° C. Cold drawing process is applied on the yarn between these rollers ( 7 ).
- the yarn coming out of secondary roller ( 72 ) is transferred to first hot chamber ( 81 ) and heated with hot air to 200-250° C. here and then transferred to tertiary roller ( 73 ).
- the temperature of tertiary roller ( 73 ) may vary between 200-250° C. Therefore, hot drawing is performed between secondary roller ( 72 ) and tertiary roller ( 73 ).
- tertiary roller ( 73 ) The yarn coming out of tertiary roller ( 73 ) enters into second hot chamber ( 82 ) at temperature of 120-180° C. It comes to quaternary roller ( 74 ) which is the last roller without heating, at room temperature; here it is relaxed in ratio of 1-2% and sent to winding unit ( 9 ) in order to be wound.
- the ratio of primary roller ( 71 ) speed to extruder ( 5 ) exiting speed is between 4-6.
- the ratio of tertiary roller ( 73 ) speed to—primary roller ( 71 ) speed may vary between 5-6,5.
- the conversion ratio is in range of 80-90% when the monofilament yarn which is produced with the inventive system is twisted as 2 layers with 50 twists.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
- This application is the national phase entry of International Application No PCT/TR2015/000117, filed on Mar. 25, 2015, which is based upon and claims priority to TR2014/03779, filed on Apr. 1, 2014, the entire contents of which are incorporated herein by reference.
- The present invention relates a system for industrial polyester yarn production, in which the mechanical properties of the yarn (tenacity, modulus, dimensional stability) are improved with additive, in order to be used in industrial fabric production.
- Improved mechanical properties and a strong structure are required in conveyor band chafer, membrane and coating fabrics. For such embodiments, processes should be improved without increasing the cost that much, and the resultant fiber should provide. high modulus and better dimensional stability compared to the reference. For this reason, studies have been carried out to produce self-reinforced composite PEN yarns.
- Liquid Crystal Polymers (LCP), which can be used as reinforcing phase in different polymeric materials, are high performance resins with a unique structure comprising long, hard, rod like high oriented molecules. Rod-like molecules orient themselves in the flow direction during injection or extrusion molding.
- The parts molded in LCP exhibit very high dimensional stability even if they are heated up to 200-250° C. Melting temperature of some LCP classes can reach up to 300° C. LCP can generally be used as an additive in many fields depending on its properties. Electronic and electrical components, fuel and gas barrier structures and sensors can be given as example for these fields.
- The objective of the present invention is to provide a system for liquid crystal polymer added industrial polyester yarn production.
- Another objective of the present invention is to provide a system for industrial yarn production wherein polyethylene naphthalate is used as polymer.
- A further objective of the present invention is to provide a system for industrial yarn production with improved tensile strength and elastic modulus.
- A system for industrial yarn production with LCP added polyethylene naphthalate developed to fulfill the objectives of the present invention is illustrated in the accompanying figure, wherein
-
FIG. 1 is the schematic view of the inventive system for yarn production. - The components shown in
FIG. 1 are each given with reference numerals as follows: -
- 10. System for industrial yarn production
- 11. Raw mixture forming unit
- 21. Raw particle loading unit
- 22. Raw molten extruder
- 23. Raw molten cooling unit
- 12. Primary mixture forming unit
- 31. Particle loading and diluting unit
- 32. Primary molten extruder
- 33. Primary molten cooling unit
- 13. Primary particle loading unit
- 14. Extruder
- 15. Cooling unit
- 16. Roller
- 71 Primary roller
- 72. Secondary roller
- 73. Tertiary roller
- 74. Quaternary roller
- 17. Hot chamber
- 81 First hot chamber
- 82. Second hot chamber
- 18. Winding unit
- The inventive system for composite polyethylene naphthalate industrial yarn production system (1) essentially comprises
-
- at least one raw mixture forming unit (2) wherein the raw polymer particles. are prepared,
- at least one primary mixture forming unit (3) wherein the primary polymer mixture is obtained diluting the raw polymer mixture with the main polymer ,
- at least one primary particle loading unit (4) wherein the polymer particles forming the primary mixture are filled and heated,
- at least one extruder (5) wherein the primary polymer mixture obtained in primary particle loading unit (4) is melted and spun as filaments with the help of the spinneret located at the exit,
- at least one cooling unit (6) wherein the material coming from ext (5) is cooled,
- at least one roller (7) wherein the material is drawn and oriented.
- at least one hot chamber (8) wherein the material is annealed,
- at least one winding unit (9) wherein the material is drawn via rollers (7) by cooling and heating is wound as yarn.
- Raw mixture forming unit (1) present in inventive system (1) comprises
-
- at least one raw particle loading unit (21) wherein polyethylene naphthalate (PEN) and liquid crystal polymer (LCP) are mixed,
- at least one raw molten extruder (22) wherein the raw molten mixture is extruded,
- at least one raw molten cooling unit (23) wherein the material going out of raw molten extruder (22) is cooled.
- In the preferred embodiment of inventive system (1), PEN:LCP ratio of the mixture prepared in raw particle loading unit (21) is 60:40 by weight. The raw material which is prepared in this ratio and solidified in cooling unit (23 melted and blended in twin screw extruder (22) is become as particles.
- Primary mixture forming unit (3) comprises
-
- at least one particle loading and diluting unit (31) wherein the polymer particles coining from raw mixture forming unit (2) are melted and diluted with PEN,
- at least one primary molten extruder (32) wherein the primary raw molten mixture is extruded,
- at least one primary molten cooling unit (33) wherein the material going out of main molten extruder (32) is cooled.
- The raw mixture particles prepared in raw mixture forming unit (2) are sent to primary molten forming unit (3), and the polymer particles diluted with pure PEN are produced here. The PEN:LCP raw mixture is mixed with PEN till the LCP ratio becomes 1-3% by weight in particle loading and diluting unit (31). At the process is preferably carried out at 260-300° C.
- In one embodiment of the invention, the molecular weight of the blended polymer particles that are obtained are increased at the outlet of primary mixture forming unit (3), and their internal viscosity (IV) is increased above 1 dL/g at 240-250° C. with solid state polymerization, which takes 12-24 hours. The purpose here is to increase molecular weight to obtain a polymer suitable for yarn drawing by decreasing the degradation and chain movement dining extrusion. %Clystallinity increase is above 100% with solid state polymerization.
- In one embodiment of the invention, the particles obtained at primary mixture forming unit (3) with increased IV via solid state polymerization are dried in vacuum furnace for at least 24 hours at 120-140° C., and loaded to primary particle loading unit (4) under nitrogen atmosphere at 120° C. In order to prevent hydrolytic degradation, the humidity value of the blended and solid state polymerized particles should be under 60 ppm before loading to extruder (32).
- The primary polymer mixture coming out of primary mixture forming unit (3) is transferred to primary particle loading unit (4), and dried here at 100-120° C. and sent to extruder (5) which is heated to 290-320° C. PEN-LCP polymer mixture comprising 1-3% LCP by weight is become filaments via spinneret at the exit of extruder (5). In the preferred embodiment of the invention, the length/diameter ratio of the spinneret used at extruder exit (5) is 2-5, the hole diameter is 1 mm. The jet velocity of the material from extruder (5) is 6-7 m/min, the residence time of the material in the extruder is 11-12 minutes. The throughput here is adjusted as 6-7 g/min.
- The PEN-LCP filament coining out of extruder (5) is transferred to cooling unit (6) preferably treated with cooling water. In one embodiment of the invention, the length of the cooling unit is 70 cm and its temperature is 80-95° C. In the same embodiment of the invention, the distance between extruder (5) and cooling unit (6) is adjusted as maximum 10 cm. The yarn coining out of cooling unit (6) first comes to primary roller (71) and it is sent to secondary roller (72) from here. In the preferred embodiment of the invention the temperature of primary roller (71) is between 100-140° C., and the temperature of secondary roller (72) is between 140-160° C. Cold drawing process is applied on the yarn between these rollers (7).
- The yarn coming out of secondary roller (72) is transferred to first hot chamber (81) and heated with hot air to 200-250° C. here and then transferred to tertiary roller (73). The temperature of tertiary roller (73) may vary between 200-250° C. Therefore, hot drawing is performed between secondary roller (72) and tertiary roller (73).
- The yarn coming out of tertiary roller (73) enters into second hot chamber (82) at temperature of 120-180° C. It comes to quaternary roller (74) which is the last roller without heating, at room temperature; here it is relaxed in ratio of 1-2% and sent to winding unit (9) in order to be wound.
- In the preferred embodiment of the invention, the ratio of primary roller (71) speed to extruder (5) exiting speed is between 4-6. The ratio of tertiary roller (73) speed to—primary roller (71) speed may vary between 5-6,5.
- When the tenacity and elastic modulus of LCP added PEN yarn in ratio of 1-3% obtained using inventive system (1) and the yarn manufactured from. pure PEN material with the total draw ratio of 6 are compared; the tenacity of the composite yarn produced in the inventive system has increased by 40-45%, and its elastic modulus has increased by 5-10%. When the total draw ratio is more than 6 the tenacity increase is between 25-30%, the elastic modulus improves by 2-5%. When the dimensional stability is considered, the dimensional stability of the 1-3% LCP added PEN yarn is 15-25% better than the pure PEN yarn in 6 drawing ratio.
- The conversion ratio is in range of 80-90% when the monofilament yarn which is produced with the inventive system is twisted as 2 layers with 50 twists.
Claims (19)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TR201403779 | 2014-04-01 | ||
| TR2014/03779 | 2014-04-01 | ||
| PCT/TR2015/000117 WO2015152844A1 (en) | 2014-04-01 | 2015-03-25 | A system for industrial yarn production from composite polyethylene naphthalate material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US20170114477A1 true US20170114477A1 (en) | 2017-04-27 |
Family
ID=53200279
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US15/301,414 Abandoned US20170114477A1 (en) | 2014-04-01 | 2015-03-25 | System for industrial yarn production from composite polyethylene naphthalate material |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20170114477A1 (en) |
| EP (1) | EP3126552B1 (en) |
| KR (1) | KR20160137641A (en) |
| CN (1) | CN106574402B (en) |
| BR (1) | BR112016023020A2 (en) |
| LU (1) | LU92889B1 (en) |
| RU (1) | RU2647386C1 (en) |
| WO (1) | WO2015152844A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220048879A (en) | 2020-10-13 | 2022-04-20 | 서무경 | Mono filament process apparatus using liquid crystal polymer |
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|---|---|---|---|---|
| US3658981A (en) * | 1967-10-23 | 1972-04-25 | Allied Chem | Process for spinning polyblend yarn |
| DE2352570A1 (en) * | 1973-10-19 | 1975-04-30 | Teijin Ltd | METHOD OF MANUFACTURING A POLYAETHYLENE-2,6-NAPHTHALATE YARN WITH GREAT TOUGHTY |
| US3945987A (en) * | 1974-05-30 | 1976-03-23 | Ernest Stossel | Carbamide adducts of polymetalophosphamate |
| GB2102853A (en) * | 1981-07-20 | 1983-02-09 | Bigelow Sanford Inc | A process for treating tufted pile fabric |
| US4398995A (en) * | 1980-05-26 | 1983-08-16 | Teijin Limited | Papery product |
| US5019316A (en) * | 1986-07-03 | 1991-05-28 | Toray Industries, Inc. | Method for producing thermoplastic synthetic yarn |
| US5487860A (en) * | 1992-03-30 | 1996-01-30 | Basf Corporation | Continuous process for spinning and drawing polyamide and apparatus thereof |
| US5794428A (en) * | 1996-05-29 | 1998-08-18 | Rhodes; Cheryl Elizabeth | Method of bulking and heat-setting a moving, continuous length of twisted thermoplastic yarn |
| US5955196A (en) * | 1996-06-28 | 1999-09-21 | Bp Amoco Corporation | Polyester fibers containing naphthalate units |
| US6109015A (en) * | 1998-04-09 | 2000-08-29 | Prisma Fibers, Inc. | Process for making poly(trimethylene terephthalate) yarn |
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2015
- 2015-03-25 BR BR112016023020A patent/BR112016023020A2/en not_active Application Discontinuation
- 2015-03-25 US US15/301,414 patent/US20170114477A1/en not_active Abandoned
- 2015-03-25 KR KR1020167030485A patent/KR20160137641A/en not_active Withdrawn
- 2015-03-25 EP EP15724103.5A patent/EP3126552B1/en not_active Not-in-force
- 2015-03-25 LU LU92889A patent/LU92889B1/en active
- 2015-03-25 CN CN201580029205.5A patent/CN106574402B/en not_active Expired - Fee Related
- 2015-03-25 WO PCT/TR2015/000117 patent/WO2015152844A1/en active Application Filing
- 2015-03-25 RU RU2016142684A patent/RU2647386C1/en not_active IP Right Cessation
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|---|---|---|---|---|
| US3658981A (en) * | 1967-10-23 | 1972-04-25 | Allied Chem | Process for spinning polyblend yarn |
| DE2352570A1 (en) * | 1973-10-19 | 1975-04-30 | Teijin Ltd | METHOD OF MANUFACTURING A POLYAETHYLENE-2,6-NAPHTHALATE YARN WITH GREAT TOUGHTY |
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| US5487860A (en) * | 1992-03-30 | 1996-01-30 | Basf Corporation | Continuous process for spinning and drawing polyamide and apparatus thereof |
| US5794428A (en) * | 1996-05-29 | 1998-08-18 | Rhodes; Cheryl Elizabeth | Method of bulking and heat-setting a moving, continuous length of twisted thermoplastic yarn |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN106574402B (en) | 2018-10-23 |
| BR112016023020A2 (en) | 2017-10-10 |
| RU2647386C1 (en) | 2018-03-15 |
| KR20160137641A (en) | 2016-11-30 |
| CN106574402A (en) | 2017-04-19 |
| LU92889B1 (en) | 2016-03-30 |
| EP3126552B1 (en) | 2018-03-21 |
| EP3126552A1 (en) | 2017-02-08 |
| WO2015152844A1 (en) | 2015-10-08 |
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