US20040209540A1 - Apparatus and process for making fibrous products of bi-component melt-blown fibers of thermoplastic polymers and the products made thereby - Google Patents

Apparatus and process for making fibrous products of bi-component melt-blown fibers of thermoplastic polymers and the products made thereby Download PDF

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US20040209540A1
US20040209540A1 US10/796,510 US79651004A US2004209540A1 US 20040209540 A1 US20040209540 A1 US 20040209540A1 US 79651004 A US79651004 A US 79651004A US 2004209540 A1 US2004209540 A1 US 2004209540A1
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nozzles
fibers
nozzle
polymeric material
spinnerette
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US10/796,510
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Eckhard Schwarz
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Biax Fiberfilm Corp
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Biax Fiberfilm Corp
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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D04H1/56Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • Y10T442/638Side-by-side multicomponent strand or fiber material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • Y10T442/641Sheath-core multicomponent strand or fiber material
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/647Including a foamed layer or component
    • Y10T442/652Nonwoven fabric is coated, impregnated, or autogenously bonded
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/68Melt-blown nonwoven fabric

Abstract

Disclosed is a novel melt blown spinnerette and process for making bicomponent fine fibers whereby a spinning nozzle fed by one type of polymer from one chamber is located inside another larger spinning nozzle fed by a second chamber, said nozzle pairs being arranged in multiple rows of spinning orifices, and directing high speed streams of gas to each row of spinning orifices. The design of having a nozzle inside a nozzle does not require laminar flow of layered molten masses of different polymers. The fibers made hereby have a broad fiber size distribution.

Description

    PRIORITY
  • This is a continuation application of U.S. patent application Ser. No. 10/122,927, filed Apr. 16, 2002. No new matter has been added to the specifications or drawings.[0001]
  • BACKGROUND OF THE INVENTION
  • This invention relates to an adaptation of bi-component fiber spinning to a melt-blowing process as described in U.S. Pat. No. 5,476,616, which is herewith incorporated as reference. More particularly, it relates to the improvement whereby the number of rows of spinning orifices can be extended beyond the number possible before and still maintain fiberforming spinning quality, using polymer pairs of greatly differing melt viscosities and other properties. [0002]
  • OBJECTS OF THE INVENTION.
  • It is an object of the present invention to provide a bi-component spinning system whereby a spinning nozzle fed by one type of polymer from one chamber is located inside another slightly larger spinning nozzle fed by a second chamber, said nozzle pairs being arranged in multiple rows of spinning orifices, and directing streams of gas to each row of spinning orifices. [0003]
  • Another object of the invention is to provide a uniform stream of attenuating gas around each spinning nozzle by centering the nozzle pairs in round holes of gas cover plates to achieve an even gas flow around the circumference of each nozzle pair. [0004]
  • SUMMARY OF THE INVENTION
  • These and other objects of the invention are achieved by directing a gas flow to the base of the spinning nozzle pair by means of baffle plates, and extending the length of the spinning nozzle pairs. The spinning nozzle pairs are guided through a family of gas cover plates providing for the centering of the round spinning nozzle pairs through round gas supply holes and supplying a uniform stream of gas to each nozzle pair and row of nozzle pairs.[0005]
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • A better understanding of the present invention as well as other objects and advantages thereof will become apparent upon consideration of the detailed disclosure Thereof, especially when taken with the accompanying drawings, wherein like numerals designate like parts throughout; and wherein FIG. 1A is a partially schematic side view of a spinnerette assembly of the present invention, showing the path of gas and the two polymer flows. [0006]
  • FIG. 1B is the same spinnerette where the [0007] inner nozzles 4 have been shortened by the distance 22.
  • FIG. 2A is a partial bottom view of the concentric spinning nozzles and gas cover plates, taken along the lines [0008] 23-23.
  • FIG. 2B is a partial bottom view of the concentric spinning nozzles and gas cover plates, taken along the lines [0009] 24-24.
  • FIG. 3 is a partial bottom view of a spinnerette assembly, wherein the inner nozzle is off-center and shaped in a half-circle to form side-by-side bi-component fibers.[0010]
  • DETAILED DESCRIPTION OF THE INVENTION
  • In previous bi-component spinning assemblies, side-by-side or sheath-core structures are being formed by having two polymers flow through capillaries in a laminar flow pattern without mixing before exiting the capillary and then solidifying. This limits the polymer pairs to such groups that are capable of laminar flow, i.e. have similar melt-viscosities and other properties at similar extrusion temperatures. Bi-component designs have been disclosed in U.S. Pat. Nos: 2,931,091 and 3,039,174. Most of these designs were used in traditional textile yarn spinning and are not easily adaptable to the melt-blowing process. [0011]
  • In U.S. Pat. No. 6,057,256 to Krueger et al. a bi-component met-blowing process is shown where the polymers are contacted with each other inside the die-body as previously described, and, by laminar flow exit the spinning orifice and are drawn down by high velocity air. This design, however, is limited to a single row of spinning orifices and consequently relatively low capacity. [0012]
  • In the present invention, a bi-component melt-blowing system is shown where bi-component fibers are being spun out of multiple rows of spinning orifices, and whereby the contact time of two or more polymers inside the die-body can be controlled from zero to any finite time chosen, by having one capillary in which a first polymer flows, being fed from one polymer manifold, is surrounded by a second, larger than the first capillary, through which a second polymer fed from a second polymer manifold flows; at the exit point, each tubular nozzle is surrounded by a concentric flow of high velocity air as described in previously cited U.S. Pat. No. No. 5,476,616. [0013]
  • Referring now to FIG. 1, the spinnerette assembly is mounted on the [0014] die body 1 which supplies polymer melt 2 to first supply cavity 3 feeding the spinning nozzles 4 which are mounted in the spinnerette body plate 5 wherein nozzles 4 are mounted. A second set of nozzles 6, larger than nozzles 4, having an identical mounting pattern as nozzles 4, is mounted on the die body plate 7 and is being fed with a second polymer 8 from the die body 1 and through plate 5 to cavity 9 which feeds nozzles 6. Nozzles 4 are inserted into nozzles 6, and have the same or shorter length than nozzles 4. The nozzles 4 and 6 lead through the gas cavity 10, which is fed with gas, air or other suitable fluids from gas inlet slot 11. The primary gas supply enters the spinnerette assembly through pipe 12 into the supply cavity 13. The baffle plate 14 diverts the gas stream and forces the gas through the slot 11 toward the base of nozzles 6. The nozzles 4 and 6 protrude through gas cover plate 15 through tight fitting holes 16 arranged in the same pattern as the nozzle mounts in spinnerette body plates 5 and 7. The gas cover plate family further consists of spacer plate 18, which forms a second gas cavity 19 between plate 15 and 20. The complete path of the gas is now from inlet pipe 12 into the gas supply cavity 13 through inlet slot 11 into gas cavity 19. The gas then flows through gas holes 17 of plate 15 into the gas cavity 19 and then around the nozzles 6 through holes 21, in which nozzles 6 are centered. The high velocity gas out of holes 21 accelerates and attenuate the exiting polymer melts to form fine fibers. FIG. 2A and B show the bottom view of plates 15 and 20, respectively. FIG. 3 shows a bottom view of plate 20, wherein the inner nozzles 4 are shaped in a half circle to produce a side-by-side bi-component fiber.
  • The following examples are included for the purpose of illustrating the invention and it is understood that the scope of the invention is not to be limited thereby. [0015]
  • EXAMPLE 1
  • A 5″ long spinnerette was used of the type shown in FIG. 1. The spinnerette had 12 rows of nozzles, spaced 0.060″ apart, within each rows, the nozzles were also spaced 0.060″ apart, resulting in a total number of nozzles of 1000. The [0016] inner nozzles 4 mounted in plate 5 had an outside diameter of 0.020″ and an inside diameter of 0.010″. The outside nozzles 6 mounted in plate 7 had an outside diameter of 0.035″ and an inside diameter of 0.023″. Air cavity 10 had a height of 0.500″, air cover plate 15 a thickness of 0.063″. Air holes 17 shown in FIG. 1 and 2A had a diameter of 0.020″. Air cavity 19 had a height of 0.100″ and air cover plate 20 a thickness of 0.063″. The air holes 21 in plate 20 had a diameter of 0.048″. The resin inlets 2 and 8 were each connected to a 1″ (24/1 length/diameter ratio) extruder, subsequently referred to as extruder A and B, respectively, each capable of extruding approximately 10 lb/hr of polymer resin.
  • Extruder B (sheath polymer) was charged with high-density polyethylene of Melt Index 105 (Dow Chemical Company's “ASPUN” 6808A) and the resin was extruded into the spinnerette at a rate of 30 gram per minute; Extruder A (core polymer) was charged with polypropylene of MFR 70 (Melt Flow Rate, as determined by ASTM-Method D-1238-65T)(HIMONT “HH442”) and extruded at a rate of 45 gram per minute, 3% of blue polypropylene color concentrate was added to the polypropylene resin to give the core fiber a blue appearance. The spinnerette temperature and the air temperature were 480 degree Fahrenheit, and the air pressure was 20 psi. 12″ below the spinnerette there was a moving screen that collected a web of highly entangled blue fibers of 3 to 6 micrometer diameter. The web had a typical slick, silk like polyethylene feel, indicating that the polyethylene from extruder B was on the outside. Parallel strands of fibers were imbedded and cured into an epoxy resin, and cross sections were cut therefrom. Microscopic examination showed a concentric sheath/core fiber structure, with the blue color visible in the core section. When the fibrous web was heated to a temperature of 250 degree F., most of the point of intersection bonded by coalescence and the web formed a stiff, shape-retaining structure. [0017]
  • EXAMPLE II
  • Additional experiments were conducted using polymer pairs as shown in Table 1: [0018]
    TABLE 1
    Experiment No.:
    1 2 3 4
    Polymer from PET 1 6,6 Nylon2 PBT3 Polypropylene
    Extruder A 0.59 IV4 35 RV5 0.59 IV 70 MFR
    Extrusion rate 30 g/min 35 g/min 45 g/min 40 g/min
    Polymer from 6,6 Nylon PET Nylon 66 Nylon 6
    Extruder B 35 RV 0.59 IV 40 RV 40 RV
    Extrusion rate 45 g/min 50 g/min 30 g/min 25 g/min
    Spinnerette 520 520 480 470
    Temp. (F.)
    Air Temp. (F.) 510 520 480 470
    Air pressure (psi)  25  25  23  24
  • Microscopic examination of the fiber cross-sections, which ranged from 3 to 7 micrometer in diameter, revealed that the sheath/core structure was concentric or near concentric. [0019]
  • EXAMPLE III
  • Example I was repeated using identical polymers and process conditions, but with a spinnerette described in FIG. 1B where the [0020] inner nozzles 4 where recessed by the length 22 of 0.150″. Under a microscope, the fiber cross-sections showed the same concentric sheath/core structure as in Example I, with the blue polypropylene inside.
  • EXAMPLE IV
  • Example I was repeated using a nozzle arrangement as shown in FIG. 3. Upon microscopic examination, the fiber cross-section showed that the two polymers had each formed a semi-circle in a side-by-side configuration. [0021]
  • While the invention has been described in connection with several exemplary embodiments thereof, it will be under stood that many modifications will be apparent to those of ordinary skill in the art, and that this application is intended to cover any adaptations and variations thereof. Therefore, it is manifestly intended that this invention be only limited by the claims and the equivalents thereof. [0022]

Claims (7)

    What is claimed is:
  1. 7. A melt blowing spinnerette for extruding two thermoplastics to produce a plurality of filaments, which individually comprise a first polymeric material extending longitudinally along the fiber through a first portion of the cross-sectional area of said fibers and a second polymeric material adhered to said first polymeric material and extending longitudinally along said fibers through a second portion of the cross-sectional area of the fibers, comprising:
    a) A first set of nozzles arranged in at least one row,
    b) A first polymer melt chamber to feed the first set of nozzles,
    c) A second set of nozzles with the same number, arranged in the same center-to-center spacing as in the first set of nozzles, said second set of nozzles surrounding each of said first set of nozzles thus forming nozzle pairs, and said second nozzles having a larger inside diameter than the outside diameter of said first set of nozzles
    d) A second polymer melt chamber to feed the second set of nozzles,
    e) A top plate with air holes surrounding and being concentric with each nozzle pair, said air holes being supplied with compressed hot air from an air chamber.
    f) A mechanism to keep the components in an assembly.
  2. 8. A melt blowing spinnerette of claim 7 wherein the first set of nozzles have a length-to-inside-diameter ratio of at least 25.
  3. 9. A melt blowing spinnerette of claim 7 wherein the second set of nozzles have a length-to-inside-diameter ratio of at least 25.
  4. 10. A melt blowing spinnerette of claim 7 wherein the air holes in said top plate are at least 0.001 inch larger than the outside diameter of the second set of nozzles.
  5. 11. A process for making products of melt blown bi-component fibers, comprising:
    a. Extruding a mass of said first polymeric material through said first set of nozzles arranged in at least one row, and a mass of said second polymeric material through said second set of nozzles arranged in the same center-to-center spacing for bicomponent extrudate
    b. Advancing said extrudate into high velocity gas streams surrounding circumferentially each individual nozzle pair of said first and second set of nozzles,
    c. Attenuating said bi-component extrudate from each of said nozzle pairs to form said bi-component fibers,
    d. Collecting the said bi-component fibers on one or more moving surfaces to form a fibrous product.
  6. 12. A fibrous product of said bicomponent fiber, in the forms of yarn, tow, nonwoven fabrics, and filter cartridge, being prepared by
    a. Extruding a mass of said first polymeric material through said first set of nozzles arranged in at least one row, and a mass of said second polymeric material through said second set of nozzles arranged in the same center-to-center spacing for bicomponent extrudate
    b. Advancing said extrudate into high velocity gas streams surrounding circumferentially each individual nozzle pair of said first and second set of nozzles,
    c. Attenuating said bi-component extrudate from each of said nozzle pairs to form said bi-component fibers,
    d. Collecting the said bi-component fibers on one or more surfaces to form a fibrous product.
  7. 13. The fibrous product of claim 12 wherein the bicomponent fibers have a broad fiber diameter distribution, ranging from 0.3 micrometer to 25 micrometer.
US10/796,510 2002-04-16 2004-03-09 Apparatus and process for making fibrous products of bi-component melt-blown fibers of thermoplastic polymers and the products made thereby Abandoned US20040209540A1 (en)

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US10/122,927 US20030194939A1 (en) 2002-04-16 2002-04-16 Fibrous webs of bi-component melt-blown fibers of thermoplastic polymers from a bi-component spinnerette assembly of multiple rows of spinning orifices
US10/796,510 US20040209540A1 (en) 2002-04-16 2004-03-09 Apparatus and process for making fibrous products of bi-component melt-blown fibers of thermoplastic polymers and the products made thereby

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US20110037194A1 (en) * 2009-08-14 2011-02-17 Michael David James Die assembly and method of using same
WO2012019035A2 (en) 2010-08-05 2012-02-09 Frank Scott Atchley Composite smokeless tobacco products, systems, and methods
US8664129B2 (en) 2008-11-14 2014-03-04 Exxonmobil Chemical Patents Inc. Extensible nonwoven facing layer for elastic multilayer fabrics
US8668975B2 (en) 2009-11-24 2014-03-11 Exxonmobil Chemical Patents Inc. Fabric with discrete elastic and plastic regions and method for making same
US8748693B2 (en) 2009-02-27 2014-06-10 Exxonmobil Chemical Patents Inc. Multi-layer nonwoven in situ laminates and method of producing the same
WO2014144254A2 (en) 2013-03-15 2014-09-18 Altria Client Services Inc. Methods and machines for pouching smokeless tobacco and tobacco substitute products
WO2014152956A1 (en) 2013-03-14 2014-09-25 Altria Client Services Inc. Product portion enrobing process and apparatus, and resulting products
US9066540B2 (en) 2010-08-05 2015-06-30 Altria Client Services Inc. Fabric having tobacco entangled with structural fibers
US9168718B2 (en) 2009-04-21 2015-10-27 Exxonmobil Chemical Patents Inc. Method for producing temperature resistant nonwovens
US9498932B2 (en) 2008-09-30 2016-11-22 Exxonmobil Chemical Patents Inc. Multi-layered meltblown composite and methods for making same
US9896228B2 (en) 2014-03-14 2018-02-20 Altria Client Services Llc Polymer encased smokeless tobacco products
US10161063B2 (en) 2008-09-30 2018-12-25 Exxonmobil Chemical Patents Inc. Polyolefin-based elastic meltblown fabrics
US10239089B2 (en) 2014-03-14 2019-03-26 Altria Client Services Llc Product portion enrobing process and apparatus

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US6776858B2 (en) * 2000-08-04 2004-08-17 E.I. Du Pont De Nemours And Company Process and apparatus for making multicomponent meltblown web fibers and webs
DE102020001132A1 (en) * 2020-02-20 2021-08-26 Oerlikon Textile Gmbh & Co. Kg Meltblown nozzle device

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US3039174A (en) * 1958-05-12 1962-06-19 Du Pont Elongated composite structure
US6057256A (en) * 1983-10-11 2000-05-02 3M Innovative Properties Company Web of biocomponent blown fibers
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US9498932B2 (en) 2008-09-30 2016-11-22 Exxonmobil Chemical Patents Inc. Multi-layered meltblown composite and methods for making same
US10161063B2 (en) 2008-09-30 2018-12-25 Exxonmobil Chemical Patents Inc. Polyolefin-based elastic meltblown fabrics
US8664129B2 (en) 2008-11-14 2014-03-04 Exxonmobil Chemical Patents Inc. Extensible nonwoven facing layer for elastic multilayer fabrics
US9168720B2 (en) 2009-02-27 2015-10-27 Exxonmobil Chemical Patents Inc. Biaxially elastic nonwoven laminates having inelastic zones
US8748693B2 (en) 2009-02-27 2014-06-10 Exxonmobil Chemical Patents Inc. Multi-layer nonwoven in situ laminates and method of producing the same
US9168718B2 (en) 2009-04-21 2015-10-27 Exxonmobil Chemical Patents Inc. Method for producing temperature resistant nonwovens
US11414787B2 (en) 2009-08-14 2022-08-16 The Procter & Gamble Company Die assembly and methods of using same
US10704166B2 (en) * 2009-08-14 2020-07-07 The Procter & Gamble Company Die assembly and method of using same
US11739444B2 (en) 2009-08-14 2023-08-29 The Procter & Gamble Company Die assembly and methods of using same
US20110037194A1 (en) * 2009-08-14 2011-02-17 Michael David James Die assembly and method of using same
US8668975B2 (en) 2009-11-24 2014-03-11 Exxonmobil Chemical Patents Inc. Fabric with discrete elastic and plastic regions and method for making same
US11540560B2 (en) 2010-08-05 2023-01-03 Altria Client Services Llc Fabric having tobacco entangled with structural fibers
US10736354B2 (en) 2010-08-05 2020-08-11 Altria Client Services Llc Fabric having tobacco entangled with structural fibers
US8978661B2 (en) 2010-08-05 2015-03-17 Altria Client Services Inc. Composite smokeless tobacco products, systems, and methods
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