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EP1068378B1 - Drawing of polyester filaments - Google Patents

Drawing of polyester filaments Download PDF

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Publication number
EP1068378B1
EP1068378B1 EP98913243A EP98913243A EP1068378B1 EP 1068378 B1 EP1068378 B1 EP 1068378B1 EP 98913243 A EP98913243 A EP 98913243A EP 98913243 A EP98913243 A EP 98913243A EP 1068378 B1 EP1068378 B1 EP 1068378B1
Authority
EP
European Patent Office
Prior art keywords
filaments
round
mixture
cross
scalloped
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP98913243A
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German (de)
English (en)
French (fr)
Other versions
EP1068378A1 (en
Inventor
Arun Pal Aneja
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
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Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP1068378A1 publication Critical patent/EP1068378A1/en
Application granted granted Critical
Publication of EP1068378B1 publication Critical patent/EP1068378B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • D01D5/253—Formation of filaments, threads, or the like with a non-circular cross section; 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
    • 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
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters

Definitions

  • This invention concerns improved drawing of polyester filaments, and more particularly a process for drawing mixed polyester filaments in the same bundle, especially drawing a tow of such mixed filaments, and the resulting drawn filaments and bundles and downstream processes therefor and products thereof.
  • Polyesters have been produced commercially on a large scale for processing into shaped articles such as fibers, primarily from poly(ethylene terephthalate). Synthetic polyester yarns have been known and used commercially for several decades, having been first suggested by W. H. Carothers, U.S. Patent No. 2,071,251, and then Whinfield and Dickson suggested poly(ethylene terephthalate) in U.S. Patent No. 2,465,319.
  • polyester polymers including copolymers
  • the polyester most widely manufactured and used hitherto for textile fibers has been poly(ethylene terephthalate), which is often referred to as homopolymer PET.
  • homopolymer PET has generally been preferred over copolymers because of its lower cost, and also because its properties have been entirely adequate, or even preferred, for most end-uses. It is known, however, that homopolymer PET requires special dyeing conditions (high temperature requiring super-atmospheric pressure) not required for nylon fibers, for example, so copolyesters have been suggested and used commercially for some purposes.
  • Homopolymer PET is often referred to as 2G-T
  • poly(trimethylene terephthalate) is referred to as 3G-T (although some have started calling this PTT)
  • poly(tetramethylene terephthalate) is referred to as 4G-T, and so on.
  • Polyester fibers are either (1) continuous filaments or (2) fibers that are discontinuous, which latter are often referred to as staple fiber or cut fibers, and are made by first being formed by extrusion into continuous polyester filaments, which are processed in the form of a tow of continuous polyester filaments before being converted into staple.
  • An important stage in the processing of such continuous polyester filaments has been "drawing" to increase the orientation of the long chain polyester molecules, and thereby improve the properties of the filaments.
  • the present invention relates to improvements in this drawing stage and to the improved products resulting therefrom.
  • the present invention has been made in the course of that work, so is described with particular reference to its value in drawing polyester filaments in tows for further processing in such systems, but is not confined to drawing such tows and is believed to have potential for use more broadly when drawing other bundles of polyester filaments.
  • a process of simultaneously drawing a mixture of polyester filaments in the same bundle of polyester filaments wherein said mixture is a mixture of filaments of different cross-sections, the mixture including polyester filaments having cross-sections selected from at least two of the following types of cross-sections: scalloped-oval; trilobal; ribbon-shaped; solid; hollow; multi-void; and round, and wherein said polyester is chain-branched with 0.1 to 0.8 mole % of chain-brancher.
  • the mole % is calculated conventionally as the molecular weight of the chain-brancher unit divided by the molecular weight of the polymer repeat unit times 100, the repeat unit for 2G-T being ethylene terephthalate by way of example.
  • a mixture of polyester filaments wherein said mixture is a mixture of filaments of different cross-sections, the mixture including polyester filaments having cross-sections selected from at least two of the following types of cross-sections: scalloped-oval; trilobal; ribbon-shaped; solid; hollow; multi-void; and round, and wherein said polyester is chain-branched with 0.1 to 0.8 mole % of chain-brancher, and wherein the boil-off shrinkage is 0.5 to 3%.
  • Such mixtures may be in the form of continuous filamentary drawn tows and drawn yarns, and downstream products of mixtures of polyester filaments resulting therefrom, including mixtures of staple (cut) fiber in various forms, including yarns, and fabrics and garments as well as the yarns themselves, and it will be understood that the resulting mixtures of polyester fibers may also be mixed with other fibers, such as of other synthetic polymers, including polyamides (nylons of various types) and polyolefins, for example, and/or natural fibers, such as cotton and wool.
  • other synthetic polymers including polyamides (nylons of various types) and polyolefins, for example, and/or natural fibers, such as cotton and wool.
  • a mixture of polyester filaments obtainable by simultaneously drawing a mixture of polyester filaments in the same bundle of polyester filaments, wherein said mixture is a mixture of filaments of different cross-sections, the mixture including polyester filaments having cross-sections selected from at least two of the following types of cross-sections: scalloped-oval; trilobal; ribbon-shaped; solid; hollow; multi-void; and round, and wherein said polyester is chain-branched with 0.1 to 0.8 mole % of chain-brancher, and wherein the boil-off shrinkage is 0.5 to 3%.
  • filament and fiber are used inclusively herein, and are not generally intended to be mutually exclusive; sometimes, however, these general terms are modified, as in terms such as “continuous filament” and “staple fiber”.
  • the essence of the invention is the use of chain-branched polyester polymer to make the polyester filaments that are drawn according to the process of the invention to provide the mixtures of filaments according to the invention.
  • chain-branchers i.e., multi-functional, polyester-forming intermediates having more than the requisite two functional groups that are required for polymerization, such as a glycol and a dibasic acid, both of which are difunctional
  • MacLean et al U.S. Patent Nos. 4,092,299 and 4,113,704
  • U.S. Patent No. 5,591,523 and WO 97/02372 have already disclosed in Example I the simultaneous drawing of a tow of polyester filaments of mixed dpf and that it was surprising that this could be accomplished to give drawn filaments that were satisfactory and with no dark dye defects. Such a process and the resulting drawn filaments of mixed dpf, all of scalloped-oval cross-section, have already been disclosed therein.
  • U.S. Patent No. 5,629,961 and WO 97/02373 have disclosed filaments of improved scalloped-oval cross-section with 6 grooves, and have incorporated the disclosure of U.S. Patent No. 5,591,523, as did WO 97/02374 and allowed U.S.
  • the average stress-strain curves were obtained as follows as an average of 10 individual filaments of each type taken from the tow bundle. Ten samples of each type of filament were separated from the tow bundle using a magnifying glass (LUXO Illuminated Magnifier). The denier per filament (DPF) of each sample filament was measured on a VIBROSCOPE (HP Model 201C Audio Oscillator). The sample filaments were mounted one at a time on an INSTRON (Model 1122 or 1123) and the stress-strain behavior was measured.
  • VIBROSCOPE HP Model 201C Audio Oscillator
  • Crimp Frequency was measured as the number of crimps per inch (CPI) after the crimping of the tow.
  • the crimp is exhibited by numerous peaks and valleys in the fiber.
  • Ten filaments are removed from the tow bundle at random and positioned (one at a time) in a relaxed state in clamps of a fiber-length measuring device.
  • the clamps are manually operated and initially moved close enough together to prevent stretching of the fiber while placing it in the clamp.
  • One end of a fiber is placed in the left clamp and the other end in the right clamp of the measuring device.
  • the left clamp is rotated to remove any twist in the fiber.
  • the right clamp support is moved slowly and gently to the right (extending the fiber) until all the slack has been removed from the fiber but without removing any crimp.
  • the crimp frequency for each filament is calculated as: Total Number of Peaks 2 x Length of Filament (uncrimped)
  • the average of the 10 measurements of all 10 fibers is recorded for the CPI (crimps per inch), the metric equivalent being CPcm.
  • CTU Chip Take Up
  • Aspect Ratios or Modification Ratios for the non-round cross-sections are given in the Tables in parentheses after indication of the type of cross-section, e.g., "SO (1.37)” indicates a scalloped-oval cross-section of Aspect Ratio 1.37.
  • void contents are given in parentheses after indication of a hollow cross-section, e.g., a void content of 7% is shown as "Hollow (7%)", being measured as described by Aneja et al. in U.S. Patent No. 5,532,060.
  • Relative Viscosity is the viscosity of polymer dissolved in HFIP solvent (hexafluoro-isopropanol) containing 100 ppm of 98% reagent grade sulfuric acid.
  • the viscosity measuring apparatus is a capillary viscometer obtainable from a number of commercial vendors (Design Scientific, Cannon, etc.).
  • the relative viscosity in centistokes is measured on a 4.75 wt. % solution of polymer in the solvent at 25°C.
  • the H 2 SO 4 used for measuring LRV destroys cross-links, specifically silicon in the case of tetraethyl ortho silicate chain-brancher.
  • Non-Acid Relative Viscosity is the viscosity of polymer similarly dissolved, measured and compared in hexafluoro-isopropanol solvent but without any sulfuric acid. Since the acid is not present, the cross-links are left intact when the NRV is measured.
  • Delta RV ( ⁇ RV) is the expression we have used herein to define the difference between the NRV and the LRV measured as described above, and express the amount of cross-linking destroyed by the acid when measuring LRV.
  • the first two defects are fibers and clumps of fibers that dye darker than normal fibers.
  • DDDs have a diameter less than 4X the normal (drawn) fiber diameter.
  • EFDs have a diameter 4X the normal fiber diameter or greater. Both defects must be longer than 0.25 inch (6.35 mm).
  • Samples are processed through a roller top type card. The sliver is dyed light blue and examined visually under a lighted magnifying glass. Fibers that dye darker than the bulk of the sample are removed, classified as EFDs or DDDs and counted. Each type of defect is reported as number of defects per 0.1 pounds (0.045 Kg) sliver. Splinters are oversized fibers or clumps of fibers.
  • this defect must also be longer than 0.25 inch (6.35 mm) but its total diameter must be greater than 0.0025 inch (0.0635 mm).
  • Splinters are concentrated in the flat strip waste when a staple sample is processed through a flat card. The flat strip waste is visually examined against a black background. Splinters are removed, classified by size, counted, and expressed on a weight of sample basis.
  • Mixed filaments were melt spun at 282°C from chain-branched ethylene terephthalate polymer, such mixed filaments being a mixture of light filaments (finer denier) of scalloped-oval (SO) cross-section and of heavy filaments (heavier denier) of round cross-section.
  • the different filaments were melt-spun simultaneously through different capillaries in the same spinneret, each containing 1000 capillaries, from polymer containing 0.24% (0.22 mole %) tetraethyl silicate (TES, essentially as described in Mead et al., U.S. Patent No.
  • the smaller non-round capillaries were located on the inner five (of 9) rings while the larger round capillaries were located on the outer four rings of the spinneret.
  • the orifice shape for the scalloped-oval capillaries was essentially as described in U.S. application No. 08/662,804 (DP-6400) and WO 97/02374 referred to hereinbefore.
  • the molten filamentary streams were quenched using radially-directed air from a profiled quench system, as described in Anderson, et al., U.S. Patent No. 5,219,582.
  • the resulting spun filament bundle consisted of a mixture of different cross-sections and of lower and higher denier filaments with properties indicated in Table 1A.
  • a conventional finish was applied to provide a finish level (on fiber) of 0.15%.
  • the nominal denier per filament i.e., the denier of the total tow bundle divided by the number of filaments
  • the nominal denier per filament i.e., the denier of the total tow bundle divided by the number of filaments
  • the round filaments were extruded at a rate of 85.2 lbs/hr (38.7 Kg/hr) from a 520 capillary spinneret.
  • the hollow filaments were extruded at a rate of 80.4 lbs./hr (36.5 Kg/hr) from a 490 capillary spinneret, using an orifice shape essentially as described in Figure 5B of U.S. Patent No. 5,356,582.
  • the scalloped-oval filaments were extruded at a rate of 73.8 lbs/hr (33.5 Kg/hr) from a 450 capillary spinneret.
  • Stress/strain curves of single filaments of each type are shown in Figure 4, together with a Curve 3C that is a stress-strain curve for a 6-grooved filament that is described in Example 3 hereinafter.
  • Example 1 Conventional finish was applied as in Example 1, and the tow was processed and scrutinized for Product Defects. It was surprising, in view of previous attempts with conventional filaments, that the sliver resulting from this Example of an intimate blend of three different cross-sections (round, hollow, and scalloped-oval), did not show any Product Defects of EFD, DDD, and SPL, despite having been drawn simultaneously.
  • the drawn tow (8.3 CPI, 3.3 CPcm, 19.9 CTU) of 2.85 nominal dpf (3.2 dtex) was processed and showed zero Product Defects (EFD, DDD, SPL).
  • Twenty bobbins of round filaments (66,924 denier, 74,360 dtex), thirty-five bobbins of trilobal filaments (64,400 denier, 71,555 dtex), four bobbins of scalloped-oval filaments (20,520 denier, 22,800 dtex), and five bobbins of hollow filaments (21,054 denier, 23,393 dtex) were combined to form a tow having nominal blend ratio of 39% round, 37% trilobal, 12% scalloped-oval and 12% hollow filaments with a total denier of 172,898 (192,108 dtex).
  • the tow was drawn, crimped and relaxed essentially as described in Example 2 to give a drawn tow of approximately 64,490 denier (71,655 dtex) of an intimate blend containing these four differently-shaped crimped (8.9 CPI, 3.5 CPcm, 20 CTU) filaments - round, trilobal, scalloped-oval, and hollow - with a nominal 4.3 dpf (4.8 dtex). Filament properties are listed in Table 4B. The drawn dpfs were significantly different although the spun dpfs were very similar, which shows the difficulty of predicting beforehand what will happen when mixed filaments are drawn together.
  • Example 1 Conventional finish was applied as in Example 1.
  • the drawn tow was processed to show zero Product Defects (EFD, DDD, SPL).
  • the crimp was measured as 8.9 CPI, 3.5 CPcm and 22.5 CTU.
  • the tow was processed to show zero Product Defects (EFD, DDD, SPL), despite the drawn dpfs and filament properties being significantly different from those in Table 4B. This confirms the difficulty of predicting behavior of filaments during drawing.
  • Example 1 Conventional finish was applied as in Example 1. Both drawn tows were processed and showed zero Product Defects (EFD, DDD, SPL), again despite the filaments having significantly different properties from those drawn in other Examples.
  • ESD Product Defects
  • Example 7 is similar to Example 1 of U.S. Patent No. 5,591,523 in that filaments of scalloped-oval cross-section of differing deniers were simultaneously drawn in the same bundle, but different in that in the present Example 7 both types of filaments were made by spinning through different capillaries in the same spinneret.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP98913243A 1998-03-31 1998-03-31 Drawing of polyester filaments Expired - Lifetime EP1068378B1 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/006154 WO1999050483A1 (en) 1998-03-31 1998-03-31 Drawing of polyester filaments

Publications (2)

Publication Number Publication Date
EP1068378A1 EP1068378A1 (en) 2001-01-17
EP1068378B1 true EP1068378B1 (en) 2004-10-13

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ID=22266706

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EP98913243A Expired - Lifetime EP1068378B1 (en) 1998-03-31 1998-03-31 Drawing of polyester filaments

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EP (1) EP1068378B1 (ja)
JP (1) JP2002509995A (ja)
AU (1) AU6783898A (ja)
DE (1) DE69827045T2 (ja)
ES (1) ES2230684T3 (ja)
PT (1) PT1068378E (ja)
TW (1) TW567255B (ja)
WO (1) WO1999050483A1 (ja)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6458455B1 (en) 2000-09-12 2002-10-01 E. I. Du Pont De Nemours And Company Poly(trimethylene terephthalate) tetrachannel cross-section staple fiber
US6752945B2 (en) 2000-09-12 2004-06-22 E. I. Du Pont De Nemours And Company Process for making poly(trimethylene terephthalate) staple fibers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5188892A (en) * 1986-10-31 1993-02-23 E. I. Du Pont De Nemours And Company Spun textile yarns
US5591523A (en) * 1995-06-30 1997-01-07 E. I. Du Pont De Nemours And Company Polyester tow

Also Published As

Publication number Publication date
DE69827045T2 (de) 2005-09-08
PT1068378E (pt) 2005-02-28
EP1068378A1 (en) 2001-01-17
WO1999050483A1 (en) 1999-10-07
TW567255B (en) 2003-12-21
ES2230684T3 (es) 2005-05-01
JP2002509995A (ja) 2002-04-02
DE69827045D1 (de) 2004-11-18
AU6783898A (en) 1999-10-18

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