WO2013055344A1 - Process for preparing poly (trimethylene arylate) fibers - Google Patents

Process for preparing poly (trimethylene arylate) fibers Download PDF

Info

Publication number
WO2013055344A1
WO2013055344A1 PCT/US2011/056151 US2011056151W WO2013055344A1 WO 2013055344 A1 WO2013055344 A1 WO 2013055344A1 US 2011056151 W US2011056151 W US 2011056151W WO 2013055344 A1 WO2013055344 A1 WO 2013055344A1
Authority
WO
WIPO (PCT)
Prior art keywords
filament
denier
spinning
ptt
filaments
Prior art date
Application number
PCT/US2011/056151
Other languages
French (fr)
Inventor
W. Douglas BATES III
Original Assignee
E. I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to PCT/US2011/056151 priority Critical patent/WO2013055344A1/en
Publication of WO2013055344A1 publication Critical patent/WO2013055344A1/en

Links

Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters

Definitions

  • poiy ⁇ irimeinyiene aryiate fibers the resultant fibers, and their use.
  • Folyftri methylene aryiate particularly po!y(trimeihyiene terephthalate) (also referred to as 3GT, Triexfa or PTT), has recently received much attention as a fiber-forming polymer useful in textiles, PTT fibers have excellent physical and chemical properties.
  • textured polyester yarns prepared from partially oriented polyester yarns (POY) or spun drawn yarns (SDY), mostly polyethylene terephthalate
  • PET PET
  • knit and woven fabrics are in wide-spread commercial use in many textile applications, such as knit and woven fabrics, as well as non-woven fabrics, such as spunbonded PET.
  • the textile term "yarn” refers to a bundle of individual fibers. For example, shirts and blouses are often made from yarns mad up of bundles of 30-40 filaments.
  • Polyester yarns including both PET and PTT yarns, are prepared by a so-called melt spinning process, and are said to be “melt spun.” Melt spinning is a process whereby the polymer is melted and extruded through a hole in a so-called spinneret.
  • melt spinning is a process whereby the polymer is melted and extruded through a hole in a so-called spinneret.
  • the spinneret is provided with a plurality of holes, often 3D ⁇ 40, eac about 0,25 mm in diameter. Multiple filaments are thereby exiruded from a single spinneret. Those filaments are combined to form a bundle that is called a yarn.
  • Polyester yarns can be used in any combinations with or without other types of yams.
  • polyester yams can make up an entire fabric, or constitute the warp, weft or fill, in a woven fabric; or as one of two or more yarns in a yarn b!end, for instance, with cotton, wool rayon, acetate, other polyesters, spandex and/or combinations thereof.
  • Fujimoto et a!. U.S. Pat, 6,284,370, discloses a process for preparing 1 -2 dp! " PIT fibers wherein a first roll is heated to 30-80 °C ( a second roi! is heated to 100-160 *C,. and the draw ratio imposed between the first and second roils was is in the range of 1.3-4, in 13 examples and 1 1 counterexamples, Fujimoto never heated the fi st roil to a temperature above 60 C except in one counterexample, in ail the example, the first roll temperature was in the range of 60-60 ft C.
  • Howell et al. U.S. Pat. 8,287,688, describes preparation of textured PTT yarns that exhibit increased stretch, luxurious bulk and improved hand, as compared to PET yarns. Howell et at. describes preparing partially oriented; PTT yarns at spinning speeds up to 2600 m m. By contrast, PET is routinely melt spun at several times that speed. For reasons of cost, it is highly desirable to be able to spin PTT yams at speeds higher than 2800 m/min.
  • Chang et al U.S. Patent 8,923,925, discloses a composition comprising PTT containing about 2% polystyrene (PS) that can be melt spun into spun drawn yarns at speeds up to 5000 m/min.
  • PS polystyrene
  • Chang et al. is completely silent in regard to the denier uniformity (Denier CV) of the yarns so produced, and silent as well regarding the temperatures of the godet rolls employed for preparing the spun drawn yarn
  • the present invention provides a filament comprising a composition comprising 0,1 to 3% by weig t of polystyrene, based on the total weight of the polymer in the composition, dispersed in poly(trtmethy!ene aryiate) wherein the filament is characterized by a denier per filament of ⁇ 3, a denier coefficient of variation of ⁇ 2,5 % and a birefringence of at least 0,055.
  • the poly(trlmethylene aryiate) is poly ⁇ tri methylene terephthalate).
  • the present invention provides a process for forming a novel spun drawn filament characterized by a denier per filament of ⁇ 3, and a denier coefficient of variation of ⁇ 2.5 > the process comprising extruding a polymer melt comprising 0.1 to 3 % by weight, based on the total weight of polymer, of polystyrene dispersed in poiy ⁇ tri methylene aryiate), through an orifice having a cross-seetionai shape, thereby forming a continuous filamentary extrudate, quenching the extrudate to solidify it into a continuous filament, wrapping the filament on a first driven roll heated to a temperature in the range of 70 to 100 °C and rotating at a first rotational speed, followed by wrapping the filament on a second driven roll heated to a temperature i the range of 100 to 130 C C and rotating at a second rotational speed; and, winding said filament onto a take-up roll at a linear speed of at least 4,000 meters/minute (rcVmin); wherein the ratio of
  • the poSy(trimethylene aryiate) is poiyftrimethy!ene terephthalate).
  • the present invention provides a fabric comprising a filament comprising a composition comprising 0.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poly ⁇ tri methylene arylate) wherein the filament is characterized by a denier per filament of ⁇ 3. a denier coefficient of variation of ⁇ 2.5 % and a birefringence of at ieast 0.955.
  • the poiy(trimethyiene arylate) is poiy ⁇ trimetbyle:ne terephthaSate).
  • Figure 1 is a schematic representation of one embodiment of melt feeding a spinneret according to the invention.
  • Figure 2 is a schematic representation of one embodiment of the fiber spinning process according to the invention.
  • Figure 3 depicts a ioom suitable for fabricating a woven fabric of the invention.
  • FIG. 4 is a schematic representation of the spinning machines employed in the Examples.
  • Figure 5 is a graph of the experimental results, showing the effect of the temperature of the first godet on the denier coefficient of variation, and contrasting the results obtained using Spinning Machine #2 with those obtained using Spinning Machine #1.
  • the present invention is directed to a filament comprising a composition comprising J3.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy ⁇ trimethyiene aryiate) wherein the filament is characterized by a denier per filament (dpf) of ⁇ 3, a denier coefficient of variation (denier CV) of ⁇ 2.5 % and a birefringence of at least 0,055.
  • dpf denier per filament
  • denier CV denier coefficient of variation
  • the poiy(thmethylene arylate) Is poiy(trimethyiene terephthaSate),
  • the filament hereof is a continuous filament
  • the filament hereof is a staple filament.
  • a plurality of the filaments hereof are combined to form a multifilament yarn.
  • the multifilameni yarn thus formed is suitable for for texturing, and for end uses in those textile applications in which fine denier yarns are desirable, such as shirts, blouses, lingerie, hosiery and the like.
  • the multifilament yarn hereof is useful for forming knitted, woven, and non-woven fabrics by methods known in the art.
  • the filament hereof is also suitable for use in a wide variety of non-woven constructions.
  • the filament hereof can be arrayed in a random or quasi-random web to form a filamentary non-woven fabric.
  • the filamentary non-woven fabric comprises a plurality of continuous filament strands hereof.
  • the filamentary non-woven fabric comprises a single continuous filament strand.
  • the filamentary non-woven fabric comprises a plurality of staple filaments prepared from the filament hereof,
  • a filamentary non- woven fabric for the purposes of the present invention is a non-woven fabric whereof the fundamental structural element is a single randomly or quasi-random!y disposed filament segment rather than a multi-filament yam segment.
  • the present invention provides a process for forming a novel spun draw filament characterized by a denier per filament of ⁇ 3, and a denier coefficient of variation of ⁇ 2,5 %, the process comprising extruding a polymer melt comprising 0.1 to 3 % by weight, based on the total weight of polymer, of polystyrene dispersed in poiy ⁇ tri methylene arySate), through an orifice having a cross-sectional shape, thereby forming a continuous filamentary extrudate, quenching the extrudate to solidify it into a continuous filament, wrapping the filament on a first driven roll heated to a temperature i the range of 70 to 100 °C and rotating at a first rotational speed, followed by wrapping the filament on a second driven roil heated to a temperature in the range of 100 to 130 °G and rotating at a second rotations! speed; and, winding said filament onto a take-up roll at a linear speed of at feast 4,000 meters/minute (m min);
  • the denser CV of yarns of ⁇ 3dpf when spun at speeds of 4,000 m/min or more when the first godet is set above 70 0 C is conspicuously iower than that of yarns of comparabie composition spun at the same speeds when the first godet is set at the commercially typical temperature of 80 "C.
  • denier CV denier coefficient of variation
  • Uster Tester measures denier variation along the length of a single continuous strand of fiber or yarn.
  • the denier CV is a standard statistical parameter that represents the value obtained by dividing the standard deviation of the denier by the mean denier, determined from the Uster Tester.
  • concentrations are stated in terms of percentages by weight unless otherwise stated, in particular, it sha l be understood that the concentration of polystyrene blended with the poly ⁇ trimethySene terephthalate) or other poly(trimethylene arylate j hereof is expressed as the percent by weight of polystyrene relative to the total weight of polymer in the composition.
  • the description shall be directed at those embodiments in which the poiy(trimethyiene arySate) is poly(tnmethyietie terephthalate) (PIT) unless otherwise explicitly stated.
  • PIT poly(tnmethyietie terephthalate)
  • Extension of the invention to other poly(trimethyiene arylates) shall be made with adjustments in concentration b weight appropriate to differences in the molecular weight of the particular arylate monomer units involved, assuming equal degrees of polymerization.
  • copolymer encompasses not only copolymers, but terpolymers, tetrapoiymers and so forth.
  • copolymer* shall be understood to encompass any number of monomers polymerized together. For practical purposes, the vast majority of applications are limited to homopolymers, dipolymers, and terpolymers.
  • the filament comprises a composition comprising 97 to 99.9 wt% of PTT and 3 to 0.1 wt% polystyrene (PS). In another embodiment, the filament comprises a composition comprising 70 to 99.5 wt% of PTT, 3 to 0.5 wt% of PS, and, optionally, up to 20.5 wt% of other polyesters. In another embodiment, the filament comprises a composition comprising 98 to 99.5 wt% of PTT and 2 to 0.5 wt% PS.
  • PS polystyrene
  • the filament consists essentially of a composition consisting essentially of 97 to 99.9 vvt% of PTT and 3 to 0.1 wt% polystyrene (PS), in another embodiment, the filament consists essentially of a composition consisting essentially of 70 to 99.5 wt% of PTT, 3 to 0.5 wt% of PS and. optionally, up to 29.5 wt of other polyesters. I another embodiment, the filament consists essentially of a composition consisting essentially of 98 to 99,5 wt% of PTT and 2 to 0.5 wt% PS.
  • PS polystyrene
  • Suitable PTT polymer is formed by the condensation polymerization of 1 , 3-propanediol and terephthalic acid or
  • copoiymerization therewith is selected from the group consisting of linear, cyclic, and branched aliphatic dicarboxySic acid or esters having 4-12 carbon atoms (for example butanedioic acid, pentanedioic acid, hexanedioic acid, dodeeanedioic add, and l ⁇ -cyciohexanedicarboxyiic acid, and their corresponding esters); aromatic dicarboxySic adds or esters other than terephthaiic acid or ester and having 8-12 carbon atoms (for example isophtha!ic acid; and 2,8-naphthatenedicarboxylic add); linear, cyclic, and branched aliphatic diois having 2-8 carbon atoms (other than 1 ,3-propanediol) for example, ethanediol, 1 ⁇ -propanedioi, 1 ,4-but
  • the PTT can contain minor amounts of other comonomers selected so that they do not have a significant adverse affect on properties.
  • Such other comonomers include 5-sodium-suifoisophthalate, for example, at a level in the range of 0.2 to 5 mole %.
  • Very small amounts of trifunetional comonomers, for example trimellitic acid, can be incorporated for viscosity control.
  • the PTT can be blended with up to 30 mole percent of other polymers. Examples are polyesters prepared from other diols, such as those recited supra.
  • the PTT contains at least 85 mo!- of trimethyiene terephth late repeat units. In a further embodiment, the PTT contains at least 90 moi-% of tri methylene terephthalate repeat units. In a still further embodiment the PTT contains at least 98 moS- % of of
  • trimethyiene terephthalate repeat units contains 100 moJ % of trimethyiene terephthalate repeat units.
  • suitable PTT is characterized by an intrinsic viscosity (IV) in the range of 0 JO to 2.0 dl/g.
  • IV intrinsic viscosity
  • suitable PTT is characierized by an IV in the range of 0.80 to 1 ,5 di/g.
  • suitable PTT is characterized by an IV in the range of 0.30 to 1.2 di/g.
  • suitable PTT is characterized by a number average molecular weight (MCo) in the range of 10,000 to 40,000 Da. In a further embodiment suitable PTT is characterized by (V1 n in the range of 20,000 to 25,000 Da.
  • a suitable polystyrene is selected from the group consisting of polystyrene homopolymer, a-methy!-polystyrene, and styrene-butadiene copolymers, and blends thereof, in one
  • the polystyrene is a polystyrene homopolymer.
  • the polystyrene homopolymer is characterized by r in the range of 5,000 to 300,000 Da.
  • M r . of the polystyrene homopolymer is in the range of 50,000 to 200,000 Da.
  • M r . of the polystyrene homopolymer is in the range of 75,000 to 200,000 Da.
  • M dur of the polystyrene homopolymer is in the range of 120,000 to 150,000 Da.
  • Useful polystyrenes can be isotactic, atactic, or syndiotactic. High molecular weight atactic polystyrene homopolymer is preferred.
  • Polystyrenes useful in this invention are commercially available from many suppliers including Dow Chemical Co. (Midland, Mich. ⁇ , BASF (Mount Olive, N.J. ) and Sigma- A!drich (Saint Louis, Mo.).
  • PTT and PS are melt blended and, then, extruded in the form of a strand that is subsequently cut into pellets.
  • the filament hereof comprises a composition comprising PTT and PS. in some embodiments, these will be the only two materials in the blend and they will total 100 weight %. However, in many instances the blend will have other ingredients such as are commonly included in polyester polymer compositions in commercial use; Such additives include but are not limited to other polymers, plasficizers, UV absorbers, flame retardants, dyestuffs, and so on. Thus the total of the
  • poly(tri:methyiene terephthaiate) and polystyrene will not be 100 weigh %
  • Other polymers can include for example polyamides that impart acid dyeabi!ity to the yarn blend.
  • the ratios of polyester to PS weight percent concentrations remain the same as for those compositions that do not include the other polymers.
  • the PS is In the form of particles having an average size of less than S00 nanometers.
  • the polystyrene is polystyrene homopo!ymer at a
  • the pol (trimethy!ene aryiafe ⁇ is PIT comprising at least 98 mol of trimeihylene terephthaiate monomer units.
  • the filament of the present invention is characterized by a dpi ⁇ 3, a denier CV of ⁇ 2,5 %, and a birefringence of at least 0.055.
  • Typical physica! properties of the filament hereof include a tenacity above 3 grams per denier, and an elongation to break of 30 to 70%.
  • the filament denier is ⁇ 2.5.
  • the birefringence is at least 0.060.
  • this invention is directed to a process for preparing a single or multifilament yarn comprising (a) preparing a melt blend consisting essentially of " PTT and 0,1 to 3 weight % (wt%) polystyrene (PS) S (b) melt spinning the polymer melt blend so prepared to form on or more filaments of PTT containing dispersed PS.
  • the filament of the present invention is conveniently prepared as a spun drawn filament - that is, a filament that has been fully drawn in the spinning process.
  • fully draw is meant that the filament after quenching has been elongated close to the ultimate elongation to break thereof.
  • the spinning comprises extruding the polymer blend hereof through the one or more holes of a spinneret at a spinning speed of at least 4,000 tn m.
  • spinning speed refers to the rate of spun fiber accumulation, such as on a mechanical wind-up.
  • the high birefringence of 3 ⁇ 4 0.055 that is characteristic of the filament of the invention is a direct result of the high draw applied to the filament in the spun-draw process.
  • High birefringence is a principle way of distinguishing spun-drawn filaments from partially-oriented spun yarn that is subsequently draw-textured.
  • Figure 1 is a schematic representation of one embodiment of a melt spinning machine suitable for use in the present invention.
  • PTT is produced in a continuous melt poiymerizer, 1 , from which it is conveyed i molten form via transfer Sine, 2, to a counter-rotating twin-screw extruder, 3, the twin screw extruder being provided with a . mixing zone.
  • pellets comprising PS are fed via a weight-loss feeder, 4, or other pellet feeder means, to a satellite extruder. 5, wherein the pellet is melted and fed i molten form via transfer line, 6, to twin-screw extruder, 3, either at or upstream from the mixing zone of the tw -screw extruder, 3.
  • a PTT/PS melt blend is formed.
  • the resulting meit blend is fed via transfer line, 7 t to a spin block comprising a spinneret, 8, from which one or more continuous filaments, 9, are extruded.
  • FIG. 2 depicts one suitable arrangement for melt spinning according to the invention
  • 34 filaments 22, (all 34 filaments are not shown) are extruded through a hole spinneret 21.
  • the filaments pass through a cooling zone 23, are formed into a yarn bundle, and passed over a finish applicator 24,
  • the cooling zone comprises an air quench zone wherein air is impinged upon the yam bundle at room temperature and at 80% relative humidity with a velocity of 40 feet/mi .
  • the air quench zone can be designed for so-eailed cross-air-quench wherein the air flows across the yarn bundle, or for so-called radial quenc wherein the air source is in the middle of the converging filaments and flows radially outward over 380 *.
  • Radial quench is a more uniform and effective quench method.
  • the yarn is passed to a first driven godet roll 25, also known as a feed roll, set at 60 to 100 °C, in one embodiment, 70 to 100 *C, coupied with a separator roll.
  • the yarn is wrapped around the first godet roli and separator roil 8 to 8 times.
  • the yarn is passed; to a second driven godet roil, also known as a draw roil set at 1 10 to 130 c C f coupled with a second separator roil.
  • the yarn is wrapped around the second godet roli and separator roil 6 to 8 times.
  • Draw roli speed is 4000 to 8000 m/min while the ratio of draw roll speed to feed roil speed is in the range of 1.75 to 3,
  • the yarn is passed to a third driven godet roli 27, coupled with a third separator ro!i, operated at room temperature and at a speed 1-2% faster than the roll speed of the second godet roil
  • the yarn is wrapped around the third pair of rolls 6 to 10 times.
  • the yarn is passed though an interlace jet 28. and then to a wind- u 29, operated at a speed to match the output of the third pair of roils.
  • a quenched filament is wound at least once but preferably a plurality of times around the first godet roll so that the first godet roll appiies a drawing force on the extruded filament, causing it to draw down before quenching; down stream from the first godet roli, the filament is wrapped at least once but preferably a plurality of times around a second godet roll in such manner that the second godet appiies a drawing force on that portion of the filament lying between the first and second godet rolls.
  • the filament is directed to a third godet roll which serves as a Set down roli, running at a speed 1-2% higher than that of the second (draw) godet roil. From the third godet, the filament is directed to a wind-up. The rate at which the filament is wound on the wind-up is described as the spinning speed. In typical installations, the wind-up is a tension controlled wind-up.
  • the first godet roll is heated to a temperature in the range of 70-100 °C and the second godet roil is heated fo a temperature in the range of 100 - 130 S C,
  • the first godet roll Is driven at a first rotational speed; the second godet roll is driven at a second rotational spaed.
  • the ratio of the second rotational speed to the first rotational speed falls within the range of 1.75 to 3.
  • a plurality of filaments are extruded through a multi-hole spinneret.
  • the filaments so extruded are combined to form a yarn.
  • the yarn is held together by the application of some agitation, twisting, or both, of the extruded filaments, or thread line, causing the interlacing of the filaments.
  • the yarn so formed comprises a plurality of filaments, each filament characterized by a dpf ⁇ 3, a denier CV of ⁇ 2.5 %, and a birefringence of at least 0.055.
  • the filament denier is ⁇ 2.5.
  • the birefringence Is at least 0.050.
  • Typical yarns comprise 34, 48, 88, and 72 filaments, although the number of filaments combined to make a yarn is not limited in any way.
  • Yams formed according to the present invention are not limited only to be made up of a plurality of filaments according to the invention, but can contain other filaments as well.
  • a yarn formed according to the invention ca contain other filament of other polyesters as well as polyamides, polyacryiates and other such filaments as may b desired.
  • the other filaments can also be staple fibers.
  • the yarn formed according to the invention which can be formed by the spun-draw process described supra, is suitable for use as a feed yarn for false twist texturing as commonly practiced in order to provide textile-like aesthetics to continuous polyester fibers.
  • the texturing process comprises a) providing a yam package as formed according to the spinning process described supra: (bjunwinding the yarn from the package, (c) threading the yarn end through a friction twisting element or false-twist spindle, d) causing the spindle to rotate, thereby imparting twist in the yarn upstream of the rotating spindle and untwisting the upstream twist downstream from the rotating spindle along with the applicatio of heat; and (e) winding the yarn onto a package.
  • the invention enables an increase in productivity in the spinning of fine denier (s 3 dpi) spun ⁇ drawn PIT yarns.
  • the filament and yarn thereof of the invention have been prepared at spinning speeds that are 30 to 70 % higher than the maximum spinning speed achievable with neat PTT.
  • the resulting yarn is characterized by an elongation and tenacity within 20% of the elongation and tenacity of a PTT multifilament yarn that only differs from the yarn of the invention in that it does not contain the PS (and that has necessarily been spun at about 3000 m/min).
  • the yarns consisting essentially of the filaments of the invention are useful in a wide variety of textile applications with only minor adjustments needed in the textile machinery being used.
  • the resultant yarns are useful in preparing inter a ia textured yarns, fabrscs and carpets, under the same or similar conditions to those used for PTT yarns not containing PS and prepared at " 3000 m/min.
  • the PTT is a continuous phase or "matrix 8 and the PS is a discontinuous phase dispersed within the PTT matrix.
  • the size of the PS particles dispersed in the PTT matrix is ⁇ 500 nm. In a further embodiment, the size of the PS particles dispersed in the PTT matrix is ⁇ 200 nm.
  • the beneficial features of the present invention include the ability to spin a fine denier, high strength, tough, spun drawn PTT yam at spinning speeds of 4000 m min or higher. These beneficial features depend upon both the fine particle size of PS and the volume homogeneity of the dispersion of PS in the PT that in turn depend upon the application of sufficiently high shear melt blending. There is no threshold particle size at which the spinning performance and/or physical properties of the spun yarn suddenly degrades. Rather, as the PS particle size gets larger, performance gradually deteriorates. At particle sizes in the range of 500 nm or larger, denier CV gets progressively larger. Similarly, there is no particular threshold of homogeneity In regard to particle distribution in the PTT matrix.
  • One particularly valuable benefit of the present invention is the production of spun-drawn yarns characterized by denier CV of less than 2.5 %, Low denier CV is especially important in the preparation of fine denie yarns for textile applications. Unless the process by which the PS is dispersed in PIT is characterized by shear forces sufficient to ensure a particle size !ess than 500 nm and a sufficiently high uniformity of dispersion, it is highly unlikely that the denier CV will be ⁇ 2,5 %.
  • the amount of shear force applied to the melt depends upon the rotational speed of the mixing elements, the viscosity of the melt, and the residence time of the melt in the mixing zone. If the shear forces are too low there is a tendency for the PS to not break up to begin with, or to agglomerate rapidly into droplets greater than 500 nm in size.
  • the meit blending process can be performed both batch- wise and continuously.
  • So called high shear mixers such as are commonly employed in the art of poiymer compounding are suitable, Examples of suitable commercially available high shear batch mixers include, but are not limited to, Banbury mixers and Brabender mixers.
  • suitable commercially available high shear batch mixers include, but are not limited to, Banbury mixers and Brabender mixers.
  • Examples of continuous high shear mixers include co-rotating twin-screw extruders and Parrel Continuous Mixers
  • Counter-rotating twin screw extruders are also suitable, in general, suitable high shear mixers are those that are capable of exerting on a polymer melt a mi imum shear rate of SO/s, with 100/s preferred.
  • the resulting blend can be palletized for later feeding to a spinning machine, or the melt biend can be fed directly into a spinning machine.
  • Another useful method is to combine poiymer melts.
  • An example of this method wou!d be to provide a PTT meit from a continuous poiyrnerizer to the first stage of a twin screw extruder, and feeding a PS meit from a satellite extruder into the mixing zone of the twin screw extruder, thereby creating a meit biend .
  • the unmeited polymers ma be dry-mixed, as by tumbling, before being fed to a twin screw extruder for melt blending.
  • Average particle size greater than 500 nm is not preferred from the standpoint of good fiber spinning performance. Additionally, spinning of uniform filaments, both along a single end, and end to end, depends expressly upon the homogeneity of the volume distribution of the PS partic!es. While in no way limiting the scope of the invention, it is speculated that in the actual melt processing thereof, the PS particles meit to form molten droplets that are dispersed within a molten PIT matrix.
  • the temperature in the melt mixer should be above the melting points of both the PTT and the PS but below the lowest decomposition temperature of any of the ingredients.
  • temperatures wi!i depend upon the particular attributes of the polymers employed, in typical practice, meit temperature is in the range of 200 *C to 270 6 C.
  • the concentration of the PS in the PTT/PS blend pellets is in the range of 0,5 to 1.5 %.
  • the polymer melt is fed to the spinneret via a transfer line.
  • the melt input to the transfer line from the extruder is in turbulent
  • the spinneret feed must be laminar in order to achieve uniform flow through the plurality of holes in the spinneret. It is in the transfer Sine that the melt flow shifts from turbulent to laminar.
  • Filament spinning can be accomplished using conventional apparatus and procedures that are in widespread commercial use. As a practical matter, it is found that for spinning fine denier filaments of 3 dpf or lower, a PS concentration of > 3% leads to a degradation in mechanical properties of the fiber so produced. It is further found that at 5% PS, fine denier filaments cannot be meit spun at all,
  • the polymer blend pellets Prior to melt spinning, the polymer blend pellets are preferably dried to a moisture levei of ⁇ 30 ppm to avoid hydroiytic degradatio during melt spinning. Any means for drying known in the art is satisfactory. In one embodiment, a closed loop hot air dryer is employed. Typically, the PTT/PS blend is dried at 130 °C and a dew point of ⁇ -40 °C for 8 h. The thus dried PTT/PS polymer blend is melt spun at 250-285 °C into fibers.
  • the dried polymer blend peliets are fed to an extruder which melts the pellets and supplies the resulting melt to a metering pump, which delivers a vo!umetrica!ly controlled flow of polymer into a heated spinning pack via a transfer line.
  • the pump must provide a pressure of 10-20 MPa to force the flow through the spinning pack, which contains filtration media (eg, a sand bed and a filter screen) to remove any particles larger than a few micrometers.
  • the mass flow rate through the spinneret is controlled by the metering pump.
  • the polymer exits into an air quench zone through a plurality of small holes in a thick plate of metal (the spinneret). While the number of holes and the dimensions thereof can vary greatly, typically a single spinneret hole has a diameter in the range of 0.2- 0.4 mm. Spinning Is adva tageously accomplished at a spinneret temperatur of 236 to 295 °C, preferabl 250 to 290 9 C.
  • a typical flow rate through a hole of that size tends to be in the range of 1-5 g min.
  • Numerous cross-sectional shapes are employed for spinneret holes, although circular cross-section is most common.
  • a highly controlled rotating roll system through which the spun filaments are wound controls the line speed.
  • the diameter of the filaments is determined by the flow rate and the take-up speed; and not by the spinneret hole size.
  • the properties of the thus produced filaments are determined by the threadline dynamics, particularly in the region between the exit from the spinneret and the solidification point of the filaments, which is known as the quenc 2one.
  • the specific design of the quench zone, air flow rate across the emerging still motile filaments has very large effects on the quenched filament properties.
  • Both cross-flow quench and radial quench are in commo use. After quenching or solidification, the filaments travel at the take-up speed, that is typically 100-200 times faster than the exit speed from the spinneret hole. Thus, considerable acceleration (and stretching) of the threadline occurs after emergence from the spinneret hole.
  • the amount of orientation that is frozen into the spun filament is directly related to the stress level in the filament at the solidification point.
  • the melt spun filament thereby produced is collected in a manner consistent with the desired end-use.
  • a plurality of continuous filaments can be combined into a tow thai is accumulated in a so-called piddling can.
  • Filament intended for use in continuous form, such as in texturing, is typically wound on a yarn package mounted on a tension- controlled wind-up. According to the invention, the rate of accumulation is at least 4,000 m/min.
  • Texturing imparts crimp by twisting, heat setting, and untwisting b the process commonly known as false tvvist texturing.
  • These multifilament yarns ' also known as "bundles" comprise the same numbe of filaments as the spun drawn yams from which they are made. Thus, they preferably comprise at ieast 10 and even more preferably at least 25 filaments, and typically can contain up to 150 or more, preferably up to 100, more preferably up to 80 filaments.
  • the yarns typically have a. total denier of at least 1 , more preferably at Ieast 20, preferably t Ieast 50, more preferably up to 250, and up to 1 ,500. Filaments are preferably at least 0.1 dpf more preferably at least 0,5 dpf, more preferably a leas 0,8 dpf, and most preferably up to 3 dpi
  • PTT staple fibers can be prepared by melt spinning the PTT/PS- blend at a temperature of 245 to 285° C. into filaments, quenching the filaments, drawing the quenched filaments, crimping the drawn filaments, and cutting the filaments into staple fibers, preferably having a length of 0.2 to 6 inches (O S to 15 cm).
  • One preferred process comprises: (a) providing a polymer blend comprising PTT and 0.1 to 3 % PS, (b) melt spinning the melted blend at a temperature of 245 to 285* C, into filaments, (c) quenching the filaments, (d) drawing the quenched filaments, (e) crimping the drawn filaments using a mechanical crimper at a crimp level of 8 to 30 crimps per inch (3 to 12 crimps/cm), (f) relaxing the crimped filaments at a temperature of 50 to 120 a c, and (g) cutting the relaxed filaments into staple fibers, preferably having a length of 0.2 to 6 inches (0.5 to 16 cm).
  • the drawn filaments are annealed at 85 to 115" C. before crimping.
  • annealing is carried out under tension using heated rollers.
  • the drawn filaments are not annealed before crimping, Stapl fibers are useful in preparing textile yarns and textile or nonwoven fabrics, and can also be used for fiberfiil applications and making carpets.
  • the filaments can be round or have other shapes, such as octa!oba!, delta, sunburst (also known as sol), scalloped oval, triloba!, tetra-channel (also known as quaira-channej), scalloped ribbon, ribbon, starburst, etc. They can be solid, hollow or multi-hollow.
  • the invention provides a fabric comprising a filament comprising a composition comprising 0,1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy(ifimethyiefte arylate) wherein the filament is
  • the poly(tnmeihyiene arylate) is poly(trimethyiene
  • the filaments are bundled into yarns, and the fabric is a woven fabric.
  • the filaments are bundieci into at least one yarn, and the fabric is a knit fabric, in stiil another embodiment, the fabric is a nonwoven fabric; in a further embodiment the fabric is a spunhonded fabric.
  • a nonwoven fabric is a fabric that is neither woven nor knit.
  • Woven and knit structures are characterized by a regular pattern of interlocking yarns produced either by interlacing (wovens) or looping (knits), in both cases, yarns follow a regular pattern that takes them from one side of the fabric to the other and back, over and over again.
  • the integrity of a woven or knitted fabric is created by the structure of the fabric itself,
  • nonwovens most commonly filaments are Said down in a random pattern and bonded to one another by chemical or thermal means rather than mechanical means.
  • One commercially available example of a nonwoven produced by such means is Sontara 3 ⁇ 4 Spun-Bonded Polyester available from the DuPont Company, in some cases nonwovens can be produced by laying down layers of fibers in a complex three dimensional topological array that does not involve interlacing or looping and in which the fibers do not alternate from one side to the other, as described in
  • Woven fabrics are made with a plurality of yarns interlaced at right angles to each other.
  • the yarns parallel to the length of the fabric are called the "warp” and the yarns orthogonal to that direction are cai!ed the Tilling" or “weft.”
  • Each warp yar is called an "end.”
  • vast variations in aesthetics can be achieved by variations in the specific ways the yarns are interlaced, the denier of the yams, the aesthetics, both tactile and visual, of the yarns themselves, the yarn density, and; the ratio of warp to filling yarns.
  • the structure of a woven fabric imparts a certain degree of rigidity to the fabric; a woven fabric does not in general stretch as much as a knitted fabric,
  • the warp comprises yarns comprising a filament comprising a composition comprising 0.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy(trimethylene arylafe) wherein the filament is characterized by a denier per filament of ⁇ 3, a denier coefficient of variation of ⁇ 2.5 % and a birefringence of at least 0 055.
  • the poly(irimethylene arylafe) is
  • both the warp and fill comprise yarns comprising the filament hereof, in one embodiment, the warp comprises at least 40 % by number of yams comprising the filament hereof and at least.40 % by number of cotton yams, in one embodiment the warp comprises at least 80% by number of yarns comprising the filament hereof, and the fiii comprises at least 80 % cotton yarn.
  • the warp comprises at least 40 % by number of yams comprising the filament hereof and at least.40 % by number of cotton yams
  • the warp comprises at least 80% by number of yarns comprising the filament hereof
  • the fiii comprises at least 80 % cotton yarn.
  • FIG 3a is a schematic depiction of an embodiment of a loom, shown in side view.
  • a warp beam, 31 made up of a plurality, often hundreds, of parallel ends, 32, is positioned as the loom feed.
  • Warp beam, 31, Is shown in front view in Figure 3b. Shown i Figure 3a is a two harness loom.
  • Each harness, 34a, and 34b is a frame that holds a plurality, often hundreds, of so called “heddles.”
  • FIG 3c showing a front, blowup view of a harness, 34, each hedd!e,311 : is a vertical wire having a hole, 312, in it The harnesses are disposed to move up or down, one moving up while the other moves down. A portion of the ends, 33a, are threaded through the holes, 312, in the heddles, 311 , of upper harness, 34a while anothe portion of the ends, 33b, are threaded through the holes in the heddles of lower harness, 34b, thereby opening up a gap between the ends 33a and 33b.
  • a shuttlecock 38
  • the shuttlecock carries a bobbin of fiiier yarn, 37 that unwinds as the shuttlecock moves through the gap in the warp ends,
  • a socalled “reed” or “batten,” 35 is a frame that holds a series of vertical wires between which the ends pass freely.
  • Figure 3d shows the reed, 35, in front view depicting the vertical wires, 313, and the spaces between, 314, through which the warp yarns pass.
  • the thickness of the vertical wires, 314, determines the spacing of and therefore density of warp yarns in the crossfabric direction .
  • the reed serves to push the newly inserted filler yarn to the right in the diagram into place in the forming fabric, 38.
  • the fabric is wound onto the fabric beam, 310.
  • the ro!is, 39, are guide roils.
  • the winding of a warp beam is a precision operation in which typically the same number of yarn packages or spools as the desired number of ends are mounted on a so-called creel, and each end is fed onto the warp beam through a series of precision guides and tensioners, and then the entire warp beam is wound at once.
  • the specific patterns of interlacing, ratios of warp to fili yarns determine the typ of woven fabric prepared.
  • Basic patterns include plain weave, twill weave, and satin. Numerous other, fancier woven patterns are also known.
  • Knitting is the process by which a fabric is prepared by the interlooping of one or more yarns. Knits tend to have more stretch and resilience than wovens. Knits tend to be less durable than wovens. As in the case of wovens, there are many knit patterns, and styles of knitting. According to the present invention, in one embodiment the fabric hereof is a knit fabric comprising yarns comprising a filament comprising a composition comprising 0,1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in
  • poly ⁇ tri methylene arylate wherein the filament is characterized by a denier per filament of ⁇ 3, a denier coefficient of variation of ⁇ 2.5 % and a birefringence of at least 0.055, in one embodiment, the poiy ⁇ trimethyiene arylate) is poiy ⁇ trtmethylene terephthalate).
  • the garments hereof comprise a fabric comprising yarns comprising a filament comprising a composition comprising 0.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy(trimeihylene arylate) wherein the filament is characterized by a denier per filament of ⁇ 3, a denier coefficient of variation of ⁇ 2.5 % and a birefringence of at least 0,055.
  • th poly(trimethy!ene arylate) is
  • the fabrication of garments from fabrics is extremely well- known art.
  • the preparation of a garment from a fabric includes preparing a pattern, usually from paper, or in computerized form for automated processes, measuring the required fabric pieces, cutting the fabric to prepare the needed pieces, and then sewing the pieces together
  • a garment may be made exclusively one or more styles of the fabric of the invention.
  • a garment may be prepared fay combining one or more styles of the fabric of the invention with other fabrics.
  • the intrinsic viscosity (IV) of the PTT was determined using a Viscotek Forced Flow Viscometer Y9Q0 ⁇ Viscotek Corporation, Houston, Tex.) Following the procedures of ASTM D-5225-92, a 0.4 g/dS solution of PTT was formed in a 50/50 vveight solvent mixture of trifluoroacetic acid and methylene chloride at 19 a C. and the viscosity determined. These measured IV values were correlated to IV values measured manually in 60/40 weight % phenoS/1,1 ,2,2-tetrachloroethane following ASTM 0 4603- 98.
  • the number average molecular weight of polystyrene was determined following ASTM D 5298-97, The same method was used fo poSyitri methylene terephihaiate) except that the calibration standard was a polyietfiyiene terephthalate) with an M w of 44,000 and
  • Fiber spinning was performed in four separate campaigns. As described in greater detail intra, Campaigns #1 , 3, and 4 were executed on Spinning Machine #2, while Campaign #2 was executed on Spinning Machine #1.
  • Figur 5 is a graph showing the denier CV versus first godet temperature wherein all of the data obtained from Campaigns 1 ,3, and 4 are combined together and plotted with a diamond shape, and the data from Campaign #2 is graphed using a triangle shape.
  • Tables 3 - 8 infra, not alt data points obtained in the three campaigns wherein Spinning yachine #2 was employed were obtained using the same set of spinning conditions. Nevertheless, as seen in Figure 5, the data from Spinning Machine #2, shown as diamond shapes, showed a clear trend, where first godet temperature i the range of ca. 75 to 85 *C corresponded to a minimum in denier CV. A similar trend was not observed in the data of Campaign #2.
  • Denier coefficient of variation is a measurement of short distance denier variability, which is in turn, an indicator of the stability of the melt spinning process.
  • the melt spinning process can be unstable because the spinning composition causes an instability, it can also be unstable because the machine is unstable. It is dear from Figure 5 that in this case the high denier CV produced in Campaign #2 was an artifact of the machine performance and design.
  • Spinning Machine #1 was a laboratory-built spinning machine provided with only the most basic equipment to effect me!t spinning. Spinning Machine #1 was employed normally only to obtain the most basic information about whether or not experimental compositions were capable of being melt-spun into fiber. It was employed in Campaign #2 herein because of a scheduling mix-up - Spinning Machine #2 was not available on the day scheduled for Campaign #2.
  • Spinning Machine #2 was a pilot plant spinning line. Conditions thereon were fully scalable to full-size commercial scale spinning lines. This was the spinning line of choice for demonstrating the differences in results that are characteristic of the invention.
  • FIG. 4 schematically depicts Spinning Machine #2.
  • a silo drier, 41 gravity fed a single screw extruder, 42, with dried resin blend pellets.
  • the output of the single screw extruder, 42 was fed directly, under pressure, to the input of a gear pump f 43, provided with an overflow port, 44.
  • the output of the gear pump was supplied via a short (inches long) transfer line, 45, to a six end spin pack, 46. of which four ends were used.
  • Each of four threadiines 47 (one shown), was extruded from a 36 hole spinneret, (not shown) whereof each hole was characterized by a round cross-section of 0.27 mm diameter and 0.50 mm in length.
  • Each threadline, 47. passed through a cross-flow quench air zone approximately 1 ,75 m in length, 48, with ambient air flowing across the threadline from one side to another in campaign 1 and a radial quench air zone
  • each thus quenched threadline was contacted to a finish roll, 49, and then wrapped 8-8 times around a first heated godet (feed roll), 410, and a corresponding first separator roil, 411 , to keep the threadiines apart.
  • the threadline was then directed to a second heated godet (draw roil), 412, and a second corresponding second separator roll 413, through an interlace jet (not shown) and thence to a windup, 414, Also not shown, each Godet was partially enclosed by a hot chest to maintain temperature.
  • the extruder was provided with 3 heating zones, and a head zone at the output.
  • Spinning Machine #1 and Spinning Machine #2 were substantialiy the same in regard to the layout described i Figure 4. Once difference was that the quench air chimney in Spinning Machine #1 was much narrower than its counterpart on Spinning Machine #2.
  • the extruder had a 30 mm diameter barrel constructed with 3 barrel sections provided in alternating arrangement wit two kneading zones and three conveying sections, the extruder having an L/D ratio of 32. Each barrel section was independently heated. Sections 1 -4 were set at 25°C, Sections 5-13 were set at 21 Q°C, the 3/18 s strand die was also set at 210°C. A vacuum was applied to barrel segment 3. Table 1 also shows the composition of the feed, the rate of output and the melt temperature. The extrudate was quenched in water immediately upon exiting the die and was then peiietszed using standard pelieiizing equipment into 1/8 * pellets.
  • the melt compounded peliets of the PTT/PS blend so prepared were dried in a drying silo overnight at 140°C to lower the moisture content to ⁇ 50 ppm.
  • the dried melt blends were gravity fed to the single screw extrude described supra, in Figure 4, of Spinning Machine #2. Extruder set points, in *C, in zones 1-3 were respectively 230/255/263,
  • the extruder output was melt-fed to the spin pack through a gear pump.
  • the spin pack was provided with six spinning positions of which four were provided with spinnerets each spinneret having 36 holes, each hole being 0,27 mm in diameter and 0.5 mm in length , and of circular cross-section.
  • Each yarn so produced was a 75 denier 36 filament yarn.
  • the settings of the first godet roli are shown in Table 3, Note that the second godet roil was maintained at 110 °C and 4500 rpm.
  • the quench air was a cross-flow quench with an air velocity of 0.35 cm s.
  • the protocol that wa followed was as follows: The second godet roll (draw roll) was set at 4500 m min and 1 10 9 C, and was not changed in the course of the experiments. Experiments were then conducted with the first godet roll (feed roll) set at 80 S C and the speed was varied in order to identify a draw ratio that resulted in the highest tenacity when elongation to break was adjusted to be in the range of 55 - 65 %, For Polymer Blend #2 (0.055 % PS) a draw ratio of 2.00 was found to result in the highest tenacity when elongation to break was within the desired range (i.e., the feed roil was set at 2150 m/min).
  • the melt compounded peiiets of the PTT/PS blend so prepared were dried in a drying silo overnight at 140 °C to lower the moisture content to ⁇ 50 ppm.
  • the dried melt blend pellets were gravity fed to the single screw extruder described supra, in Figure 4, of Spinning Machine #1. Extrude set points, in °C ⁇ in zones 1 -3 were respectively
  • the extruder output was melt-fed to the spin pack through a gear pump.
  • the spin pack was provided with six spinning positions of which four were provided with spinnerets eac spinneret having 36 holes, each hole being 0.27 mm in diameter and 0,5 mm in length, and of circular cross-section.
  • Each yarn so produced was a 75 denier 38 filament yarn.
  • the settings of the first godet roil are shown in Table 4. Note that the second godet roll was maintained at 1 10 °C and 4500 rpm.
  • the quench air was a cross-flow quench with an air velocity of 0.35 era's.
  • the protocol that was foifowed was as follows: The second godet roll (draw roll) was set at 4500 m/min and 110 , and was not changed in the course of the experiments. Experiments were then conducted with the first godet roli (feed roll) set at 60 and the speed was varied in order to identify a dra ratio that resulted in the highest tenacity when elongation to break was adjusted to be in the range of 56 - 65 %. The followed for Polymer Blend #1 (0.8% PS) was: a draw ratio of 2.37 was found to result in the highest tenacity when elongation to break was within the desired range (i.e., first godet roll speed-1900 m/min).
  • Melt spinning was effected using the same spinning machine procedures and settings as described for Campaign #1 , supra, except that in these examples a 75 denier/36 filament yarn was spun and the quench was a radiai quench. Spinning conditions are shown in Table 3 and Table 5. Again the extruder heating zones were set respectively to 230/255/283 S C. Spinneret diameter was 0.27 mm. Flow rates were controlled to 3 5 g/min. Results are shown in Table 5.
  • a third blend of 0.8 % PS in PTT was made in a manner identical to that of Blend #2, described supra.
  • Melt spinning was effected using the same spinning machine procedures and settings as described for Campaign #3, supra, except that in these examples a 75 denier/72 filament yam was spun. Spinning conditions are shown in Table 3 and Table 6. Again the extrude heating zones were set respectively to 230/255/283 C. Spinneret diameter was 0.27 mm. Flow rates were controlled to 37.5 g/min except where noted in

Abstract

A fine denier poly(trimethylene arylate) spun drawn fiber is characterized by high denier uniformity. A process for preparing uniform fine denier yarns at spinning speeds of 4000 to 6000 m/min is further disclosed. The poly(trimethylene arylate) fiber hereof comprises 0.1 to 3% by weight of polystyrene dispersed therewithin. Fabrics prepared therefrom are also disclosed.

Description

TITLE
PROCESS FOR PREPARING POLY (TRIMETHYLENE ARYLATE) FIBERS
FIELD OF THE INVENTION This invention relates to a process for spinning
poiy{irimeinyiene aryiate) fibers, the resultant fibers, and their use.
BACKGROUND
Folyftri methylene aryiate). particularly po!y(trimeihyiene terephthalate) (also referred to as 3GT, Triexfa or PTT), has recently received much attention as a fiber-forming polymer useful in textiles, PTT fibers have excellent physical and chemical properties. Continuous
textured polyester yarns, prepared from partially oriented polyester yarns (POY) or spun drawn yarns (SDY), mostly polyethylene terephthalate
(PET), are in wide-spread commercial use in many textile applications, such as knit and woven fabrics, as well as non-woven fabrics, such as spunbonded PET. The textile term "yarn" refers to a bundle of individual fibers. For example, shirts and blouses are often made from yarns mad up of bundles of 30-40 filaments.
Polyester yarns, including both PET and PTT yarns, are prepared by a so-called melt spinning process, and are said to be "melt spun." Melt spinning is a process whereby the polymer is melted and extruded through a hole in a so-called spinneret. In typical textile
applications, the spinneret is provided with a plurality of holes, often 3D ~ 40, eac about 0,25 mm in diameter. Multiple filaments are thereby exiruded from a single spinneret. Those filaments are combined to form a bundle that is called a yarn.
Polyester yarns can be used in any combinations with or without other types of yams. Thus, polyester yams can make up an entire fabric, or constitute the warp, weft or fill, in a woven fabric; or as one of two or more yarns in a yarn b!end, for instance, with cotton, wool rayon, acetate, other polyesters, spandex and/or combinations thereof.
Fujimoto et a!., U.S. Pat, 6,284,370, discloses a process for preparing 1 -2 dp!" PIT fibers wherein a first roll is heated to 30-80 °C( a second roi! is heated to 100-160 *C,. and the draw ratio imposed between the first and second roils was is in the range of 1.3-4, in 13 examples and 1 1 counterexamples, Fujimoto never heated the fi st roil to a temperature above 60 C except in one counterexample, in ail the example, the first roll temperature was in the range of 60-60 ftC.
Ding, US, Pat. 7,785,507, discloses a process for preparing
2-3 dpf PTT fibers wherein a first godet is heated to 85-1 SO^C, a second godet is heated to 125-195°CS and the draw ratio imposed between the first and second roils was in the range of 1.1-2. Ding teaches that a first godet temperature of 75 °C caused excessive line breaks, liste results were ca. 0.90-0.95 %. In all the examples, the temperature of the first godet was 90 *C or more.
Howell et al., U.S. Pat. 8,287,688, describes preparation of textured PTT yarns that exhibit increased stretch, luxurious bulk and improved hand, as compared to PET yarns. Howell et at. describes preparing partially oriented; PTT yarns at spinning speeds up to 2600 m m. By contrast, PET is routinely melt spun at several times that speed. For reasons of cost, it is highly desirable to be able to spin PTT yams at speeds higher than 2800 m/min.
Chang et al,, U.S. Patent 8,923,925, discloses a composition comprising PTT containing about 2% polystyrene (PS) that can be melt spun into spun drawn yarns at speeds up to 5000 m/min. Chang et al. is completely silent in regard to the denier uniformity (Denier CV) of the yarns so produced, and silent as well regarding the temperatures of the godet rolls employed for preparing the spun drawn yarn
There is a need for a Sow denier spun-drawn filament yarn of
PTT that can be spun at commercially viable spinning speeds and that is
? of sufficient denier uniformity to have practical utility in the preparation of high quality fabrics and garments.
SUMMARY' OF THE I VENTION In a first aspect, the present invention provides a filament comprising a composition comprising 0,1 to 3% by weig t of polystyrene, based on the total weight of the polymer in the composition, dispersed in poly(trtmethy!ene aryiate) wherein the filament is characterized by a denier per filament of≤ 3, a denier coefficient of variation of≤ 2,5 % and a birefringence of at least 0,055.
In one embodiment, the poly(trlmethylene aryiate) is poly{tri methylene terephthalate).
in another aspect, the present invention provides a process for forming a novel spun drawn filament characterized by a denier per filament of≤ 3, and a denier coefficient of variation of≤2.5> the process comprising extruding a polymer melt comprising 0.1 to 3 % by weight, based on the total weight of polymer, of polystyrene dispersed in poiy{tri methylene aryiate), through an orifice having a cross-seetionai shape, thereby forming a continuous filamentary extrudate, quenching the extrudate to solidify it into a continuous filament, wrapping the filament on a first driven roll heated to a temperature in the range of 70 to 100 °C and rotating at a first rotational speed, followed by wrapping the filament on a second driven roll heated to a temperature i the range of 100 to 130 CC and rotating at a second rotational speed; and, winding said filament onto a take-up roll at a linear speed of at least 4,000 meters/minute (rcVmin); wherein the ratio of the first rotational speed to the second rotational speed lies in the range of 1.75 to 3; thereby forming a spun drawn filament having a denier per filament of≤ 3, and a denier coefficient of variation of 2 5 %.
In one embodiment the poSy(trimethylene aryiate) is poiyftrimethy!ene terephthalate). In another aspect, the present invention provides a fabric comprising a filament comprising a composition comprising 0.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poly{tri methylene arylate) wherein the filament is characterized by a denier per filament of≤ 3. a denier coefficient of variation of≤ 2.5 % and a birefringence of at ieast 0.955.
fn one embodiment the poiy(trimethyiene arylate) is poiy{trimetbyle:ne terephthaSate).
B iEF DESCRJPTiO OF THE DRAWING
Figure 1 is a schematic representation of one embodiment of melt feeding a spinneret according to the invention.
Figure 2 is a schematic representation of one embodiment of the fiber spinning process according to the invention.
Figure 3 depicts a ioom suitable for fabricating a woven fabric of the invention.
Figure 4 is a schematic representation of the spinning machines employed in the Examples.
Figure 5 is a graph of the experimental results, showing the effect of the temperature of the first godet on the denier coefficient of variation, and contrasting the results obtained using Spinning Machine #2 with those obtained using Spinning Machine #1.
P E JAi L£ O D E SC R jfiTlO QF TH E I VE TiQrj in one aspect, the present invention is directed to a filament comprising a composition comprising J3.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy{trimethyiene aryiate) wherein the filament is characterized by a denier per filament (dpf) of≤ 3, a denier coefficient of variation (denier CV) of≤ 2.5 % and a birefringence of at least 0,055.
In one embodiment, the poiy(thmethylene arylate) Is poiy(trimethyiene terephthaSate), In one embodiment the filament hereof is a continuous filament In an alternative embodiment, the filament hereof is a staple filament. In one embodiment, a plurality of the filaments hereof are combined to form a multifilament yarn. The multifilameni yarn thus formed is suitable for for texturing, and for end uses in those textile applications in which fine denier yarns are desirable, such as shirts, blouses, lingerie, hosiery and the like.
The multifilament yarn hereof . is useful for forming knitted, woven, and non-woven fabrics by methods known in the art.
In an alternative. embodiment, the filament hereof is also suitable for use in a wide variety of non-woven constructions. The filament hereof can be arrayed in a random or quasi-random web to form a filamentary non-woven fabric. In a further embodiment, the filamentary non-woven fabric comprises a plurality of continuous filament strands hereof. In an alternative further embodiment, the filamentary non-woven fabric comprises a single continuous filament strand. In an alternative embodiment, the filamentary non-woven fabric comprises a plurality of staple filaments prepared from the filament hereof, A filamentary non- woven fabric for the purposes of the present invention is a non-woven fabric whereof the fundamental structural element is a single randomly or quasi-random!y disposed filament segment rather than a multi-filament yam segment.
in another aspect, the present invention provides a process for forming a novel spun draw filament characterized by a denier per filament of≤ 3, and a denier coefficient of variation of≤2,5 %, the process comprising extruding a polymer melt comprising 0.1 to 3 % by weight, based on the total weight of polymer, of polystyrene dispersed in poiy{tri methylene arySate), through an orifice having a cross-sectional shape, thereby forming a continuous filamentary extrudate, quenching the extrudate to solidify it into a continuous filament, wrapping the filament on a first driven roll heated to a temperature i the range of 70 to 100 °C and rotating at a first rotational speed, followed by wrapping the filament on a second driven roil heated to a temperature in the range of 100 to 130 °G and rotating at a second rotations! speed; and, winding said filament onto a take-up roll at a linear speed of at feast 4,000 meters/minute (m min); wherein the ratio of the first rotational speed to the second rotational speed iies in the range of 1.75 to 3.
As demonstrated in the examples presented infra, the denser CV of yarns of≤ 3dpf when spun at speeds of 4,000 m/min or more when the first godet is set above 70 0C is conspicuously iower than that of yarns of comparabie composition spun at the same speeds when the first godet is set at the commercially typical temperature of 80 "C.
The term "denier coefficient of variation" (denier CV) refers to the coefficient of variation in denier determined by a Uster Yarn Evenness tester availabl from Uster Technologies. The so called "Uster Tester" measures denier variation along the length of a single continuous strand of fiber or yarn. The denier CV is a standard statistical parameter that represents the value obtained by dividing the standard deviation of the denier by the mean denier, determined from the Uster Tester.
I the present invention concentrations are stated in terms of percentages by weight unless otherwise stated, in particular, it sha l be understood that the concentration of polystyrene blended with the poly{trimethySene terephthalate) or other poly(trimethylene arylate j hereof is expressed as the percent by weight of polystyrene relative to the total weight of polymer in the composition.
Whe a range of numerical values is provided herein, it snail be understood to encompass the end-points of the range unless
specifically stated otherwise. Numerical values are to be understood to have the precisio of the number of significant figures provided as described in AST E29-08. For example, the number 3 shall be understood to encompass a range from 2.5 to 3,4, whereas the number 3.0 shall be understood to encompass a range from 2,95 to 3.04.
For the purposes of the present invention, the description shall be directed at those embodiments in which the poiy(trimethyiene arySate) is poly(tnmethyietie terephthalate) (PIT) unless otherwise explicitly stated. Extension of the invention to other poly(trimethyiene arylates) shall be made with adjustments in concentration b weight appropriate to differences in the molecular weight of the particular arylate monomer units involved, assuming equal degrees of polymerization.
Both homopolymers and copolymers of both polystyrene and PTT are suitable for use in the present invention. For the purposes of the present invention, it shall be understood that the term "copolymer" encompasses not only copolymers, but terpolymers, tetrapoiymers and so forth. The term "copolymer* shall be understood to encompass any number of monomers polymerized together. For practical purposes, the vast majority of applications are limited to homopolymers, dipolymers, and terpolymers.
I one embodiment, the filament comprises a composition comprising 97 to 99.9 wt% of PTT and 3 to 0.1 wt% polystyrene (PS). In another embodiment, the filament comprises a composition comprising 70 to 99.5 wt% of PTT, 3 to 0.5 wt% of PS, and, optionally, up to 20.5 wt% of other polyesters. In another embodiment, the filament comprises a composition comprising 98 to 99.5 wt% of PTT and 2 to 0.5 wt% PS.
In one embodiment, the filament consists essentially of a composition consisting essentially of 97 to 99.9 vvt% of PTT and 3 to 0.1 wt% polystyrene (PS), in another embodiment, the filament consists essentially of a composition consisting essentially of 70 to 99.5 wt% of PTT, 3 to 0.5 wt% of PS and. optionally, up to 29.5 wt of other polyesters. I another embodiment, the filament consists essentially of a composition consisting essentially of 98 to 99,5 wt% of PTT and 2 to 0.5 wt% PS.
Suitable PTT polymer is formed by the condensation polymerization of 1 , 3-propanediol and terephthalic acid or
dimeihylterephthalafe. One or more suitable comonomers for
copoiymerization therewith is selected from the group consisting of linear, cyclic, and branched aliphatic dicarboxySic acid or esters having 4-12 carbon atoms (for example butanedioic acid, pentanedioic acid, hexanedioic acid, dodeeanedioic add, and l ^-cyciohexanedicarboxyiic acid, and their corresponding esters); aromatic dicarboxySic adds or esters other than terephthaiic acid or ester and having 8-12 carbon atoms (for example isophtha!ic acid; and 2,8-naphthatenedicarboxylic add); linear, cyclic, and branched aliphatic diois having 2-8 carbon atoms (other than 1 ,3-propanediol) for example, ethanediol, 1 ^-propanedioi, 1 ,4-butanediol, 3~methyi-1 ,5-pentanedioi, 2;2-dimethyl-1 ;3-propanedio!, 2-methy!-1 ,3- propanedioi, and 1 ,4-cyclohexanedioi; and aliphatic and aromatic ether glycols having 4-10 carbon atoms, fo example, hydroquinone bis(2 - hydroxyethyS) ether, or a poly (ethylene ether) glycol having a molecular weight below 460, including diethyieneeiher glycol. The comonomer typically is present in the PTT copoiymer at a level in the range of 0,5- 15 mol %, and can be present in amounts up to 30 mole %.
The PTT can contain minor amounts of other comonomers selected so that they do not have a significant adverse affect on properties. Such other comonomers include 5-sodium-suifoisophthalate, for example, at a level in the range of 0.2 to 5 mole %. Very small amounts of trifunetional comonomers, for example trimellitic acid, can be incorporated for viscosity control. The PTT can be blended with up to 30 mole percent of other polymers. Examples are polyesters prepared from other diols, such as those recited supra.
In one embodiment, the PTT contains at least 85 mo!- of trimethyiene terephth late repeat units. In a further embodiment, the PTT contains at least 90 moi-% of tri methylene terephthalate repeat units. In a still further embodiment the PTT contains at least 98 moS- % of of
trimethyiene terephthalate repeat units. In a still further embodiment the PTT contains 100 moJ % of trimethyiene terephthalate repeat units.
In one embodiment suitable PTT is characterized by an intrinsic viscosity (IV) in the range of 0 JO to 2.0 dl/g. In a further embodiment, suitable PTT is characierized by an IV in the range of 0.80 to 1 ,5 di/g. in a still further embodiment, suitable PTT is characterized by an IV in the range of 0.30 to 1.2 di/g.
in one embodiment suitable PTT is characterized by a number average molecular weight (M„) in the range of 10,000 to 40,000 Da. In a further embodiment suitable PTT is characterized by (V1n in the range of 20,000 to 25,000 Da.
in one embodiment, a suitable polystyrene is selected from the group consisting of polystyrene homopolymer, a-methy!-polystyrene, and styrene-butadiene copolymers, and blends thereof, in one
embodiment, the polystyrene is a polystyrene homopolymer. In a further embodiment/the polystyrene homopolymer is characterized by r in the range of 5,000 to 300,000 Da. In a still further embodiment, Mr. of the polystyrene homopolymer is in the range of 50,000 to 200,000 Da. in a still further embodiment Mr. of the polystyrene homopolymer is in the range of 75,000 to 200,000 Da. In a still further embodiment, M„ of the polystyrene homopolymer is in the range of 120,000 to 150,000 Da. Useful polystyrenes can be isotactic, atactic, or syndiotactic. High molecular weight atactic polystyrene homopolymer is preferred.
.Polystyrenes useful in this invention are commercially available from many suppliers including Dow Chemical Co. (Midland, Mich.}, BASF (Mount Olive, N.J. ) and Sigma- A!drich (Saint Louis, Mo.).
PTT and PS are melt blended and, then, extruded in the form of a strand that is subsequently cut into pellets. Other forms of melt blending and subsequent comminution, such as into flake, chips, or powder, can also be performed. Under some circumstances it may be convenient to prepare pellets comprising a first PTT/PS blend with a concentration of PS greater than 5% fo!loweb by remelting the pellets and diluting the remelf with additional PTT to form a second melt blend having a concentration of PS that is≤ 3 %, and to extrude the second melt blend into the filament hereof.
The filament hereof comprises a composition comprising PTT and PS. in some embodiments, these will be the only two materials in the blend and they will total 100 weight %. However, in many instances the blend will have other ingredients such as are commonly included in polyester polymer compositions in commercial use; Such additives include but are not limited to other polymers, plasficizers, UV absorbers, flame retardants, dyestuffs, and so on. Thus the total of the
poly(tri:methyiene terephthaiate) and polystyrene will not be 100 weigh %, Other polymers can include for example polyamides that impart acid dyeabi!ity to the yarn blend. In those instances in which additional, non- polyester, polymers are added, the ratios of polyester to PS weight percent concentrations remain the same as for those compositions that do not include the other polymers.
According to the present invention, the PS is In the form of particles having an average size of less than S00 nanometers. In one embodiment, the polystyrene is polystyrene homopo!ymer at a
concentration of≤ 2 %; and, the pol (trimethy!ene aryiafe} is PIT comprising at least 98 mol of trimeihylene terephthaiate monomer units.
The filament of the present invention is characterized by a dpi≤ 3, a denier CV of≤ 2,5 %, and a birefringence of at least 0.055. Typical physica! properties of the filament hereof include a tenacity above 3 grams per denier, and an elongation to break of 30 to 70%. In one embodiment, the filament denier is≤ 2.5. in another embodiment, the birefringence is at least 0.060.
in another aspect, this invention is directed to a process for preparing a single or multifilament yarn comprising (a) preparing a melt blend consisting essentially of" PTT and 0,1 to 3 weight % (wt%) polystyrene (PS)S (b) melt spinning the polymer melt blend so prepared to form on or more filaments of PTT containing dispersed PS.
The filament of the present invention Is conveniently prepared as a spun drawn filament - that is, a filament that has been fully drawn in the spinning process. By fully draw is meant that the filament after quenching has been elongated close to the ultimate elongation to break thereof. Preferably, the spinning comprises extruding the polymer blend hereof through the one or more holes of a spinneret at a spinning speed of at least 4,000 tn m. The term "spinning speed" refers to the rate of spun fiber accumulation, such as on a mechanical wind-up.
The high birefringence of ¾ 0.055 that is characteristic of the filament of the invention is a direct result of the high draw applied to the filament in the spun-draw process. High birefringence is a principle way of distinguishing spun-drawn filaments from partially-oriented spun yarn that is subsequently draw-textured.
Figure 1 is a schematic representation of one embodiment of a melt spinning machine suitable for use in the present invention.
Referring to Figure 1 , PTT is produced in a continuous melt poiymerizer, 1 , from which it is conveyed i molten form via transfer Sine, 2, to a counter-rotating twin-screw extruder, 3, the twin screw extruder being provided with a . mixing zone. Simultaneously, pellets comprising PS are fed via a weight-loss feeder, 4, or other pellet feeder means, to a satellite extruder. 5, wherein the pellet is melted and fed i molten form via transfer line, 6, to twin-screw extruder, 3, either at or upstream from the mixing zone of the tw -screw extruder, 3. I the twin-screw extruder a PTT/PS melt blend is formed. The resulting meit blend is fed via transfer line, 7t to a spin block comprising a spinneret, 8, from which one or more continuous filaments, 9, are extruded.
Figure 2 depicts one suitable arrangement for melt spinning according to the invention, 34 filaments 22, (all 34 filaments are not shown) are extruded through a hole spinneret 21. The filaments pass through a cooling zone 23, are formed into a yarn bundle, and passed over a finish applicator 24, The cooling zone comprises an air quench zone wherein air is impinged upon the yam bundle at room temperature and at 80% relative humidity with a velocity of 40 feet/mi . The air quench zone can be designed for so-eailed cross-air-quench wherein the air flows across the yarn bundle, or for so-called radial quenc wherein the air source is in the middle of the converging filaments and flows radially outward over 380 *. Radial quench is a more uniform and effective quench method. Following the finish applicator 24, the yarn is passed to a first driven godet roll 25, also known as a feed roll, set at 60 to 100 °C, in one embodiment, 70 to 100 *C, coupied with a separator roll. The yarn is wrapped around the first godet roli and separator roil 8 to 8 times. From the first godet roll, the yarn is passed; to a second driven godet roil, also known as a draw roil set at 1 10 to 130 cCf coupled with a second separator roil. The yarn is wrapped around the second godet roli and separator roil 6 to 8 times. Draw roli speed is 4000 to 8000 m/min while the ratio of draw roll speed to feed roil speed is in the range of 1.75 to 3, From the draw roils, the yarn is passed to a third driven godet roli 27, coupled with a third separator ro!i, operated at room temperature and at a speed 1-2% faster than the roll speed of the second godet roil The yarn is wrapped around the third pair of rolls 6 to 10 times. From the third pair of roils, the yarn is passed though an interlace jet 28. and then to a wind- u 29, operated at a speed to match the output of the third pair of roils.
Referring to Figure 2, according to the process hereof, a quenched filament is wound at least once but preferably a plurality of times around the first godet roll so that the first godet roll appiies a drawing force on the extruded filament, causing it to draw down before quenching; down stream from the first godet roli, the filament is wrapped at least once but preferably a plurality of times around a second godet roll in such manner that the second godet appiies a drawing force on that portion of the filament lying between the first and second godet rolls. In the embodiment depicted in Figure 2, from the second godet roll, the filament is directed to a third godet roll which serves as a Set down roli, running at a speed 1-2% higher than that of the second (draw) godet roil. From the third godet, the filament is directed to a wind-up. The rate at which the filament is wound on the wind-up is described as the spinning speed. In typical installations, the wind-up is a tension controlled wind-up.
According to the present invention, the first godet roll is heated to a temperature in the range of 70-100 °C and the second godet roil is heated fo a temperature in the range of 100 - 130 SC, The first godet roll Is driven at a first rotational speed; the second godet roll is driven at a second rotational spaed. According to the present invention the ratio of the second rotational speed to the first rotational speed (the draw ratio) falls within the range of 1.75 to 3.
In one embodiment, a plurality of filaments, each individually of the invention, are extruded through a multi-hole spinneret. The filaments so extruded are combined to form a yarn. Typically the yarn is held together by the application of some agitation, twisting, or both, of the extruded filaments, or thread line, causing the interlacing of the filaments. The yarn so formed comprises a plurality of filaments, each filament characterized by a dpf≤ 3, a denier CV of≤ 2.5 %, and a birefringence of at least 0.055. In one embodiment, the filament denier is≤ 2.5. In another embodiment, the birefringence Is at least 0.050. Typical yarns comprise 34, 48, 88, and 72 filaments, although the number of filaments combined to make a yarn is not limited in any way.
Yams formed according to the present invention are not limited only to be made up of a plurality of filaments according to the invention, but can contain other filaments as well. For example, a yarn formed according to the invention ca contain other filament of other polyesters as well as polyamides, polyacryiates and other such filaments as may b desired. The other filaments can also be staple fibers.
The yarn formed according to the invention, which can be formed by the spun-draw process described supra, is suitable for use as a feed yarn for false twist texturing as commonly practiced in order to provide textile-like aesthetics to continuous polyester fibers. White there are several types of texturing equipment, all well-known in the art, the texturing process comprises a) providing a yam package as formed according to the spinning process described supra: (bjunwinding the yarn from the package, (c) threading the yarn end through a friction twisting element or false-twist spindle, d) causing the spindle to rotate, thereby imparting twist in the yarn upstream of the rotating spindle and untwisting the upstream twist downstream from the rotating spindle along with the applicatio of heat; and (e) winding the yarn onto a package. The invention enables an increase in productivity in the spinning of fine denier (s 3 dpi) spun ~ drawn PIT yarns. The filament and yarn thereof of the invention have been prepared at spinning speeds that are 30 to 70 % higher than the maximum spinning speed achievable with neat PTT. The resulting yarn is characterized by an elongation and tenacity within 20% of the elongation and tenacity of a PTT multifilament yarn that only differs from the yarn of the invention in that it does not contain the PS (and that has necessarily been spun at about 3000 m/min). Thus, the yarns consisting essentially of the filaments of the invention are useful in a wide variety of textile applications with only minor adjustments needed in the textile machinery being used. The resultant yarns are useful in preparing inter a ia textured yarns, fabrscs and carpets, under the same or similar conditions to those used for PTT yarns not containing PS and prepared at" 3000 m/min.
In the filament of the invention, the PTT is a continuous phase or "matrix8 and the PS is a discontinuous phase dispersed within the PTT matrix. In one embodiment, the size of the PS particles dispersed in the PTT matrix is≤ 500 nm. In a further embodiment, the size of the PS particles dispersed in the PTT matrix is≤ 200 nm.
The beneficial features of the present invention include the ability to spin a fine denier, high strength, tough, spun drawn PTT yam at spinning speeds of 4000 m min or higher. These beneficial features depend upon both the fine particle size of PS and the volume homogeneity of the dispersion of PS in the PT that in turn depend upon the application of sufficiently high shear melt blending. There is no threshold particle size at which the spinning performance and/or physical properties of the spun yarn suddenly degrades. Rather, as the PS particle size gets larger, performance gradually deteriorates. At particle sizes in the range of 500 nm or larger, denier CV gets progressively larger. Similarly, there is no particular threshold of homogeneity In regard to particle distribution in the PTT matrix. The better the uniformity of dispersion, the more uniform the resulting spun filament will be. One particularly valuable benefit of the present invention is the production of spun-drawn yarns characterized by denier CV of less than 2.5 %, Low denier CV is especially important in the preparation of fine denie yarns for textile applications. Unless the process by which the PS is dispersed in PIT is characterized by shear forces sufficient to ensure a particle size !ess than 500 nm and a sufficiently high uniformity of dispersion, it is highly unlikely that the denier CV will be≤2,5 %.
The amount of shear force applied to the melt depends upon the rotational speed of the mixing elements, the viscosity of the melt, and the residence time of the melt in the mixing zone. If the shear forces are too low there is a tendency for the PS to not break up to begin with, or to agglomerate rapidly into droplets greater than 500 nm in size.
The meit blending process can be performed both batch- wise and continuously. So called high shear mixers such as are commonly employed in the art of poiymer compounding are suitable, Examples of suitable commercially available high shear batch mixers include, but are not limited to, Banbury mixers and Brabender mixers. Examples of continuous high shear mixers include co-rotating twin-screw extruders and Parrel Continuous Mixers Counter-rotating twin screw extruders are also suitable, in general, suitable high shear mixers are those that are capable of exerting on a polymer melt a mi imum shear rate of SO/s, with 100/s preferred. After melt blending the resulting blend can be palletized for later feeding to a spinning machine, or the melt biend can be fed directly into a spinning machine. Another useful method is to combine poiymer melts. An example of this method wou!d be to provide a PTT meit from a continuous poiyrnerizer to the first stage of a twin screw extruder, and feeding a PS meit from a satellite extruder into the mixing zone of the twin screw extruder, thereby creating a meit biend . In another method the unmeited polymers ma be dry-mixed, as by tumbling, before being fed to a twin screw extruder for melt blending.
Average particle size greater than 500 nm is not preferred from the standpoint of good fiber spinning performance. Additionally, spinning of uniform filaments, both along a single end, and end to end, depends expressly upon the homogeneity of the volume distribution of the PS partic!es. While in no way limiting the scope of the invention, it is speculated that in the actual melt processing thereof, the PS particles meit to form molten droplets that are dispersed within a molten PIT matrix.
The temperature in the melt mixer should be above the melting points of both the PTT and the PS but below the lowest decomposition temperature of any of the ingredients. Specific
temperatures wi!i depend upon the particular attributes of the polymers employed, in typical practice, meit temperature is in the range of 200 *C to 270 6C.
in one embodiment the concentration of the PS in the PTT/PS blend pellets is in the range of 0,5 to 1.5 %.
As indicated in Figure 1 , and as is generally true for meit spinning of polymer fibers, the polymer melt is fed to the spinneret via a transfer line. The melt input to the transfer line from the extruder is in turbulent However, the spinneret feed must be laminar in order to achieve uniform flow through the plurality of holes in the spinneret. It is in the transfer Sine that the melt flow shifts from turbulent to laminar.
Filament spinning can be accomplished using conventional apparatus and procedures that are in widespread commercial use. As a practical matter, it is found that for spinning fine denier filaments of 3 dpf or lower, a PS concentration of > 3% leads to a degradation in mechanical properties of the fiber so produced. It is further found that at 5% PS, fine denier filaments cannot be meit spun at all,
Prior to melt spinning, the polymer blend pellets are preferably dried to a moisture levei of <30 ppm to avoid hydroiytic degradatio during melt spinning. Any means for drying known in the art is satisfactory. In one embodiment, a closed loop hot air dryer is employed. Typically, the PTT/PS blend is dried at 130 °C and a dew point of <-40 °C for 8 h. The thus dried PTT/PS polymer blend is melt spun at 250-285 °C into fibers. in a typical melt spinning process, one embodiment of which is described in detail, infra, the dried polymer blend peliets are fed to an extruder which melts the pellets and supplies the resulting melt to a metering pump, which delivers a vo!umetrica!ly controlled flow of polymer into a heated spinning pack via a transfer line. The pump must provide a pressure of 10-20 MPa to force the flow through the spinning pack, which contains filtration media (eg, a sand bed and a filter screen) to remove any particles larger than a few micrometers. The mass flow rate through the spinneret is controlled by the metering pump. At the bottom of the pack, the polymer exits into an air quench zone through a plurality of small holes in a thick plate of metal (the spinneret). While the number of holes and the dimensions thereof can vary greatly, typically a single spinneret hole has a diameter in the range of 0.2- 0.4 mm. Spinning Is adva tageously accomplished at a spinneret temperatur of 236 to 295 °C, preferabl 250 to 290 9C.
A typical flow rate through a hole of that size tends to be in the range of 1-5 g min. Numerous cross-sectional shapes are employed for spinneret holes, although circular cross-section is most common.
Typically a highly controlled rotating roll system through which the spun filaments are wound controls the line speed. The diameter of the filaments is determined by the flow rate and the take-up speed; and not by the spinneret hole size.
The properties of the thus produced filaments are determined by the threadline dynamics, particularly in the region between the exit from the spinneret and the solidification point of the filaments, which is known as the quenc 2one. The specific design of the quench zone, air flow rate across the emerging still motile filaments has very large effects on the quenched filament properties. Both cross-flow quench and radial quench are in commo use. After quenching or solidification, the filaments travel at the take-up speed, that is typically 100-200 times faster than the exit speed from the spinneret hole. Thus, considerable acceleration (and stretching) of the threadline occurs after emergence from the spinneret hole. The amount of orientation that is frozen into the spun filament is directly related to the stress level in the filament at the solidification point.
The melt spun filament thereby produced is collected in a manner consistent with the desired end-use. For example, for filament intended to be converted into staple fiber, a plurality of continuous filaments can be combined into a tow thai is accumulated in a so-called piddling can. Filament intended for use in continuous form, such as in texturing, is typically wound on a yarn package mounted on a tension- controlled wind-up. According to the invention, the rate of accumulation is at least 4,000 m/min.
Texturing imparts crimp by twisting, heat setting, and untwisting b the process commonly known as false tvvist texturing. These multifilament yarns '{also known as "bundles") comprise the same numbe of filaments as the spun drawn yams from which they are made. Thus, they preferably comprise at ieast 10 and even more preferably at least 25 filaments, and typically can contain up to 150 or more, preferably up to 100, more preferably up to 80 filaments. The yarns typically have a. total denier of at least 1 , more preferably at Ieast 20, preferably t Ieast 50, more preferably up to 250, and up to 1 ,500. Filaments are preferably at least 0.1 dpf more preferably at least 0,5 dpf, more preferably a leas 0,8 dpf, and most preferably up to 3 dpi
PTT staple fibers can be prepared by melt spinning the PTT/PS- blend at a temperature of 245 to 285° C. into filaments, quenching the filaments, drawing the quenched filaments, crimping the drawn filaments, and cutting the filaments into staple fibers, preferably having a length of 0.2 to 6 inches (O S to 15 cm). One preferred process comprises: (a) providing a polymer blend comprising PTT and 0.1 to 3 % PS, (b) melt spinning the melted blend at a temperature of 245 to 285* C, into filaments, (c) quenching the filaments, (d) drawing the quenched filaments, (e) crimping the drawn filaments using a mechanical crimper at a crimp level of 8 to 30 crimps per inch (3 to 12 crimps/cm), (f) relaxing the crimped filaments at a temperature of 50 to 120a c, and (g) cutting the relaxed filaments into staple fibers, preferably having a length of 0.2 to 6 inches (0.5 to 16 cm). In one preferred embodiment of this process, the drawn filaments are annealed at 85 to 115" C. before crimping.
Preferably, annealing is carried out under tension using heated rollers. In another preferred embodiment, the drawn filaments are not annealed before crimping, Stapl fibers are useful in preparing textile yarns and textile or nonwoven fabrics, and can also be used for fiberfiil applications and making carpets.
While the invention is primarily described with respect to multifilament yarns, it should be understood that the preferences described herein are applicable to monofilaments.
The filaments can be round or have other shapes, such as octa!oba!, delta, sunburst (also known as sol), scalloped oval, triloba!, tetra-channel (also known as quaira-channej), scalloped ribbon, ribbon, starburst, etc. They can be solid, hollow or multi-hollow.
in another aspect, the invention provides a fabric comprising a filament comprising a composition comprising 0,1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy(ifimethyiefte arylate) wherein the filament is
characterized by a denier per filament of 3, a denie coefficient of variation of≤ 2,5 % and a birefringence of at least 0,055, In on
embodiment, the poly(tnmeihyiene arylate) is poly(trimethyiene
terephthaiate).
in one embodiment the filaments are bundled into yarns, and the fabric is a woven fabric. In an alternative embodiment, the filaments are bundieci into at least one yarn, and the fabric is a knit fabric, in stiil another embodiment, the fabric is a nonwoven fabric; in a further embodiment the fabric is a spunhonded fabric.
In one definition, a nonwoven fabric is a fabric that is neither woven nor knit. Woven and knit structures are characterized by a regular pattern of interlocking yarns produced either by interlacing (wovens) or looping (knits), in both cases, yarns follow a regular pattern that takes them from one side of the fabric to the other and back, over and over again. The integrity of a woven or knitted fabric is created by the structure of the fabric itself,
in nonwovens, most commonly filaments are Said down in a random pattern and bonded to one another by chemical or thermal means rather than mechanical means. One commercially available example of a nonwoven produced by such means is Sontara¾ Spun-Bonded Polyester available from the DuPont Company, in some cases nonwovens can be produced by laying down layers of fibers in a complex three dimensional topological array that does not involve interlacing or looping and in which the fibers do not alternate from one side to the other, as described in
Popper et al., U.S. Patent 6,579,815.
Woven fabrics are made with a plurality of yarns interlaced at right angles to each other. The yarns parallel to the length of the fabric are called the "warp" and the yarns orthogonal to that direction are cai!ed the Tilling" or "weft." Each warp yar is called an "end." As can be seen in any fabric or clothing store, tremendous variations in aesthetics can be achieved by variations in the specific ways the yarns are interlaced, the denier of the yams, the aesthetics, both tactile and visual, of the yarns themselves, the yarn density, and; the ratio of warp to filling yarns. As a general rule, the structure of a woven fabric imparts a certain degree of rigidity to the fabric; a woven fabric does not in general stretch as much as a knitted fabric,
in the woven fabrics of the invention, at least a portion of the warp comprises yarns comprising a filament comprising a composition comprising 0.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy(trimethylene arylafe) wherein the filament is characterized by a denier per filament of≤ 3, a denier coefficient of variation of≤ 2.5 % and a birefringence of at least 0 055. In one embodiment, the poly(irimethylene arylafe) is
poiy{i.rtmet!iySerie terephthaiate). In one embodiment, both the warp and fill comprise yarns comprising the filament hereof, in one embodiment, the warp comprises at least 40 % by number of yams comprising the filament hereof and at least.40 % by number of cotton yams, in one embodiment the warp comprises at least 80% by number of yarns comprising the filament hereof, and the fiii comprises at least 80 % cotton yarn. As a general rule, there are greater physical demands place upon warp yarns than fill yarns.
Woven fabrics are fabricated on looms, as they have been for thousands of years. While the ioom has undergone tremendous changes, the basic principles of operation remain the same. Figure 3a is a schematic depiction of an embodiment of a loom, shown in side view. A warp beam, 31 , made up of a plurality, often hundreds, of parallel ends, 32, is positioned as the loom feed. Warp beam, 31, Is shown in front view in Figure 3b. Shown i Figure 3a is a two harness loom. Each harness, 34a, and 34b, is a frame that holds a plurality, often hundreds, of so called "heddles." Referring to Figure 3c, showing a front, blowup view of a harness, 34, each hedd!e,311 : is a vertical wire having a hole, 312, in it The harnesses are disposed to move up or down, one moving up while the other moves down. A portion of the ends, 33a, are threaded through the holes, 312, in the heddles, 311 , of upper harness, 34a while anothe portion of the ends, 33b, are threaded through the holes in the heddles of lower harness, 34b, thereby opening up a gap between the ends 33a and 33b. In the type of ioom shown, a shuttlecock, 38, is impelled by means not shown » typically wooden paddles » to move or shuttle from sid to side as the harnesses move up and down. The shuttlecock carries a bobbin of fiiier yarn, 37 that unwinds as the shuttlecock moves through the gap in the warp ends, A socalled "reed" or "batten," 35, is a frame that holds a series of vertical wires between which the ends pass freely.
Figure 3d shows the reed, 35, in front view depicting the vertical wires, 313, and the spaces between, 314, through which the warp yarns pass. The thickness of the vertical wires, 314, determines the spacing of and therefore density of warp yarns in the crossfabric direction . The reed serves to push the newly inserted filler yarn to the right in the diagram into place in the forming fabric, 38. The fabric is wound onto the fabric beam, 310. The ro!is, 39, are guide roils.
The winding of a warp beam is a precision operation in which typically the same number of yarn packages or spools as the desired number of ends are mounted on a so-called creel, and each end is fed onto the warp beam through a series of precision guides and tensioners, and then the entire warp beam is wound at once.
The specific patterns of interlacing, ratios of warp to fili yarns determine the typ of woven fabric prepared. Basic patterns include plain weave, twill weave, and satin. Numerous other, fancier woven patterns are also known.
Knitting is the process by which a fabric is prepared by the interlooping of one or more yarns. Knits tend to have more stretch and resilience than wovens. Knits tend to be less durable than wovens. As in the case of wovens, there are many knit patterns, and styles of knitting. According to the present invention, in one embodiment the fabric hereof is a knit fabric comprising yarns comprising a filament comprising a composition comprising 0,1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in
poly{tri methylene arylate) wherein the filament is characterized by a denier per filament of≤ 3, a denier coefficient of variation of≤ 2.5 % and a birefringence of at least 0.055, in one embodiment, the poiy{trimethyiene arylate) is poiy{trtmethylene terephthalate).
Further contemplated in the present invention are garments sewn from fabrics of the invention. The garments hereof comprise a fabric comprising yarns comprising a filament comprising a composition comprising 0.1 to 3% by weight of polystyrene, based on the total weight of the polymer in the composition, dispersed in poiy(trimeihylene arylate) wherein the filament is characterized by a denier per filament of≤ 3, a denier coefficient of variation of≤ 2.5 % and a birefringence of at least 0,055. In one embodiment, th poly(trimethy!ene arylate) is
poly{trimethyiene terephthalate). The fabrication of garments from fabrics is extremely well- known art. The preparation of a garment from a fabric includes preparing a pattern, usually from paper, or in computerized form for automated processes, measuring the required fabric pieces, cutting the fabric to prepare the needed pieces, and then sewing the pieces together
according to the pattern. A garment may be made exclusively one or more styles of the fabric of the invention. Alternatively, a garment may be prepared fay combining one or more styles of the fabric of the invention with other fabrics.
The invention is further described in the following specific embodiments, but is not limited thereto.
EXAMPLES TEST METHODS
INTRINSIC VISCOSITY
The intrinsic viscosity (IV) of the PTT was determined using a Viscotek Forced Flow Viscometer Y9Q0 {Viscotek Corporation, Houston, Tex.) Following the procedures of ASTM D-5225-92, a 0.4 g/dS solution of PTT was formed in a 50/50 vveight solvent mixture of trifluoroacetic acid and methylene chloride at 19a C. and the viscosity determined. These measured IV values were correlated to IV values measured manually in 60/40 weight % phenoS/1,1 ,2,2-tetrachloroethane following ASTM 0 4603- 98.
NUMBE AVERAGE MOLECULAR WEIGHT
The number average molecular weight of polystyrene was determined following ASTM D 5298-97, The same method was used fo poSyitri methylene terephihaiate) except that the calibration standard was a polyietfiyiene terephthalate) with an Mwof 44,000 and
hexafluoroisopropanoi solvent.
TENACITY A D ELONGATION AT BREAK The physical properties of the filaments and yarns were measured using an !nstron Corp. tensile tester, model no. 1122. More specifically, elongation to break, E& , and tenacity were measured according to ASTM D-2258.
Fiber spinning was performed in four separate campaigns. As described in greater detail intra, Campaigns #1 , 3, and 4 were executed on Spinning Machine #2, while Campaign #2 was executed on Spinning Machine #1.
The results obtained from Spinning Machine #1 were scattered, as shown in Table 4 and Figure 5, and are not considered definitive. In particular, the denier coefficient of variation was higher than the limit as specified in the Invention, and did not appear to var
systematically with the iemperature of the first godet
Figur 5 is a graph showing the denier CV versus first godet temperature wherein all of the data obtained from Campaigns 1 ,3, and 4 are combined together and plotted with a diamond shape, and the data from Campaign #2 is graphed using a triangle shape. As shown in Tables 3 - 8, infra, not alt data points obtained in the three campaigns wherein Spinning yachine #2 was employed were obtained using the same set of spinning conditions. Nevertheless, as seen in Figure 5, the data from Spinning Machine #2, shown as diamond shapes, showed a clear trend, where first godet temperature i the range of ca. 75 to 85 *C corresponded to a minimum in denier CV. A similar trend was not observed in the data of Campaign #2.
Denier coefficient of variation is a measurement of short distance denier variability, which is in turn, an indicator of the stability of the melt spinning process. The melt spinning process can be unstable because the spinning composition causes an instability, it can also be unstable because the machine is unstable. It is dear from Figure 5 that in this case the high denier CV produced in Campaign #2 was an artifact of the machine performance and design. Spinning Machine #1 was a laboratory-built spinning machine provided with only the most basic equipment to effect me!t spinning. Spinning Machine #1 was employed normally only to obtain the most basic information about whether or not experimental compositions were capable of being melt-spun into fiber. It was employed in Campaign #2 herein because of a scheduling mix-up - Spinning Machine #2 was not available on the day scheduled for Campaign #2. Spinning Machine #2 was a pilot plant spinning line. Conditions thereon were fully scalable to full-size commercial scale spinning lines. This was the spinning line of choice for demonstrating the differences in results that are characteristic of the invention.
Figure 4 schematically depicts Spinning Machine #2. A silo drier, 41, gravity fed a single screw extruder, 42, with dried resin blend pellets. The output of the single screw extruder, 42, was fed directly, under pressure, to the input of a gear pumpf43, provided with an overflow port, 44. The output of the gear pump was supplied via a short (inches long) transfer line, 45, to a six end spin pack, 46. of which four ends were used. Each of four threadiines 47 (one shown), was extruded from a 36 hole spinneret, (not shown) whereof each hole was characterized by a round cross-section of 0.27 mm diameter and 0.50 mm in length. Each threadline, 47. passed through a cross-flow quench air zone approximately 1 ,75 m in length, 48, with ambient air flowing across the threadline from one side to another in campaign 1 and a radial quench air zone
approximately 1,75 m in length, 48, with ambient air flowing radially around the threadline to produce even more uniform filaments in campaigns 3 and 4. Each thus quenched threadline was contacted to a finish roll, 49, and then wrapped 8-8 times around a first heated godet (feed roll), 410, and a corresponding first separator roil, 411 , to keep the threadiines apart. The threadline was then directed to a second heated godet (draw roil), 412, and a second corresponding second separator roll 413, through an interlace jet (not shown) and thence to a windup, 414, Also not shown, each Godet was partially enclosed by a hot chest to maintain temperature. The extruder was provided with 3 heating zones, and a head zone at the output.
Spinning Machine #1 and Spinning Machine #2 were substantialiy the same in regard to the layout described i Figure 4. Once difference was that the quench air chimney in Spinning Machine #1 was much narrower than its counterpart on Spinning Machine #2.
In all the Examples and Comparative Examples, the average results for four threadiines spun simultaneously under each set of conditions ar reported , The spinning machines were allowed to reach steady state after a change in set-point conditions by running for ca. 45 minutes before a test sample was prepared. When the composition of the polymer was changed, the spinning machine was purged with PTT not containing PS. When the spinneret was changed, the machine was purged in between spinning experiments. P EPA ATION OF POLYMER BLENDS
Samples of PS in PTT (0.8 and 0.55 wt%) were made by co- feeding dried PTT and PS to a 30 mm T/S extruder . Sorona1* Semi- Dull PTT resin pellets (1 ,0.2 IV available from the DuPont Company,
Wilmington, DE) poSytrlmethyiene terephthaiate was combined with polystyrene (168 M KG 2 available from BASF) pellets in the amounts shown in Table 1 , The PTT was dried in a vacuum oven with a nitrogen purge at 120 aC for 14 hours prior to use, The two polymers were individually weight-loss fed to the fourth barrel sectio of a Werner & Pf!eiderer ZS -30 counter-rotating twin screw extruder. The feed rates employed are shown in Table 1 in pounds per hour (pph). The extruder had a 30 mm diameter barrel constructed with 3 barrel sections provided in alternating arrangement wit two kneading zones and three conveying sections, the extruder having an L/D ratio of 32. Each barrel section was independently heated. Sections 1 -4 were set at 25°C, Sections 5-13 were set at 21 Q°C, the 3/18s strand die was also set at 210°C. A vacuum was applied to barrel segment 3. Table 1 also shows the composition of the feed, the rate of output and the melt temperature. The extrudate was quenched in water immediately upon exiting the die and was then peiietszed using standard pelieiizing equipment into 1/8* pellets.
Table 1
Figure imgf000029_0001
MELT SPINNING'
Melt spinning of fiber was conducted in four separate spinning campaigns as described infra. Table 2 shows the spinning parameters that were held constant during each campaign.
Table 2: Fixed Spinning Parameters by Campaign
Campaign #: 1 2 3 4
Spinning
Machine 2 1 2 2
[PS] Variable o.so 0,80 0.80
Capillary
Diameter {mm) 0,27 Variable 0.27 0.27
Polymer Flow
Rate {g/mifi} 37. S 373 Variable 37.5
Quench Cross-flow Cross-Flow Radial Radial
Second Godet
Speed (rpm) 4500 4500 Variable 4500
Second Godet
Temperature f C) 110 110 140 0
CAMPAIGN #1 - SPINNING MACHINE #2
The melt compounded peliets of the PTT/PS blend so prepared were dried in a drying silo overnight at 140°C to lower the moisture content to <50 ppm. The dried melt blends were gravity fed to the single screw extrude described supra, in Figure 4, of Spinning Machine #2. Extruder set points, in *C, in zones 1-3 were respectively 230/255/263, The extruder output was melt-fed to the spin pack through a gear pump. The spin pack was provided with six spinning positions of which four were provided with spinnerets each spinneret having 36 holes, each hole being 0,27 mm in diameter and 0.5 mm in length , and of circular cross-section. Each yarn so produced was a 75 denier 36 filament yarn. The settings of the first godet roli are shown in Table 3, Note that the second godet roil was maintained at 110 °C and 4500 rpm. The quench air was a cross-flow quench with an air velocity of 0.35 cm s.
The protocol that wa followed was as follows: The second godet roll (draw roll) was set at 4500 m min and 1 10 9C, and was not changed in the course of the experiments. Experiments were then conducted with the first godet roll (feed roll) set at 80 SC and the speed was varied in order to identify a draw ratio that resulted in the highest tenacity when elongation to break was adjusted to be in the range of 55 - 65 %, For Polymer Blend #2 (0.055 % PS) a draw ratio of 2.00 was found to result in the highest tenacity when elongation to break was within the desired range (i.e., the feed roil was set at 2150 m/min). Spinning was then continued at additional feed roll temperatures of 85 and 110°C, The same procedure was followed for Polymer Blend #1 (0,8% PS); a draw ratio of 2.37 was found to result in the highest tenacity vvhen elongation to break was within the desired range (i.e., feed roil speed-1900 m min).
Results are shown in Table 3
Figure imgf000030_0001
Ex.3 0.55 2150 85 I 2.09 \ 2.1 1 2.07 j
Ex.4 0,55 2150 ϊϊο ! 2.09 i 2.0 1 2.69 j
CAMPAIGN #2 - SPINNING MACHINE #1
A new melt blend of 0.80 % by weight in PIT identical to that of Blend #1 supm. The melt compounded peiiets of the PTT/PS blend so prepared were dried in a drying silo overnight at 140 °C to lower the moisture content to <50 ppm. The dried melt blend pellets were gravity fed to the single screw extruder described supra, in Figure 4, of Spinning Machine #1. Extrude set points, in °C< in zones 1 -3 were respectively
230/255/283, The extruder output was melt-fed to the spin pack through a gear pump. The spin pack was provided with six spinning positions of which four were provided with spinnerets eac spinneret having 36 holes, each hole being 0.27 mm in diameter and 0,5 mm in length, and of circular cross-section. Each yarn so produced was a 75 denier 38 filament yarn. The settings of the first godet roil are shown in Table 4. Note that the second godet roll was maintained at 1 10 °C and 4500 rpm. The quench air was a cross-flow quench with an air velocity of 0.35 era's.
The protocol that was foifowed was as follows: The second godet roll (draw roll) was set at 4500 m/min and 110 , and was not changed in the course of the experiments. Experiments were then conducted with the first godet roli (feed roll) set at 60 and the speed was varied in order to identify a dra ratio that resulted in the highest tenacity when elongation to break was adjusted to be in the range of 56 - 65 %. The followed for Polymer Blend #1 (0.8% PS) was: a draw ratio of 2.37 was found to result in the highest tenacity when elongation to break was within the desired range (i.e., first godet roll speed-1900 m/min).
Examples 5 and 6 were performed with spinneret orifices
0,27 mm in diameter. Examples 7 and 8 were performed with spinneret orifices 0,32 mm in diameter. Other spinning conditions are shown in Table 2 and Table 4, Results are shown in Table 4,
Figure imgf000032_0001
Figure imgf000033_0001
The same batch of PS/PIT contains 09 0.80 % by weight PS as employed in Campaign #2 was employed.
Melt spinning was effected using the same spinning machine procedures and settings as described for Campaign #1 , supra, except that in these examples a 75 denier/36 filament yarn was spun and the quench was a radiai quench. Spinning conditions are shown in Table 3 and Table 5. Again the extruder heating zones were set respectively to 230/255/283 SC. Spinneret diameter was 0.27 mm. Flow rates were controlled to 3 5 g/min. Results are shown in Table 5.
Figure imgf000034_0001
CAMPAIGN #4 - SPINNING MACHINE #2
A third blend of 0.8 % PS in PTT was made in a manner identical to that of Blend #2, described supra.
Melt spinning was effected using the same spinning machine procedures and settings as described for Campaign #3, supra, except that in these examples a 75 denier/72 filament yam was spun. Spinning conditions are shown in Table 3 and Table 6. Again the extrude heating zones were set respectively to 230/255/283 C. Spinneret diameter was 0.27 mm. Flow rates were controlled to 37.5 g/min except where noted in
Ex 12 and Ex 13. Results are shown in Table 6,
Figure imgf000035_0001

Claims

CLAIMS What is claimed is:
1. A process comprising extruding a polymer melt comprising 0.1 to 3 % by weight, based on the totai weight of polymer, of polystyrene dispersed in poly{tfimeihyiene ary!ate), through an orifice forming a continuous filamentary exirudate, quenching the extrudate to solidify it into a continuous filament, wrapping the continuous filament around a first driven roil heated to a temperature in the range of 80 to 100 ;C and rotating at a first rotational speed, followed by wrapping the filament around a second driven roll heated to a temperature in the range of 100 to 130 °C and rotating at a second rotational speed wherein the ratio of the first rotational spaed to the second rotational speed lies in the range of 1.75 to 3; and, thereby forming a spun drawn filament having a denier of≤ 3, a denier coefficient of variation of≤ 3 %, and a birefringence of≥0.056.
2. The process of Claim 1 wherein the po yitrimethylene ary!ate) is paly(tri methylene terephthalate).
3. The process of Claim 1 wherein the polymer melt consists essentially of 0.5 to 3% by weight of polystyrene dispersed in
poly{tri meth ylene arylate) .
4. The process of Claim 2 wherein the polymer melt consists essentially 0.5 to 3 by weight of polystyrene dispersed in
pa iy{tri methylene ferephthaSate).
5. The process of Claim 2 wherein the polymer meif comprises 0 5 to 2 % by weight of polystyrene dispersed in poly(irimethylene
terephthalate),
6. The process of Claim 1 wherein the first driven roll is heated to a temperature in the range of 70 to 100 °C.
7. The process of Claim 1 further comprising wrapping the filament around a third driven roll rotating at a third rotational speed, and wherein the ratio of the third rotational speed to the second rotational speed Is < 1.
8. The process of Claim 1 further comprising accumuiating the filament at a rate of at least 4,000 rrs/min.
PCT/US2011/056151 2011-10-13 2011-10-13 Process for preparing poly (trimethylene arylate) fibers WO2013055344A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2011/056151 WO2013055344A1 (en) 2011-10-13 2011-10-13 Process for preparing poly (trimethylene arylate) fibers

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2011/056151 WO2013055344A1 (en) 2011-10-13 2011-10-13 Process for preparing poly (trimethylene arylate) fibers

Publications (1)

Publication Number Publication Date
WO2013055344A1 true WO2013055344A1 (en) 2013-04-18

Family

ID=45688079

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2011/056151 WO2013055344A1 (en) 2011-10-13 2011-10-13 Process for preparing poly (trimethylene arylate) fibers

Country Status (1)

Country Link
WO (1) WO2013055344A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5993712A (en) * 1997-02-25 1999-11-30 Lurgi Zimmer Aktiengesellschaft Process for the processing of polymer mixtures into filaments
JP2001151997A (en) * 1999-11-30 2001-06-05 Toray Ind Inc Melt spinning polyester composition, polyester high orientation undrawn yarn and its production method
WO2004003270A2 (en) * 2002-06-27 2004-01-08 E. I. Du Pont De Nemours And Company Poly(trimethylene dicarboxylate) fibers, their manufacture and use
WO2011022624A1 (en) * 2009-08-20 2011-02-24 E. I. Du Pont De Nemours And Company Poly(trimethylene arylate)/polystyrene composition and process for preparing
WO2011022616A1 (en) * 2009-08-20 2011-02-24 E. I. Du Pont De Nemours And Company Process for producing shaped articles of poly(trimethylene arylate)/polystyrene

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5993712A (en) * 1997-02-25 1999-11-30 Lurgi Zimmer Aktiengesellschaft Process for the processing of polymer mixtures into filaments
JP2001151997A (en) * 1999-11-30 2001-06-05 Toray Ind Inc Melt spinning polyester composition, polyester high orientation undrawn yarn and its production method
WO2004003270A2 (en) * 2002-06-27 2004-01-08 E. I. Du Pont De Nemours And Company Poly(trimethylene dicarboxylate) fibers, their manufacture and use
WO2011022624A1 (en) * 2009-08-20 2011-02-24 E. I. Du Pont De Nemours And Company Poly(trimethylene arylate)/polystyrene composition and process for preparing
WO2011022616A1 (en) * 2009-08-20 2011-02-24 E. I. Du Pont De Nemours And Company Process for producing shaped articles of poly(trimethylene arylate)/polystyrene

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"Uster Tester 4", 1 January 2003 (2003-01-01), XP055011924, Retrieved from the Internet <URL:http://www.fuster.com/pdf/uster/uster_texter4sx_eng.pdf> [retrieved on 20111111] *
HOE H. CHUAH: "Intrinsic birefringence of poly(trimethylene terephthalate)", JOURNAL OF POLYMER SCIENCE PART B: POLYMER PHYSICS, vol. 40, no. 14, 6 June 2002 (2002-06-06), pages 1513 - 1520, XP055031548, ISSN: 0887-6266, DOI: 10.1002/polb.10211 *
TAE HWAN OH ET AL: "Effect of polystyrene mixing on mechanical properties and structural changes in melt spinning", FIBERS AND POLYMERS, vol. 11, no. 8, 1 December 2010 (2010-12-01), pages 1165 - 1169, XP055031544, ISSN: 1229-9197, DOI: 10.1007/s12221-010-1165-7 *

Similar Documents

Publication Publication Date Title
US10351973B2 (en) Process for the preparation of a fiber, a fiber and a yarn made from such a fiber
JP6127969B2 (en) Polyamide fiber and method for producing the same
JP3966043B2 (en) Production method of polylactic acid fiber excellent in heat resistance
JP2006336125A (en) Bulky sheath-core conjugated filaments and method for producing the same
US20120009418A1 (en) Poly(trimethylene arylate) fibers, process for preparing, and fabric prepared therefrom
US20030129393A1 (en) Bulky polyester multifilament composite yarn and process for producing the same
US10400358B2 (en) Nylon based filaments, yarns, and fabrics
US20140234623A1 (en) Poly(trimethylene arylate) fibers, process for preparing, and fabric prepared therefrom
JP5964437B2 (en) Poly (trimethylene arylate) fiber, method for making the same, and fabric made therefrom
US8753741B2 (en) Poly(trimethylene arylate) fibers, process for preparing, and fabric prepared therefrom
KR102575877B1 (en) Core-sheath composite cross-sectional fiber with excellent hygroscopicity and wrinkle resistance
US20110263171A1 (en) Poly(trimethylene arylate) fibers, process for preparing, and fabric prepared therefrom
JP4604797B2 (en) Polylactic acid fiber package and manufacturing method
US8540912B2 (en) Process of making poly(trimethylene arylate) fibers
CN114787433A (en) Carpet made of self-expandable PTT-containing bicomponent fibers
WO2013055344A1 (en) Process for preparing poly (trimethylene arylate) fibers
WO2017165552A1 (en) Nylon based yarns and fabrics
JP2003293230A (en) Polylactic acid crimped yarn having excellent heat resistance and method for producing the same

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11771384

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11771384

Country of ref document: EP

Kind code of ref document: A1