EP0452405B1 - Procede pour un fil polyester indeformable - Google Patents

Procede pour un fil polyester indeformable Download PDF

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Publication number
EP0452405B1
EP0452405B1 EP90902093A EP90902093A EP0452405B1 EP 0452405 B1 EP0452405 B1 EP 0452405B1 EP 90902093 A EP90902093 A EP 90902093A EP 90902093 A EP90902093 A EP 90902093A EP 0452405 B1 EP0452405 B1 EP 0452405B1
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EP
European Patent Office
Prior art keywords
yarn
multifilament yarn
filaments
polyethylene terephthalate
undrawn
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Expired - Lifetime
Application number
EP90902093A
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German (de)
English (en)
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EP0452405A1 (fr
Inventor
Maxwell Charles Hamlyn
Thomas Howard Luck
Charles Jay Nelson
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Honeywell International Inc
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AlliedSignal Inc
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    • 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
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • 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
    • D01D5/08—Melt spinning methods

Definitions

  • This invention relates to a process for production of polyester multi-filament drawn yarn of 2.5 denier per filament (pf) (2.8 dtexpf) or greater, whereby high birefringence ( ⁇ n) yarns are prepared at lower spinning speeds and lower intrinsic viscosity than prior art processes.
  • Polyethylene terephthalate filaments of high strength are well known in the art and are commonly utilized in industrial applications including tire cord for rubber reinforcement, conveyor belts, seat belts, V-belts and hosing.
  • DSP Dimensionally stable polyester
  • SWI sidewall indentations
  • An additional objective is to make advanced DSP's having the strength and modulus equivalent to rayon at elevated tire service temperatures, while using up to 30 percent less material. While the current polyester tire cords have sufficient strength, their elevated temperature modulus is too low.
  • U.S. Patent 4,101,525 to Davis et al. provides a high strength multifilament polyester yarn with low shrinkage and work-loss characteristics. While yarns exhibiting the features taught by Davis are classified as DSP's, they do not meet the modulus requirements for rayon replacement.
  • U.S. Patent 4,491,657 to Saito et al. discloses high modulus, low shrinkage polyester yarn, but requires a low terminal modulus to achieve good yarn to treated cord conversion efficiency for such dimensionally stable yarns. The low terminal modulus is translated into the treated cord and results in a lower tenacity than the high terminal modulus cords made by present invention.
  • the process of Saito et al. requires high spinning speeds, which makes it difficult to incorporate the Saito process into a continuous spin-draw process, whereas the present invention permits the use of lower spinning speeds whereby more readily available and/or less costly equipment can be used.
  • the invention relates to a process for production of a dimensionally stable drawn polyethylene terephthalate multifilament yarn having filaments of at least 2.5 denier per filament (2.8 dxpf) comprising the steps of:
  • the dimensionally stable polyester multifilament yarns made by the process of the present invention provide dimensionally stable treated cords when incorporated as fibrous reinforcement into rubber composites such as tires.
  • Dimensional stability is defined as high modulus at a given shrinkage and directly relates to tire sidewall indentations (SWI) and tire handling. While the modulus of the cord in the tire is the primary variable governing both SWI and handling, shrinkage is important in two ways. First, excessive cord shrinkage during tire curing can significantly reduce the modulus from that of the starting treated cord. Second, cord shrinkage is a potential source of tire non-uniformity. Thus, comparison of modulus and tenacity at a given shrinkage is a meaningful comparison for tire cords. Since tire cords experience deformations of a few percent during service, a good practical measure of modulus is LASE-5 (load at 5 percent elongation). Alternatively, E 4.5 (elongation at 4.5 g/d load (4.0 cN/dtex)) can be used as a practical measure of compliance.
  • modulus at elevated temperature is the important parameter governing performance. Due to the highly crystalline nature of treated cords based on conventional or dimensionally stable tire yarns, the modulus retention (in percent) at elevated tire temperatures is essentially similar for all current commercial treated cords and for those of this invention when loss modulus peaks occur at 110°C or greater. Thus, room temperature measurement of LASE-5 is sufficient to establish meaningful differences in polyester cord dimensional stability.
  • the polyester yarn contains at least 90 mol percent polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • the polyester is substantially all polyethylene terephthalate.
  • the polyester may incorporate as copolymer units minor amounts of units derived from one or more ester-forming ingredients other than ethylene glycol and terephthalic acid or its derivatives.
  • ester forming ingredients which may be copolymerized with the polyethylene terephthalate units include glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, etc., and dicarboxylic acids such as isophthalic acid, hexahydroterephthalic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc.
  • glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, etc.
  • dicarboxylic acids such as isophthalic acid, hexahydroterephthalic acid, bibenzoic acid, adipic acid, sebacic acid, azelaic acid, etc.
  • the polymer may be polymerized in a separate operation or polymerized in a directly coupled continuous polymerization and direct melt spinning process.
  • An important aspect of this invention permits obtaining high undrawn birefringence yarn without the need to utilize molecular weight enhancing additives such as multifunctional coupling agents exemplified by 2,2′-bis(2-oxazoline). Catalysts for the polymerization reaction are not considered to be included in the definition of molecular weight enhancing additive.
  • the multifilament yarn of the present invention commonly possesses a denier per filament of about 2.5 to 20 (e.g. about 3 to 10) (about 2.8 to 22, e.g. about 3.3 to 11 dtexpf), and commonly consists of about 6 to 600 continuous filaments (e.g. about 20 to 400 continuous filaments).
  • the denier per filament (texpf) and the number of continuous filaments present in the yarn may be varied widely within the ranges of this invention as will be apparent to those skilled in the art.
  • the multifilament yarn made by the process is particularly suited for use in industrial applications including rubber composites, ropes, cordage and tarps.
  • the fibers are particularly suited for use in environments where elevated temperatures (e.g. 80°C to 110°C) are encountered.
  • the yarn characterization parameters referred to herein may conveniently be determined by testing the multifilament yarn which consists of substantially parallel filaments.
  • Undrawn birefringence ( ⁇ n u ) was determined using a polarizing light microscope equipped with a Berek compensator.
  • Intrinsic viscosity (IV) of the polymer and yarn is a convenient measure of the degree of polymerization and molecular weight. IV is determined by measurement of relative solution viscosity ( ⁇ r ) of PET sample in a mixture of phenol and tetrachloroethane (60/40 by weight) solvents. The relative solution viscosity ( ⁇ r ) is the ratio of the flow time of a PET/solvent solution to the flow time of pure solvent through a standard capillary. Billmeyer approximation (J. Polym. Sci.
  • IV .25 ( ⁇ r -1) C + .75 1n ⁇ r C
  • C concentration in gm/100 ml.
  • concentration was 1.3 gms/100 ml.
  • IV is expressed in units of deciliters per gram (dl/g), even when such units are not indicated.
  • Comparison to IV measurements in other solvents is given in an article by C. J. Nelson and N. L. Hergenrother, J. Poly. Sci., 12 2905 (1974).
  • the invention makes possible obtaining high modulus drawn yarn without the need to utilize exceptionally high IV polymer. Satisfactory drawn yarns with high ⁇ n u with IV of at least 0.80, for example 0.85 to 0.95 can be obtained by this invention.
  • the tensile properties referred to herein were determined on yarns conditioned for two hours through the utilization of an Instron tensile tester (Model TM) using a 10-inch (25.4 cm) gauge length and a strain rate of 120 percent per minute in accordance with ASTM D885. All tensile measurements were made at room temperature.
  • Model TM Instron tensile tester
  • the drawn yarn of the present invention is produced with ⁇ n u greater than 0.020 and posses a dimensional stability defined by E4.5 + FS ⁇ 16%.
  • Free shrinkage (FS) values were determined in accordance with ASTM D885 with the exception that the testing load was 0.009 g/d (0.008 cN/dtex). Such improved dimensional stability is of particular importance if the product serves as fibrous reinforcement in a radial tire.
  • FIG. 1 illustrate apparatus which may be utilized to practice the process of this invention, though it will be recognized by those of skilled in the art that the apparatus illustrated may be modified in known ways.
  • Figs. 1 and 2 like numbers indicate like apparatus.
  • Molten polymer is fed by extruder 11 to spin pump 12 which feeds spin block 13 containing a spinneret and a spinning filter disposed between the spin pump and spinneret.
  • the spinneret is designed for the extrusion of one or more ends of filaments, each end containing a plurality of filaments.
  • Fig. 1 illustrates the simultaneous extrusion of two ends 14 and 15 of multifilament, continuous filament yarn from one spinneret.
  • Ends 14 and 15 are extruded from the spinneret at a spinning temperature in the range of 282 to 320°C and at a desired polymer volumetric flowrate (Q, cm3/min/capillary), and are passed downwardly from the spinneret into a delay zone, chamber 16, which preferably is a quiescent delay zone or a heated sleeve of a desired delay length preferably 1 to 40 inches (2.5 to 102 cm), maintained at a desired heated sleeve temperature preferably 100 to 450°C.
  • Yarn leaving chamber 16 is passed directly into the top of the quenching zone, apparatus 17, preferably a radial inflow quench.
  • the quench chamber is an elongated chimney of conventional length for example 1 to 40 inches (2.5 to 102 cm).
  • Ends 14 and 15 of yarn are lubricated by finish applicator 18.
  • a spinning finish composition is used to lubricate the filaments.
  • finish applicator 18 was a lube roll which is rotated with the direction of the yarn movement. Other means of applying finish could also be used.
  • V is the spinning speed given in kilometers/ minute.
  • IV is the intrinsic viscosity of the undrawn yarn given in dl/g.
  • R f is a value characteristic of the additional processing variables other than V and IV.
  • R f is typically ⁇ 8 x 10 ⁇ 3, whereas for the process of this invention R f is > 9.0 x 10 ⁇ 3.
  • R f is typically ⁇ 8 x 10 ⁇ 3
  • R f is > 9.0 x 10 ⁇ 3.
  • IV the higher the R f value
  • the combination of high molecular weight (IV > 0.80) and inherent stiffness of the PET molecule results in a sufficiently slow relaxation rate in the molten state to achieve high R f values.
  • High R f values for example R f ⁇ 15 x 10 ⁇ 3, are readily attainable by this invention and are of prime commercial interest.
  • R f R r R e
  • R r has a value which is related to the retention in orientation after thermally induced polymer relaxation with the constraint that O ⁇ R r ⁇ 1. This parameter increases with increasing severity of the quenching and decreases with increasing extruded polymer temperature and heated sleeve length and temperature.
  • One skilled in the art can adjust these parameters to maximize ⁇ n u and still maintain good spinnability.
  • the core of the invention is in the R e term which is related to the effective polymer extension from flow orientation in the spinneret and draw-down in the spin column. The net result is substantial orientation even at moderate spinning speeds.
  • This invention also teaches the proper combination of D and Q to achieve R e of at least 10.5 x 10 ⁇ 2. More preferred, R e is at least 13 x 10 ⁇ 2.
  • the extension rate per hole (Q) was 0.88 cm3/min.
  • the filaments were passed through a 1 inch (2.54 cm) heated sleeve and then quenched in a radial quench stack.
  • the spun yarn was subsequently drawn on a panel similar to figure 2, with roll 1 maintained at 90°C, the yarn drawn 1.5/1 to unheated rolls 2, 3 with a normal ambient temperature of 40-50°C, then drawn 1.6/1 from rolls 2, 3 to rolls 5, 6 maintained at 200°C, the yarn was then relaxed to rolls 7, 8 at 1 to 1.5 percent.
  • Rolls 7 and 8 had an operating temperature of 150°C.
  • the drawn yarn was taken up at 2.98 km/min. Polymer thruput for the two ends was 85 Ibs./hour (39 kg/hour).
  • the drawn yarn was 1004 denier (1114 dtex), 3.3 dpf (3.7 texpf), 17.5 lbs. breaking strength (77.8N), 7.9 g/d tenacity (7.0 cN/dtex) , 10.6 percent ultimate elongation, 3.9 g/d LASE-5 (3.44 cN/dtex), 5.5% E 4.5 and 9.2 percent FS.
  • the sum E 4.5 + FS is 14 percent.
  • the undrawn yarn birefringence ( ⁇ n u ) was 0.026 and IV was 0.92 dl/g.
  • R f was 24 x 10 ⁇ 3.
  • R f and R e were 24 x 10 ⁇ 3 and 19 x 10 ⁇ 2, respectively.
  • Q was 1.3 cm3/min/cap.
  • HST heated sleeve
  • the spun yarn was first drawn 1.4/1 between rolls at 90°C and unheated rolls, then drawn 1.15/1 between these and rolls maintained at 220°C.
  • the drawn yarn was then relaxed at 3% to rolls maintained at 135°C.
  • the yarn was taken up by a high speed winder at 4.60 km/min.
  • the drawn yarn was 924 denier (1026 dtex), 3.3 dpf (3.7 texpf), 5.8 g/d tenacity (5.1 cN/dtex), 4.1 g/d LASE-5 (3.6 cN/dtex), 6.5 percent E 4.5 , 10.3 percent ultimate elongation, 4.3 percent free shrinkage. The sum E 4.5 , + FS was 10.8 percent.
  • the undrawn yarn birefringence was 0.082 and IV was 0.92 dl/g.
  • R f was 11 x 10 ⁇ 3 and R e was 14 x 10 ⁇ 2.
  • This yarn had similar properties to Example I: 3.3 dpf (3.7 dtexpf), tenacity of 8.1 g/d (7.15 cN/dtex), ultimate elongation of 10.0%, LASE-5 of 3.9 g/d (3.44 cN/dtex), E 4.5 of 5.5%, and free shrinkage of 10.0%.
  • the 0.028 undrawn birefringence corresponded to a R f of 11 x 10 ⁇ 3.
  • R e was 13 x 10 ⁇ 2.
  • Drawn dpf was 2.7 (3.0 dtexpf) and R e was 11 x 10 ⁇ 2.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Abstract

L'invention concerne un procédé pour la production d'un fil multibrin de polyéthylène-téréphtalate étiré indéformable présentant des brins d'au moins 2,5 deniers par brin. Ce procédé consiste a) à extruder un polymère de polyéthylène-téréphtalate filé dans une filière comportant une pluralité d'orifices d'extrusion afin de former des brins; b) à faire passer le fil multibrin extrudé tout d'abord à travers une zone d'attente puis à travers une zone de refroidissement rapide pour solidifier les brins de manière régulée; c) à retirer de la zone de refroidissement rapide, à une vitesse de filature désirée V, le fil multibrin solidifié; les étapes a) à c) étant réalisées dans des conditions permettant de former un fil multibrin à orientation partielle ayant une biréfringence à l'état non étiré (Δnu) d'au moins 0,020, Δnu étant égal à Rf V?2,0 IV2,4¿ où IV est la viscosité intrinsèque du fil non étiré et est égal à au moins 0,80 et R¿f? est égal à au moins 9,0 x 10?-3¿; puis d) à étirer à chaud le fil multibrin à orientation partielle. Ce procédé permet la production de fils de biréfringence élevée à l'état non étiré, à des vitesses et à des viscosités intrinsèques plus faibles que ne l'a précédemment démontré la technique antérieure.

Claims (9)

1 - Procédé pour la fabrication d'un fil à multifilaments en polytéréphtalate d'éthylène étiré, dimensionnellement stable, ayant des filaments d'au moins 2,5 deniers par filament (2,8 dtexpf) comprenant les étapes consistant à :
a) extruder une masse fondue d'un polymère de polytéréphtalate d'éthylène dans une filière comportant une multitude d'orifices d'extrusion afin de former des filaments;
b) faire avancer le fil extrudé à multifilaments tout d'abord dans une zone à retard, puis dans une zone de refroidissement de manière à solidifier les filaments de façon contrôlée;
c) extraire le fil solidifié à multifilaments de la zone de refroidissement à une vitesse de filage V désirée (km/min);
   d'où il résulte que les étapes a) à c) sont exécutées dans des conditions permettant de former un fil à multifilaments partiellement orienté, ayant une biréfringence à l'état non étiré (Δnu) d'au moins 0,020 et dans lequel Δnu = Rf V²,0 IV²,4, où IV est la viscosité intrinsèque du fil non étiré et est au moins égal à 0,80 et Rf=RrRe est d'au moins 9,0 x 10⁻³, Rr étant une constante (0<Rr<1) pour des conditions de traitement données dans les étapes a) et b), et Re est au moins 10,5 x 10⁻², Re étant la relation D⁰,5/Q0,7 (D = diamètre du capillaire de la filière, en cm; Q = débit du polymère dans le capillaire, en cm³/min/capillaire); puis
d) étirer à chaud le fil à multifilaments partiellement orienté.
2 - Procédé selon la revendication 1, dans lequel Rf est égal à au moins 15 x 10⁻³.
3 - Procédé selon la revendication 1, dans lequel Re est égal à au moins 14 x 10⁻².
4 - Procédé selon la revendication 1, dans lequel IV est égal à 0,80-0,95 et Δnu est égal à au moins 7,0 x 10⁻³ V².
5 - Procédé selon la revendication 1, dans lequel Δnu est égal à au moins 11,5 x 10⁻³ V².
6 - Procédé selon la revendication 1, dans lequel IV est égal à au moins 0,85.
7 - Procédé selon la revendication 1, dans lequel le diamètre D desdits orifices d'extrusion est égal à au moins 0,069 cm.
8 - Procédé selon la revendication 1, comprenant en outre l'étape de polymérisation dudit polymère de polytéréphtalate d'éthylène, d'où il résulte qu'on a un procédé de polymérisation en continu et de filage direct d'une masse fondue.
9 - Procédé selon la revendication 1 ou la revendication 8, dans lequel ledit polymère de polytéréphtalate d'éthylène est polymérisé en l'absence d'un additif d'amélioration de la masse moléculaire.
EP90902093A 1989-01-03 1989-11-17 Procede pour un fil polyester indeformable Expired - Lifetime EP0452405B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US29286489A 1989-01-03 1989-01-03
US292864 1989-01-03

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EP0452405A1 EP0452405A1 (fr) 1991-10-23
EP0452405B1 true EP0452405B1 (fr) 1992-09-16

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EP (1) EP0452405B1 (fr)
KR (1) KR0140230B1 (fr)
CN (1) CN1021919C (fr)
AU (1) AU635241B2 (fr)
BR (1) BR8907870A (fr)
CA (1) CA2004942C (fr)
ES (1) ES2034855T3 (fr)
ID (1) ID1015B (fr)
MX (1) MX170066B (fr)
TR (1) TR25058A (fr)
WO (1) WO1990007592A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ID846B (id) † 1991-12-13 1996-08-01 Kolon Inc Serat benang, benang ban poliester dan cara memproduksinya
KR100392965B1 (ko) * 1995-03-02 2003-10-30 도레이 가부시끼가이샤 폴리에스테르고배향미연신섬유및그제조방법
CN1044500C (zh) * 1995-09-12 1999-08-04 南亚塑胶工业股份有限公司 制造聚酯异纤度异断面混纤丝的改进方法
KR100523809B1 (ko) * 2000-10-06 2005-10-25 주식회사 효성 폴리에스터 섬유의 제조방법
CN102925999A (zh) * 2011-08-12 2013-02-13 江苏省衣维新投资发展有限公司 一种用于细旦纺丝的丝束缓冷却方法
CN102925998A (zh) * 2011-08-12 2013-02-13 江苏省衣维新投资发展有限公司 一种用于细旦纺丝的丝束缓冷却装置

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101525A (en) * 1976-10-26 1978-07-18 Celanese Corporation Polyester yarn of high strength possessing an unusually stable internal structure
JPS57154410A (en) * 1981-03-13 1982-09-24 Toray Ind Inc Polyethylene terephthalate fiber and its production
US4690866A (en) * 1984-07-09 1987-09-01 Teijin Limited Polyester fiber

Also Published As

Publication number Publication date
CA2004942A1 (fr) 1990-07-03
KR910700365A (ko) 1991-03-15
MX170066B (es) 1993-08-05
AU635241B2 (en) 1993-03-18
CN1021919C (zh) 1993-08-25
WO1990007592A1 (fr) 1990-07-12
ES2034855T3 (es) 1993-04-01
CN1043965A (zh) 1990-07-18
AU4969690A (en) 1990-08-01
EP0452405A1 (fr) 1991-10-23
BR8907870A (pt) 1991-10-22
TR25058A (tr) 1992-11-01
CA2004942C (fr) 1999-10-05
ID1015B (id) 1996-10-17
KR0140230B1 (ko) 1998-07-01

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