WO1992013119A1 - Procede de preparation de minces filaments de polyester - Google Patents

Procede de preparation de minces filaments de polyester

Info

Publication number
WO1992013119A1
WO1992013119A1 PCT/US1992/000359 US9200359W WO9213119A1 WO 1992013119 A1 WO1992013119 A1 WO 1992013119A1 US 9200359 W US9200359 W US 9200359W WO 9213119 A1 WO9213119 A1 WO 9213119A1
Authority
WO
WIPO (PCT)
Prior art keywords
range
filaments
shrinkage
denier
less
Prior art date
Application number
PCT/US1992/000359
Other languages
English (en)
Inventor
Robert James Collins
Hans Rudolf Edward Frankfort
Stephen Buckner Johnson
Benjamin Hughes Knox
Elmer Edwin Most, Jr.
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=27179019&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1992013119(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU12310/92A priority Critical patent/AU653207B2/en
Priority to KR1019930702247A priority patent/KR0181183B1/ko
Priority to DE69221739T priority patent/DE69221739T2/de
Priority to JP4504583A priority patent/JP3043414B2/ja
Priority to CA002101788A priority patent/CA2101788C/fr
Priority to EP92904563A priority patent/EP0646189B1/fr
Priority to TW081102473A priority patent/TW215113B/zh
Publication of WO1992013119A1 publication Critical patent/WO1992013119A1/fr
Priority to BR9205719A priority patent/BR9205719A/pt
Priority claimed from PCT/US1994/013189 external-priority patent/WO1996016206A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/082—Melt spinning methods of mixed yarn
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/22—Formation of filaments, threads, or the like with a crimped or curled structure; with a special structure to simulate wool
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G1/00—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics
    • D02G1/18—Producing crimped or curled fibres, filaments, yarns, or threads, giving them latent characteristics by combining fibres, filaments, or yarns, having different shrinkage characteristics
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch

Definitions

  • This invention concerns improvements in, and relating to, polyester fine filaments and their
  • polyester fibers for use in apparel, including polyester fibers
  • synthetic fibers for use in apparel have generally been supplied to the textile industry for use in fabrics and garments with the object of more or less duplicating and/or improving on natural fibers.
  • commercial synthetic textile filaments such as were made and used for apparel, were mostly of deniers per filament (dpf) in a similar range to those of the commoner natural fibers; i.e., cotton and wool.
  • polyester filaments have been available commercially in a range of dpf similar to that of natural silk, i.e. of the order of 1 dpf, and even in subdeniers, i.e., less than about 1 dpf, despite the increased cost.
  • dpf deniers per filament
  • subdeniers i.e., less than about 1 dpf
  • the present invention is concerned with the preparation of fine filaments by a novel direct
  • the filaments of the invention are "spin-oriented", the significance of which is discussed in the art and hereinafter.
  • polyester filaments were made initially by "split" processes that involved a separate drawing stage after spinning and winding undrawn filaments.
  • Hebeler suggested in U. S. Patents Nos. 2,604,667 and 2,604,689, the possibilities of high speed spinning of polyester melts.
  • high speed spinning of polyester melts as described by Petrille in U. S. Patent No. 3,771,307 and by Piazza and Reese in U. S. Patent No. 3,772,872, were made the basis of a process for preparing spin-oriented yarns that have been used as draw-texturing feed yarns.
  • High speed spinning of polyester melts has also been the basis of other processes that were first disclosed in the 1970's, such as Knox in U. S. Patent No.
  • the art discloses fundamental differences in fine structure and properties between filaments that are spin-oriented, indicating orientation of the polyester molecules obtained from the (high speed) spinning, and drawn filaments, indicating orientation derived from drawing of the filaments as an entirely separate process, after winding the spun filaments, or even as a continuous process, before winding, but after cooling the melt to form solid filaments before drawing such filaments.
  • An object of the present invention is to provide fine filaments that have the characteristics of being spin-oriented, because of the advantageous properties that are provided by this characteristic.
  • polyester fine filaments wherein,
  • the polyester polymer is selected to have a relative viscosity (LRV) in the range of about 13 to about 23, a zero-shear melting point (T M o ) in the range of about 240°C to about 265°C, and a glass transition temperature (T g ) in the range of about 40°C to about 80°C;
  • said polyester is melted and heated to a temperature (T P ) in the range of about 25°C to about 55°C, preferably in the range of about 30°C to about 50°C, above the apparent polymer melting point (T M ) a ;
  • residence time (t r ) at polymer melt temperature (T P ) is less than about 4 minutes;
  • the filtered melt is extruded through a spinneret capillary at a mass flow rate (w) in the range about 0.07 to about 0.7 grams per minute (g/min), and the capillary is selected to have a cross-sectional area (A c ) in the range about 125 ⁇ 10 -6 cm 2 (19.4 mils 2 ) to about 1250 ⁇ 10 -6 cm 2 (194 mils 2 ) preferably in the range of about 125 ⁇ 10 -6 cm 2 (19.4 mils 2 ) to about
  • D RND diameter (D RND ) such that the (L/D RND )-ratio is at least about 1.25 and preferably less than about 6, and especially less than about 4;
  • DS average along-end denier spread
  • a tenacity-at-7%-elongation (T7) in the range of about 0.5 to about 1.75 g/d, and such that the [ (T B ) n /T 7 ]-ratio is of at least about (5/T7) and preferably at least about (6/T 7 ); wherein, (T B ) n is the tenacity-at-break normalized to a reference LRV of 20.8 and % delusterant (such as TiO 2 ) of 0%; (iv) desireably an average along-end denier spread (DS) of less than about 4%, preferably less than about 3%, and especially less than about 2%.
  • DS average along-end denier spread
  • S boil-off shrinkage
  • E ⁇ elongation-at-break
  • T7 tenacity-at-7%-elongation
  • ⁇ S DHS - S
  • DHS dry heat shrinkage
  • ABO filament denier after boil-off shrinkage
  • T7 tena ⁇ ity-at-7%-elongation
  • Eg elongation-at-break
  • M py post-yield modulus
  • a tenacity-at-7%-elongation (T7) of at least about 1 g/d such that the [ (T B ) n /T7]-ratio is at least about (5/T7); preferably at least about (6/T7), wherein, (T B ) n is the tenacity-at-break normalized to a reference LRV of 20.8 and percent delusterant (such as TiO 2 ) of 0%; and an elongation-at-break (E B ) in the range of about 15% to about 55%;
  • a post-yield modulus (M py ), preferably in the range about 5 to about 25 g/d;
  • DS average denier spread
  • ABO denier after boil-off shrinkage
  • DHS dry heat shrinkage
  • E B elongation-at-break
  • T 7 tenacity-at-7%-elongation
  • M py post-yield modulus
  • RDDR relative disperse dye rate
  • Mixed filament yarns wherein the fine filaments are of this invention; and especially mixed filament yarns, wherein, all filaments are of this invention, but differ in denier, cross-section, and/or shrinkage potential.
  • Preferred such spin-oriented, bulked and drawn flat filaments are capable of being dyed with cationic dyestuffs, on account of containing in the range of about 1 to about 3 mole % of ethylene-5-M-sulfo-isophthalate structural units, where M is an alkali metal cation, such sodium or lithium.
  • spin-oriented, bulked, and drawn flat filaments capable of being disperse dyed uniformly under atmospheric conditions without carriers, are characterized by a dynamic loss modulus peak temperature T(E" max ) of less than about 115°C, preferably less than about 110°C; and are of polyester polymer, essentially poly(ethylene
  • hydrocarbolenedicarbonyl structural units B [-O-C 2 H 4 -O-], and hydrocarbolenedicarbonyl structural units B, [-C(O)-C 6 H 4 -C(O)-], modified with minor amounts of other hydrocarbolenedioxy structural units A and/or hydrocarbolenedicarbonyl structural units B, that are different from the first structural units, such as to provide a polyester polymer with a zero-shear melting point (T M °) in the range about 240°C to about 265°C and a glass-transition temperature (Tg) in the range of about 40oC to about 80°C.
  • T M ° zero-shear melting point
  • Tg glass-transition temperature
  • the filaments of the present invention may be nonround for enhanced tactile and visual aesthetics, and comfort, where said nonround filaments have a shape factor (SF) at least about 1.25, wherein the shape factor (SF) is defined by the ratio of the measured filament parameter (P M ) and the calculated parameter (P RND ) for a round filament of equivalent cross-sectional area.
  • Hollow filaments may be spun via post-coalescence from segmented spinneret capillary orifices to provide lighter weight fabrics with greater bulk and filament bending modulus for improved fabric drape.
  • FIG. 1 is a graphical representation of spinline velocity (V) plotted versus distance (x) where the spin speed increases from the velocity at extrusion (V o ) to the final (withdrawal) velocity after having completed attenuation (typically measured downstream at the point of convergence, V c ); wherein, the apparent internal spinline stress ( ⁇ a ) is taken as being
  • the spin line temperature is also plotted versus spinline distance (x) and is observed to decrease uniformly with distance as compared to the sharp rise in spinline velocity at the neck point.
  • FIG. 2 is a graphical representation of the birefringence ( ⁇ n ) of the spin-oriented filaments versus the apparent internal spinline stress ( ⁇ ) a ;
  • slope is referred to as the "stress-optical coefficient, SOC" and Lines A, B, and C have SOC values of 0.75, 0.71, and 0.645 (g/d) -1 , respectively; with an average SOC of about 0.7; and wherein Lines A and C are typical relationships found in literature for 2GT polyester.
  • SOC stress-optical coefficient
  • FIG. 3 is a graphical representation of the tenacity-at-7%-elongation (T7) of the spin-oriented filaments versus the apparent internal spinline stress ( ⁇ a ) .
  • T7 apparent internal spinline stress
  • Birefringence ( ⁇ n ) is typically very difficult structural parameter to measure for fine filaments with deniers less than 1.
  • FIG. 4 is a graphical representation of the preferred values of the apparent internal spinline stress ( ⁇ a ) and the spin-oriented filament yarn
  • FIG. 5 is a representative Instron load- extension curve showing the graphical calculation of the "secant" post-yield modulus (M py ) calculated from the tenacity-at-7%-elongation (T 7 ), denoted by point C, and from the tenacity-at-20%-elongation (T 20 ), denoted by point A, and defined by the expression
  • FIG. 6 is a graphical representation of the secant M py (tan ß in FIG. 5) versus birefringence ( ⁇ n ) of spin-oriented filaments.
  • M py post-yield modulus
  • FIG. 7 is a graphical representation of the Relative Disperse Dye Rate (RDDR), as normalized to 1 dpf, versus the average filament birefringence ( ⁇ n ) .
  • RDDR Relative Disperse Dye Rate
  • FIG. 8 is a graphical representation of the filament amorphous free-volume of the fiber (V f,am , as defined herein after), versus the peak temperature of the fiber dynamic loss modulus, T(E" max ), taken herein as a measure of the glass transition temperature which is typically 20°C to about 50°C above the Tg of the polymer.
  • T(E" max) the peak temperature of the fiber dynamic loss modulus
  • a decreasing T(E"max) value corresponds to greater amorphous free-volume (Vf am ), and hence to improved dyeability, as measured herein by a Relative Disperse Dye Rate (RDDR) value (normalized to 1 dpf) of at least about 0.1.
  • RDDR Relative Disperse Dye Rate
  • FIG. 9 is a graphical representation of the filament density (p) versus birefringence ( ⁇ n ); wherein the diagonal lines represent combinations of density (p) and ( ⁇ n ) of increasing fractional amorphous
  • FIG. 10 is a representative Differential Scanning Calorimetry (DSC) spectrum showing the thermal transitions corresponding to the glass-transition temperature (T g ), onset of "cold" crystallization
  • FIG. 11 is a representative shrinkage tension (ST)-temperature spectrum for the spin-oriented fine polymer filaments of the invention showing the maximum shrinkage tension ST( max ), peak temperature T(ST max ) and the preferred "heat set” temperature T set below which heat setting does not appreciably adversely affect dye ability.
  • FIG. 13 is a graphical representation of the preferred values for the tenacity-at-break (T B ) n , normalized for the affects of LRV and percent
  • FIG. 14 is a plot of the ratio, T 7 /(V 2 /dpf) versus the product of the number of filaments per yarn extrusion bundle (# c ) and the ratio, (D ref /D sprt ) 2 , where D ref and D sprt are the diameters of a reference spinneret (e.g., about 75 cm) and the test spinneret, respectively.
  • the slope "n" from a ln-ln plot is found to be about negative 0.7 (-0.7); that is, the tenacity-at-7%-elongation (T 7 ) is found to vary proportionally to (V 2 /dpf) and to [(# c )(D ref /D sprt ) 2 ] -0.7 ; that is, the tenacity-at-7%-elongation (T7) decreases
  • the filament extrusion density may be used to as a process parameter to spin finer denier filaments at higher spinning speeds (V) .
  • V spinning speeds
  • higher spin speeds e.g., in the range of about 4 to 6 km/min, it is found that the apparent spinline stress increases less rapidly with spin speed (V); i.e., is found to be proportional to (V 3 / 2 /dpf).
  • the polyester polymer used for preparing spin-oriented filaments of the invention is selected to have a relative viscosity (LRV) in the range about 13 to about 23, a zero-shear melting point (T M °) in the range about 240°C to about 265°C; and a glass- transition temperature (T g ) in the range about 40oC to about 80°C (wherein T M ° and T g are measured from the second DSC heating cycle under nitrogen gas at a heating rate of 20°C per minute).
  • LUV relative viscosity
  • T M ° zero-shear melting point
  • T g glass- transition temperature
  • the said polyester polymer is a linear condensation polymer composed of alternating A and B structural units, where, A is a hydrocarbolenedioxy unit of the form [-O-R'-O-] and B is a hydrocarbolenedicarbonyl unit of the form
  • R' is primarily [-C 2 H 4 -], as in the ethylenedioxy (glycol) unit [-O-C 2 H 2 -O-], and R" is primarily [-C 6 H 4 -], as in the 1,4-benzenedicarbonyl unit [-C(O)-C 6 H 4 -C(O)-], such to provide, for example, at least about 85 percent of the recurring structural units as ethylene terephthalate,
  • Suitable poly(ethylene terephthalate), herein denoted as PET or 2GT, based polymer may be formed by the DMT-process as described by H. Ludwig in his book “Polyester Fibers, Chemistry and Technology", John Wiley and Sons Limited (1971), and by the TPA-process as described in Edging U. S. Patent No. 4,110,316.
  • copolyesters in which, for example, up to about 15 percent of the hydrocarbolenedioxy and/or hydrocarbolenedicarbonyl units are replaced with different hydrocarbolenedioxy and
  • hydrocarbolenedicarbonyl units to provide enhanced low temperature disperse dyeability, comfort, and aesthetic properties.
  • Suitable replacement units may be found in Most U. S. Patent No. 4,444,710 (Example VI), Pacofsky U. S. Patent No. 3,748,844 (Col. 4), and Hancock, et al. U. S. Patent No. 4,639,347 (Col. 3).
  • the polyester polymer may also be modified with ionic dye sites, such as ethylene-5-M-sulfo- isophthalate residues, where M is an alkali metal cation, such as sodium or lithium; for example, in the range of 1 to about 3 mole percent ethylene-5-sodium-sulfo-isophthalate residues may be added to provide dyeability of the polyester filaments with cationic dyestuffs, as disclosed by Griffing and Remington U. S. Patent No. 3,018,272, Hagewood etal in U. S. Patent No. 4,929,698, Duncan and Scrivener U. S. Patent No.
  • DEG diethylene glycol
  • polyester filaments having a fineness, for example, in the range of about 1 to about 0.2 denier per filament (dpf), preferably in the range about 0.8 to about 0.2 denier per filament (dpf); (a) by melting and heating said polyester polymer, as described herein before, to a temperature (T p ) in the range of about 25°C to about 55°C,
  • t r is defined by ratio (V F/ Q) of the free-volume (V F , cm 3 ) of the filter cavity (filled with the inert filtration medium) and the polymer melt volume flow rate (Q, cm 3 /min) through the filter cavity.
  • the free-volume (V F ,cm 3 ) of the filter cavity (filled with the inert filtration medium) is experimentally
  • the residence time t r decreases with increasing filament denier, withdrawal speed (V) and number of filaments (# c ) per filter cavity, and decreases with a reduction in the filter cavity free-volume (V F ).
  • the cavity free-volume (V F ) may be decreased by altering the pack cavity dimensions and by utilizing inert material which provides sufficient filtration capabilities with less free-volume.
  • capillaries) per filter cavity (# c ) may be increased for a given yarn count by extruding more than one multifilament bundle from a single filter cavity, that is, spinning a larger number of filaments and then splitting (herein, called multi-ending) the filament bundle into smaller filament bundles of desired yarn denier, preferably by using metered finish tip
  • separator guides positioned between about 50 cm to about (50+90dpf 1 ⁇ 2 )cm;
  • the filtered polymer melt is extruded through a spinneret capillary at a mass flow rate (w) in the range of about 0.07 to about 0.7 grams per minute (g/min) and the capillary is selected to have a cross-sectional area, A c - ( ⁇ /4)DRND 2 , in the range of about 125 ⁇ 10 -6 cm 2 (19.4 mils 2 ) to about 1250 ⁇ 10 -6 cm 2 (194 mils 2 ), preferably in the range of about 125 ⁇ 10 -6 cm 2 (19.4 mils 2 ) to about 750 ⁇ 10 -6 cm 2 (116 mils 2 ), and a length (L) and diameter (D RND ) such that the L/D RND - ratio is in the range of about 1.25 to about 6,
  • G a (sec -1 ) [(32/60 ⁇ )(W/P)/D RND 3 ], and w is the capillary mass flow rate (g/min), ⁇ is the polyester melt density (taken as 1.2195 g/cm 3 ), and D RND is the capillary diameter (defined herein before) in centimeters (cm);
  • ⁇ a k(LRV/LRV 20 . 8 )(TR/Tp) 6 (V 2 /dpf)(A o /# c ) 0.7 , wherein k has an approximate value of 10 -2 (Pm/SOC), where ⁇ m is the density of the spin-oriented filaments (e.g., in the range of about 1.345 to about 1.385 g/cm 3 , that is about 1.36 g/cm 3 ) and SOC is the
  • stress-optical coefficient for the polyester polymer (e.g., about 0.7 in reciprocal g/d for 2GT
  • TR is the polymer reference temperature defined by (T M ° + 40°C) where T M o is the zero-shear (DSC) polymer melting point; Tp is the polymer melt spin temperature, °C; V is the withdrawal speed
  • LRV the measured polymer (lab) viscosity
  • LRV 20.8 the corresponding reference LRV-value (where LRV is defined herein after) of the polyester polymer having the same zero-shear "Newtonian" melt viscosity ( ⁇ 0 ) at 295°C as that of 2GT homopolymer having an LRV-value of 20.8 (e.g.,
  • cationic-dyeable polyester of 15 LRV is found to have a melt viscosity as indicated by capillary pressure drop in the range of 2GT homopolymer of about 20 LRV and thereby a preferred reference LRV for such modified polymers is about 15.5 and is determined experimentally from standard capillary pressure drop measurements);
  • finish-on-yarn is about 0.4% to about 2% by weight solids, depending on the end-use processing
  • RPC rapid pin count
  • V withdrawal speed
  • V the surface speed of the first driven roll
  • the retractive forces from aerodynamic drag are reduced by relaxing the spinline between the first driven roll and the windup roll by overfeeding in the range of about 0.5 to about 5%, without the application of heat (except for use of heated interlace jet fluid (such as heated air or water-saturated air) for preventing finish deposits forming on the interlace jet surfaces as described by Harris in U. S. Patent No. 4,932,109.
  • polyester fine filaments of this invention are manufactured by a simplified direct spin-orientation (SDSO) process which does not incorporate drawing or heat treatment, and therein provides a preferred balance of shrinkage and dyeability behavior making the polyester fine filaments of the invention especially suitable for replacement of natural
  • SDSO direct spin-orientation
  • fine filaments with excellent mechanical quality and uniformity are made; such that the fine filaments, having shrinkages less than about 12%, may be used in multifilament direct-use yarns (DUY) and processed without forming broken filaments in high speed weaving and knitting; and filaments, having shrinkages preferably greater than about 12%, may be used in multifilament draw-feed yarns (DFY) in high speed textile draw processes, such as friction-twist texturing, air-jet texturing,
  • the fine filaments of this invention are characterized by having excellent mechanical quality permitting yarns made from these filaments to be used in high speed textile processes, such as draw false-twist and air-jet texturing, warp drawing, draw gear and stuffer-box crimping, and air and water jet weaving and warp knitting, without broken filaments; and the filaments of this invention are further characterized by having excellent denier uniformity (as defined herein by along-end denier spread, DS) permitting use in critically dyed fabrics.
  • denier uniformity as defined herein by along-end denier spread, DS
  • the filaments of this invention may be used as filaments in draw feed yarns (and tows), preferably filaments having boil-off shrinkage (S) and dry heat shrinkage (DHS) greater than about 12% are especially suitable for draw feed yarns; and filaments of this invention, having shrinkages less than about 12%, are especially suitable flat untextured multifilament yarns, and as yarns for such texturing processes as air-jet texturing, gear crimping, and stuffer-box crimping, wherein, no draw need be taken, and the flat and textured filaments of this invention may be cut into staple fibers and flock; but the filaments with shrinkages less than about 12% may be uniformly cold drawn as described by Knox and Noe in U. S. Patent No. 5,066,447.
  • fine filaments made by such spinning technologies which incorporate, for example, aerodynamic or mechanical draw and/or heat treatment steps for the reduction in filament denier and/or for the increase in molecular orientation and/or crystallinity, which are generally characterized by: 1) high shrinkage tension (ST max ) greater than about 0.2 g/d; 2) peak shrinkage tension occurring at
  • T(ST max ) greater than about 100°C (i.e., greater than atmospheric dyeing temperatures); 3) dry heat shrinkage (DHS) which increases with treatment temperature over the normal textile dyeing and
  • shrinkage and DHS is the dry heat shrinkage, and thereby requiring high temperature treatments of the polyester fine filaments, or textile products made therefrom, prior to, or after dyeing, to impart
  • a tenacity-at-7%-elongation (T7) in the range of about 0.5 to about 1.75 g/d and a [(T B ) n /T 7 ])- ratio at least about (5/T 7 ); preferably at least about (6/T7), wherein, (T B ) n is the tenacity-at-break
  • Spin-oriented fine filaments are further characterized by: (a) boil-off shrinkage (S) and dry heat shrinkage (DHS) between in the range of about 2% to about 12%, preferably in the range of about 6% to about 12% for woven and preferably in the range of about 2% to about 6% for knits, such that the filament denier after boil-off, dpf (ABO) - dpf (BBO) ⁇ [ (100/(100-S)], is in the range of about 1 to about 0.2 dpf, preferably in the range of about 0.8 to about 0.2 dpf, and especially in the range of about 0.6 to about 0.2 dpf; (b) tenacity-at-7%-elongation (T7) in the range of about 1 to about 1.75 g/d with
  • DSC differential scanning calorimetry
  • the shrinkage (S) of said drawn filaments may be reduced, if desired, without significant loss in dyeability provided that the post heat set temperature (T set ) is less than about the temperature at which the shrinkage tension undergoes no significant further reduction with increasing temperature; that is, it is preferred to maintain T set less than about the
  • Preferred drawn yarns made by drawing the said spin-oriented filaments of this invention and said drawn yarns are characterized by:
  • boil-off shrinkages S
  • DHS dry heat shrinkages
  • (T B ) n is the tenacity-at-break normalized to a reference LRV of 20.8 and percent delusterant (such as TiO 2 ) of 0%, and having an E B in the range of about 15% to about 55%; (e) post-yield modulus (M py ) in the range of about 5 to about 25 g/d;
  • T(E"max) a dynamic loss modulus peak temperature, T(E"max) less than about 115°C; and preferably less than about 110oC;
  • Bulky fine filament yarns are provided by passing the fine filament yarns of this invention through a bulking process, such as air-jet texturing, false-twist texturing, stuffer-box and gear crimping; wherein, said bulky filaments are
  • T(E" max ) of less than about 115°C, preferably less than about 110oC, and a RDDR of at least about 0.1, and preferably at least about 0.15.
  • Especially preferred filaments for use in direct-use yarns are also characterized by:
  • intrinsic birefringence (defined herein with a value of 0.22), between about 0.25 and about 0.5, with a
  • f c (180-COA)/180, where COA is the crystalline orientation angle as measured by WAXS;
  • Vf /am an amorphous free-volume (Vf /am ) of at least about 0.5 ⁇ 10 6 cubic angstroms (A 3 ), preferably at least about 1 ⁇ 10 6 ⁇ 3 , where V f,am is defined herein by (CS) 3 [(1-X v )/X v )] [(1-f a )/f a ], providing a dynamic loss modulus peak temperature, T(E" max ), less than about 115°C, and preferably less than about 110°C;
  • RDDR atmospheric relative disperse dye rate
  • Poly(ethylene terephthalate) having a polymer LRV in the range of about 13 to about 23 (which
  • T M o zero-shear melting point
  • T g glass-transition temperature
  • delusterants and surface friction modifiers e.g., TiO 2 and SiO 2
  • Tp polymer temperature
  • filaments of most of the examples herein were spun from spinnerets having a filament density per extrusion surface area in the range of typically about 2.5 to about 13, while it was possible to spin and quench filament bundles with a extrusion filament density as high as about 25 provided capillary hole pattern (filament array) was optimized for the type of quench (i.e., radial vs.
  • extrusion filament density is defined by the ratio of the number of filaments (# c ) divided by the extrusion surface area (A 0 ),(i.e., # c /A 0 , cm -2 ), into a "shroud” which protects the freshly extruded filaments from direct quench air for a distance at least about 2 cm and not greater than about (12dpf 1 ⁇ 2 ,cm); and then carefully cooled to a temperature less than about polymer T g , preferably by radially directed air having a temperature T a (herein about 22°C) less than about the polymer T g (herein T a was about 70°C for 2GT homopolymer) and of linear velocity V a (m/min) in the range of about 10 to about 30 m/min.
  • Suitable spinning apparatus used are
  • the along-end denier spread (DS) and draw tension variation (DTV) were minimized by balancing the values for the delay quench length (L DQ ), the quench air temperature (T a ), the quench air flow rate (V a ), and the convergence length (L c ), while selecting Tp for spinning continuity.
  • Increasing the polymer spin temperature (Tp) (but less than about [ (T M ) a + 55°C] usually increases spinning continuity and mechanical quality (i.e., T B , g/d), but usually decreases along- end uniformity and increases shrinkage.
  • the apparent internal spinline stress ( ⁇ a ) at the "neck-point" is controlled in the range of about 0.045 to about 0.195 g/d while controlling the melt extension strain ⁇ a in the range of about 5.7 to about 7.6.
  • the attenuated and cooled filaments are converged into a multifilament bundle and withdrawn at a spinning speed (V, km/min) as defined by the surface speed of the first driven roll.
  • the external spinline tension arising from frictional surfaces (and air drag) is removed prior to packaging by slightly over feeding the spinline between the first driven roll and the windup, usually between about 0.5% and 5%. Finish is applied at the point of convergence and interlace is provided, preferably after the first driven roll.
  • the values for finish-on-yarn (weight, %) and degree of filament entanglement (RPC) are selected to meet end-use
  • Polyester fine filaments of the invention are of good mechanical quality and uniformity having a linear density less than about of that of natural worm silk, but greater than that of spider silk, that is between about 1 and about 0.2 denier per filament, and having the capability of being uniformly dyed without use of high temperatures and chemical dye assists; that is, more akin to that of natural silks.
  • the fine denier filament yarns may be treated with caustic in spin finish (according to the invention as taught by
  • filaments of different deniers and/or cross-sections may be used to reduce filament-to-filament packing and thereby improve tactile aesthetics and comfort.
  • Unique dyeability effects may be obtained by co-mingling filaments of differing polymer modifications, such as homopolymer dyeable with disperse dyes and ionic
  • copolymers dyeable with cationic dyes.
  • Fine filaments of lower shrinkage may be obtained, if desired, by incorporating chain branching agents, on the order of about 0.1 mole percent, as described in part in Knox U. S. Patent No. 4,156,071, MacLean U. S. Patent No. 4,092,229, and Reese in U. S. Patents Nos. 4,883,032, 4,996,740, and 5,034,174;
  • the fine filament yarns of this invention are suitable for warp drawing, air jet texturing, false-twist texturing, gear crimping, and stuffer-box
  • the low shrinkage filament yarns may be used as direct-use flat textile yarns and a feed yarns for air-jet texturing and stuffer-box crimping wherein no draw is need be taken.
  • filaments (and tows made therefrom) may also be crimped (if desired) and cut into staple and flock.
  • the fabrics made from these improved yarns may be surface treated by conventional sanding and brushing to give suede-like tactility.
  • the filament surface frictional characteristics may be changed by selection of cross-section, delusterant, and through such treatments as alkali-etching.
  • the improved combination of filament strength and uniformity makes these filaments,
  • the fine denier filament polyester yarns of the invention are especially suitable for making of high-end density moisture-barrier fabrics, such as rainwear and medical garments.
  • the surface of the knit and woven fabrics can be napped (brushed or sanded).
  • the filaments may be treated (preferably in fabric form) with conventional alkali procedures.
  • the fine filament yarns especially those capable of being cationic dyeable, may also be used as covering yarns of elastomeric treatments yarns (and strips), preferably by air entanglement as described by Strachan in U. S. Patent No. 3,940,917.
  • the fine filaments of the invention may be co-mingled on-line in spinning or off-line with higher denier polyester (or nylon) filaments to provide for cross- dyed effects and/or mixed shrinkage post-bulkable potential, where the bulk may be developed off-line, such as over feeding in presence of heat while
  • the degree of interlace and type/amount of finish applied during spinning is selected based on the textile processing needs and final desired yarn/fabric aesthetics.
  • Yarns of 100 and 300 filaments of nominal 0.5 dpf were spun from poly(ethylene terephthalate) of 19 LRV (corresponding to about 0.60 [ ⁇ ] ) and containing 0.3 weight percent of TiO 2 .
  • the 300-filament yarns were spun using spinnerets of varying construction;
  • T B n The normalized values for T ⁇ (denoted herein by (T B ) n ) are defined by the product the measured tenacity-at-break (T ⁇ ) and the factor (20.8/LRV) 0.75 (1-X) -4 which for these yarns is about 1.057; thereby, the normalized break tenacities (T B ) n are about 6% higher when compared to reference LRV and % TiO 2 of 20.8 and 0%, respectively.
  • the fine filament yarns of this example were capable of being dyed to deep shades at atmospheric conditions (100°C) without use of dye carriers as given by an Relative Disperse Dye rate (RDDR)-value
  • the 300-filament yarn bundle into 2,3 or 4 individual bundles of 150, 100, and 75-filament yarn bundles, respectively, preferably by use of metered finish tip separating guides at the exit of the radial quench chamber.
  • Multi-ending permits a higher mass flow rate (w) through the filter pack cavity and thereby reducing the residence time (t r ) in the pack cavity per
  • Fine filaments were spun from poly(ethylene terephthalate) of nominal 20.8 LRV (about 0.65 [ ⁇ ]) and containing 0.1 weight percent TiO 2 at a withdrawal speed (V) of 4000 ypm (3.66 km/min) using a radial quench apparatus, essentially as described in Example I, except for having a delay "shroud" length (L DQ ) of about 2.25 inches (5.72 cm).
  • L DQ delay "shroud" length
  • Examples II-5 and II-6 had poor operability and no yarn was collected.
  • capillaries (0.38 ⁇ 1.52 mm, 0.038 ⁇ 0.152 cm) capillaries is believed to contribute to the poor operability and broken filaments. Even increasing temperatures T p to about 299°C did not provide an acceptable process.
  • Example III 68-and 136-(unplied and plied) filament yarns were spun, essentially according to Example I, except convergence was by a metered finish tip as described in U. S. Patent No. 4,926,661 for Examples III-1 through III-9 and III-11 through 111-25.
  • Example 111-10 used a metering finish roll surface to converge the filaments as described in
  • Example III-l through III-5 and 111-12 through 111-15 have ⁇ 7-values greater than about 1 g/d making them especially suitable for use as filaments in direct-use textile filament yarns and as feed yarns in air-jet textured, wherein no draw is taken; and, if desired, can be drawn uniformly without heat (cold) in warp drawing (and air-jet texturing) as described in Knox and Noe U. S. Patent No. 5,066,447.
  • the filaments of 111-6,7, and 111-16 through 111-25 with T 7 -values less than about 1 g/d are especially suitable as filaments in draw feed yarns (DFY) , such as draw false-twist texturing (FTT) and draw air-jet texturing (AJT) or as draw feed yarns in warp drawing.
  • DTY draw feed yarns
  • FTT draw false-twist texturing
  • AJT draw air-jet texturing
  • Example III-4 had a spinning continuity of 0.39 breaks per 1000 lbs. (0.86 per 1000 kg) which is equivalent to about 9.5 breaks per 10 9 meters.
  • the yarns of Example III-4 were wound with about 10 cm interlace (as measured by the rapid pin count procedure described in U. S. Patent No. 3,290,932) for air-jet texturing on a Barmag FK6T-80 without drawing and wound with about 5-7 RPC interlace for direct-use as a flat textile yarn in wovens and warp knits.
  • Example III-6 and 7 were drawn without broken filaments at 1.44X and 1.7X, respectively, to give drawn 35 denier 68-filament yarns.
  • Example III-6 is preferred versus III-7 since the spinning productivity (spun denier x spin speed) of III-6 is about 25% greater than Example III-7.
  • Yarns of Example III-6 were successfully cold warp drawn using a 1.44X draw-ratio.
  • capillary spinnerets from 2.22 to 5.56, as per the teaching of Frankfort and Knox in U. S. Patent No.
  • the yarn bundle could be withdrawn as a single 136-filament bundle or split to wind-up two 68-filament yarn bundles.
  • Residence times (t r ) less than about 4 minutes for high L/D RND capillary spinnerets are found to be necessary to spin without having to use high "input" polymer temperatures (T p ). See Example IX for a more detailed discussion about the spinning with high shear capillary spinnerets.
  • T p high "input" polymer temperatures
  • the high filament count yarns are especially suitable for draw air-jet texturing (AJT) and for false-twist texturing (FTT), wherein, a
  • Example III-10 The structural properties of the filaments of Example III-10 are representative of spin-oriented filaments of this invention having shrinkages less than 6%.
  • Poly(ethylene terephthalate) of nominal 21.1 LRV (about 0.655 [ ⁇ ] ) and containing 0.3 weight percent TiO 2 was spun using apparatus similar to Example IV.
  • Examples V-1 through V-4, IV-9 and IV-10 use 12 ⁇ 50 mil (0.305 ⁇ 1.270 mm, 0.0305 ⁇ 0.127 cm) spinneret
  • Examples V-5, 7, 8, and 11 through 13 use 9x36 mil (0.229 ⁇ 0.914 mm, 0.0229 ⁇ 0.0914 cm) spinneret capillaries, and Example V-6 uses 6x18 mil (0.152 ⁇ 0.457 mm, 0.0152 ⁇ 0.0457 cm) spinneret capillaries to spin 100-filament 85 denier feed yarns for warp draw and draw air-jet texturing (AJT).
  • the length of delay quench (L DQ ) was increased from 2-5/8 inches (6.7 cm) to 4-5/8 inches (11.7 cm) in EX. V-8 and V-10.
  • Examples V- 11 through V-13 have tenacity-at-7%-elongation (T7) values less than about 1 g/d making them especially suitable as draw feed yarns even though the shrinkages of the undrawn yarns were less than 12%.
  • T7 tenacity-at-7%-elongation
  • Example VI Example V-13 was repeated at 3300 ypm (3.02 km/min) for varying spun deniers, delay quench lengths (L DQ ), spinning temperatures (T p ), and convergence guide lengths (L C ).
  • Example VI-2 with a denier spread (DS) of 3.8% was successfully drawn 1.35X to give a drawn 0.3 dpf 100-filament yarn with a 2.3% denier spread, tenacity of 4.4 g/d.
  • E B 32.5% and a boil-off shrinkage(S) of 6.3%. In this example it was observed that as total yarn bundle denier and
  • the along-end denier spread (DS) was improved from 12.1% (EX. VI-1) to less than 4% by reducing the delay length (LDQ) to about 2.9 cm and decreasing the convergence length (LQ) from 109 cm to 81 cm. For yarns with dpf less than 0.5 it is
  • capillaries provided better mechanical quality and along-end denier uniformity than the 12 ⁇ 50 mil metering capillaries.
  • the 100-filament yarns could be drawn without forming broken filaments to nominal 50 denier, or about 0.5 dpf.
  • isophthate having a nominal LRV of about 15.3 was spun using a laminar cross-flow quench apparatus with a 2.2 inches (5.6 cm) delay, essentially as described in U. S. Patent No. 4,529,638, and converging the filament bundle at about 43-inches (109 cm) with metered finish tip guides.
  • the lower LRV is usually preferred for ionically modified polyesters because the ionic sites act as cross linking agents and provide higher melt viscosity.
  • the 15 LRV used, herein, had a melt
  • viscosity about that of a 20 LRV homopolymer. If, however, one wanted to spin low LRV homopolymer, then typically it is advantageous to add viscosity builders, such as tetra-ethyl silicate (as described in Mead and Reese, U. S. Patent No. 3,335,211). It is generally preferred to spin ionically modified polyesters with LRV in the range of about 13 to about 18 and
  • nonionically modified polyesters with LRV in the range of about 18 to about 23. Withdrawal speeds were increased from 2400 ypm (2.2 km/min) to 3000 ypm (2.74 km/min). As expected the cationic copolymer yarns had lower T B -values based on their lower LRV.
  • the lower LRV is preferred for filaments yarns used in napped and brushed fabrics and for tows to be cut into flock.
  • the as-spun yarns could be drawn without breaking filaments to about 50 denier 100-filament yarns.
  • cationically modified polyester had a RDDR value of 0.225 versus 0.125 for the 2GT homopolymer spun under similar conditions.
  • Example IV LRV (about 0.67 [ ⁇ ]) and containing 0.3 weight percent Ti ⁇ 2 was spun using apparatus similar to Example IV with a air flow rate of about 30 m/min.
  • Examples IX-1 through IX-3 use 12 ⁇ 50 mil (0.305 ⁇ 1.270 mm,
  • Examples IX-4 through IX-8 use 9x36 mil (0.229 ⁇ 0.914 mm,
  • spinneret capillaries to spin nominal 50 denier 100-filament low-shrinkage yarns suitable as direct-use textile yarns for warp knits and wovens and as feed yarns for air-jet and stuffer-box texturing wherein no draw is required.
  • (T M ) a T M ° + 2 ⁇ 10 -4 [(L/D RND ) (Ga), °C.
  • the differential polymer spin temperature defined herein by: [T p -(T M ) a ] - [(T p -T M o ) -[2 ⁇ 10-4 (L/D RND )Ga], is effectively reduced as the product of the apparent shear rate (G a ) and L/D RND -ratio is increased; and thereby requiring an increase in polymer temperature Tp to maintain a minimum differential spin temperature at least about 25°C and, preferably at least about 30°C for spinning continuity. This is contrary to what is expected from the teachings of Frankfort and Knox.
  • Poly(ethylene terephthalate) of nominal 21.9 LRV (about 0.67 [ ⁇ ] ) and containing 0.3 weight percent Ti ⁇ 2 was spun using apparatus similar to Example IV with an air flow rate varied from about 11 to about 30 m/min.
  • Examples X-1 through X-9 use 12 ⁇ 50 mil
  • the fine filament feed yarns of Example V-11, 12, and 13 were uniformly drawn cold and at 155°C at 1.45X, 1.5X, and 1.55X draw-ratios, respectively, to give nominal 50 denier 100-filament drawn yarns that can be used as flat textile yarns.
  • the drawn fine filament yarns have excellent mechanical quality and along-end denier uniformity with boil-off shrinkages (S) less than about 6%.
  • S boil-off shrinkages
  • the cold drawn yarns had slightly less shrinkage than the hot drawn yarns and also were slightly more uniform. With less interlace levels and a different finish, these yarns may be cold drawn air-jet textured, consistent with the teachings of Knox and Noe in U. S. Patent No. 5,066,447.
  • These fine filament spun yarns could also be used as feed yarns for draw air-jet/stuffer-box/friction-twist texturing. Warp draw process and product details are summarized in Table VII.
  • EXAMPLE XII Examples III-20 through 25 were repeated by varying spin speed and spun denier to provide draw feed yarns capable of being drawn to provide 35 denier 68-filament yarns. Nominal 50 to 60 denier as-spun yarns with excellent mechanical quality and denier uniformity were drawn cold and heat set at 160°C to 180°C to obtain low shrinkage filaments of nominal 0.5 dpf yarns without loss in mechanical quality and along-end denier uniformity. Spin process and product details are summarized in Tables IV and V, and the corresponding draw process and product details are summarized in Table VII. EXAMPLE XIII
  • Example XIII the ability to obtain high T 7 fine filament yarns was explored. Spinning apparatus similar to that in Example X was used. Poly(ethylene terephthalate) of nominal 20.8 LRV (0.65 [ ⁇ ])
  • Example II containing 0.3 weight percent Ti ⁇ 2 was extruded through 9x36 mil (0.229 ⁇ 0.914 mm, 0.0229 ⁇ 0.0914 cm) spinneret capillaries and cooled using a radial quench apparatus as described in Example I, except for having a delay length L DQ of about 2.25 inches (5.7 cm). The cooled filaments were converged into yarn bundles at a
  • a 91 denier 100-filament yarn made according to Example IV was air-jet textured using a Barmag
  • the denier of the textured filament yarn showed an increase in yarn denier of about 11% due to bulk (e.g., filament loops), where the ratio (denier) AJT / (denier) FLAT is preferably greater than about 1.1); however, the filament denier showed no increase in denier.
  • Textured yarn strengths, as expected, were lower than that of a drawn flat yarn due to the filament loops; but are adequate for bulky fabric end-uses. Even at a 1.32X draw-ratio, giving a textured yarn with a 27.2% residual elongation
  • Example XIV-1 and 2 were uniformly cold partially drawn, as defined herein, by providing a RDR of at least about 1.4X in the drawn yarn. The capability of these fine filaments to be uniformly partially drawn is attributed to the crystalline structure of the as-spun filaments providing a thermal shrinkage less than about 12%, preferably less than about 10%, and especially less than about 8%, as per Knox and Noe in U. S. Patent No. 5,066,447. In Example XIV-5 through 8, 68-filament yarns were sequentially draw cold and air-jet textured. The shrinkage
  • Example XIV The process and product data for Example XIV is given in Table VIII.
  • Co-mingling (plying) 2 or more cold drawn AJT yarn textile yarns wherein at least one AJT yarn has been heat set to shrinkages less than about 3%, and a second AJT yarn has not been heatset, so has
  • shrinkage AJT yarns may be provided with the lower shrinkage component provided by alternate techniques, for instance by hot drawing, with or without heat setting.
  • mixed shrinkage AJT yarns may be provided by co-mingling 2 or more drawn filament bundles wherein both bundles are drawn by cold drawing, without post heat treatment, but the bundles are cold drawn to different elongations, preferably by about 10% or more.
  • the resulting mixed shrinkage drawn yarn may be AJT to provide a mixed shrinkage textured (bulked) yarn.
  • Incorporating filaments of different deniers and/or cross-sections may also be used to reduce filament-to-filament packing and thereby improve tactile aesthetics and comfort.
  • Example XV yarns were spun for use as draw feed yarns (DFY) in false twist texturing (FTT).
  • Example XV-1 a nominal 58 denier 68-filament yarn was textured at 500 m/min on a L900 PU machine with a 1.707 D/Y-ratio at a 1.628X draw to provide 68-filament textured yarns of nominal 37 denier (0.54 dpf) with a tenacity (T) of 4.1 g/d, an elongation-at-break (E B ) of 26.8%, a tenacity-at-7%-elongation (T 7 ) of 2.19 g/d, and an initial modulus (M) of 44.6 g/d.
  • T tenacity
  • E B elongation-at-break
  • T 7 tenacity-at-7%-elongation
  • M initial modulus
  • Example XV-2 a nominal 118 denier 200-filament draw feed yarn was prepared for false twist texturing, as in Example XV-1, except with a D/Y-ratio of 1.59 at a 1.461X draw-ratio to provide 200-filament textured yarns of 83.5 nominal denier (0.42 dpf) with a tenacity (T) of about 3.25 g/d and an elongation-at-break (E B ) of about 23.9%.
  • the 200-filament yarns were also successfully "partially" warp drawn as per the teachings of Knox and Noe in U. S. Patent No.
  • Example XV-3 a nominal 38 denier 100-filament yarn was prepared for use as a draw feed yarn in false-twist texturing and in warp drawing.
  • the process operability for Example XV-3 was better with 6x18 mil (0.152 ⁇ 0.457 mm) capillaries than with 9 ⁇ 36 mil (0.229 ⁇ 0.914 mm) capillaries.
  • the yarns of Example XV-3 were warp drawn over a range of conditions in Example XVIII to provide 0.22 to 0.27 dpf 100-filament yarns for wovens and knit fabrics.
  • Example XVI 21.2 LRV polyester polymer containing 0.035 weight percent TiO 2 was extruded at 285°C through 9 ⁇ 36 mil (0.229 ⁇ 0.914 mm) metering capillaries with a four-diamond-shaped corrugated ribbon cross-section exiting orifice of area 318 mils 2 (0.205 mm 2 ).
  • the 80 denier 100-filament bundles were quenched using radial quench apparatus similar to that used in Example III having a delay length of 2.9 cm and converged by a metered finish tip applicator at 109 cm from the face of the spinneret and withdrawn at a spin speed of 2350 ypm (2.15 km/min).
  • Example XVII nominal 43 denier 50- filaments with a concentric void of about 16-17% were spun at 3500 ypm (3.2 km/min) and at 4500 ypm (4.12 km/min).
  • the hollow filaments were formed by post- coalescence of nominal 21.2 LRV polymer at 290°C using segmented capillary orifices with 15 ⁇ 72 mil
  • the void content is found to increase with extrusion void area ( ⁇ ID 2 /4), mass flow rate, polymer melt viscosity (i.e., proportional to LRV/Tp) and with increasing withdrawal speed (V) and the above process parameters are selected to obtain at least about 10% and preferably at least about 15% void content (VC).
  • void content VC
  • the fine hollow filaments were quenched using radial quench apparatus fitted with a short delay shroud as described in Example XVI, except air flow was reduced to about 16 m/min and converged via a metered finish tip applicator at a distance less than about 140 cm.
  • the yarns spun at 3.2 km/min had
  • Example XVIII the spun yarns of Example XV-3 were drawn over a range of draw-ratios from 1.4X to 1.7X to provide drawn filament yarns of deniers 26.6 to 22.2, respectively; with tenacities increasing from 4.38 g/d to 5.61 g/d and elongations-at-break (E B ) decreasing from 36.6% to 15.8% with increasing drawratio. All the draw yarns had boil-off shrinkages (S) of about 4%. See Table VIII for process and product summery.
  • Example XIX-1 and XIX-2 200-filament and 168-filament yarns (feed yarns from Example XV-3 and 4, repsectively) of nominal 0.5 dpf were spun at 4400 ypm (4.02 km/min) for use as direct-use flat yarns in woven and knit fabrics. These yarns can also be air-jet textured (AJT) without draw to provide low-shrinkage AJT yarns of nominal 3% shrinkage.
  • Example XX mixed filament yarns were prepared by co-spinning sub denier filaments of the invention with higher denier filaments, such as the low shrinkage filaments as described by Knox in U. S.
  • shrinkage tension (e.g., at least about 0.15 g/d) which permits development of the bulk from the mixed- shrinkage even in very tightly constructed woven fabrics.
  • shrinkage power The combination of high shrinkage and high shrinkage tension (herein called shrinkage power) was heretofore only obtained, for example, by fully drawing conventional LOY/MOY/POY followed by no or low
  • the sub denier filaments of the invention migrate to the surface on mixed shrinkage and provide a soft luxurious tactile aesthetics even in the most tightly constructed fabrics.
  • the heat treatment is typically carried out after the filaments are fully attenuated and quenched to below their glass transition temperature and in a manner that the increase in tension during the heat treatment is of the magnitude equal to that of the observed increase in shrinkage tension by said heat treatment.
  • T CC cold crystallization temperature
  • T C maximum crystallization temperature
  • T C temperature of maximum crystallization
  • the filaments may be heated either by passing through high pressure superheated steam (e.g., 40-140 psi at about 245°C) or by passing through a heated tube.
  • the high and low dpf filaments may be spun from separate pack cavities and then combined to form a single mixed-dpf filament bundle or may be spun from a single pack cavity, wherein the capillary dimensions (L and D) and the number of capillaries # c are selected to provide for differential mass flow rates; e.g., by selecting capillaries such that the ratio of spun filament deniers, [ (dpf) b/ (dpf) a ], is approximately equal to [ (LaD b /L b D a ) n ⁇ (V a /V b ) ⁇
  • Example XXII 50 denier 68-filament undrawn flat textile yarns were uniformly cold drawn and heat treated at 160, 170, and 180°C to provide nominal 36 denier 50 filament drawn yarns of about 4-5% boil-off shrinkage (S) with a T 7 of about 3.5 g/d, a tenacity of about 4.5 g/d with an elongation-at-break (E ⁇ ) of about 27%.
  • the drawn yarns have a percent Uster of about 2.1-2.4% and may be used for critically dyed fabrics.
  • the fine denier filaments of this invention may be used to cover elastomeric yarns (and tapes) by high speed air-jet entanglement as taught by Strachan in U. S. Patent No. 3,940,917. Polyester fine
  • filaments prepared from polymer modified for cationic dyeability are especially suitable for elastomeric yarns, such as Lycra® to prevent "bleeding" of the dyestuff from the elastomeric yarns, such as observed for Lycra® covered with homopolymer polyester dyed with nonionic disperse dyes.
  • the direct-use filaments of this invention are preferred (and those with increased shrinkage, shrinkage tension, and shrinkage power as described in Example XX are especially preferred) for air-entanglement covering and permit the covered elastomeric yarns to be dyed under atmospheric
  • Some example fabrics made from the yarns of the invention are: 1) a medical barrier fabric
  • T M Zero-shear polymer melting point (°C)
  • T M a Apparent melting point of polymer
  • V F Spin pack (filled) free-volume (cm 3 )
  • Mi Instantaneous tensile modulus (g/d) M Initial (Young's) tensile modulus (g/d) M py Post yield modulus (g/d)
  • V f am Amorphous free-volume ( ⁇ 3 )

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  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

On prépare de minces filaments de polyester dont la qualité mécanique et l'uniformité sont excellentes, et présentant de préférence un équilibre de bonne qualité de teinture et de rétrécicement, à l'aide d'un procédé simplifié d'orientation du filage direct dans lequel on sélectionne la viscosité du polymère et les conditions du filage.
PCT/US1992/000359 1991-01-29 1992-01-29 Procede de preparation de minces filaments de polyester WO1992013119A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU12310/92A AU653207B2 (en) 1991-01-29 1992-01-29 Preparing polyester fine filaments
KR1019930702247A KR0181183B1 (ko) 1991-01-29 1992-01-29 폴리에스테르 미세 필라멘트의 제조
DE69221739T DE69221739T2 (de) 1991-01-29 1992-01-29 Herstellung von feinen polyesterfilamenten
JP4504583A JP3043414B2 (ja) 1991-01-29 1992-01-29 ポリエステルの細いフィラメントの製造法
CA002101788A CA2101788C (fr) 1991-01-29 1992-01-29 Preparation de filaments fins de polyester
EP92904563A EP0646189B1 (fr) 1991-01-29 1992-01-29 Procede de preparation de minces filaments de polyester
TW081102473A TW215113B (fr) 1991-01-29 1992-04-01
BR9205719A BR9205719A (pt) 1991-01-29 1994-11-21 Preparaçao de filamentos delgados de polièster

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US64737191A 1991-01-29 1991-01-29
US64738191A 1991-01-29 1991-01-29
US647,371 1991-01-29
US647,381 1991-01-29
CN92103680A CN1047634C (zh) 1991-01-29 1992-04-11 纺丝—取向的聚酯细丝及其制备方法
PCT/US1994/013189 WO1996016206A1 (fr) 1993-06-29 1994-11-21 Ameliorations apportees a des filaments, des fils et des cables continus

Publications (1)

Publication Number Publication Date
WO1992013119A1 true WO1992013119A1 (fr) 1992-08-06

Family

ID=27179019

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/000359 WO1992013119A1 (fr) 1991-01-29 1992-01-29 Procede de preparation de minces filaments de polyester

Country Status (10)

Country Link
EP (1) EP0646189B1 (fr)
JP (1) JP3043414B2 (fr)
CN (1) CN1047634C (fr)
AU (1) AU653207B2 (fr)
BR (1) BR9205719A (fr)
CA (1) CA2101788C (fr)
DE (1) DE69221739T2 (fr)
ES (1) ES2104898T3 (fr)
TW (1) TW215113B (fr)
WO (1) WO1992013119A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994003661A1 (fr) * 1992-08-05 1994-02-17 E.I. Du Pont De Nemours And Company Fins filaments creux en polyester
WO1994003660A1 (fr) * 1992-08-05 1994-02-17 E.I. Du Pont De Nemours And Company Filaments melanges a du polyester a brins fins
WO1997006295A1 (fr) * 1995-08-04 1997-02-20 E.I. Du Pont De Nemours And Company Fabrication de fils de filament de polyester, de titre fin, a nombre de filaments eleve
WO2000070132A1 (fr) * 1999-05-14 2000-11-23 Lurgi Zimmer Aktiengesellschaft Procede de production de fils synthetiques ultrafins
WO2003091485A1 (fr) * 2002-04-25 2003-11-06 Teijin Fibers Limited Procede pour produire un fil multifilament extra-fin en polyester et un fil texture par fausse torsion extra-fin en polyester, fil multifilament extra-fin en polyester et fil texture par fausse torsion extra-fin en polyester
US6736624B1 (en) 1999-05-29 2004-05-18 Zimmer Aktiengesellschaft Spinning device for spinning molten polymers and method for heating the spinning device
US7087299B2 (en) 2003-01-16 2006-08-08 Teijin Fibers Limited Polyester fibers and false twist-textured yarn comprising same
US8940209B2 (en) 2006-07-10 2015-01-27 Sabic Global Technologies B.V. Polyetherimide polymer for use as a high heat fiber material
US9416465B2 (en) 2006-07-14 2016-08-16 Sabic Global Technologies B.V. Process for making a high heat polymer fiber

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1092721C (zh) * 1995-08-04 2002-10-16 纳幕尔杜邦公司 高支长丝细聚酯纱的制造方法及由该方法制得的产品
DE19821778B4 (de) 1998-05-14 2004-05-06 Ems-Inventa Ag Vorrichtung und Verfahren zur Herstellung von Mikrofilamenten von hoher Titer-Gleichmäßigkeit aus thermoplastischen Polymeren
DE19951067B4 (de) * 1999-10-22 2004-04-08 Inventa-Fischer Ag Polyesterfasern mit verminderter Pillingneigung sowie Verfahren zu ihrer Herstellung
MXPA01011167A (es) * 2000-03-03 2002-05-06 Du Pont Hilo de poli(tereftalato de trimetileno).
JP5908811B2 (ja) * 2012-09-07 2016-04-26 有限会社ナイセム 長期間生体内植え込み用極細繊維製医療材料
CN110938882B (zh) * 2019-12-11 2020-12-29 诸暨市百乐化纤有限公司 一种高性能涤纶poy制备装置及方法
CN111041578B (zh) * 2019-12-24 2022-03-18 江苏恒力化纤股份有限公司 粘度不同的pet双组份弹性丝及其制备方法
CN111893586B (zh) * 2020-07-21 2021-11-09 合肥洁诺无纺布制品有限公司 一种聚酯纤维加工用过滤装置
CN112923904B (zh) * 2021-01-26 2022-09-23 四川融鑫信息科技有限公司 面向多无人机协同摄影测量的地质灾害隐患探测方法
CN115233324B (zh) * 2022-08-05 2023-11-03 常州德利斯护理用品有限公司 一种制备不同截面异型纤维的纺黏牵伸装置

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US4134882A (en) * 1976-06-11 1979-01-16 E. I. Du Pont De Nemours And Company Poly(ethylene terephthalate)filaments
US4156071A (en) * 1977-09-12 1979-05-22 E. I. Du Pont De Nemours And Company Poly(ethylene terephthalate) flat yarns and tows
US4529368A (en) * 1983-12-27 1985-07-16 E. I. Du Pont De Nemours & Company Apparatus for quenching melt-spun filaments
US4926661A (en) * 1989-03-15 1990-05-22 E. I. Du Pont De Nemours And Company Yarn finish applicator

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JPS5562209A (en) * 1978-10-30 1980-05-10 Toray Ind Inc Melt spinning of ultra-fine fiber

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US4134882A (en) * 1976-06-11 1979-01-16 E. I. Du Pont De Nemours And Company Poly(ethylene terephthalate)filaments
US4156071A (en) * 1977-09-12 1979-05-22 E. I. Du Pont De Nemours And Company Poly(ethylene terephthalate) flat yarns and tows
US4529368A (en) * 1983-12-27 1985-07-16 E. I. Du Pont De Nemours & Company Apparatus for quenching melt-spun filaments
US4926661A (en) * 1989-03-15 1990-05-22 E. I. Du Pont De Nemours And Company Yarn finish applicator

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PATENT ABSTRACTS OF JAPAN vol. 11, no. 75 (C-408)(2522) 6 March 1987 & JP,A,61 231 227 ( ASAHI CHEM IND CO LTD ) 15 October 1986 *
PATENT ABSTRACTS OF JAPAN vol. 12, no. 122 (C-488)(2969) 15 April 1988 & JP,A,62 243 824 ( TEIJIN LTD ) 24 October 1987 *
PATENT ABSTRACTS OF JAPAN vol. 4, no. 101 (C-19)(583) 19 July 1980 & JP,A,55 062 209 ( TORAY K.K. ) 10 May 1980 *

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994003661A1 (fr) * 1992-08-05 1994-02-17 E.I. Du Pont De Nemours And Company Fins filaments creux en polyester
WO1994003660A1 (fr) * 1992-08-05 1994-02-17 E.I. Du Pont De Nemours And Company Filaments melanges a du polyester a brins fins
WO1997006295A1 (fr) * 1995-08-04 1997-02-20 E.I. Du Pont De Nemours And Company Fabrication de fils de filament de polyester, de titre fin, a nombre de filaments eleve
WO2000070132A1 (fr) * 1999-05-14 2000-11-23 Lurgi Zimmer Aktiengesellschaft Procede de production de fils synthetiques ultrafins
US6736624B1 (en) 1999-05-29 2004-05-18 Zimmer Aktiengesellschaft Spinning device for spinning molten polymers and method for heating the spinning device
WO2003091485A1 (fr) * 2002-04-25 2003-11-06 Teijin Fibers Limited Procede pour produire un fil multifilament extra-fin en polyester et un fil texture par fausse torsion extra-fin en polyester, fil multifilament extra-fin en polyester et fil texture par fausse torsion extra-fin en polyester
US7078096B2 (en) 2002-04-25 2006-07-18 Teijin Fibers Limited Method for producing polyester extra fine multi-filament yarn and polyester extra fine false twist textured yarn, polyester extra fine multi-filament yarn, and polyester extra-fine false twist textured yarn
KR100984991B1 (ko) * 2002-04-25 2010-10-04 데이진 화이바 가부시키가이샤 폴리에스테르 극세 멀티필라멘트사 및 폴리에스테르 극세가연 가공사의 제조 방법, 폴리에스테르 극세멀티필라멘트사, 폴리에스테르 극세 가연 가공사
US7087299B2 (en) 2003-01-16 2006-08-08 Teijin Fibers Limited Polyester fibers and false twist-textured yarn comprising same
US8940209B2 (en) 2006-07-10 2015-01-27 Sabic Global Technologies B.V. Polyetherimide polymer for use as a high heat fiber material
US9416465B2 (en) 2006-07-14 2016-08-16 Sabic Global Technologies B.V. Process for making a high heat polymer fiber

Also Published As

Publication number Publication date
EP0646189A1 (fr) 1995-04-05
CA2101788C (fr) 2002-05-28
AU653207B2 (en) 1994-09-22
TW215113B (fr) 1993-10-21
CN1077233A (zh) 1993-10-13
DE69221739D1 (de) 1997-09-25
BR9205719A (pt) 1994-04-26
CN1047634C (zh) 1999-12-22
EP0646189B1 (fr) 1997-08-20
AU1231092A (en) 1992-08-27
CA2101788A1 (fr) 1992-07-30
JPH06507212A (ja) 1994-08-11
DE69221739T2 (de) 1998-03-12
JP3043414B2 (ja) 2000-05-22
ES2104898T3 (es) 1997-10-16

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