EP0456495A2 - Fil de polyester ayant une haute ténacité, un haut module initial, et une faible rétraction - Google Patents

Fil de polyester ayant une haute ténacité, un haut module initial, et une faible rétraction Download PDF

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Publication number
EP0456495A2
EP0456495A2 EP91304189A EP91304189A EP0456495A2 EP 0456495 A2 EP0456495 A2 EP 0456495A2 EP 91304189 A EP91304189 A EP 91304189A EP 91304189 A EP91304189 A EP 91304189A EP 0456495 A2 EP0456495 A2 EP 0456495A2
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EP
European Patent Office
Prior art keywords
yarn
spun
tenacity
temperature
drawn
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EP91304189A
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German (de)
English (en)
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EP0456495A3 (en
Inventor
F. Holmes Simons
Ronald L. Griffith
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CNA Holdings LLC
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Hoechst Celanese Corp
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Publication of EP0456495A2 publication Critical patent/EP0456495A2/fr
Publication of EP0456495A3 publication Critical patent/EP0456495A3/en
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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

Definitions

  • the instant invention is directed to a drawn polyester yarn having a high tenacity, a high initial modulus and a low shrinkage.
  • non-textile uses include: tire cord; sewing thread; sail cloth; cloth, webs or mats used for road bed construction or other geo-textile applications; industrial belts; composite materials; architectural fabrics; reinforcement in hoses; laminated fabrics; ropes; and the like.
  • the drawn yarn obtained has the following properties: tenacity, 7.5 and 9.5 gpd; elongation, approximately 2 to 5% at a load of 5 gpd; elongation at break, 9 to 15%; and shrinkage, 1 to 4%.
  • polyethylene terephthalate spun yarn having an HRV of 24 to 28, is heated to 75 to 250°C while being drawn, is then passed over a heated draw roll, and finally relaxed.
  • the drawn yarn has the following properties: tenacity, 7.5 to 9 gpd; shrinkage, about 4%; elongation at break, 12 to 20%; and load bearing capacity of 3 to 5 gpd at 7% elongation.
  • the intrinsic viscosity (I.V.) of the polyethylene terephthalate is greater than 0.90.
  • the as-spun (undrawn) fiber properties are as follows: elongation at break, 52 to 193%; birefriengence, 0.0626 to 0.136; and degree of crystallinity, 19.3 to 36.8%.
  • the drawn fiber properties are as follows: tenacity, 5.9 to 8.3 gpd; elongation, 10.1 to 24.4%; and dry shrinkage (at 210°C), 0.5 to 10.3%.
  • U. S. Patent No. 4,867,936 the drawn fiber properties are follows: tenacity, about 8.5 gpd; elongation at break, about 9.9%; and shrinkage (at 177°C), about 5.7%.
  • the as-spun yarn has a low birefriengence (11 to 35 x 10 ⁇ 3) and drawn yarn properties are as follows: tenacity, 6.9 to 9.4 gpd; initial modulus, 107 to 140 gpd/100%; and elongation at break, 7.7 to 9.9%.
  • fibers are spun from a spinneret and solidifled at a temperature below 80°C.
  • the solidified fibers are then reheated to a temperature between the polymer's glass transition temperature (Tg) and its melting temperature. This heated fiber is withdrawn from the heating zone at a rate of between 1,000 to 6,000 meters per minute.
  • Spun yarn properties are as follows: tenacity, 3.7 to 4.0 gpd; initial modulus, 70 to 76 gpd/100%; and birefriengence, 0.1188 to 0.1240.
  • polyester multifilament yarn is melt-spun at high speed and solidified. Solidification occurs in a zone comprising, in series, a heating zone and a cooling zone.
  • the heating zone is a barrel shaped heater (temperature ranging from the polymer's melting temperature to 400°C) ranging in length from 0.2 to 1.0 meters.
  • the cooling zone is cooled by air at 10° to 40°C.
  • Drawn yarn made by this process has the following properties: initial modulus, 90 - 130 gpd; and shrinkage (at 150°C) less than 8.7%.
  • Fiber is spun into a chamber having a subatmospheric pressure.
  • Spun yarn properties are as follows: strength, 3.7 to 4.4 gpd; birefriengence, 104.4 to 125.8 (x 10 ⁇ 3); and dry heat contraction, 4.2 to 5.9% at 160°C for 15 minutes.
  • the polyester filaments (the polymer having an intrinsic viscosity of 0.5 to 2.0 deciliters per gram) are melt spun from a spinneret. Molten filaments are passed through a solidification zone where they are uniformly quenched and transformed into solid fibers. The solid fibers are drawn from the solidification zone under a substantial stress (0.015 to 0.15 gpd). These as-spun solid fibers exhibit a relatively high birefriengence (about 9 to 70 x 10 ⁇ 3). The as-spun fibers are then drawn and subsequently heat treated.
  • the drawn filament properties are as follows: tenacity, 7.5 to 10 gpd; initial modulus, 110 to 150 gpd/100%; and shrinkage, less than 8.5% in air at 175°C.
  • the instant invention is directed to a drawn polyester yarn.
  • This yarn is characterized by an initial secant modulus greater than 150 grams per denier/100%.
  • the yarn may be further characterized by either a shrinkage of less than 8% or a tenacity of greater than 7.5 grams per denier.
  • the yarn is characterized by a tenacity of at least 10 grams per denier, an initial modulus of at least 120 grams per denier/100% and a shrinkage of less than 8%.
  • Figure 1 is a schematic elevational view of the spinning process.
  • Figure 2 is a schematic elevational view of the drawing process.
  • the term “yarn” or “filament” or “fiber” shall refer to any fiber made from a melt spinnable synthetic organic polymer.
  • Such polymers may include, but are not limited to, polyesters and polyamides.
  • the invention has particular relevance to polyesters such as, for example; polyethylene terephthalate (PET), blends of PET and polybutylene terephthalate (PBT), and PET cross-linked with multifunctional monomers (e.g. pentaerithritol). Any of the foregoing polymers may include conventional additives.
  • the yarn I.V. (for PET based polymer) may be between 0.60 and 0.87.
  • the instant invention is not dependent upon the intrinsic viscosity (I.V.) of the polymer.
  • a spinning apparatus 10 is illustrated.
  • a conventional extruder 12 for melting polymer chip is in fluid communication with a conventional spinning beam 14.
  • a conventional spinning pack 16 Within spinning beam 14, there is a conventional spinning pack 16.
  • Pack 16 may be of an annular design and it filters the polymer by passing the polymer through a bed of finely divided particles, as is well known in the art. Included as part of the pack 16 is a conventional spinneret (not shown). Flow rates of polymers through the pack may range from about 10 to 55 pounds per hour. The upper limit of 55 pounds is defined only by the physical dimensions of the pack 16 and greater flow rates may be obtained by the use of larger packs.
  • the spun denier per filament (dpf) ranges from 3 to 20; it being found that the optimum properties and mechanical qualities for the yarn appear between 5 and 13 dpf.
  • the fiber, as it leaves the spinneret may be quenched with a hot inert gas (e.g. air).
  • a hot inert gas e.g. air
  • the gas is about 230°C and is provided at about six standard cubic feet per minute (scfm). If the air is too hot, i.e. over 260°C, the spun yarn properties are significantly deteriorated.
  • the column comprises an insulated tube having a length of about 5 meters or greater. Column length will be discussed in greater detail below.
  • the tube's internal diameter is sufficiently large (e.g. twelve inches) so that all filaments from the spinneret may pass the length of the tube without obstruction.
  • the column is equipped with a plurality of conventional band heaters so that the temperature within the tube can be controlled along its length. Column temperatures will be discussed in greater detail below.
  • the column is, preferably, subdivided into a number of discrete temperature zones for the purpose of better temperature control. A total of 4 to 7 zones have been used.
  • the column 18 may include an air sparger 17 that is used to control temperature in the column. Sparger 17 is designed to evenly distribute an inert gas around the circumference of the column.
  • the cone 19, which is preferably three feet in length and having a diameter co-extensive with the tube diameter at its uppermost end and a diameter of about one half that at the bottom end, is used to exhaust air, via a valved exhaust port 21, from the bottom-most end of the tube so that movement in the thread line, due to air turbulence, is substantially reduced or eliminated completely.
  • the thread line is converged below the bottom-most end of the column. This convergence may be accomplished by a finish applicator 20. This is the first contact the yarn encounters after leaving the spinneret.
  • the length of the column, non-convergence of the individual filaments, and the air temperature profile within the column are of particular importance to the instant invention.
  • the temperature profile it is chosen so that the fibers are maintained at a temperature above their Tg over a significant length of the column (e.g. at least 3 meters). This temperature could be maintained over the entire length of the column, but the wound filaments would be unstable. Therefore, for practical reasons, the temperature within the column is reduced to below the Tg, so that the filaments will undergo no further changes in crystal structure before being wound up.
  • the temperature profile is chosen to reflect the temperature profile that would be established within the tube if no external heat was applied. However, the "no external heat" situation is impractical because of numerous variables that influence the column temperature. So, the temperature profile is controlled, preferably in a linear fashion, to eliminate temperature as a variable in the process.
  • the air temperature within the column is controlled by the use of the band heaters.
  • the column is divided into a plurality of sections and the air temperature in each section is controlled to a predetermined value.
  • the temperature within the column can be varied over the length of the column.
  • the temperature within the column may range from as high as the polymer spinning temperature to at or below the glass transition (Tg) temperature of the polymer (Tg for polyester is about 80°C).
  • Tg glass transition
  • the polymer spinning temperature occurs around the spinneret, i.e. as the molten polymer exits the spinneret.
  • air temperatures within the column are preferably controlled from about 155°C to about 50°C.
  • the first section adjacent the spinneret is preferably controlled to a temperature of about 155°C and the section furthest from the spinneret is controlled to about 50°C.
  • the temperature profile (when the column is divided into four discrete zones) may be as follows: (starting from the spinneret down) the first zone - about 105°C to about 110°C; the second zone - about 110°C to about 115°C; the third zone - about 125° to about 130°C; and the fourth zone - 115°C to about 120°C.
  • column length a minimum column length of five meters (with column temperature over the polymer's Tg for at least 3 meters) with filament convergence thereafter appears to be necessary for the instant invention. Column lengths between five and nine meters are suitable for the invention., The upper limit of nine meters is a practical limit and may be increased, room permitting. To optimize the tenacity properties, a column length of about seven meters is preferred.
  • the fibers are converged after exiting the column 18. This convergence may be accomplished by use of a finish applicator.
  • the yarn is taken around a pair of godet rolls 22. Thereafter, a second application of finish may be made (i.e. at finish applicator 23).
  • the first finish application may be made to reduce static electricity built up on the fibers. But this finish is sometimes thrown off as the fibers pass over the godet rolls. Thus, the finish may be reapplied after the godet rolls.
  • the fibers are then passed onto a conventional tension control winder 24.
  • the wind-up speed is typically greater than 3,000 mpm (9,800 fpm) with a maximum speed of 5,800 mpm (19,000 fpm).
  • An optimum range exists of about 10,500 to 13,500 fpm (about 3,200-4,100 mpm).
  • the most preferred range exists between about 3200 and 3800 mpm (10,500 and 12,500 fpm). At speeds below 9,800 fpm (3,000 mpm), the yarn uniformity properties deteriorate.
  • the as spun polyester yarn produced by the foregoing process may be generally characterized as having relatively small crystals and a relatively high orientation. It is believed that these qualities of the as spun yarn enable the attainment of the unique drawn yarn properties discussed below.
  • the small crystals are defined in terms of crystal size (measured in ⁇ ) and orientation is defined in one of the following terms: optical birefringence; amorphous birefringence; or crystal birefringence.
  • the spun polyester yarn is characterized in term of crystal size and long period spacing (the distance between crystals).
  • the as spun polyester yarn may be characterized as having a crystal size less than 55 ⁇ and either an optical birefringence greater than 0.090 or an amorphous birefringence greater than 0.060 or a long period spacing of less than 300 ⁇ .
  • the as spun polyester yarn may be characterized as having a crystal size ranging from about 20 to about 55 ⁇ and either an optical birefringence ranging from about 0.090 to about 0.140 or an amorphous birefringence ranging from about 0.060 to about 0.100 or a long period spacing ranging from about 100 to about 250 ⁇ .
  • the as spun polyester yarn may be characterized as having a crystal size ranging from about 43 to about 54 ⁇ and either an optical birefringence ranging from about 0.100 to about 0.130 or an amorphous birefringence ranging from about 0.060 to about 0.085 or a long period spacing ranging from about 140 to about 200 ⁇ .
  • the crystal size of the spun yarn is about 1/3 that of conventional yarns in the optimum wind-up speed range.
  • the crystal size increases with speed, but it still remains low.
  • the spun amorphous orientation is very high, about twice normal. This spun yarn has such a high orientation and low shrinkage, that it could be used without any drawing.
  • the spun polyester yarn has the following properties: a crystal content (i.e. crystallinity level as determined by density) of 10 to 43%; a spun tenacity of about 1.7 to 5.0 gpd; a spun modulus in the range of 10 to 140 gpd/100%; a hot air shrinkage of about 5 to 45%; and an elongation of 50-160%.
  • a crystal content i.e. crystallinity level as determined by density
  • the spun yarn is drawn.
  • a one or two stage drawing operation may be used. However, it has been determined that a second stage offers little-to-no additional benefit. It is possible that the spinning operation may be coupled directly to a drawing operation (i.e., spin/draw process).
  • the as-spun yarn may be fed from a creel 30 onto a feed roll 34 that may be heated from ambient temperatures up to about 150°C. Thereafter, the fiber is fed onto a draw roll 38 which may be heated from ambient temperatures to approximately 255°C. If heated rolls are not available, a hot plate 36, which may be heated from 180° - 245°, may be used. The hot plate 36 (having a six inch curved contact surface) is placed in the draw zone, i.e., between feed roll 34 and draw roll 38. The draw speed ranges from 75 to 300 meters per minute. The typical draw ratio is about 1.65 (for spun yarn made at about 3,800 meters per minute). The optimum feed roll temperature, giving the highest tensile strength, was found to be about 90°C.
  • the optimum draw roll temperature is about 245°C. If the hot plate is used, the optimum temperature is between about 240° - 245°C.
  • the draw roll temperature gives some control over hot air shrinkage. In general, low shrinkages are desirable as they give rise to the best treated cord stability ratings. However, at least one end use, sail cloth, requires higher drawn yarn shrinkages and these can be controlled with lower draw roll temperatures.
  • the drawn fiber properties may be controlled as follows: Tenacity may range from 4.0 to 10.8 grams per denier. The elongation may range from 7% to approximately 80%. The initial secant modulus may range from 60 to 170 gpd/100%. The hot air shrinkage (at 177°C) is 6% to 15%. The denier of the fiber bundle may range from 125 to 1100 (the latter number may be obtained by plying tows together) and the denier per filament ranges from 1.5 to 6 dpf. Such a yarn could be used as the fibrous reinforcement of a rubber tire.
  • Polyester (i.e., PET) drawn yarns made according to the process described above, can obtain an initial secant modulus greater than 150 grams per denier/100. Moreover, those yarns may also have a shrinkage of less than 8%, or those yarns may have a tenacity of greater than 7.5 grams per denier.
  • Another preferred embodiment of the drawn polyester yarn may be characterized as follows: a tenacity of at least 8.5 grams per denier; an initial modulus of at least 150 grams per denier/100%, and a shrinkage of less than 6%.
  • Another preferred embodiment of the drawn polyester yarn may be characterized as follows: a tenacity of at least 10 grams per denier; an initial modulus of at least 120 grams per denier/100%; and a shrinkage of less than 6%.
  • Yet another preferred embodiment of the drawn polyester yarn may be characterized as follows: a tenacity ranging from about 9 to about 9.5 grams per denier; an initial modulus ranging from about 150 to about 158 grams per denier/100%; and a shrinkage less than 7.5%.
  • Any drawn yarn made according to the above described process, may be utilized in the following end uses: tire cord, sewing thread; sail cloth; cloth, webs or mats used in road bed construction or other geo-textile applications; industrial belts; composite materials; architectural fabrics; reinforcement in hoses; laminated fabrics; ropes; etc.
  • Tenacity refers to the "breaking tenacity" as defined in ASTM D-2256-80.
  • Initial modulus (or "initial secant modulus") is defined per ASTM D-2256-80, Section 10.3, except that the line representing the initial straight line portions of the stress-strain curve is specified as a secant line passing through the 0.5% and 1.0% elongation points on the stress-strain curve.
  • Shrinkage is defined as the linear shrinkage in a hot air environment maintained at 177 ⁇ 1°C per ASTM D-885-85.
  • Density, crystal size, long period spacing, crystal birefringence, and amorphous birefringence are the same as set forth in U.S. Patent No. 4,134,882 which is incorporated herein by reference. Specifically, each of the foregoing may be found in U.S. Patent No. 4,134,882 at or about: density - column 8, line 60; crystal size - column 9, line 6; long period spacing - column 7, line 62; crystal birefringence - column 11, line 12; and amorphous birefringence - column 11, line 27.
  • Birefringence (optical birefringence or ⁇ n) is as set forth in U.S. Patent No. 4,101,525 at column 5, lines 4-46.
  • U.S. Patent No. 4,101,525 is incorporated herein by reference.
  • Bi CV is the coefficient of variation of optical birefringence between filaments calculated from 10 measured filaments.
  • polyester PET, IV-0.63
  • the fibers were wound up at a rate of 10,500 fpm.
  • the polymer was extruded at a rate of 19.5 pounds per hour through a 72 hole spinneret (hole size 0.009 inches by 0.012 inches) and a spinning beam at 300°C.
  • the fibers were quenched with 6.5 scfm air at 232°C.
  • the column was 6.4 meters long and divided into 4 sections having the following air temperature profile (in descending order): 135°C; 111°C; 92°C; and 83°C at the center of the zones.
  • the spun yarn had the following properties: denier - 334; tenacity - 4.09 gpd; elongation 71.7%; initial modulus - 55.0 gpd/100%; hot air shrinkage - 11.8% at 350°F.; Uster 1.10; I.V. -0.647; FOY - 0.35%; birefringence - 110 x 10 ⁇ 3; and crystallinity - 21.6%.
  • PET with a molecular weight characterized by an I.V. of 0.92 was dried to a moisture level of 0.001% or less.
  • This polymer was melted and heated to a temperature of 295°C in an extruder and subsequently forwarded to a spinning pack by a metering pump.
  • This pack was of an annular design, and provided filtration of the polymer by passing it through a bed of finely divided metal particles. After filtration the polymer was extruded through an 80 hole spinneret. Each spinneret hole had a round cross section with a diameter of 0.457 mm and a capillary length of 0.610 mm.
  • An insulated heated tube 9 meters in length was mounted snugly below the pack and the multifilament spinning threadline passed through the entire length of this tube before being converged or coming into contact with any guide surfaces.
  • the tube was divided down its length into seven zones for the purposes of temperature control. Individual controllers were used to set the air temperature at the center of each of these zones. Using a combination of process heat and the external heaters around the tube, individual controller settings were selected to arrive at a uniform air temperature profile down the vertical distance of this tube. In a typical situation the air temperature was 155°C at the top zone of the tube and the temperature was reduced in an approximately uniform gradiert to 50°C at the bottom.
  • Wind up speeds were typically in the range 3200 - 4100 mpm.
  • Drawing of this yarn was effected in a second step, in which the as spun yarn was passed over one set of pretension rolls to a heated feed roll maintained at a temperature set between 80 and 150°C. The yarn was then drawn between these rolls and a set of draw rolls maintained at a set point chosen in the range 180 to 255°C.
  • a typical draw ratio for a spun yarn made at 3800 mpm would be 1.65, with samples spun at higher and lower speeds requiring lower or higher draw ratios, respectively.
  • Polyester with a molecular weight characterized by an I.V. of 0.92 was dried to a moisture level of 0.001%. This polymer was melted and heated to a temperature of 295°C in an extruder and the melt subsequently forwarded to a spinning pack by a metering pump. After filtration in a bed of finely divided metal particles, the polymer was extruded through an 80 hole spinneret. Each spinneret hole had a diameter of 0.457 mm and a capillary length of 0.610 mm. On extrusion the measured I.V. of this polymer was 0.84.
  • the extruded polymer was spun into heated cylindrical cavity 9 meters in length. An approximately linear temperature profile (gradient) was maintained over the length of this tube. At the center of the top zone the air temperature was 155°C and at the bottom of the tube this temperature was 50°C.
  • the multifilament yarn bundle was not converged until it came in contact with a finish guide just below the exit of the heated tube. From this point the yarn was advanced by a pair of godet rolls to a tension controlled winder. Under these conditions a series of four spun yarns were made at different spinning (wind-up) speeds. These yarns are referred to as examples A through D in Table V. A.
  • Example E and F in Table V. A were spun through 7 and 5 meter columns. Other polymers with different molecular weights (I.V.'s) were also spun on this system to give Examples G and H.
  • Example I in Table VA illustrates a case in which lower column temperatures were used. In this case a linear gradient from 125°C to 50°C was established down the column.
  • Example A In a further series of tests the same spun yarn which was described in Example A was drawn using different feed roll temperatures. The results from testing these yarns are given in Examples A, J and K in Table V. B.
  • the nylon made by the inventive process was spun under the following conditions: throughput- 37 lbs. per hour; spinning speed - 2,362 fpm; denier - 3500; number of filaments - 68; spun relative viscosity - 3.21 (H2 SO4) or 68.4 (HCOOH equiv.) quench air - 72 scfm; winding tension 80g; column length - 24 ft; column temperature top 240°C and bottom 48°C.
  • the as-spun properties of this yarn were as follows: tenacity - 0.95 gpd; elongation 235%; TE 1 ⁇ 2 - 14.6. Thereafter the yarn was drawn under the following conditions: draw ratio 3.03; draw temperature 90°C.
  • the drawn yarn properties are as follows: tenacity 6.2 gpd; elongation -70%; TE 1 ⁇ 2 - 52; 10% modulus - 0.87 gpd; hot air shrinkage (HAS) at 400°F - 1.4%.
  • One comparative nylon was spun in the following conventional fashion: throughput - 23.4 lbs. per hour; spinning speed - 843 fpm; denier - 5556; number of filaments - 180; spun relative viscosity - 3.3 (H2 SO4) or 72.1 (HCOOH equiv.); quench - 150 scfm. Thereafter, the yarn was drawn under the following conditions: Draw ratio - 2.01; draw temperature - 90°C. The drawn yarn properties are as follows: tenacity 3.8 gpd; elongation - 89%; TE 1 ⁇ 2 - 33; 10% modulus - .55 gpd.
  • Another comparative yarn was spun in the following conventional fashion: throughput - 57.5 lbs. per hour; spinning speed - 1048 fpm; denier - 12400; number of filaments - 240; spun relative viscosity - 42 (HCOOH equiv.); quench air - 150 scfm. Thereafter, the yarn was drawn under the following conditions: draw ratio - 3.60; draw temperature - 110°C.
  • the drawn yarn properties are as follows: tenacity - 3.6 gpd; elongation - 70%; TE 1 ⁇ 2 - 30.1; modulus at 10% elongation - 0.8 gpd; HAS (at 400°F) - 2.0%.
  • low I.V. e.g. 0.63
  • high I.V. e.g. 0.92 conventional polyester (i.e. PET) as spun yarn
  • PET conventional polyester
  • Examples 1-8 are low I.V. polyester (PET) and are made in the manner set forth in Example I.
  • Examples 9-11 are high I.V. polyester (PET) and are made in the manner set forth in Example V.
  • Examples 12-17 correspond to Examples 1, 5, 12, 17, 36 and 20 of U.S. Patent No. 4,134,882.
EP19910304189 1990-05-11 1991-05-09 A drawn polyester yarn having a high tenacity, a high initial modulus and a low shrinkage Withdrawn EP0456495A3 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US52310090A 1990-05-11 1990-05-11
US523100 1990-05-11

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EP0456495A2 true EP0456495A2 (fr) 1991-11-13
EP0456495A3 EP0456495A3 (en) 1992-03-25

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EP (1) EP0456495A3 (fr)
JP (1) JPH04228612A (fr)
KR (1) KR910020213A (fr)
CN (1) CN1056543A (fr)
AU (1) AU7625091A (fr)
BR (1) BR9101811A (fr)
CA (1) CA2039851A1 (fr)
NO (1) NO911821L (fr)
PT (1) PT97629A (fr)
ZA (1) ZA912980B (fr)

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CN103233283A (zh) * 2013-04-27 2013-08-07 可隆（南京）特种纺织品有限公司 高强高伸聚酯轮胎帘子线原丝的制造方法、帘子线原丝及帘子线
CN103556241A (zh) * 2013-10-30 2014-02-05 苏州龙杰特种纤维股份有限公司 纺织纤维生产系统

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KR100687032B1 (ko) * 2006-04-14 2007-02-26 주식회사 효성 카펫용 3차원 크림프 폴리에틸렌테레프탈레이트멀티필라멘트
JP4881057B2 (ja) * 2006-05-09 2012-02-22 信号器材株式会社 レール継ぎ目用絶縁プレート

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EP0169415A2 (fr) * 1984-07-09 1986-01-29 Teijin Limited Fibre de polyester
EP0251313A2 (fr) * 1986-07-02 1988-01-07 Toyo Boseki Kabushiki Kaisha Fibres de polyéthylène-téréphtalate à haute résistance et à haut module et leur procédé de fabrication
EP0164624B1 (fr) * 1984-05-23 1988-04-13 E.I. Du Pont De Nemours And Company Procédé continu de fabrication de fils entrelacés en polyester
FR2624887A1 (fr) * 1987-12-21 1989-06-23 Toyo Boseki Procede de fabrication de fibres de polyester par filage
JPH01229807A (ja) * 1988-03-03 1989-09-13 Toyobo Co Ltd 低収縮高弾性率ポリエステル繊維
EP0341920A2 (fr) * 1988-05-09 1989-11-15 Toray Industries, Inc. Fibre de polyester, à usage industriel et son procédé de préparation

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CN103233283A (zh) * 2013-04-27 2013-08-07 可隆（南京）特种纺织品有限公司 高强高伸聚酯轮胎帘子线原丝的制造方法、帘子线原丝及帘子线
CN103233283B (zh) * 2013-04-27 2016-01-06 可隆（南京）特种纺织品有限公司 高强高伸聚酯轮胎帘子线原丝的制造方法、帘子线原丝及帘子线
CN103556241A (zh) * 2013-10-30 2014-02-05 苏州龙杰特种纤维股份有限公司 纺织纤维生产系统

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KR910020213A (ko) 1991-12-19
PT97629A (pt) 1993-08-31
BR9101811A (pt) 1991-12-17
EP0456495A3 (en) 1992-03-25
CN1056543A (zh) 1991-11-27
JPH04228612A (ja) 1992-08-18
ZA912980B (en) 1992-12-30
NO911821D0 (no) 1991-05-10
NO911821L (no) 1991-11-12
AU7625091A (en) 1991-11-14
CA2039851A1 (fr) 1991-11-12

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