US3558420A - Hollow filaments - Google Patents
Hollow filaments Download PDFInfo
- Publication number
- US3558420A US3558420A US661348A US3558420DA US3558420A US 3558420 A US3558420 A US 3558420A US 661348 A US661348 A US 661348A US 3558420D A US3558420D A US 3558420DA US 3558420 A US3558420 A US 3558420A
- Authority
- US
- United States
- Prior art keywords
- polymer
- spinnerette
- filaments
- orifices
- orifice
- 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
Links
- 229920000642 polymer Polymers 0.000 abstract description 96
- 239000003658 microfiber Substances 0.000 abstract description 14
- 229920000728 polyester Polymers 0.000 abstract description 10
- 239000004952 Polyamide Substances 0.000 abstract description 8
- 229920002647 polyamide Polymers 0.000 abstract description 8
- 229920001059 synthetic polymer Polymers 0.000 abstract description 7
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 description 32
- 238000001125 extrusion Methods 0.000 description 19
- 238000004581 coalescence Methods 0.000 description 15
- 229920001410 Microfiber Polymers 0.000 description 13
- 238000002074 melt spinning Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 238000002844 melting Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- -1 polyethylene terephthalate Polymers 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- 238000009987 spinning Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229920002959 polymer blend Polymers 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 239000003570 air Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000004753 textile Substances 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 230000009969 flowable effect Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 229920005621 immiscible polymer blend Polymers 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LRLYTJCVZKVBIH-UHFFFAOYSA-N 3,10-dioxatricyclo[10.2.2.25,8]octadeca-1(15),5,7,12(16),13,17-hexaene-2,11-dione Chemical compound C1OC(=O)C(C=C2)=CC=C2C(=O)OCC2=CC=C1C=C2 LRLYTJCVZKVBIH-UHFFFAOYSA-N 0.000 description 1
- 241000272517 Anseriformes Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000112 cooling gas Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000005865 ionizing radiation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920006149 polyester-amide block copolymer Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009958 sewing Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/30—Extrusion nozzles or dies
- B29C48/345—Extrusion nozzles comprising two or more adjacently arranged ports, for simultaneously extruding multiple strands, e.g. for pelletising
-
- 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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
- B29C48/11—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels comprising two or more partially or fully enclosed cavities, e.g. honeycomb-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/12—Articles with an irregular circumference when viewed in cross-section, e.g. window profiles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2973—Particular cross section
- Y10T428/2975—Tubular or cellular
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
- Y10T428/31736—Next to polyester
Definitions
- a hollow filament of synthetic polymer material consisting of a sheath surrounding a longitudinally extended cavity.
- the sheath comprises a continuous phase polyamide polymer containing dispersed therein a polyester in the form of microfibers lying predominantly in the direction of the axis of the filament.
- This invention relates to novel hollow synthetic filaments and to the production thereof. More particularly, it relates to the production of said filaments by extruding a molten synthetic polymer material through a spinnerette containing at least one unobstructed orifice followed by controlled cooling of the freshly spun filaments to effect solidification thereof.
- hollow synthetic filaments have certain advantages over solid filaments having the same outside diameter. Some of the advantages which hollow filaments have compared to solid filaments include improved insulating properties, increased bouyancy, and greater covering power (e.g., in carpet yarn) per unit weight. Hollow filaments composed of polymer blends also have less tendency to fibrillate under flexing conditions than corsponding solid filaments.
- spinnerette employs orifices containing an internal obstructing member which causes the orifice to function as an annulus, said obstructing member being joined to the spinnerette body by internal support members upstream from the extrusion face of the spinnerette.
- This type of spinnerette and others which have been designed to prod-nee hollow filaments are not only hard to make but are extremely difiicult to maintain in a good state of repair and cleanliness.
- spinnerettes which have been studied employ a multitude of simple, unobstructed orifices grouped in a perimeter. They are so closely spaced that, upon extrusion, molten polymer emerging from each of the orifices" coalesces with extrudates from the adjacent orifices of the group to form a continuum of the polymer substrate which, after rapid cooling, forms a hollow-shaped filament.
- the filament is hollow because the area encompassed by the perimeter of orifices contains no openings and thereby blocks passage of polymer.
- These spinnerettes require very close spacing between adjacent orifices to permit coalescence of extrudate streams with the result that the thickness of the intervening metal between ori- Ice fices is so small as to cause structural weakness and difficulties of fabrication.
- Another object is to provide an improved melt-spinning process for the production of hollow synthetic filaments.
- Yet another object of the present invention is to provide a melt-spinning process for the production of hollow synthetic filaments using a spinnerette having unobstructed orifices which provide at least one gap in an otherwise continuous periphery of openings encompassing a polymer occluding area.
- FIG. 1 is a vertical sectional view of part of a spinnerette useful in the practice of the present invention
- FIGS. 2 to 8 are plan views of spinnerette orifice arrangements according to the present invention comprising more than one discrete unobstructed orifice, each of said orifice arrangements having a perimetric configuration about a polymer occluding area.
- the spinnerette illustrated in FIG. 8 is disclosed and claimed in copending U.S. application Ser. No. 687,170, :filed Dec. 1, 1967.
- FIG. 9 is a plan view of a spinnerette orifice arrangement according to the present invention comprising a single discrete orifice conformed into an encircling configuration about a polymer occluding area.
- FIG. 10 is a partial sectional view showing the coalescence of polymer extrudates downstream from the spinnerette.
- FIGS. 11 and 12 are cross-sectional views of hollow filaments produced in accordance with the present invention.
- spinnerette 1 has an upstream face 3 and downstream extrusion face 5.
- Spinnerette 1 being typical of those employed in melt-spinning of synthetic fibers, is generally about 0.2-1.0 inch thick and may be of monolithic or laminated construction. It is generally made of steel or other high strength metal or alloy.
- Counterbore depression 7 may be formed in the upstream face of spinnerette 1 in order to minimize the length of capillaries 9 leading to orifices 11 which define polymer occluding area 13.
- the capillaries of spinnerettes useful in the practice of the present invention are generally of constant cross section throughout their length, i.e., the capillary wall is a cylindric surface as may be formed by circular movement of a straight line parallel to a given fixed centrally located straight line.
- the capillary may however, be slightly chamfered at either or both ends.
- the capillaries may be made by standard techniques which include: drilling with rotary drills; drilling with pneumatic devices or electrodes; punching techniques; and insertion of shaped wires into differently shaped capillaries (as disclosed in US Pat. 3,174,364).
- the capillaries are preferably perpendicular to the extrusion face but may be angled to direct extrudate streams toward one another for improved coalescence.
- portion 15 of spinnerette .1 contains a circumscribing arrangement of six individual orifices 17, each having diameter, D Orifices 17 are perimetrically disposed in symmetrical arrangement about central point 19, thereby defining central polymer occluding area 21, having average diameter D taken as the diameter of the circle which tangentially contacts the orifices at points closest to central point 19.
- Spacings 23 provide passages through which the occluding area 2.1 communicates with the rest of the spinnerette face. As will be explained more fully hereinafter, adjacent polymer streams coalesce just below these passages. If, for a given set of extrusion conditions, the following relationship holds:
- D is greater than 2AD
- D is the maximum distance within an orifice in a direction radial to the center of the polymer occluding area.
- D may be taken as the average length of all the straight lines which can be drawn between the inside walls of the orifices through the center of the polymer occluding area.
- FIG. 9 illustrates an orifice arrangement consisting of a single discrete orifice having a spiral shape.
- a center of gravity may be chosen for the configuration, and D may be taken as the average length of straight lines which can be drawn through said center of gravity between opposing orifice boundaries.
- the individual orifices may be of any cross-sectional shape, e.g., circular, rectangular, crescent shape, or other curvilinear or polygonal shape. Elongated orifices are preferred, especially those having a shape factor of from 1.4 to 20.
- the shape factor is defined as the ratio of the longest straight line which can be drawn within a cross section of the orifice to D Accordingly, circular orifices are not preferred since the shape factor in this case is one.
- the cross-sectional area of each orifice is preferably between about 12x10" and about 25 10 in. In the case of circular orifices, this would correspond to a diameter of between about 4 and about 55 mils.
- the orifice arrangement which may consist of one, two, three, or more discrete orifices serving to produce a single hollow filament, generally has an axis of symmetry, and preferably a point of symmetry on the face of the spinnerette.
- a spinnerette may contain any feasible number of 4 such orifice arrangements.
- the hollow, centrally positioned cavity of the resultant filament is produced by the absence of polymer extrudate within the perimeter of the orifice arrangement.
- the passages between the orifices consisting essentially of material of which the spinnerette is composed, are made small enough to permit coalescence of the individual extrudate streams, yet far enough apart to preserve the strength of the spinnerette structure and to permit the atmosphere or gas to enter between individual extrudate streams prior to their coalescence.
- the minimum distance of separation between the orifices should be greater than 3 mils to insure spinnerette strength, and less than about 15 mils to secure satisfactory interstream coalescence.
- spinnerettes are made useful in the practice of the present invention by virtue of operating conditions which provide a polymer die swell factor greater than 2.5.
- the die swell factor of filament-forming synthetic polymers is a known measureable value and is defined as the ratio of the maximum diameter of the extrudate stream to the diameter of the orifice opening when employing a circular orifice removed from the influence of coalescing streams.
- the extrudate stream diameter may be measured by photographic or visual methods.
- the die swell factor is measured on a circular orifice having the same area as said noncircular orifice, all other conditions being the same.
- the die swell factor in the course of melt-spinning of homogeneous thermoplastic polymers is dependent upon several factors. It can be determined by simple tests, and the spinnerette for producing the best hollow core filaments selected on the basis of the factor as determined. Alternatively, the die swell factor can be varied to accommodate a particular spinnerette in accordance with known procedures for varying said die swell factor. Thus, holding all other variables constant, the die swell factor can be increased by:
- the site of maximum swelling or stream diameter is generally within the first inch downstream from the spinnerette. The actual distance, however, tends to increase with higher throughput values.
- the die swell factor In the case of the usual production of synthetic fibers by melt-spinning from polymers such as polyamide, polyesters, and polyolefins, the die swell factor rarely exceeds 1.5. The occurrence of die swell factors above 1.5 has generally been considered undesirable since it is normally associated with the production of filaments of varying diameters along their lengths. The phenomenon of the swelling or expansion of a freshly extruded polymer stream is attributable to the elastic characteristics of the polymer and to the tendency of the aligned polymer molecules to become disoriented upon emerging from the capillary.
- the behavior of the molten extrudate becomes such that the spinnerettes described herein could not be used for making hollow filaments. It is possible, however that the polymer could be spun by modifying the spinning conditions so as to bring the die swell factor within the desired range.
- Thermoplastic polymers suitable for use in the present invention include:
- Polyesters such as polyethylene terephthalate and polyhexahydro p-xylylene terephthalate.
- Polyamides such as polyhexamethylene adipamide (nylon-66) and polycaproamide (nylon-6).
- Suitable nylon polymers having satisfactory fiber-forming properties generally have molecular weights which are preferably in the range of about 15,000 to 40,000. Such polymers will have formic acid relative viscosities of 30 to 150, and preferably between 30 and 100, as determined at a concentration of 11 grams of polymer in 100 ml. of 90% formic acid at 25 C. (ASTM D-789-62T).
- Suitable polyester polymers having satisfactory fiberforming properties generally have a reduced viscosity above 0.50.
- the reduced viscosity of polymers useful in the compositions employed in this invention is determined by viscosity measurements carried out at 25 C. on a 0.5% by weight solution of polymer in purified orthochlorophenol containing 0.1% water. Employing a standard Cannon-Fenske 150 bore viscometer, the flow time of the polymer solution (t is measured relative to the flow time of the solvent (t and the reduced viscosity iscalculated using the following equation:
- N red (11,-1 /C where:
- thermoplastic compositions for use in the practice of this invention comprises heterogeneous compositions consisting of a dispersion of discrete regions or particles of one polymer within a continuous phase of a second polymer.
- heterogeneous compositions afford unexpectedly higher die swell factors under conditions which are not adverse to the general requisites of good spinning practice.
- the aforesaid heterogeneous compositions provide suitable die swell factors at higher temperatures, a factor which also favors interstream coalescence and good fiber formation.
- the high values for the die swell factor obtained with such heterogeneous systems may be due to the tendency of the minute globules of dispersed phase polymer, which emerge from the orifice in an elongated molten condition, to reassume a spherical shape in order to decrease their free energy content.
- the dispersed phase polymer globules tend to slow down the polymer stream or cause a shortening thereof, which causes a bulge immediately beneath the spinnerette.
- Particularly desirable heterogeneous polymer compositions comprising polyester particles dispersed in polyamides are disclosed in copending US. patent application Ser. No. 368,028, filed May 18, 1964, in the name of I. C. Twilley, now Pat. No. 3,369,057.
- FIG. 10 illustrates the melt spinning process of this invention employing a heterogeneous polymer composition.
- a molten composition comprising a continuous phase polymer 25 and dispersed discontinuous phase polymer 27 is extruded through closely adjacent orifices 29 and 31 of spinnerette 33.
- a dispersed polymer globule assumes an elongated form 35.
- the elongated dispersed polymer globule assumes the more spherical form 37.
- the diameter of the extrude composition expands to a maximum value at a site 39 which leads to coalescence of the two streams of polymer emerging from spinnerette orifices 29 and 31.
- the generally spherical globules again become elongated as exemplified by globules 37a, 37b and 37c.
- the diameter of the extrudate (now a hollow filament) decreases as it comes under the influence of drawing and stretching forces exerted by the take-up roll.
- both polymers should be capable of elongation at temperatures above their melting point and preferably also capable of elongation under cold-drawing conditions below the melting point.
- the dispersed polymer need not be fiberforming, i.e., capable of forming a continuous filament of useful strength by a standard melt-spinning operation. It should also be sufiiciently incompatible with the continuous phase polymer so as to remain a distinct, discontinuous phase dispersed within the continuous phase during melt-spinning. It is preferable that the dispersed phase polymer have a melting point in the range of between about 50 C. below to about C. above the melting point of the continuous phase polymer.
- a particularly preferred range for the polyester-polyamide blends described in the aforementioned Twilley application is for the melting point of the polyester to be between about 10 C. to about 90 C. higher than the melting point of the polyamide.
- polymer melting points may be determined by using a hot-stage microscope. For those polymers having indistinct melting points, the melting point is taken as the temperature at which the polymer becomes fiowable at atmospheric pressure.
- Hollow filaments prepared from said preferred heterogeneous polymer mixtures are found to present a visual appearance characterized as having aesthetically pleasing sparkle or glitter.
- the novel filaments are also found to have improved strength and rigidity in view of the reinforcing eifect of the dispersed phase polymer which, in the drawn fiber is in the form of microfiber reinforcing elements dispersed within the continuous phase polymer structure in a direction generally parallel to the axis of the filament.
- Polymer die swell factors greater than 2.5 may also be secured by incorporating a gas or gas-forming material within the polymer melt prior to extrusion.
- Said gasforming material may be in the nature of a gaseous or volatile liquid material which, upon extrusion and consequent sudden decrease in pressure, will have a tendency to increase in gaseous volume.
- gaseous or gas-liberating substances may conveniently be employed in amounts ranging from about 0.1% to about 2% by weight based on the total weight of the polymer composition prior to extrusion.
- the resultant hollow filament obtained when employing polymer compositions containing gas-forming agents may or may not retain bubbles, depending upon the rate of bubble formation and quenching of the extrudate in the course of forming the solidified hollow filament.
- gas-forming agents include, for example, methanol, methylene chloride, hexane, benzene, fluorocarbons, water, and the like.
- the molten polymer composition is metered to the spinnerette at pressures which vary somewhat with the composition, but generally are in the range of about 1,000 to about 10,000 p.s.i.g.
- the composition is preferably passed through a filtration device such as a sand pack prior to entering the capillaries.
- the temperature of the polymer mixture at the spinnerette is maintained generally at between about C. and about 50 C. above the melting point of the highest melting polymer component of the composition.
- melt-spinning is preferably conducted under conditions which are interadjusted to maintain the value of the dimensionless ratio R/Pu in the range between about 0.0001 and 0.002, where R is the rate of throughput per orifice, P is the orifice diameter or average orifice diameter in the case of noncircular openings (which may be approximated by the average diameter of a series of circles inscribed within the orifice on the plane of the spinnerette), and u is the viscosity of the molten polymer blend at the extrusion temperature all factors being expressed in self-consistant units. In this manner, uniform hollow filaments will be consistently produced.
- R/Pu is greater than 0.002 If the value of R/Pu is greater than 0.002, then discontinuities or drips may occur during spinning. If, on the other hand, the value of R/Pu is less than 0.0001, then a pulsing effect may occur, which results in erratic control of filament denier.
- the plastic extrudates of this invention are cooled to solidification by contact with a gaseous medium of controlled thermal properties.
- the spinnerette usually forms the upper end of an enclosed cylinder known as a quench stack wherein controlled cooling to solidify the extruded polymer is effected. Cooling is usually brought about by contacting the extrudate with air or other gas which is chemically inert to the polymer under controlled conditions of temperature, fiow rate, and flow pattern.
- the cooling gas flow pattern may be cocurrent, countercurrent, or crosscurrent to the filaments.
- Gas temperatures may be as high as about 50 C.
- the solidified filaments are removed from the quench stack by means of a driven take-up roll which is generally located below the quench stack.
- a driven take-up roll which is generally located below the quench stack.
- controlled elongation of the molten extrudate stream prior to solidification may be effected, the extent of said elongation being known as stack draw-down."
- the speed of the take-up roll may also effect the die swell ratio.
- the polymer remain flowable for at least 5 mm. downstream from the spinnerette orifices and that the stack drawn-down be maintained between about 10 and about 1,000.
- the extrudate, while still molten may be subjected to ultrasonic energy, electrostatic radiation or other physical treatment to secure specialized effects such as periodically closing the hollow filament core to form cells, imparting a crimpability to the filaments, and other effects.
- the filaments may be subjected to a drawing operation at temperatures below their melting point to confer molecular orientation along the filament axis and increase the strength of the filaments.
- Dra w ratios of between about 2 and about 12 have been found to impart maximum yarn strength. The optimum draw ratio, however, will vary with the selected polymer or polymer mixture.
- the drawing operation is preferably carried out by standard methods which may use a draw pin to localize the region of drawing.
- the yarn may be drawn in either a single or successive stages, and at least one of said drawing stages may be carried out while the yarn is heated, e.g., to a temperature between about C. and about C. for nylon 6 yarns.
- the optimum temperature will, of course, vary with the selected polymers.
- the heat can be applied to the yarn by known means such as stationary or rotating contact heaters, steam chambers, heated liquid sprays or baths, infrared, radio frequency heating, and other means.
- Finishing compositions comprising lubricating ingredients and/or Wax can be applied to the yarn prior to drawing to facilitate the drawing operation.
- the drawn yarn Prior to packaging, or in subsequent operations, the drawn yarn can be subjected to annealing at constant length or to relaxation with controlled shrinkage in order to reduce the shrinkage and/ or ultimate elongation of the yarn.
- One suitable method of effecting such treatments is disclosed in Wincklhofer US.
- the drawn yarn can be subjected to treatment with ionizing radiation, ultrasonics, crosslinking agents such as formaldehyde and isocyanates, and other finishing treatments to secure various desired effects, none of which, however are to be considered as limiting the scope of the invention.
- the product of this invention is a synthetic filament consisting essentially of a sheath and an internal, longitudinally extended cavity.
- the cavity may occupy between about 10% and about 80% of the entire cross-sectional area of the filament.
- the sheath may be of circular or noncircular shape.
- the cavity may be centrally or eccentrically disposed with respect to the filament axis, and the peripheral contour of the cross section of the cavity may be of the same or different from the shape of the cross-sectional periphery of the sheath.
- the shapes of both the cavity and sheath will, however, be essentially constant along the length of the filament.
- the sheath portion consisting of the extruded polymer composition, will contain, in the case of heterogeneous polymer blends, the dispersed polymer in the form of microfibers.
- these microfibers will have an average diameter generally not greater than about 1 micron, and an average length of at least about 5 times their diameter.
- the microfibers lie predominantly in the direction of the filament axis, and there may be from 500 to more than 150,000 microfibers per 1,000 square microns of transverse area of the drawn filament.
- the presence of microfibers in the hollow filaments of the present invention imparts improved bending modulus, or stiffness characteristics which are especially appreciated in textile apparel and in carpeting where improved resiliency is usually a desirable feature.
- FIG. 11 represents a cross-sectional view of filament 41 comprising annular round sheath portion 43 of uniform thickness and circular cavity 45 which is substantially centrally disposed with respect to sheath 43.
- FIG. 12 illustrates a cross-sectional view of a filament 47 of this invention containing dispersed microfibers 49 within continuous phase polymer 51 of the noncircular sheath 53.
- Cavity 55 also is noncircular, but it is differently shaped than the outer periphery of the sheath 53.
- the hollow filaments of this invention may be made to contain various additive ingredients which impart specialized properties.
- ingredients which may be added to the filaments either by incorporation within the polymer prior to spinning, or by aftertreatment of the yarn or fabric include: flame retarding agents such as compounds of antimony, phosphorous, and halogens; delustrants such as titanium dioxide, calcium acetate and other opaque metal compounds; antistatic agents; adhesion promoting agents such as isocyanates and epoxides, heat and light stabilizers such as inorganic reducing ions, metal ions such as manganese, copper and tin, phosphites, and organic amines such as alkylated aromatic amines and keto-aromatic amine condensates; thermally stable organic and inorganic pigments; fluorescent agents and brighteners; crosslinking agents; bacteriostats such as phenols and quaternary amines; colloidal reinforcing particles; antisoiling agents such as colloidal silica and boehmite;
- Gaseous mateirals may also be incorporated within the internal cavity of the fibers of this invention. Such additives may be incorporated by serving as the quenching media for the filaments. In this respect, fibers of this invention may serve asuseful containers for the controlled use of such gases.
- Thermally stable flow controlling agents or surface active agents which decrease surface free energy may be included within the polymer prior to extrusion to increase the extent of extrudate coalescence, and thereby improve the circularity of the sheath structure where such is desired.
- examples of such agents include metal salts of long chain aliphatic carboxylic acids, long chain aliphatic alcohols, long chain aliphatic amides, and other surface active agents.
- the filaments of the present invention are useful in numerous textile applications in the form of monofilament and multifilament yarn and tow, cords, and staple spun yarns.
- the filaments may be blended with other fibrous materials, and may be employed in crimped or uncrimped conditions.
- Typical textile applications include apparel products such as woven suitings, shirtings, sheeting and lingerie, tricot, circular knitted fabrics, broadcloths, satins, and the like.
- the blended polymer filaments of this invention are further useful in textile applications such as sewing thread, tire cord, fiber-reinforced laminates upholstery, carpeting, drapery, curtains, ducks, parachutes, reinforced belts and hoses, marine lines, ropes and netting, and other applications.
- the filaments may be admixed with solid core filamentary structures of various modified cross section, of the same or different denier and the same or different chemical composition to produce various special effects.
- thermoplastic polymer composition comprising a uniform heterogeneous molten blend of 30% polyethylene terephthalate of 0.7 6' reduced orthochlorophenol viscosity, and 70% polycaproamide of 50 formic acid relative viscosity is prepared in the presence of trace amounts of sebacic acid which serves as a chain length terminator, whereby fewer than 40% of the terminal groups are amino groups.
- the blended composition is prepared by meltblending the two polymer components under conditions of high shear so that the dispersed polyester in the composition has an average particle size of 0.8 micron. The composition is then extruded at 280 C.
- each orifice is 0.004 inch wide (average diameter) and 0.032 inch long, and the capillaries are 0.020 inch deep.
- the three rectangular orifices having a shape factor of 8.0, are arranged about the center of a circle having a radius of .020 inch.
- the effective value of D is about 0.050 inch.
- the closest spacing between the orifices is 0.004 inch.
- the polymer has a die swell factor of 3.5 as measured on a circular orifice having a diameter of 0.013 (which provides the same orifice area as one of the rectangular orifices).
- Upstream from the surface of the spinnerette is a sandand-screen filter pack.
- the pressure on the polymer at the upstream face of the spinnerette is about 1900 p.s.i.g.
- the value of R/Pu is 0.00137.
- the value of AD is 0.004 3.50.014".
- the filaments are extruded into an atmosphere of air at 72 C., flowing concurrently to the extrudate at a rate of 20 cubic feet per minute.
- the solidified yarn is wound up at a rate of 1170 feet per minute.
- the yarn thus obtained is cold-drawn at a draw ratio of 3.83 between feed rolls and draw rolls, employing a snubbing pin of /2 inch diameter operating at ambient temperature to localize the draw zone.
- the resultant yarn has a denier of 210.
- the individual filaments have a cross section resembling that shown in FIG. 12 wherein the hollow core occupies about 12% of the over-all cross-sectional area of the filament.
- the filaments have a sparkling luster, particularly when observed after fabriaction into a carpet sample, and have good resiliency. Microscopic examination of the fibers reveals the presence of microfibers of the polyester component, said microfibers having an average diameter of 0.18 and average length of 165,u., there being about 9,500 of such microfibers in a given cross section.
- the same spinnerette is employed for the spinning of a composition consisting entirely of the polycaproamide employed above.
- the polymer temperature, extrusion rate, and all other process conditions are maintained the same as above. Under such conditions the die swell factoris only 1.5 and the extrudate streams do not coalesce to form hollow filaments.
- the above experiment using the polymer blend composition is repeated using a spinnerette of essentially the same configuration but wherein the minimum spacing between the individual orifice is 0.002 inch.
- the filaments obtained have no hollow core.
- the polymer occluding areas within the orifice groups of the spinnerette are observed to distort or bulge outwardly. This causes spinning discontinuities and makes it impossible to wipe the spinning face of the spinnerette, i.e., to scrape it clean for restarting satisfactory extrusion.
- Example 2 A sample of linear polyethylene having a density of 0.960 and melt index of 2.0 (determined according to ASTM D1238-52T) is extruded at 190 C. through a spinnerette having twenty seven groups of six circular orifices whose centers are equidistantly spaced on a circle having a diameter of 0.072 inch generally as shown in FIG. 2. Each orifice has a diameter of 0.023 inch and a capillary length of 0.046 inch. The diameter D of the occluding area is thus 0.049 inch.
- the entrance angle to the capillary from the countcrbore is i.e., the countcrbore has a fiat bottom.
- the polymer is extruded at a rate calculated to give a capillary shear rate of 800 secsaid capillary shear rate being given by the formula where Q is the flow rate in m/sec., R is the radius of the orifice in cm. and n is a constant expressing the degree to which the flow deviates from the Newtonian condition. In this test, n is taken as equal to 1.0.
- the die swell factor, measured on an orifice isolated from the regular groups is 3.0.
- the value of AD is 0.069 inch.
- the extrudate is solidified by contact with a countercurrent flow of heated nitrogen in a confining column.
- the rate of quenching is such as to maintain the polymer in molten or plastic form for at least 12 mm. downstream from the spinnerette.
- the solidified, hollow core filaments are taken up on a winder positioned below the column.
- the extrudates from the individual orifices of each group coalesced, forming an integral molten structure which upon cooling yields hollow filaments.
- the yarn is drawn at a draw ratio of six at ambient room tempera ture between standard feed rolls and draw rolls.
- the resultant drawn filaments retain their hollow configuration, the area of the hollow interior being about 40% of the complete cross-sectional area of the filaments.
- the die plate after continued use, shows no evidence of bulging or rupture of the occluding area within the groups of orifices.
- Example 3 A sample of Hoechst Hostalen GF-5200 polyethylene having a melt index of 0.4 (determined as in Example 2), and a density of 0.947 is extruded at 220 C. through a spinnerette having 16 groups of three orifices as shown in FIG. where each orifice has a width of 0.004 inch, and a cross-sectional area of 0.000128 square in. The distance of separation between the orifices is 0.004 inch. The diameter, D of the polymer occluding area is 0.0304 inch, and the shape factor of the orifices is 5.6.
- the capillaries are perependicular to the extrusion face of the spinnerette and have a length of 0.030 inch.
- the polymer is extruded at a rate such that the capillary shear rate is 350 secr' the shear rate being determined from the equation of Example 2.
- R denotes the radius of a circular orifice of comparable area, and n is equal to 2.4.
- a die swell factor of 3.3 is observed.
- the value of AD is 0.013 inch. This swell factor is sufl'icient to cause the polymer streams from the separate orifices to contact each other and coalesce to form an integral structure which yields a hollow fiber on cooling.
- Example 4 A sample of polycaproamide having a melting point of 215 C. and relative formic acid viscosity of 50 is extruded at 250 C. through a spinnerette of the same general type employed in Example 3.
- the spinnerette in this case, however, has 12 groups of three orifices wherein each orifice has a width of 0.005 inch, a cross-sectional area of 0.000303 square inch and a capillary length of 0.018 inch. The distance of separation between the orifices is 0.006 inch.
- the diameter D of the polymer occluding area is 0.060 inch, and the shape factor of the orifices is 8.0.
- Example 5 A sample of polyethylene terephthalate having a reduced orthochlorophenol viscosity of 0.83 is extruded at 12 270 C. through the spinnerette of Example 4. A die swell factor of 3.6 is obtained with proper adjustment of flow rate, and under these conditions satisfactory coalescence is obtained to secure hollow filaments. The value of AD is 0.018 inch.
- Example 6 A sample of polycaproamide terminated with acetic acid, and having a relative formic acid viscosity of 52 with about 23 milliequivalents of amine end groups per kilogram of polymer is extruded at 260 C. at a throughput of 0.96 lbs/hr. through a spinnerette having four groups of trislots as shown in FIG. 8. Each orifice is 0.003 inch wide. The closest spacing between the orifices is 0.0035 inch. The orifices are arranged about a circle having a diameter, D of 0.026 inch. Upstream from the spinnerette is a filter pack containing sand having an average particle size of 400 U.S. mesh.
- the filaments are extruded into an atmosphere of air at a take-up speed of 1600-1625 feet per minute, followed by drawing at a draw ratio of 3.4-to-1 at 1000 feet per minute.
- the resultant drawn hollow filament has a denier of 41, with a tensile strength of 4.8 am./denier.
- the hollow portion of the filament occupies 911% of the cross-sectional area of the product filament.
- a hollow filament consisting essentially of a sheath containing an internal longitudinally extended cavity occupying at least 10 percent of the cross-section of said filament, said sheath comprising a continuous phase polyamide polymer containing dispersed therein a polyester in the form of microfibers lying predominantly in the dirrection of the axis of said filament.
- microfibers have a length-to'diameter ratio greater than about 5.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
A HOLLOW FILAMENT OF SYNTHETIC POLYMER MATERIAL IS DISCLOSED CONSISTING OF A SHEATH SURROUNDING A LINGITUDINALLY EXTENDED CAVITY. THE SHEATH COMPRISES A CONTINUOUS PHASE POLYAMIDE POLYMER CONTAINING DISPERSED THEREIN A POLYESTER IN THE FORM OF MICROFIBERS LYING PREDOMINANTLY IN THE DIRECTION OF THE AXIS OF THE FILAMENT.
Description
Jan. 26, 1971 J. OPFELL I HOLLOW FILAMENTS Filed Aug. 17. 1967 INVENTOR JAMES E.OPFELL Raimi 61' Huh/ W F'IG.| I.
AT TOR N EY United States Patent (1) 3,558,420 HOLLOW FILAMENTS James E. Opfell, Colonial Heights, Va., assiguor to Allied Chemical Corporation, New York, N.Y., a corporatloll of New York Filed Aug. 17, 1967, Ser. No. 661,348 Int. Cl. D01d 5/24 US. Cl. 161176 3 Claims ABSTRACT OF THE DISCLOSURE A hollow filament of synthetic polymer material is disclosed consisting of a sheath surrounding a longitudinally extended cavity. The sheath comprises a continuous phase polyamide polymer containing dispersed therein a polyester in the form of microfibers lying predominantly in the direction of the axis of the filament.
BACKGROUND OF THE INVENTION This invention relates to novel hollow synthetic filaments and to the production thereof. More particularly, it relates to the production of said filaments by extruding a molten synthetic polymer material through a spinnerette containing at least one unobstructed orifice followed by controlled cooling of the freshly spun filaments to effect solidification thereof.
It is recognized that hollow synthetic filaments have certain advantages over solid filaments having the same outside diameter. Some of the advantages which hollow filaments have compared to solid filaments include improved insulating properties, increased bouyancy, and greater covering power (e.g., in carpet yarn) per unit weight. Hollow filaments composed of polymer blends also have less tendency to fibrillate under flexing conditions than corsponding solid filaments.
However, it has proved to be extremely difficult to manufacture hollow filaments in a commercially feasible manner by melt-spinning. Considerable time, effort and money have been spent on attempts to adapt existing methods to the production of hollow filaments on a commercial scale. Processes which have been devised for this purpose have necessitated the use of special and often expensive processing conditions and equipment. Such improvements as have been made have generally been related to the spinnerette. Unfortunately, the spinnerettes that have been designed thus far are difficult to construct and are subject to frequent breakdowns which may be attributed at least in part to their complex construction.
One type of spinnerette employs orifices containing an internal obstructing member which causes the orifice to function as an annulus, said obstructing member being joined to the spinnerette body by internal support members upstream from the extrusion face of the spinnerette. This type of spinnerette and others which have been designed to prod-nee hollow filaments are not only hard to make but are extremely difiicult to maintain in a good state of repair and cleanliness.
Other spinnerettes which have been studied employ a multitude of simple, unobstructed orifices grouped in a perimeter. They are so closely spaced that, upon extrusion, molten polymer emerging from each of the orifices" coalesces with extrudates from the adjacent orifices of the group to form a continuum of the polymer substrate which, after rapid cooling, forms a hollow-shaped filament. The filament is hollow because the area encompassed by the perimeter of orifices contains no openings and thereby blocks passage of polymer. These spinnerettes require very close spacing between adjacent orifices to permit coalescence of extrudate streams with the result that the thickness of the intervening metal between ori- Ice fices is so small as to cause structural weakness and difficulties of fabrication. The weakened nature of these spinnerettes is particularly significant in the melt-spinning of synthetic fibers because the high extrusion pressures required will often cause distortion or actual rupture of spinnerettes of inadequate strength. Another disadvantage of orifices which are too closely spaced in forming a perimeter is that polymer coalescence may occur too close to the face of the spinnerette, thereby preventing the entrance of air into the hollow cavity of the filament. The resultant vacuum within. the filament causes internal coalescence of the molten polymer, thus minimizing or eliminating the central cavity.
SUMMARY -OF THE INVENTION Therefore, it is an object of the present invention to provide a filament having an internal cavity extending along its length.
Another object is to provide an improved melt-spinning process for the production of hollow synthetic filaments.
Yet another object of the present invention is to provide a melt-spinning process for the production of hollow synthetic filaments using a spinnerette having unobstructed orifices which provide at least one gap in an otherwise continuous periphery of openings encompassing a polymer occluding area.
Other objects and a fuller understanding of the present invention may be had by reference to the following description, drawings, and appended claims.
The objects of this invention are accomplished in general by:
(a) Extr-uding a molten synthetic polymer composition having a die swell factor greater than about 2.5, and preferably between about 2.5 and about 10, through a spinnerette containing at least one circumscribing orifice arrangement. Said orifice arrangement comprises at least one unobstructed orifice and defines, without completely surrounding, a polymer occluding area which is devoid of orifices. This occluding area communicates with the area outside the orifice arrangement by means of at least one passage through said arrangement. The average diameter, D of the polymer occluding area is greater than AD wherein A is the die swell factor and D is the maximum orifice width in a direction radial to the center of said occluding area; and
(b) Cooling the polymer extrudate to effect solidification thereof.
In the accompanying drawings:
FIG. 1 is a vertical sectional view of part of a spinnerette useful in the practice of the present invention;
FIGS. 2 to 8 are plan views of spinnerette orifice arrangements according to the present invention comprising more than one discrete unobstructed orifice, each of said orifice arrangements having a perimetric configuration about a polymer occluding area. The spinnerette illustrated in FIG. 8 is disclosed and claimed in copending U.S. application Ser. No. 687,170, :filed Dec. 1, 1967.
FIG. 9 is a plan view of a spinnerette orifice arrangement according to the present invention comprising a single discrete orifice conformed into an encircling configuration about a polymer occluding area.
FIG. 10 is a partial sectional view showing the coalescence of polymer extrudates downstream from the spinnerette; and
FIGS. 11 and 12 are cross-sectional views of hollow filaments produced in accordance with the present invention.
In FIG. 1, spinnerette 1 has an upstream face 3 and downstream extrusion face 5. Spinnerette 1, being typical of those employed in melt-spinning of synthetic fibers, is generally about 0.2-1.0 inch thick and may be of monolithic or laminated construction. It is generally made of steel or other high strength metal or alloy. Counterbore depression 7 may be formed in the upstream face of spinnerette 1 in order to minimize the length of capillaries 9 leading to orifices 11 which define polymer occluding area 13.
The capillaries of spinnerettes useful in the practice of the present invention are generally of constant cross section throughout their length, i.e., the capillary wall is a cylindric surface as may be formed by circular movement of a straight line parallel to a given fixed centrally located straight line. The capillary may however, be slightly chamfered at either or both ends. The length of a typical capillary is preferably between about 8 and about 70 mils (l mil=0.00l inch). If the capillary length is appreciably below 8 mils, the spinnerette plate may be undesirably weakened, while capillary lengths substantially greater than about 70 mils may cause difficulties in obtaining satisfactory hollow filaments by the process of this invention. The capillaries may be made by standard techniques which include: drilling with rotary drills; drilling with pneumatic devices or electrodes; punching techniques; and insertion of shaped wires into differently shaped capillaries (as disclosed in US Pat. 3,174,364). The capillaries are preferably perpendicular to the extrusion face but may be angled to direct extrudate streams toward one another for improved coalescence.
In FIG. 2, portion 15 of spinnerette .1 contains a circumscribing arrangement of six individual orifices 17, each having diameter, D Orifices 17 are perimetrically disposed in symmetrical arrangement about central point 19, thereby defining central polymer occluding area 21, having average diameter D taken as the diameter of the circle which tangentially contacts the orifices at points closest to central point 19. Spacings 23 provide passages through which the occluding area 2.1 communicates with the rest of the spinnerette face. As will be explained more fully hereinafter, adjacent polymer streams coalesce just below these passages. If, for a given set of extrusion conditions, the following relationship holds:
then separate polymer streams from adjacent orifices will coalesce to form the desired hollow filaments.
In preferred embodiments of the present invention, D is greater than 2AD In FIGS. 3 through 8, D is the maximum distance within an orifice in a direction radial to the center of the polymer occluding area. D may be taken as the average length of all the straight lines which can be drawn between the inside walls of the orifices through the center of the polymer occluding area.
FIG. 9 illustrates an orifice arrangement consisting of a single discrete orifice having a spiral shape. For the purpose of ascertaining the value of D since there is no center of symmetry, a center of gravity may be chosen for the configuration, and D may be taken as the average length of straight lines which can be drawn through said center of gravity between opposing orifice boundaries.
The individual orifices may be of any cross-sectional shape, e.g., circular, rectangular, crescent shape, or other curvilinear or polygonal shape. Elongated orifices are preferred, especially those having a shape factor of from 1.4 to 20. The shape factor is defined as the ratio of the longest straight line which can be drawn within a cross section of the orifice to D Accordingly, circular orifices are not preferred since the shape factor in this case is one. The cross-sectional area of each orifice is preferably between about 12x10" and about 25 10 in. In the case of circular orifices, this would correspond to a diameter of between about 4 and about 55 mils. The orifice arrangement, which may consist of one, two, three, or more discrete orifices serving to produce a single hollow filament, generally has an axis of symmetry, and preferably a point of symmetry on the face of the spinnerette.
A spinnerette may contain any feasible number of 4 such orifice arrangements. The hollow, centrally positioned cavity of the resultant filament is produced by the absence of polymer extrudate within the perimeter of the orifice arrangement.
There is at least one and preferably several passages leading from within the otherwise complete annulus formed by the circumscribing orifice arrangement. The passages between the orifices, consisting essentially of material of which the spinnerette is composed, are made small enough to permit coalescence of the individual extrudate streams, yet far enough apart to preserve the strength of the spinnerette structure and to permit the atmosphere or gas to enter between individual extrudate streams prior to their coalescence. In general, the minimum distance of separation between the orifices should be greater than 3 mils to insure spinnerette strength, and less than about 15 mils to secure satisfactory interstream coalescence. Such spinnerettes are made useful in the practice of the present invention by virtue of operating conditions which provide a polymer die swell factor greater than 2.5.
The die swell factor of filament-forming synthetic polymers is a known measureable value and is defined as the ratio of the maximum diameter of the extrudate stream to the diameter of the orifice opening when employing a circular orifice removed from the influence of coalescing streams. The extrudate stream diameter may be measured by photographic or visual methods. In the case of noncircular orifices the die swell factor is measured on a circular orifice having the same area as said noncircular orifice, all other conditions being the same.
The die swell factor in the course of melt-spinning of homogeneous thermoplastic polymers is dependent upon several factors. It can be determined by simple tests, and the spinnerette for producing the best hollow core filaments selected on the basis of the factor as determined. Alternatively, the die swell factor can be varied to accommodate a particular spinnerette in accordance with known procedures for varying said die swell factor. Thus, holding all other variables constant, the die swell factor can be increased by:
(a) Decreasing the speed of the take-up roll.
(b) Decreasing the orifice extrusion temperature.
(0) Decreasing the residence time within the capillary (i.e., increasing the throughput). In this connection it should be noted that increased throughput even when compensated by increased take-up speed to maintain constant denier of the wound filament, still increases the die swell factor.
(d) Increasing the polymer melt viscosity; and
(e) Decreasing the diameter of the orifice.
The site of maximum swelling or stream diameter is generally within the first inch downstream from the spinnerette. The actual distance, however, tends to increase with higher throughput values.
In the case of the usual production of synthetic fibers by melt-spinning from polymers such as polyamide, polyesters, and polyolefins, the die swell factor rarely exceeds 1.5. The occurrence of die swell factors above 1.5 has generally been considered undesirable since it is normally associated with the production of filaments of varying diameters along their lengths. The phenomenon of the swelling or expansion of a freshly extruded polymer stream is attributable to the elastic characteristics of the polymer and to the tendency of the aligned polymer molecules to become disoriented upon emerging from the capillary.
In accordance with the present invention, when synthetic polymers are spun under conditions such that the die swell factor exceeds 2.5, a sufficiently large bulge is formed in the still molten extrudate to permit location of the separate orifices sufiiciently far apart to permit ambient air or gas to enter the space between individual extrudate streams prior to coalescence, thereby preventing collapse of the individual streams into a solid filament. The location of the orifices at greater distances of separation has the further advantage of giving increased strength to the spinnerette. In prior art methods, deficiencies in spinnerette strength have manifested themselves in a bulging or actual rupture of the central polymer occluding area.
With polymers spun under conditions such that the die swell factor is appreciably below 2.5 or above 10, the behavior of the molten extrudate becomes such that the spinnerettes described herein could not be used for making hollow filaments. It is possible, however that the polymer could be spun by modifying the spinning conditions so as to bring the die swell factor within the desired range.
Thermoplastic polymers suitable for use in the present invention include:
(a) Polyesters such as polyethylene terephthalate and polyhexahydro p-xylylene terephthalate.
(b) Polyamides such as polyhexamethylene adipamide (nylon-66) and polycaproamide (nylon-6).
(c) Polyolefins.
(d) Polyurethanes.
(e) Polyesteramides.
(f) Polyethers; and other synthetic polymers and mixtures thereof which may be spun under conditions which ensure a die swell factor within the preferred range. When only one polymer entity is employed it must be fiber-forming. If a mixture of polymers in which one polymer is in the form a dispersed phase within a continuous phase of the other polymer, the dispersed phase is not necessarily fiber-forming.
Suitable nylon polymers having satisfactory fiber-forming properties generally have molecular weights which are preferably in the range of about 15,000 to 40,000. Such polymers will have formic acid relative viscosities of 30 to 150, and preferably between 30 and 100, as determined at a concentration of 11 grams of polymer in 100 ml. of 90% formic acid at 25 C. (ASTM D-789-62T).
Suitable polyester polymers having satisfactory fiberforming properties generally have a reduced viscosity above 0.50. The reduced viscosity of polymers useful in the compositions employed in this invention is determined by viscosity measurements carried out at 25 C. on a 0.5% by weight solution of polymer in purified orthochlorophenol containing 0.1% water. Employing a standard Cannon-Fenske 150 bore viscometer, the flow time of the polymer solution (t is measured relative to the flow time of the solvent (t and the reduced viscosity iscalculated using the following equation:
N red: (11,-1 /C where:
N red=reduced viscosity C=concentration of dissolved polymer in grams/ 100 ml. n,.= relative viscosity=tp/t We have found that a particularly preferred class of thermoplastic compositions for use in the practice of this invention comprises heterogeneous compositions consisting of a dispersion of discrete regions or particles of one polymer within a continuous phase of a second polymer. Such heterogeneous compositions afford unexpectedly higher die swell factors under conditions which are not adverse to the general requisites of good spinning practice. For example, whereas many single-component polymer systems require lower than normal extrusion temperatures to obtain an adequate die swell factor, for the purpose of this invention the aforesaid heterogeneous compositions provide suitable die swell factors at higher temperatures, a factor which also favors interstream coalescence and good fiber formation. Although it is not intended that the present invention be bound by theory, it is felt that the high values for the die swell factor obtained with such heterogeneous systems may be due to the tendency of the minute globules of dispersed phase polymer, which emerge from the orifice in an elongated molten condition, to reassume a spherical shape in order to decrease their free energy content. In tending toward the spherical form, the dispersed phase polymer globules tend to slow down the polymer stream or cause a shortening thereof, which causes a bulge immediately beneath the spinnerette. Particularly desirable heterogeneous polymer compositions comprising polyester particles dispersed in polyamides are disclosed in copending US. patent application Ser. No. 368,028, filed May 18, 1964, in the name of I. C. Twilley, now Pat. No. 3,369,057.
FIG. 10 illustrates the melt spinning process of this invention employing a heterogeneous polymer composition. As depicted therein, a molten composition comprising a continuous phase polymer 25 and dispersed discontinuous phase polymer 27 is extruded through closely adjacent orifices 29 and 31 of spinnerette 33. Under the shear conditions within the capillary a dispersed polymer globule assumes an elongated form 35. Upon emerging from the capillaries, the elongated dispersed polymer globule assumes the more spherical form 37. Concurrently, the diameter of the extrude composition expands to a maximum value at a site 39 which leads to coalescence of the two streams of polymer emerging from spinnerette orifices 29 and 31. Downstream from this point, the generally spherical globules again become elongated as exemplified by globules 37a, 37b and 37c. At the same time, the diameter of the extrudate (now a hollow filament) decreases as it comes under the influence of drawing and stretching forces exerted by the take-up roll.
In the preferred heterogeneous compositions, both polymers should be capable of elongation at temperatures above their melting point and preferably also capable of elongation under cold-drawing conditions below the melting point. The dispersed polymer need not be fiberforming, i.e., capable of forming a continuous filament of useful strength by a standard melt-spinning operation. It should also be sufiiciently incompatible with the continuous phase polymer so as to remain a distinct, discontinuous phase dispersed within the continuous phase during melt-spinning. It is preferable that the dispersed phase polymer have a melting point in the range of between about 50 C. below to about C. above the melting point of the continuous phase polymer. A particularly preferred range for the polyester-polyamide blends described in the aforementioned Twilley application is for the melting point of the polyester to be between about 10 C. to about 90 C. higher than the melting point of the polyamide. For the purposes of the present invention, polymer melting points may be determined by using a hot-stage microscope. For those polymers having indistinct melting points, the melting point is taken as the temperature at which the polymer becomes fiowable at atmospheric pressure.
Hollow filaments prepared from said preferred heterogeneous polymer mixtures are found to present a visual appearance characterized as having aesthetically pleasing sparkle or glitter. The novel filaments are also found to have improved strength and rigidity in view of the reinforcing eifect of the dispersed phase polymer which, in the drawn fiber is in the form of microfiber reinforcing elements dispersed within the continuous phase polymer structure in a direction generally parallel to the axis of the filament.
Polymer die swell factors greater than 2.5 may also be secured by incorporating a gas or gas-forming material within the polymer melt prior to extrusion. Said gasforming material may be in the nature of a gaseous or volatile liquid material which, upon extrusion and consequent sudden decrease in pressure, will have a tendency to increase in gaseous volume. Such gaseous or gas-liberating substances may conveniently be employed in amounts ranging from about 0.1% to about 2% by weight based on the total weight of the polymer composition prior to extrusion. There may also be incorporated within the polymer composition finely divided and dispersed particles which serve as nucleation sites for bubbles and which therefore control the uniformity of bubble size and distribution upon extrusion. The resultant hollow filament obtained when employing polymer compositions containing gas-forming agents may or may not retain bubbles, depending upon the rate of bubble formation and quenching of the extrudate in the course of forming the solidified hollow filament. Suitable gas-forming agents include, for example, methanol, methylene chloride, hexane, benzene, fluorocarbons, water, and the like.
For extrusion, the molten polymer composition is metered to the spinnerette at pressures which vary somewhat with the composition, but generally are in the range of about 1,000 to about 10,000 p.s.i.g. The composition is preferably passed through a filtration device such as a sand pack prior to entering the capillaries. The temperature of the polymer mixture at the spinnerette is maintained generally at between about C. and about 50 C. above the melting point of the highest melting polymer component of the composition. In the case of heterogeneous polymer blends, melt-spinning is preferably conducted under conditions which are interadjusted to maintain the value of the dimensionless ratio R/Pu in the range between about 0.0001 and 0.002, where R is the rate of throughput per orifice, P is the orifice diameter or average orifice diameter in the case of noncircular openings (which may be approximated by the average diameter of a series of circles inscribed within the orifice on the plane of the spinnerette), and u is the viscosity of the molten polymer blend at the extrusion temperature all factors being expressed in self-consistant units. In this manner, uniform hollow filaments will be consistently produced. If the value of R/Pu is greater than 0.002, then discontinuities or drips may occur during spinning. If, on the other hand, the value of R/Pu is less than 0.0001, then a pulsing effect may occur, which results in erratic control of filament denier.
In accordance with the usual melt-spinning techniques, the plastic extrudates of this invention are cooled to solidification by contact with a gaseous medium of controlled thermal properties. In such processes, the spinnerette usually forms the upper end of an enclosed cylinder known as a quench stack wherein controlled cooling to solidify the extruded polymer is effected. Cooling is usually brought about by contacting the extrudate with air or other gas which is chemically inert to the polymer under controlled conditions of temperature, fiow rate, and flow pattern. The cooling gas flow pattern may be cocurrent, countercurrent, or crosscurrent to the filaments. Gas temperatures may be as high as about 50 C. or more above the temperature of the extruded polymer at the face of the spinnerette and may decrease in a predetermined manner down the stack thereby controlling the length of time or traveling distance during which the extrudate is in a flowable form. Gas flow rates in the range of about to about 1,000 ft. min. may generally be employed.
The solidified filaments are removed from the quench stack by means of a driven take-up roll which is generally located below the quench stack. By suitable adjustment of the peripheral speed of said take-up roll, controlled elongation of the molten extrudate stream prior to solidification may be effected, the extent of said elongation being known as stack draw-down." The speed of the take-up roll may also effect the die swell ratio. In order to obtain satisfactory coalescence so as to produce hollow fibers, it is preferred that the polymer remain flowable for at least 5 mm. downstream from the spinnerette orifices and that the stack drawn-down be maintained between about 10 and about 1,000.
The extrudate, while still molten may be subjected to ultrasonic energy, electrostatic radiation or other physical treatment to secure specialized effects such as periodically closing the hollow filament core to form cells, imparting a crimpability to the filaments, and other effects.
After being taken-up below the quench stack, the filaments may be subjected to a drawing operation at temperatures below their melting point to confer molecular orientation along the filament axis and increase the strength of the filaments. Dra w ratios of between about 2 and about 12 have been found to impart maximum yarn strength. The optimum draw ratio, however, will vary with the selected polymer or polymer mixture. The drawing operation is preferably carried out by standard methods which may use a draw pin to localize the region of drawing. The yarn may be drawn in either a single or successive stages, and at least one of said drawing stages may be carried out while the yarn is heated, e.g., to a temperature between about C. and about C. for nylon 6 yarns. The optimum temperature will, of course, vary with the selected polymers. The heat can be applied to the yarn by known means such as stationary or rotating contact heaters, steam chambers, heated liquid sprays or baths, infrared, radio frequency heating, and other means.
Finishing compositions comprising lubricating ingredients and/or Wax can be applied to the yarn prior to drawing to facilitate the drawing operation. Prior to packaging, or in subsequent operations, the drawn yarn can be subjected to annealing at constant length or to relaxation with controlled shrinkage in order to reduce the shrinkage and/ or ultimate elongation of the yarn. One suitable method of effecting such treatments is disclosed in Wincklhofer US.
Pat. 2,859,472, issued Nov. 11, 1958. The drawn yarn can be subjected to treatment with ionizing radiation, ultrasonics, crosslinking agents such as formaldehyde and isocyanates, and other finishing treatments to secure various desired effects, none of which, however are to be considered as limiting the scope of the invention.
The product of this invention is a synthetic filament consisting essentially of a sheath and an internal, longitudinally extended cavity. The cavity may occupy between about 10% and about 80% of the entire cross-sectional area of the filament. The sheath may be of circular or noncircular shape. The cavity may be centrally or eccentrically disposed with respect to the filament axis, and the peripheral contour of the cross section of the cavity may be of the same or different from the shape of the cross-sectional periphery of the sheath. The shapes of both the cavity and sheath will, however, be essentially constant along the length of the filament. The sheath portion, consisting of the extruded polymer composition, will contain, in the case of heterogeneous polymer blends, the dispersed polymer in the form of microfibers. In preferred drawn filaments these microfibers will have an average diameter generally not greater than about 1 micron, and an average length of at least about 5 times their diameter. The microfibers lie predominantly in the direction of the filament axis, and there may be from 500 to more than 150,000 microfibers per 1,000 square microns of transverse area of the drawn filament. The presence of microfibers in the hollow filaments of the present invention imparts improved bending modulus, or stiffness characteristics which are especially appreciated in textile apparel and in carpeting where improved resiliency is usually a desirable feature.
FIG. 11 represents a cross-sectional view of filament 41 comprising annular round sheath portion 43 of uniform thickness and circular cavity 45 which is substantially centrally disposed with respect to sheath 43.
FIG. 12. illustrates a cross-sectional view of a filament 47 of this invention containing dispersed microfibers 49 within continuous phase polymer 51 of the noncircular sheath 53. Cavity 55 also is noncircular, but it is differently shaped than the outer periphery of the sheath 53.
The hollow filaments of this invention may be made to contain various additive ingredients which impart specialized properties. For example, ingredients which may be added to the filaments either by incorporation within the polymer prior to spinning, or by aftertreatment of the yarn or fabric include: flame retarding agents such as compounds of antimony, phosphorous, and halogens; delustrants such as titanium dioxide, calcium acetate and other opaque metal compounds; antistatic agents; adhesion promoting agents such as isocyanates and epoxides, heat and light stabilizers such as inorganic reducing ions, metal ions such as manganese, copper and tin, phosphites, and organic amines such as alkylated aromatic amines and keto-aromatic amine condensates; thermally stable organic and inorganic pigments; fluorescent agents and brighteners; crosslinking agents; bacteriostats such as phenols and quaternary amines; colloidal reinforcing particles; antisoiling agents such as colloidal silica and boehmite; dyeing modifiers; lubricants such as molybdenum disulfide and silicones; lasticizers; dispersing agents to facilitate and maintain dispersion of one polymer of a heterogeneous blend within the other; and other additives and treatments. Gaseous mateirals may also be incorporated within the internal cavity of the fibers of this invention. Such additives may be incorporated by serving as the quenching media for the filaments. In this respect, fibers of this invention may serve asuseful containers for the controlled use of such gases.
Thermally stable flow controlling agents or surface active agents which decrease surface free energy may be included within the polymer prior to extrusion to increase the extent of extrudate coalescence, and thereby improve the circularity of the sheath structure where such is desired. Examples of such agents include metal salts of long chain aliphatic carboxylic acids, long chain aliphatic alcohols, long chain aliphatic amides, and other surface active agents.
The filaments of the present invention are useful in numerous textile applications in the form of monofilament and multifilament yarn and tow, cords, and staple spun yarns. The filaments may be blended with other fibrous materials, and may be employed in crimped or uncrimped conditions. Typical textile applications include apparel products such as woven suitings, shirtings, sheeting and lingerie, tricot, circular knitted fabrics, broadcloths, satins, and the like. In view of their relatively high stiffness, strength, and low weight, the blended polymer filaments of this invention are further useful in textile applications such as sewing thread, tire cord, fiber-reinforced laminates upholstery, carpeting, drapery, curtains, ducks, parachutes, reinforced belts and hoses, marine lines, ropes and netting, and other applications. The filaments may be admixed with solid core filamentary structures of various modified cross section, of the same or different denier and the same or different chemical composition to produce various special effects.
DESCRIPTION OF THE PREFERRED EMBODIMENTS In the following examples, all parts and percentages are by weight unless otherwise indicated.
Example 1 A thermoplastic polymer composition comprising a uniform heterogeneous molten blend of 30% polyethylene terephthalate of 0.7 6' reduced orthochlorophenol viscosity, and 70% polycaproamide of 50 formic acid relative viscosity is prepared in the presence of trace amounts of sebacic acid which serves as a chain length terminator, whereby fewer than 40% of the terminal groups are amino groups. The blended composition is prepared by meltblending the two polymer components under conditions of high shear so that the dispersed polyester in the composition has an average particle size of 0.8 micron. The composition is then extruded at 280 C. at a rate of 4.6 pounds per hour, and a residence time within the capillary of 3.8 seconds through a spinnerette having 16 groups of rectangular orifices essentially as shown in FIG. 4 wherein each orifice is 0.004 inch wide (average diameter) and 0.032 inch long, and the capillaries are 0.020 inch deep. The three rectangular orifices, having a shape factor of 8.0, are arranged about the center of a circle having a radius of .020 inch. The effective value of D is about 0.050 inch. The closest spacing between the orifices is 0.004 inch. Under these conditions, the polymer has a die swell factor of 3.5 as measured on a circular orifice having a diameter of 0.013 (which provides the same orifice area as one of the rectangular orifices). Upstream from the surface of the spinnerette is a sandand-screen filter pack. The pressure on the polymer at the upstream face of the spinnerette is about 1900 p.s.i.g. The value of R/Pu is 0.00137. The value of AD is 0.004 3.50.014".
The filaments are extruded into an atmosphere of air at 72 C., flowing concurrently to the extrudate at a rate of 20 cubic feet per minute. The solidified yarn is wound up at a rate of 1170 feet per minute. The yarn thus obtained is cold-drawn at a draw ratio of 3.83 between feed rolls and draw rolls, employing a snubbing pin of /2 inch diameter operating at ambient temperature to localize the draw zone.
The resultant yarn has a denier of 210. The individual filaments have a cross section resembling that shown in FIG. 12 wherein the hollow core occupies about 12% of the over-all cross-sectional area of the filament. The filaments have a sparkling luster, particularly when observed after fabriaction into a carpet sample, and have good resiliency. Microscopic examination of the fibers reveals the presence of microfibers of the polyester component, said microfibers having an average diameter of 0.18 and average length of 165,u., there being about 9,500 of such microfibers in a given cross section.
For purposes of comparison, the same spinnerette is employed for the spinning of a composition consisting entirely of the polycaproamide employed above. The polymer temperature, extrusion rate, and all other process conditions are maintained the same as above. Under such conditions the die swell factoris only 1.5 and the extrudate streams do not coalesce to form hollow filaments.
By way of further comparison, the above experiment using the polymer blend composition is repeated using a spinnerette of essentially the same configuration but wherein the minimum spacing between the individual orifice is 0.002 inch. The filaments obtained have no hollow core. Furthermore, after several hours of use, the polymer occluding areas within the orifice groups of the spinnerette are observed to distort or bulge outwardly. This causes spinning discontinuities and makes it impossible to wipe the spinning face of the spinnerette, i.e., to scrape it clean for restarting satisfactory extrusion.
Example 2 A sample of linear polyethylene having a density of 0.960 and melt index of 2.0 (determined according to ASTM D1238-52T) is extruded at 190 C. through a spinnerette having twenty seven groups of six circular orifices whose centers are equidistantly spaced on a circle having a diameter of 0.072 inch generally as shown in FIG. 2. Each orifice has a diameter of 0.023 inch and a capillary length of 0.046 inch. The diameter D of the occluding area is thus 0.049 inch. The entrance angle to the capillary from the countcrbore is i.e., the countcrbore has a fiat bottom. The polymer is extruded at a rate calculated to give a capillary shear rate of 800 secsaid capillary shear rate being given by the formula where Q is the flow rate in m/sec., R is the radius of the orifice in cm. and n is a constant expressing the degree to which the flow deviates from the Newtonian condition. In this test, n is taken as equal to 1.0. The die swell factor, measured on an orifice isolated from the regular groups is 3.0. The value of AD, is 0.069 inch.
The extrudate is solidified by contact with a countercurrent flow of heated nitrogen in a confining column. The rate of quenching is such as to maintain the polymer in molten or plastic form for at least 12 mm. downstream from the spinnerette. The solidified, hollow core filaments are taken up on a winder positioned below the column.
The extrudates from the individual orifices of each group coalesced, forming an integral molten structure which upon cooling yields hollow filaments. The yarn is drawn at a draw ratio of six at ambient room tempera ture between standard feed rolls and draw rolls. The resultant drawn filaments retain their hollow configuration, the area of the hollow interior being about 40% of the complete cross-sectional area of the filaments.
The die plate, after continued use, shows no evidence of bulging or rupture of the occluding area within the groups of orifices.
Example 3 A sample of Hoechst Hostalen GF-5200 polyethylene having a melt index of 0.4 (determined as in Example 2), and a density of 0.947 is extruded at 220 C. through a spinnerette having 16 groups of three orifices as shown in FIG. where each orifice has a width of 0.004 inch, and a cross-sectional area of 0.000128 square in. The distance of separation between the orifices is 0.004 inch. The diameter, D of the polymer occluding area is 0.0304 inch, and the shape factor of the orifices is 5.6. The capillaries are perependicular to the extrusion face of the spinnerette and have a length of 0.030 inch. The polymer is extruded at a rate such that the capillary shear rate is 350 secr' the shear rate being determined from the equation of Example 2. Here R denotes the radius of a circular orifice of comparable area, and n is equal to 2.4. Under these conditions, a die swell factor of 3.3 is observed. The value of AD is 0.013 inch. This swell factor is sufl'icient to cause the polymer streams from the separate orifices to contact each other and coalesce to form an integral structure which yields a hollow fiber on cooling.
Example 4 A sample of polycaproamide having a melting point of 215 C. and relative formic acid viscosity of 50 is extruded at 250 C. through a spinnerette of the same general type employed in Example 3. The spinnerette in this case, however, has 12 groups of three orifices wherein each orifice has a width of 0.005 inch, a cross-sectional area of 0.000303 square inch and a capillary length of 0.018 inch. The distance of separation between the orifices is 0.006 inch. The diameter D of the polymer occluding area is 0.060 inch, and the shape factor of the orifices is 8.0. At an extrusion pressure of 5,000 p.s.i., a die swell factor of 3.4 is obtained. The value of AD is 0.0175 inch. Under these conditions coalescence of adjacent extrudate streams gives hollow filaments. The filaments are cooled to solidification by countercurrent contact with heated air, and are wound up at a rate of 1580 feet/min. The yarn is drawn at a draw ratio of 4 between feed and draw rolls using a draw pin to localize the draw point. The drawn yarn retained a continuous hollow cavity which occupied about 40% of the total cross-sectional area. Fabrics woven from the drawn yarn in this example are light in weight, have high covering power, and additionally possess the usual desirable characteristics of a nylon fabric.
Example 5 A sample of polyethylene terephthalate having a reduced orthochlorophenol viscosity of 0.83 is extruded at 12 270 C. through the spinnerette of Example 4. A die swell factor of 3.6 is obtained with proper adjustment of flow rate, and under these conditions satisfactory coalescence is obtained to secure hollow filaments. The value of AD is 0.018 inch.
Example 6 A sample of polycaproamide terminated with acetic acid, and having a relative formic acid viscosity of 52 with about 23 milliequivalents of amine end groups per kilogram of polymer is extruded at 260 C. at a throughput of 0.96 lbs/hr. through a spinnerette having four groups of trislots as shown in FIG. 8. Each orifice is 0.003 inch wide. The closest spacing between the orifices is 0.0035 inch. The orifices are arranged about a circle having a diameter, D of 0.026 inch. Upstream from the spinnerette is a filter pack containing sand having an average particle size of 400 U.S. mesh.
The filaments are extruded into an atmosphere of air at a take-up speed of 1600-1625 feet per minute, followed by drawing at a draw ratio of 3.4-to-1 at 1000 feet per minute.
The resultant drawn hollow filament has a denier of 41, with a tensile strength of 4.8 am./denier. The hollow portion of the filament occupies 911% of the cross-sectional area of the product filament.
The foregoing examples were presented for the purpose of illustrating the melt-spinning process and hollow synthetic filaments of the present invention. It is, of course, understood that variations in the procedures described in those examples as well as changes in the materials used therein may be made without departing from the spirit of the invention and scope of the appended claims.
I claim:
1. A hollow filament consisting essentially of a sheath containing an internal longitudinally extended cavity occupying at least 10 percent of the cross-section of said filament, said sheath comprising a continuous phase polyamide polymer containing dispersed therein a polyester in the form of microfibers lying predominantly in the dirrection of the axis of said filament.
2. The filament of claim 1 wherein said microfibers have a length-to'diameter ratio greater than about 5.
3. The filament of claim 1 wherein the dispersed phase is a polyethylene terephthalate and the continuous phase is a fiber-forming polycaproamide.
References Cited UNITED STATES PATENTS 3,160,193 12/1964 Baggett et al 152359 3,369,057 2/1968 Twilley 260857 3,382,305 5/1968 Breen 16lMicrofiber Dig.
ROBERT F. BURNETT, Primary Examiner R. O. LINKER, JR., Assistant Examiner U.S. C1. X.R.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US66134867A | 1967-08-17 | 1967-08-17 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3558420A true US3558420A (en) | 1971-01-26 |
Family
ID=24653218
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US661348A Expired - Lifetime US3558420A (en) | 1967-08-17 | 1967-08-17 | Hollow filaments |
Country Status (1)
Country | Link |
---|---|
US (1) | US3558420A (en) |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3728428A (en) * | 1969-12-03 | 1973-04-17 | Allied Chem | Process for producing hollow filaments |
US3981948A (en) * | 1975-01-02 | 1976-09-21 | Eastman Kodak Company | Arrangements in spinnerets of spinning orifices having significant kneeing potential |
US4056597A (en) * | 1975-04-03 | 1977-11-01 | Phillips Petroleum Company | Process and die for extrusion of a resinous material |
US4112166A (en) * | 1975-01-02 | 1978-09-05 | Monsanto Company | Method of extruding thermoplastic sheets |
US4176150A (en) * | 1977-03-18 | 1979-11-27 | Monsanto Company | Process for textured yarn |
EP0007237A1 (en) * | 1978-07-17 | 1980-01-23 | Fiber Industries, Inc. | Spun-like yarn |
US4254181A (en) * | 1977-03-18 | 1981-03-03 | Monsanto Company | Filaments having alternate S-twisted and Z-twisted helical sections produced by crimping filaments provided with an eccentric anisotropy of shrinkable property by a preferential cooling on one side upon extrusion thereof through a spinneret |
US4302509A (en) * | 1979-02-22 | 1981-11-24 | Albany International Corp. | Sorbent-cored textile yarns |
US4315877A (en) * | 1979-02-22 | 1982-02-16 | Albany International Corp. | Methods of fabricating sorbent-cored textile yarns |
US4336307A (en) * | 1978-01-27 | 1982-06-22 | Teijin Limited | Hollow water absorbing polyester filaments and a process for producing the same |
US4357390A (en) * | 1980-03-25 | 1982-11-02 | Teijin Limited | Antistatic polyester fibers |
US4361617A (en) * | 1979-07-26 | 1982-11-30 | Teijin Limited | Hollow water-absorbing polyester filaments and a process for producing the same |
US4376746A (en) * | 1980-04-01 | 1983-03-15 | Ametek, Inc. | Formation of hollow tapered brush bristles |
US4457885A (en) * | 1980-10-30 | 1984-07-03 | Bayer Aktiengesellschaft | Process for the production of dry-spun hollow polyacrylonitrile fibers and filaments |
US4850847A (en) * | 1988-05-10 | 1989-07-25 | E. I. Du Pont De Nemours And Company | Spinneret for hollow fibers having curved spacing members projecting therefrom |
US5208107A (en) * | 1991-05-31 | 1993-05-04 | Basf Corporation | Hollow trilobal cross-section filament |
US5320512A (en) * | 1992-09-24 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Apparatus for spinning multicomponent hollow fibers |
US5360584A (en) * | 1986-06-23 | 1994-11-01 | Raychem Corporation | Method of forming a wrap-around heat-recoverable article |
LT4149B (en) | 1994-02-02 | 1997-04-25 | Froystad Fiskevegn As | Floating line or rope |
US6589653B2 (en) | 2001-08-08 | 2003-07-08 | E. I. Du Pont De Nemours And Company | Filament having a quadrilobate exterior cross-section and a four-sided void |
CN100402713C (en) * | 1999-03-01 | 2008-07-16 | 卡尔·弗罗伊登伯格公司 | Method for producing multiple section filament or fiber, and the filament of fiber therfrom, and fabric therefrom |
CN102947503A (en) * | 2010-06-21 | 2013-02-27 | Php纤维有限公司 | Buoyant rope |
US20150118928A1 (en) * | 2012-05-21 | 2015-04-30 | Lg Hausys, Ltd. | Lint-preventing yarn and woven floor decoration material using the same |
WO2016085848A1 (en) * | 2014-11-30 | 2016-06-02 | Sabic Global Technologies B.V. | Extruder die plate for reduced strand surging |
US11608571B2 (en) | 2016-08-18 | 2023-03-21 | Aladdin Manufacturing Corporation | Trilobal filaments and spinnerets for producing the same |
-
1967
- 1967-08-17 US US661348A patent/US3558420A/en not_active Expired - Lifetime
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3728428A (en) * | 1969-12-03 | 1973-04-17 | Allied Chem | Process for producing hollow filaments |
US3981948A (en) * | 1975-01-02 | 1976-09-21 | Eastman Kodak Company | Arrangements in spinnerets of spinning orifices having significant kneeing potential |
US4112166A (en) * | 1975-01-02 | 1978-09-05 | Monsanto Company | Method of extruding thermoplastic sheets |
US4056597A (en) * | 1975-04-03 | 1977-11-01 | Phillips Petroleum Company | Process and die for extrusion of a resinous material |
US4254181A (en) * | 1977-03-18 | 1981-03-03 | Monsanto Company | Filaments having alternate S-twisted and Z-twisted helical sections produced by crimping filaments provided with an eccentric anisotropy of shrinkable property by a preferential cooling on one side upon extrusion thereof through a spinneret |
US4176150A (en) * | 1977-03-18 | 1979-11-27 | Monsanto Company | Process for textured yarn |
US4336307A (en) * | 1978-01-27 | 1982-06-22 | Teijin Limited | Hollow water absorbing polyester filaments and a process for producing the same |
EP0007237A1 (en) * | 1978-07-17 | 1980-01-23 | Fiber Industries, Inc. | Spun-like yarn |
US4302509A (en) * | 1979-02-22 | 1981-11-24 | Albany International Corp. | Sorbent-cored textile yarns |
US4315877A (en) * | 1979-02-22 | 1982-02-16 | Albany International Corp. | Methods of fabricating sorbent-cored textile yarns |
US4361617A (en) * | 1979-07-26 | 1982-11-30 | Teijin Limited | Hollow water-absorbing polyester filaments and a process for producing the same |
US4391872A (en) * | 1979-07-26 | 1983-07-05 | Teijin, Ltd. | Hollow water-absorbing polyester filament textile material |
US4357390A (en) * | 1980-03-25 | 1982-11-02 | Teijin Limited | Antistatic polyester fibers |
US4376746A (en) * | 1980-04-01 | 1983-03-15 | Ametek, Inc. | Formation of hollow tapered brush bristles |
US4457885A (en) * | 1980-10-30 | 1984-07-03 | Bayer Aktiengesellschaft | Process for the production of dry-spun hollow polyacrylonitrile fibers and filaments |
US5360584A (en) * | 1986-06-23 | 1994-11-01 | Raychem Corporation | Method of forming a wrap-around heat-recoverable article |
US4850847A (en) * | 1988-05-10 | 1989-07-25 | E. I. Du Pont De Nemours And Company | Spinneret for hollow fibers having curved spacing members projecting therefrom |
US5208107A (en) * | 1991-05-31 | 1993-05-04 | Basf Corporation | Hollow trilobal cross-section filament |
US5320512A (en) * | 1992-09-24 | 1994-06-14 | E. I. Du Pont De Nemours And Company | Apparatus for spinning multicomponent hollow fibers |
LT4149B (en) | 1994-02-02 | 1997-04-25 | Froystad Fiskevegn As | Floating line or rope |
US5694755A (en) * | 1994-02-02 | 1997-12-09 | Froystad Fiskevegn As | Buoyant line and method for forming |
CN100402713C (en) * | 1999-03-01 | 2008-07-16 | 卡尔·弗罗伊登伯格公司 | Method for producing multiple section filament or fiber, and the filament of fiber therfrom, and fabric therefrom |
US6589653B2 (en) | 2001-08-08 | 2003-07-08 | E. I. Du Pont De Nemours And Company | Filament having a quadrilobate exterior cross-section and a four-sided void |
CN102947503A (en) * | 2010-06-21 | 2013-02-27 | Php纤维有限公司 | Buoyant rope |
KR20130036286A (en) * | 2010-06-21 | 2013-04-11 | 피에이치피 피버스 게엠베하 | Buoyant rope |
US20130091822A1 (en) * | 2010-06-21 | 2013-04-18 | Php Fibers Gmbh | Buoyant rope |
US8850785B2 (en) * | 2010-06-21 | 2014-10-07 | Php Fibers Gmbh | Buoyant rope |
US20150118928A1 (en) * | 2012-05-21 | 2015-04-30 | Lg Hausys, Ltd. | Lint-preventing yarn and woven floor decoration material using the same |
WO2016085848A1 (en) * | 2014-11-30 | 2016-06-02 | Sabic Global Technologies B.V. | Extruder die plate for reduced strand surging |
US11608571B2 (en) | 2016-08-18 | 2023-03-21 | Aladdin Manufacturing Corporation | Trilobal filaments and spinnerets for producing the same |
US11692284B2 (en) * | 2016-08-18 | 2023-07-04 | Aladdin Manufacturing Corporation | Trilobal filaments and spinnerets for producing the same |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3558420A (en) | Hollow filaments | |
US3117362A (en) | Composite filament | |
US3095258A (en) | Melt spinning process for producing hollow-core filament | |
US3118012A (en) | Melt spinning process | |
US3188689A (en) | Spinneret assembly | |
EP0607174B1 (en) | Oriented profiled fibers | |
US3227793A (en) | Spinning of a poly(polymethylene) terephthalamide | |
US3308221A (en) | Melt spinning of modified cross section yarn | |
US5618479A (en) | Process of making core-sheath filament yarns | |
US4562022A (en) | Producing foamed fibers | |
US3350488A (en) | Process for the production of sharp-edge fibers | |
IE23508B1 (en) | Fibres and filaments having improved crimp characteristics and method for their production | |
US3109195A (en) | Spinneret plate | |
US4544594A (en) | Foamed polyamide fibers | |
US4355075A (en) | Novel filament-like fibers and bundles thereof, and novel process and apparatus for production thereof | |
US4626390A (en) | Self-crimped foamed fibers | |
US3936253A (en) | Apparatus for melt-spinning synthetic fibers | |
US4045534A (en) | Process for melt-spinning synthetic fibers | |
US3174364A (en) | Process for the manufacture of spinnerets for melt spinning | |
US3497585A (en) | Self-crimping filament process | |
US3728428A (en) | Process for producing hollow filaments | |
KR0140074B1 (en) | Yarns made from core-seed filaments and preparation methods thereof | |
US3001265A (en) | Flat low melting point metal filament having an oriented synthetic resin sheath | |
JPH026613A (en) | Production of conductive filament and antistatic yarn containing polystyrene | |
EP0126519B1 (en) | Process for producing self-crimping polyester yarn |