PT97629A - STRIPED WIRE - Google Patents

Description

72 471 F-8091 -2-

The present invention relates to a spinning process for the production of low shrink, high modulus, high strength synthetic yarns.

BACKGROUND OF THE INVENTION

Since the melt-reliable, fiber-forming synthetic polymers have been introduced, fiber manufacturers have attempted to find ways to increase the strength and stability properties of fibers made from these polymers. The additional properties of strength and stability of the fibers are necessary, so that in addition to the textile uses other applications for their products can be found. Such non-textile uses (also known as " industrial uses ") include: tire wires; line sewing; cloth for candles; rags, strips or mats used in the construction of road beds or other geotextile applications; industrial belts; composite materials; architectural fabrics; reinforcement of hoses; laminated fabrics; ropes and the like.

Originally, raione was used in some of these industrial uses. Then the " nylon " surpassed the raione as chosen material. Conventional polyesters from the 1970s, such as polyethylene terephthalate, were introduced in the competition against " nylon ". In 1985, polyesters of higher quality, i.e., higher strength and high stability, were introduced.

A brief review of a number of prior art patents, summarized below, indicates that the three general areas have been investigated as possible ways of improving the strength and stability properties of these synthetic fibers. These general areas include: stretching processes; processes directed to polymers; and spinning processes. Then, the term " stretch " refer to the heating and stretching performed on a two-wire wire. The term " treatment for the polymer " refer to what is done to the polymer before the

72 471 F-8091 -3- spinning. The term " spinning " will refer to the process for the formation of filaments from the polymer, but excluding the drawing.

The processes directed to the drawing are as follows.

In U.S. Patent 3,909,997, there is disclosed the stretching of multiple stages of polyamides for use as tire wires. The fibers (" nylon ") are melt-spun in a conventional manner. Thereafter, the spun fibers are drawn in a three-stage process (stretched, then heated, then stretched again) to obtain a " nylon " having the following properties: toughness ranging from 10.4 to 11.1 grams per denier (gpd); elongation ranging from 12.9 to 17.1%; and initial modulus cf 48 to 71 gpd / 100%. U.S. Patent 3,303,169, discloses a single stage drawing process for polyamides which produce high modulus high tenacity low contraction polyamide yarns. The spun polyamide is drawn and heated to at least 115øC to yield a yarn having: tenacity in the range of 5 to 8.7 gpd; elongation ranging from 16.2 to 30.3%; initial modulus of 28 to 59 gpd / 100%; and contraction ranging from 3.5 to 15%. U.S. Patent 3,966,887 describes the two-stage stretch process for polyethylene terephthalate having a relative viscosity of 1.5 to 1.7. In the first stage, the fibers are subjected to a temperature between 70 and 100Â ° C and a draw ratio of 3.8 to 4.2. In the second stage, the fibers are subjected to a temperature between 210 and 250 ° C and a draw ratio in the aggregate of the first draw ratio and the second draw ratio in the range of 5.6 to 6.1. The obtained drawstring has the following properties: toughness 7.5 to 9.5 gpd; elongation, about 2 to 5% at a load of 5 gpd; elongation at break, 9 to 15%; and contraction, 1 to 4%.

In US Pat. No. 4,003,974, spun polyethylene terephthalate yarn having a HRV of 24 to 28 is heated from 75 to 72,471 Âμl / F-8091 to 77-250Â ° C while being drawn, and then passed by a heated stretching roller, and finally relaxed. The drawn wire has the following properties: toughness 7.5 to 9 gpd; contraction around 4%; elongation at break, 12 to 20%, and load bearing capacity of 3 to 5 gpd in 7% elongation.

Methods for improving the properties of the yarns by the treatment of the polymer are as follows.

In U.S. Patent Nos. 4 690 866 and 4 867 963, the intrinsic viscosity (V.I.) of polyethylene terephthalate is greater than 0.90. In U.S. Patent 4 690 868, the properties of the spun (unstretched) fiber are as follows: elongation at break, 52 to 193%; birefringence, 0.0626 to 0.136; and degree of crystallinity, 19.3 to 36.8%. The properties of the drawn fiber are as follows: toughness, 5.9 to 8.3 gpd; elongation, 10.1 to 24.4%; and dry shrinkage (at 210 ° C) 0.5 to 10.3%. In US 4 867 936, the stretched fiber properties are as follows: toughness, about 8.5 gpd; elongation at break, about 9.9%; and contraction (at 177 ° C) about 5.7%.

The processes directed to spinning are as follows.

In U.S. Patent 3,053,611, polyethylene terephthalate, after leaving the spinnerette, is heated to 220øC on a spinning shaft of two meters in length. Thereafter, cold water is sprayed onto the fibers on a second shaft. The fibers are wound at a speed of 1600 meters per minute and are subsequently drawn to obtain a toughness of 3.5 gpd.

In U.S. Patent 3,291,880, a polyamide is spun from a spinnerette and then cooled to 15Â ° C, the fiber is then sprayed with live steam. The spun fiber has low orientation and low birefringence.

In U.S. Patent 3,361,859, a synthetic organic polymer is spun in fiber form. As the fibers exit the die, they are subjected to " controlled retardation cooling ". This one

72 471 F-8091 -5-cooling is conducted in the first 17.80 cm of the spinneret. At the top (i.e., adjacent to the die), the temperature is 300 ° C and at the bottom (approximately 17.80 cm from the die), the minimum temperature is 132 ° C. The two-wire yarn has low birefringence (11 to 35 x 10-3) and the drawn yarn properties are as follows: toughness, 6.9 to 9.4 gpd; initial modulus, 107 to 140 gpd / 100%; and elongation at break of 7.7 to 9.9%.

In U.S. Patents 3 936 253 and US 3 969 462, the use of a heated reinforcing ring (varying in length from 0.16 m to 0.61 m) with temperatures ranging from 115 to 460 ° C is described. In the matrix, the temperature is higher at the top of the ridge than at the bottom. The properties of the drawstring of the matrix are as follows: tenacity, 9.25 gpd; elongation, about 13.5%; and contraction, about 9.5%. In the latter, the temperature is constant within the reinforcing ring and the properties of the drawn wire are as follows: toughness, 8 to 11 gpd; and elongation at break, 12.5 to 13.2%.

In U.S. Patent 3,946,100 the fibers are spun from a spinneret and solidified at a temperature below 80Â ° C. The solidified fibers are then reheated at a temperature between the glass transition temperature of the polymer (Tg) and its melting temperature. This heated fiber is withdrawn from the heating zone at a speed of 1 000 to 6 000 meters per minute. The properties of the spun yarn are as follows: toughness 3.7 to 4.0 gpd; initial modulus 70 to 76 gpd / 100%; and birefringence, 0.1188 to 0.1240.

In U.S. Patent 4,491,657 the polyester multifilament yarn is spun by high speed melt 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 melt temperature of the polymer to 400øC), ranging in length from 0.2 to 1.0 meter. The cooling zone is air cooled at 10 ° to 40 ° C. The drawn wire made by this process has the following properties: initial modulus, 90 to 130 gpd; and

(150Â ° C) of less than 8% by weight.

In U.S. Patent 4,702,871, the fiber is spun in a chamber having a pressure lower than atmospheric pressure. The properties of the spun yarn are as follows: strength 3.7 to 4.4 gpd; birefringence, 104.4 to 125.8 (x 10-3); and shrinkage in dry heat 4.2 to 5.9% at 160 ° C for 15 minutes.

In U.S. Patent 4,869,958 the fiber is spun in the absence of heat and then wound. At this point, the fiber has a lower degree of crystallinity, but is highly oriented. Thereafter, the fiber is heat treated. The properties of the drawn fiber are as follows; toughness, 4.9 to 5.2 gpd; initial modulus, 92.5 to 96.6 gpd / 100%; and elongation, 28.5 to 32.5%. The foregoing patent specification states that while some fibers produced by these various processes have high strength or low shrinkage properties, none of the foregoing patents has described a yarn or a process for the production of such a drawn yarn, having in combination high tenacity, high initial modulus and low contraction.

Patents which closely approximate the description of such stretched wire are U.S. Patents 4,101,525 and 4,195,052, related patents, which have been assigned to the assignee of the present invention. In these patents, the polyester filaments (the polymer having an intrinsic viscosity of 0.5 to 2.0 deciliters per gram) are spun-cast in a die. The fused filaments are passed through a solidification zone, where they undergo sudden thermal shock and become solid fibers. The solid fibers are drawn from the solidification zone with a substantial tension (0.015 to 0.15 gpd). These solid solid fibers exhibit relatively high birefringence (about 9 to 70 x 10-3). The spun fibers are then drawn and subsequently treated by heating. The properties of the drawn filaments are as follows: toughness, " 7.5 to 10 gpd; initial modulus, lio at 150 gpd / 100%; and contraction, less than 8.5% in air at 175 ° C. 72 471 F-8091 / f J-mm *

SUMMARY OF THE INVENTION The present 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 further be characterized by shrinkage of less than 8% or a toughness of more than 7.5 grams per denier. Alternatively, 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%.

DESCRIPTION OF THE DRAWINGS

In order to illustrate the invention, there is shown in the drawings a process scheme which is presently preferred; it being understood, however, that this invention is not limited to the precise arrangement and means shown. Figure 1 is a schematic elevational view of the spinning process; and Figure 2 is a schematic elevational view of the drawing process.

DETAILED DESCRIPTION OF THE INVENTION High tensile, high modulus, and low shrinkage drawn yarns and the process by which such yarns are spun are described below. The term " wire " or " filament " or " fiber " will refer to any fiber made of a melt-reliable synthetic organic polymer. Such polymers may include polyesters and polyamides, but are not limited thereto. The invention, however, has particular relevance with respect to polyesters such as, for example, polyethylene terephthalate (TPE), combinations of TPE and polybutylene terephthalate (TPB), and TPE cross-linked with monomers (for example, pentaerythritol). Any of the foregoing polymers may include conventional additives. I.V. of the TPE-based polymer yarn 72 471 F-8091) may be between 0.60 to 0.87. The present invention, however, does not depend on the intrinsic viscosity (V.I.) of the polymer.

Referring to Figure 1, there is shown a spinning apparatus 10. A conventional extruder 12 for melting the polymer pellet is in fluid communication with a conventional spinning holder 14. Within the spinning holder 14, there is a set The assembly 16 may have 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 assembly 16 is a conventional spinneret (not shown). The flow rates of the polymers throughout the assembly can range from 4.53 to 24.95 kg per hour. The upper limit of 24.95 kg is defined solely by the physical dimensions of the set 16 and larger flow rates can be obtained by using larger sets. Filament spin denier (dpf) ranges from 3 to 20; it has been found that the optical properties and mechanical qualities for the yarn are between 5 and 13 dpf.

Optionally, the fiber, upon leaving the die, may undergo a sudden thermal shock with a hot inert gas (e.g., air). Vidé patent US 4 378 325, which is hereby incorporated by reference. Typically, the gas is at 230 ° C and is supplied at 0.170 m3 per minute (m3 / min). If the air is too hot, ie above 260 ° C, the yarn properties are significantly deteriorated.

Immediately below and mounted tightly to the spinning support 14 (i.e. hermetically), there is an elongate column 18. The column comprises an insulated tube, having a length of 5 meters or more. The length of the column will be explained in more detail below. The inner diameter of the tube is sufficiently large (e.g. 30.48 cm), so that all the filaments of the die can pass through the length of the tube, without obstruction. The column is equipped with a plurality of conventional belt heaters, so that the temperature inside the tube can be controlled throughout its length.

72 471 F-8091 -9-length. The column temperatures will be described in more detail below. The column is preferably subdivided into several discrete temperature zones to better control the temperature. A total of 4 to 7 zones were used. Optionally, the column 18 may include an air sparger 17, which is used to control the temperature in the column. The sprinkler 17 is indicated to eventually distribute an inert gas around the circumference of the column.

Within the lowermost end of the column 18 is a truncated, perforated cone 19, i.e. a device for reducing air turbulence. The cone 19, which is preferably 0.91 meters in length, has a diameter having the same size as the diameter of the tube at its uppermost end and a diameter of about half that at the lower end, is used to evacuate air through an evacuated outlet with valve 21 from the lowermost end of the tube so that movement in the wire line due to air turbulence is substantially reduced or completely eliminated.

Below the lower end of the column, the wire line converges. This convergence can be accomplished by a finish applicator 20. This is the first contact the filament encounters after leaving the die. The length of the column, the non-convergence of the individual filaments, and the air temperature profile within the column are of particular importance to the present invention. Regarding the temperature profile, it is chosen such that the fibers are maintained at a temperature above their Tg in a significant length of the column (for example at least three meters). This temperature could be maintained across the entire length of the column, however, the coiled filaments could be unstable. Accordingly, for practical reasons, the temperature within the column is reduced below the Tg, so that the filaments do not undergo changes in the crystalline structure, prior to being wound. Preferably, the temperature profile is chosen, 72 471 F-8091

To reflect the profile of the temperature that would be present in the tube if no external heat were applied. However, the situation " no external heat " is impractical because of the various variables that influence the temperature of the column. Thus, the temperature profile is preferably controlled, in a linear manner, to eliminate the temperature as a variable in the process. The air temperature inside the column is controlled by the use of belt heaters. Preferably, the column is divided into a plurality of sections and the air temperature in each section is controlled to a predetermined value. Thus, the temperature within the column can be varied, across the length of the column. The temperature within the column may vary from as high as the spinning temperature of the polymer to or below the glass transition temperature (Tg) of the polymer (Tg to polyester is 80 ° C). The spinning temperature of the polymer occurs around the spinnerette, i.e., as the molten polymer exits the spinnerette. Meanwhile, air temperatures within the column are preferably controlled from 155Â ° C to 50Â ° C. At winding speeds of less than 4 270 meters per minute, the first section adjacent the die is preferably controlled at a temperature of 155 ° C and the section furthest from the die is controlled at about 50 ° C.

However, a linear temperature profile is not the only temperature pattern which will provide the beneficial results described herein. At winding speeds greater than 4 270 m / min, the temperature profile (when the column is divided into four distinct zones) can be as follows: (from the spinneret down) the first zone - about 105øC at 110øC; the second zone - about 110 ° C to 115 ° C; the third zone - about 125 ° C to 130 ° C; and the fourth zone - 115Â ° C to 120Â ° C.

With respect to the column length, a minimum column length of five meters (with the column temperature above the Tg of the polymer of at least 3 meters) with the convergence of the filament then appears to be necessary for the present invention.

72 471 F-8091 tion. Column lengths between five and nine meters are suitable for the invention, the upper limit of nine meters is a practical limit and can be increased if space permits. To optimize the tenacity properties, a column length of seven meters is preferred.

The fibers converge after exiting the column 18. This convergence can be accomplished by using a finishing applicator.

Following the first finish application (i.e., finish applicator 20), the yarn is taken around a pair of gould rollers 22. Thereafter, a second finisher application (i.e. finishing applicator 23). The first finishing application can be made to reduce the formation of static electricity in the fibers. But this finish is sometimes lost, when the fibers pass over the gode rolls. Thus, the finish can be applied again after the gode rollers.

The fibers are then passed in a conventional tension control winding machine 24. The winding speed is typically greater than 2998 m / min, with a maximum speed of 5 795 m / min. An optimum range is between about 3 202-411 m / min. The most preferred range is between 3 202 and 3 812 m / min. At speeds below 2998 m / min, the uniformity properties of the wire deteriorate. The spun polyester yarn produced by the foregoing process may generally be characterized as having relatively small crystals and a relatively high orientation. It is believed that these qualities of the spun yarn enable one to achieve the unique drawability properties, explained below.

In order to quantify the overall characterization of spun polyester yarn, the small crystals are defined in terms of crystal size (measured in nm) and an orientation is defined in one of the following terms: optical birefringence; birefringence

72 471 F-8091 -12-amorphous; or crystal birefringence. Additionally, the spun polyester yarn is characterized in terms of crystal size and long period spacing (the distance between the crystals). In broader terms, the polyester spun yarn can be characterized as having a crystal size of less than 5.5 nm and both an optical birefringence greater than 0.090, as well as an amorphous birefringence greater than 0.060 or a lower long period spacing at 30 nm. More preferably, the spun yarn of polyester can be characterized as having a crystal size ranging from 2 to 5.5 nm and therefore, an optical birefringent ranging from 0.090 to 0.140, as well as an amorphous birefringent ranging from 0.060 to 0.100, or a long period spacing of 10 to 25 nm. More preferably, the polyester blend may be characterized as having a crystal size ranging from 4.3 to 5.4 nm and, therefore, an optical birefringination ranging from 0.100 to 0.130, as well as an amorphous birefringent ranging from 0.060 to 0.085 or a long period spacing of 14 to 20 nm.

As will be clear to those of ordinary skill in the art, the crystal size of the spun yarn is about 1/3 that of the conventional yarns at the optimum winding rate ratio. The crystal size increases with speed, but still remains low. The amorphous orientation of the yarn is very high, although twice as normal. This spun yarn has such a high orientation and low shrinkage, and can be used without any stretch.

In addition, conventional polyester spun yarn has the following properties: a crystal content (i.e., crystallinity level as determined by density) of 10 to 43%; a spinning tenacity of 1.7 to 5.0 gpd; a spinning module in the range of 10 to 140 gpd / 100%; a contraction in hot air of 5 to 45%; and an elongation of 50-160%.

Then the spun yarn is drawn. Referring to Figure 2, both one and two stage stretching operations may be used. However, it has been determined that a second stage provides little or no additional benefit. It is possible that

The spinning operation can be coupled directly to drawing (i.e., drawing / spinning). The spun yarn can be fed to a warp 30 on a feed roller 34, which can be heated from room temperature to about 150 ° C. Thereafter, the fiber is fed to a draw roll 38, which can be warmed from room temperature to about 255 ° C. If the heated rollers are not available, a heated plate 36, which can be heated from 180 to 245ø, may be used. The heated plate 36 (having a curved contact surface of 15.24 cm) is placed in the drawing zone, i.e. between the feed roller 34 and the drawing roller 38. The drawing speed ranges from 75 to 300 meters per minute. The typical draw ratio is 1.65 (for spun yarn made at approximately 3 800 meters per minute). The optimum feed roller temperature, giving the greatest tensile strength, was checked to be around 90 ° C. The optimum draw roller temperature is 245 ° C. If the heated plate is used, the optimum temperature is between 240 and 245 ° C. The temperature of the draw roller gives some control over the contraction by hot air. In general, the low contractions are desirable, since they give rise to better qualities of treated wire stability. However, at least one end use, that of sailcloths, requires larger draw contractions of yarn and these can be controlled with lower draw roller temperatures.

Based on the foregoing, the stretched fiber properties can be controlled as follows: the toughness may range from 4.0 to 10.8 grams per denier. The elongation may range from 7% to about 80%. The initial blotting modulus may range from 60 to 170 gpd / 100%. The contraction in hot air (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 co-application of tow) and the denier per filament varies from 1.5 to 6 dpf. Such wire could be used as a fibrous reinforcement of a rubber tire.

The stretched polyester (i.e. TPE) yarns, made of F 478091 according to the process described above, can obtain an initial sizing modulus of greater than 150 grams per denier / 100. Further, these yarns may also have a shrinkage of less than 8%, or they may have a tenacity greater than 7.5 grams per denier.

Another preferred embodiment of the stretched polyester yarn can 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 stretched polyester yarn can 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 contraction of less than 6%. Yet another preferred embodiment of the stretched polyester yarn can be characterized as follows: toughness ranging from 9 to 9.5 grams per denier; an initial modulus ranging from 150 to 158 grams per denier / 100%; and a contraction of less than 7.5%.

Any stretched yarn made according to the process described above may be used in the following end uses; wires for tires; line sewing; candle cloths; cloths, strips or mats used in road bed construction or other geotextile applications; industrial belts; composite materials; architectural fabrics; reinforcement of hoses; laminated fabrics; ropes; etc..

The following critical tests, which are used in the following explanation of the invention and the examples which follow, were carried out as follows.

Tenacity refers to " rupture toughness " as defined in ASTM D-2256-80. Initial module (or " initial secant modulus ") is defined by ASTM D-2256-80, Section 10.3, except that the line representing the initial straight line portions of the voltage curve is specified as a secant line passing through the elongation points 72 471 F-8091 -15- 0.5% and 1.0% in the voltage curve.

All other voltage properties are as defined in ASTM D-2256-80. Shrinkage (SH) is defined as the linear contraction in a warm air environment maintained at 177 ± 1 ° per ASTM D-885-85.

Density, crystal size, long period spacing, birefringination and amorphous birefringination are the same as set forth in US 4 134 882, which is hereby incorporated by reference. Specifically, each of the foregoing can be found in U.S. Patent 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; an amorphous bifurcation-column 11, line 27. The birefringence (optical birefringence of Δη) is as set forth in U.S. Patent 4,101,525, at column 5, lines 4-46. U.S. Patent 4,101,525 is incorporated by reference herein. " BiCV " is the coefficient of variation of optical birefringence between filaments, calculated from 10 measured filaments.

Other tests cited herein are carried out by conventional methods.

Reference may be made to the Examples which will more fully illustrate the present invention. EXAMPLE 1

In the ensuing ensemble of experimental operations, a conventional polyester polymer (TPE, VI-0.63) was spun. Spinning rates were increased from 3 812 m / min to 5 795 m / min (meters per minute). The column length was 6.4 meters and divided into four temperature control zones. The temperature was controlled by measuring the air temperature near the wall in the center of each zone. The polymer was extruded 72 471 F-8091 -16-

at a rate of 10.39 kg per hour through a spinning rack at 285 ° C and an orifice die 40 (hole size 0.023 cm by 0.033 cm). The fibers did not undergo thermal shock. The spun fibers were not drawn, but they were heated. The results are shown in Table I.

(SECTION TABLE I)

72 471 F-8091 -17-

TABLE I N2. 1 N 2. 2 N 2. 3 N 2. 4 Spinning Speed, m / min 3 812 4 117 4 422 4 727 Column - Top, BC 110 108 105 104 Temperat. second, 0 C 105 104 104 107 third, 0 C 131 130 129 132 lower, ° C 109 107 105 111 Denier 340 310 290 270 dpf 8.5 7.8 7.2 6.8 " True Tension " in gpd Rupture 6.51 6.41 6.55 6.65 Spun: Denier 340 316 289 270 Toughness, gpd 3.93 3.89 4.10 4.18 Elongation,% 65.7 64.8 59.8 59 , 2 τ / E 31.8 31.3 31.7 32.3 MI, gpd / 100% 54.0 56.4 52.1 59.2 HAS,% 177eC 6.0 6.5 7.0 7, 5 " Uster ",% 0.96 1.29 1.14 1.28 Finishing,% 0.098 0.358 0.119 0.168 VI 0.623 0.630 0.629 0.631% Crystalline. 34.2 35.3 37.2 39.0 Δ nx 10 " 3 108 106 115 112 BiCV% 3.2 4.3 6.5 5.8 Density, gms / c3 1.3728 1.3742 1.3766 1 , 3788 Production Point Toughness, gpd 1.18 1.26 1.38 1.48 Heat Adjustment: Denier 338 308 287 271 Toughness, gpd 4.06 4.19 4.26 4.34 Elongation,% 62.3 58.6 53.2 51.0 τ and 32.0 32.1 31.1 31.0 IM, gpd / 100% 60.2 62.2 66.3 70.0 HAS,% 177 ° C 2.0 2.2 2.8 2.8% Crystalline. 55.7 55.9 56.6 56.9 Δη x 10 3 152 142 143 145 BiCB% 5.8 7.9 7.9 6.3 Density, gms / c3 1.3996 1.3999 1.4007 1 , 4011 Production Point Tenacity, gpd 0.89 0.97 1.04 1.11 72 471 & F-8091 M TABLE -18- I - CONT • **** Na .5 Ns. 6 N B. 7 Na. 8B Spinning Speed, m / min 5 032 5 337 5 642 5 795 Column - Top, ac 105 105 106 105 Temperat. second, 0 C 109 110 106 110 third, ° C 132 132 130 133 lower, ° C 111 111 109 119 Denier 255 240 225 220 dpf 6.4 6.0 5.6 5.5 " Actual Voltage " in gpd Rupture 7.23 6.98 6.86 7.14 Spun: Denier 254 240 228 222 Toughness, gpd 4.55 4.52 4.57 4.71 Stretching,% 59.0 54.5 50.0 51 , 6 Τ / E 34.9 33.4 32.3 33.8 MI, gpd / 100% 65.4 60.1 66.6 76.2 HAS,% 177 ° C 7.2 7.5 7.0 7.2 " Uster ",% 1.33 1.59 1.34 1.52 Finishing,% .263 0.037 0.160 0.267 VI 0.630 0.629 0.626 0.627% Crystalline. 40.3 42.2 43.2 43.3 Δ nx 10 " 3 118 124 127 130 BiCV% 4.7 6.7 6.9 8.4 Density, gms / c3 1.3804 1.3827 1.3840 1 , 3841 Production Point Toughness, gpd 1.57 1.67 1.75 1.80 Heat Adjuster: Denier 252 240 226 231 Toughness, gpd 4.33 4.46 4.65 4.64 Stretch,% 49, 5 46.6 44.4 45.1 τ and " i 30.5 30.5 31.0 31.2 IM, gpd / 100% 68.8 64.0 73.2 72.6 HAS,% 177 ° C 3.0 3.2 3.0 2.5% Crystalline. 56.9 57.0 57.3 57.2 An x 10-3 3 150 146 156 160 BiCB% 7.0 6.5 9.1 6.3 Density, gms / c3 1.4011 1.4013 1.4016 1 , 4015 Production Point Tenacity, gpd 1.19 1.25 1.33 1.30

72 471 F-8091 -19-

EXAMPLE II

In the ensemble of experiments that follow, a conventional polyester (PTE, IV-0.63) was spun. Column temperatures were varied as indicated (air temperature, center of zones). The length of the column was 6.4 meters. The polymer was extruded at a rate of 10.48 kg per hour through a spinning support at 300øC and a spinneret with 72 holes (orifice size 0.023 cm by 0.030 cm. The fibers were not subjected to thermal shock. The results are shown in Table II (FOLLOWING TABLE II) 72 471 F-8091

TABLE II

Speed. Wiring-m / min-305 Arref. Sub. at-m3pm / ° C Air purge * -m3pm / ° C Air temp. Upper Column, ° C second, ° C third, ° C lower, ° C

Thread: Denier

Tenacity-gpd Stretching,% I.M.-gpd / 100% HAS-% 177 ° C ,, Uster ,, -%

Finishing,% V.I. Δn x 10-3% Crystallization

Denier Max Stretch Ratio

Tenacity-gpd Stretching,% I.M.-gpd / 100%

HAS-% 177 ° C

Stretch Ratio Max 0.03 Denier

Tenacity-gpd Stretching,% I.M.-gpd / 100%

HAS-% 177 ° C

At. 1 Na. 4 Na. 5 Na. 2 3.2 3.2 3.8 3.8 0.17 0.85 70 68 120 80 83 101 99 81 75 88 85 75 62 72 79 64 370 367 369 344 2.87 3.68 3.77 3, 50 122 81.8 83.2 82.6 63 93 93 86 65.5 27.2 41.0 49.5 1.38 1.14 1.41 0.99 1.82 0.44 0.74 0, 96 0.63 0.64 0.64 0.64 78 115 113 105 11.0 17.9 16.6 14.8 1.70 1.80 1.80 1.60 224 210 213 218 5.60 8, 72 8.63 7.31 18.4 8.9 8.6 11.0 92 137 133 127 6.2 10.0 9.8 9.2 1.65 1.77 1.77 1.54 230 214 217 227 5.34 8.30 8.72 7.04 19.9 9.3 9.2 13.1 82 120 137 123 6.0 9.8 10.0 9/0 *

Air sprinkler, item 17, figure 1 72 471 F-8091 -21- TABLE II - CONT.

At . 3 Na. 6 • Ot to Speed. Wiring-m / min-305 choq. Therm. of Water-m3pm / 0C Air Sprinkler * -m3pm / ° C 3.8 3.8 3.8 Temp. Upper Column, eC 98 121 135 second, ° C 88 101 107 third, ° C 78 86 88 lower, ° c 65 80 81 Spun: Denier 342 342 342 Toughness-gpd 3.72 3.86 3.75 Stretching,% 79 , 6 70.9 69.0 IM-gpd / 100% 86 73 75 HAS-% 177 ° C 42.0 11.2 9.5 " UsterH-% 1.13 1.23 2.29 Finishing% , 85 0.50 0.54 VI 0.64 0.64 0.64 A nx 10 " 3 111 107 106% Crystallization 15.9 20.5 24.7 Max Stretch Ratio 1.57 1.77 1.74 Denier 227 202 206 Tenacity-gpd 7 , 04 8 * 74 8.67 Elongation,% 11.6 7.5 8.1 IM-gpd / 100% 110 146 140 HAS-% 177 ° C 7.8 10.0 10.0 Max. Stretch Ratio , 03 1.54 1.74 1.72 Denier 231 205 205 Tenacity-gpd 7.09 8.61 8.31 Elongation,% 13.1 7.7 7.6 IM-gpd / 100% 107 145 124 HAS- % 177 ° C 7.8 10.2 10.0 *

Air Sprayer, item 17, figure 1

72 471 F-8091 -22-

In the above set of experiments, (i.e., shown in Table II), Numbers 4, 5, 6 and 7 represent the present invention.

EXAMPLE III

In the ensembles of experiments which follow, the conventional polyester (TPE, VI-0.63) was spun. The fibers were wound at a ratio of 3 202 m / min. The polymer was extruded at a rate of 8.84 kg per hour through a spinneret with 72 holes (hole size 0.023 cm by 0.30 cm) and a spinning rack at 300 ° C. The fibers underwent thermal shock with 0.18 m3 / min of air in 232 ° C. The column was 6.4 meters long and divided into four sections having the following air temperature profile (in descending order): 135 ° C; 111 ° C; 92 ° C; and 83 ° C in the center of the zones, the spun yarn had the following properties: denier - 334; toughness - 4.09 gpd; elongation 71.7%; initial modulus - 55.0 gpd / 100%; contraction in hot air - 11.8% in 177%; " Uster "1.10; SAW. - 0.647; " FOY " - 0.35%; birefringence - 100 x 10 "3; and crystallinity - 21.6%.

In Table IIIA, the effect of the draw ratio on the properties of the drawn yarn is illustrated.

TABLE IIIA

Stretch Ratio 1.65 1.60 X-.54 Denier 209 218 226 Tenacity gpd 8.15 7.53 7.12 Elongation,% 8.4 8.9 10.4 Initial modulus gpd / 100% 123 115 115 Hot Air Contraction% , 177 ° C 12.0 12.4 12.0 In table ΪΪΙΒ, the effect of the heating process during stretching (the draw ratio was 1.65 and the yarn was not relaxed) is illustrated.

& Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ η Φ η η η η η η η η η η η η η η η η η η η η η Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ Φ 23

or

Ο Ο Ο Ο Ο Ο Ο Ο Ο ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ ΙΛ η η η η η η η η η η η η η η η η. i • Η Η Η Η Η Η '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' Η Η Ά η Φ co co co co co co co co co Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Λ Λ η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η Ό Ό Ό Ό Ό Ό Ό η Ό Ό Ό Ό Ca '' 'η η η Ο Ο Ο' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' ' Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο K k Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η. <tf ω φ ω 00 ω η »00

U Φ • Η Μ 1 '* ca ca Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο Ο

Q

72 471 F-8091 -24-

In Table IIIC, the effect of larger draw temperatures and draw ratios (the feed roller is at room temperature and the draw roll is 240 ° C) is illustrated. (SECTION TABLE IIIC) -25- 72 471 F-8091

St / w.

H H <0 00 tn tn «o *% H VD t '• VD < VO vo <JV P 'vo n • O% *% H OJ vo vo

67 n 73 r * tn s H H O M O V O O 0 ω ω co ω • σν * * 1 H pH ω vo u u H H H 3w

c \ M n · <51 * OJ H o \ s «fc H H OV VO 76 tn 50 H co • OV * fcl * H H 0 \ VO vo

0 +> g) (0p + Hg) (flw fl) ΌO i (0 N O O R * H df> 0) +>

&lt; * &gt; 0) θ 'Ό O 0) -P O Ό C t t O O O fl fl fl fl t t t. • O B O. . -Η <β «J fl) ϋ ^ M

• HR

(O + R)

(F) 0) H 72 471 F-8091 -26-

EXAMPLE IV

In the ensemble of experiments, a conventional polyester (TPE, VJ-0.92) was spun. In experiments Nos. 1-5, the fibers were spun and drawn according to the procedures set forth in patents US 4 101 525 and US 4 195 052. Experiments numbers 6-9 were made as follows: TPE with a molecular weight characterized by a VI of 0.92 was dried at 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 advanced into a spinning assembly by a metering pump. This assembly had an annular design, and provided polymer filtration by passage therethrough through a bed of finely divided metal particles. After filtration, the polymer was extruded through a 80-hole spinneret. Each bore of the die 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 long was mounted together below the set and the multifilament spinning yarn line passed through the entire length of this tube before converging or coming into contact with any of the guide surfaces. The tube was divided below its length into seven zones in order to control the temperature. Individual controllers were used to adjust the air temperature in the center of each of these zones. Using a combination of heating processes and external heaters around the tube, individual controller adjustments were selected to arrive at a uniform air temperature profile below the vertical length of this tube. In a typical situation, the air temperature was 155øC at the top of the tube and the temperature was reduced with an approximately uniform gradient to 50øC at the bottom.

Approximately 10 cm below the tube, the wire line came in contact with a finishing applicator, which also served as the convergence guide and as the first contact the wire found. At the outlet of the tube, the cross-section of the wire does not

i; &gt;

72 471 F-8091 27 was very small due to the proximity of the finishing guide. This allowed a very small aperture to be used, thereby minimizing the amount of hot air lost from the tube.

Following the application of the spinning finish, the yarn was taken up by a pair of goblet rollers, and then by a controlled tensioner. Winding speeds were typically in the range of 3 200 to 4,100 m / min. The stretching of this yarn was carried out in a second step in which the spun yarn was passed through a set of pre-tension rolls to a heated feed roller maintained at a temperature set between 80 and 150 ° C. The yarn was then stretched between these rollers and a set of draw rolls held at a given point, chosen in the range of 180 to 255Â ° C. A typical draw ratio for yarn made at 3 800 m / min would be 1.65, with yarn samples at higher and lower speeds, requiring larger or smaller draw ratios, respectively.

The results are shown in Table IV. (SECTION TABLE IV) 72 471 F-8091

1 ϋ (d 0 • • H 0 73 73 cd cd 0 0 0 0 0 0 0 0 0 0 0 0 cd cd cd cd cd cd cd vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo to vo to r · vo d) 0 10 73> cd w θ 'uo &lt; N &gt; 0 Ό Ό Ό Ό Ό Ό Ό 0 0 0 ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι HHHHHHHHS 0 0 0 0 H 0 fd 0 cu 73 v o HH b 'M * CM co co-P (dnao \ σι CM co vo ovet IO to C fy cd tyv (U d) 73 o V o t o cn σι σι β BH • H rH <0> 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 &lt; d 73 cd -μ H r- C &quot; (v à U U vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo CM «r H 73 • H 73 • HH CM CM CM IO TO TO Ό c 0 * rH rH rH rH HHHHH £ • H tF 1 • H 73 0 to 10 vo H CM CM CM co 73 CM co 10 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 | • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • • HHHH • d • HH • θ • Pm X d) 73 0 cd «cd 73 0 < Λ • H cd and 10 o IO or IO CM CM Γ &quot; 0 • H to CM co co M * O o rH H 0 Pm n 10 co H CM 10 co H H H H CM CM CM CO co co d) d) &gt; 73 • α H CM CO to vo co cn 72 471 F-8091

-29-

EXAMPLE V

Polyester with molecular weight characterized by a V.I. of 0.92 was dried at 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 advanced to a spinning assembly by a metering pump. After filtration in a bed of finely divided metal particles, the polymer was extruded through a die of 80 holes. Each bore of the die had a diameter of 0.457 mm and a capillary length of 0.610 mm. The VI measurement of this polymer, in extrusion, was 0.84. The extruded polymer was spun into a heated electric cavity 9 meters in length. An approximately linear temperature profile (gradient) was maintained across the length of this tube. In the center of the upper or top zone, the air temperature was 155 ° C and at the lower the tube temperature was 50 ° C. The bundle of multifilament yarn did not converge until it came into contact with a trim guide immediately below the outlet of the heated tube. From this point, the wire has been advanced by a pair of rollers, for a controlled tensioner. Under these conditions, a series of four spun yarns were made at different spinning (winding) speeds. These wires are quoted in Examples A to D in Table VA.

In another series of experiments, the heated tube was shortened by taking out some of its movable sections. Examples E and F in Table VA were spun through columns of 7 and 5 meters. Other polymers of different molecular weights (V.I) were also spun in this system to give Examples 6 and Η. Example I in Table VA illustrates a case in which the temperatures of the lower columns were used. In this case, a linear gradient of 125 ° C to 50 ° C was established below the column.

All yarns of the series A through I were drawn in a single stage process using a feed roller at room temperature and a draw roll at 245 ° C. 72 471 F-8091

-30-

In an additional series of tests, the same wire as described in Example A was drawn using different feed roller temperatures. The test results of these wires are given in Examples A, J and K in Table VB. (FOLLOW VA AND VB TABLES) 72 471F-8091 -31- ϋ W t &quot; &lt; t &quot; ιη C0 ιη ο η ο ο η η H r r νο ι> Η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η Η Η '' '' 'Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η η α θ 'θ' θ 'θ' θ '00 σι 00 θ'- Γ &quot; ο • μ μ σι σι &lt;, OJ σ' ω ιη Γ &quot; η 0 (0 G C0 Γ &gt; σι νο ιη ιη «ti ) Η η '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '. (η η η η η η η C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C C σ 'Η C0 ο (Μ ο 0) ο ο r Η ο Η Ο Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Ν Η Η Η Η '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' '' ' Ν η η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η (C c ο ο ο ο ο ο ο ο ο • • • • • (η η η η η η Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ r • Η β C0 η η Ίϋ · η η η 00 • tf α Ρκ oi &gt; * 0 (0 dl • 0 1 c • r 0 • H u • c θ 'σι σ' σι Γ &quot; ιη σ 'σν σν c d) c c β o u 131 d 0 £ 2. &lt; η Ο α W Pu Ο Κ Η 72 471 F-8091 "32

a a w a a) Ό ο <D ο 0 μ c * · ιλ * · «d μ * θ 'α) Η t &quot; Ο Ο Ο Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ H ΙΑ ΙΑ Μ Μ * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * * μ <Λ Ο Ο (d tf 0) θ 'Η Η μ Β <D α> Bi σ

I (0 tf 0 μα) μ (Λ OJ * ΰ 0) C0 C0 C0 £ * * ο id Η Η Η «d μ N -rt (d -μ rH 0 υ <ΰ 0 ο ΙΑ Ο ο α ) η) • CJ σ \ ΙΑ Ό • μ α Η μ Β 0 ω α &gt; Η

Tf

O

H h tf o)

72 471 F-8091 -33-

EXAMPLE VI

In the following experiment, a conventional polymer, &quot; nylon &quot; was spun according to the process of the invention and compared to &quot; nylon &quot; made according to conventional processes. 0 &quot; nylon &quot; made according to the process of the invention was spun under the following conditions: flow rate - 16.78 kg per hour; spinning speed - 720 m / min; denier - 3 500? number of filaments 68; relative spinning speed - 3.21 (H2SO4) or 68.4 (HCOOH equivalent) thermal shock - 72 scfm; winding voltage 80 g; column length: 7.32 m; top column temperature 240 ° C and lower 48 ° C. The yarn properties of this yarn are as follows: toughness - 0.95 gpd; 235% elongation; te1 / 2 = 14.6. Thereafter the yarn was drawn under the following conditions: draw ratio 3.03; draw temperature 90 ° C. The properties of drawn wire are as follows: toughness 6.2 gpd; elongation - 70%; TE1 / 2-52; 10% modulus - 0.87 gpd; contraction in hot air (HAS) at 205 ° C - 1.4%.

A &quot; nylon &quot; The conventional method was as follows: flow rate - 10.61 kg per hour? spinning speed - 257 m / min; denier 5,556; number of filaments - 180? spinning relative viscosity - 3.3 (H2 SO4) or 72.1 (HCOOH equivalent); thermal shock - 4.25 m3pm. Thereafter, the yarn was drawn under the following conditions: draw ratio - 2.01; draw temperature - 90Â ° C. The properties of drawn wire are as follows: toughness 3.8 gpd? elongation - 89%; TE1 / 2-33? 10% modulus - 0.55 gpd.

Another comparison yarn was spun in the conventional manner as follows: of the total length - 1.63 kg per hour? spinning speed - 320 m / min; denier - 12 400; number of filaments - 240; relative spinning viscosity - 42 (HCOOH equivalent); tempered air - 4.25 m3pm. Thereafter, the yarn was drawn under the following conditions: draw ratio - 3.60; draw temperature - 10 ° C. The properties of drawn wire are as follows: toughness - 3.6 gpd; elongation - 70%; TE1 / 2 - 30.1? 10% modulus elongation - 0.8 gpd; HAS (204 ° C) - 2.0%.

72 471 F-8091 -34-

EXAMPLE VII

In the following experiments, V.I. low (e.g. 0.63) and V.I. (e.g. 0.92) of a conventional polyester spun yarn (i.e., TPE) is compared to the spun yarn described in US Pat. No. 4,134,888. Examples 1-8 are V.I. polyester (TPE). and were made in the manner described in Example I. Examples 9-11 are V.I. polyester (TPE). high and were made in the manner described in Example V. Examples 12-17 correspond to Examples 1, 5, 12, 17, 36 and 20 of U.S. Patent 4,134,888. Data are given, for each example, spinning speed (m / min), density (gms / c3), crystal size (nm, 010), long period spacing (LPS), birefringence, crystal birefringence and amorphous birefringence. The results are shown in Table VII. (SECTION TABLE VII) 72 471 F-8091 35

TABLE VII

(H o o VO H co co co IO co f CO CO co d) <H vo VO C- 've VO r-' [> Γ * ΙΟ ΙΟ ΙΟ vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo vo. &lt; k. k. k "fc. &lt; &lt; &lt; H. -H o O o O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o CM co σ Η Η \ \ Η Η Η Η Η Η Η Η & & & Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η H CM U u VV κ v V k κ V Ν * ss UOOOOOOOOOOO O O O • H 0) pq u • OOOO o O oo H (Ο 00 CM CO H VO IO «H co vo in CM co oo VO tf Η ΙΟ ΙΟ ΙΟ ΙΟ CO CO vo vo vo vo vo vo vo vo vo vo vo vo. (Μ σι Ο H CM CM σ PHHHHHHHHOH Η Η Η M Η Η Η PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN PN • • • • ΓΟ »» ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι ι CO CM co 10 ω H H H H H N. N. N. N. N. h h h h h h h h Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό Ό The covariance of the covariance function is shown in Fig. 4. The covariance curve is shown in Fig. co co tf co Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι Ι (H) -Hydroxycarbonyl-N-methyl-N- g d) X g (M i &gt; CM r · 'CM t> CM IO O CM (Μ o I> io io CM 3 3 3 3 3 3 3 3 3 3 3 3 3 ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν ν Η Η Η Η & & & & & & & & & M M M M M M M M + (H 2 O) • H 2 O • H 2 O • H 2 O • H 2 O • H 2 O • H 2 O • H 2 O 3 »» »» »» »» »» Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η

The present invention may be embodied in specific forms without departing from its spirit or essential attributes and, consequently, reference should be made to the appended claims, rather than to the foregoing specification, as indicating the scope of the invention.

Claims (9)

A drawn wire having an initial secant modulus greater than 150 grams per denier / 100%. A drawn wire as claimed in claim 1, further characterized in that it has a shrinkage of less than The drawn wire of claim 1, further characterized in that it has a toughness greater than 7.5 grams per denier. A drawn wire, characterized in that it has: a toughness of at least 7.5 grams per denier; an initial secant modulus of at least 150 grams per denier / 100%; and a shrinkage of less than 8%. A drawn wire, characterized in that it has a tenacity of at least 8.5 grams per denier; an initial secant modulus of at least 150 grams per denier / 100%; and a shrinkage of less than 8%. A drawn wire having a tenacity of at least 10 grams per denier, an initial secant modulus of at least 120 grams per denier / 100%; and a shrinkage of less than 8%. A drawn wire having a toughness greater than 9.0 grams per denier, an initial secant modulus of greater than 150 grams per denier / 100%, and a shrinkage of less than 7.5%. The yarn according to claim 1, or 4, or 5, or 6, 38, 47, 471, F-8091 or 7, characterized in that the yarn comprises a plurality of fibers having a denier per filament between about 1.5 to about 6. Lisbon, -9. MÀi 1991 By HOECHST CELANESE CORPORATION - THE OFFICIAL AGENT -