WO1998007906A1 - Polymere file eclair - Google Patents

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Publication number
WO1998007906A1
WO1998007906A1 PCT/US1997/014513 US9714513W WO9807906A1 WO 1998007906 A1 WO1998007906 A1 WO 1998007906A1 US 9714513 W US9714513 W US 9714513W WO 9807906 A1 WO9807906 A1 WO 9807906A1
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WO
WIPO (PCT)
Prior art keywords
polyethylene
molecular weight
flash
nonwoven sheet
less
Prior art date
Application number
PCT/US1997/014513
Other languages
English (en)
Inventor
Hyunkook Shin
David Jackson Mc Ginty
Larry Ray Marshall
Thomas A. Pakurar
Gary Stephen Huvard
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to JP51087398A priority Critical patent/JP2001521585A/ja
Priority to CA002260881A priority patent/CA2260881A1/fr
Priority to EP97937308A priority patent/EP0917599A1/fr
Publication of WO1998007906A1 publication Critical patent/WO1998007906A1/fr

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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
    • D01D5/11—Flash-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING 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
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/724—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged forming webs during fibre formation, e.g. flash-spinning

Definitions

  • This invention relates to flash spinning polymer and particularly to the products made from flash spinning polymer such as fibrous webs and consolidated sheets and fabrics.
  • Flash-spun fibers were originally created by Herbert Blades and James White, employees of E. I. du Pont de Nemours and Company (DuPont), and disclosed in US Patent 3,081,510 on 19 March 1962.
  • a variety of polymeric materials were disclosed in the patent primarily including linear polyethylene with some examples of polypropylene. Further examples of polymeric materials which may be spun into plexifilaments were described in a subsequent patent, US Patent 3,227,784 on 4 January 1966, also to Blades et al.
  • DuPont has scaled up to commercial production of flash-spun products under the trademark Tyvek® spunbonded olefin.
  • Tyvek® spunbonded olefin has many uses for which its properties have been adapted and engineered such as air infiltration barriers, banners, envelopes, medical packaging, and protective apparel.
  • DuPont has developed two basic styles of flash-spun nonwoven sheet products: area bonded material and point bonded material.
  • Area bonded material is thermally bonded generally uniformly across the area of the sheet.
  • Point or pattern bonded material is thermally bonded at points or in a pattern where the pattern creates portions which are more strongly bonded and not as strongly bonded.
  • area bonded products are typically stiffer than point bonded and have a paper-like feel.
  • Point bonded flash-spun nonwoven products tend to have softer fabric-like feel.
  • Point bonded flash-spun material is most commonly used in protective apparel. Area bonded products are used in envelopes, medical packaging and air infiltration barriers in construction applications. In several end uses, the tensile and elongation properties of the flash-spun nonwoven fabrics are of considerable importance such as in packaging and protective apparel.
  • the material for protective apparel is preferably quite strong; however, if it were to fail, then it is desired that it fail by stretching and deforming rather than ripping or breaking. It is particularly desirable that both tensile strength and elongation are high at the same time.
  • a polyethylene flash-spun plexifilamentary film-fibril material having a BET surface area of at least about two m 2 /gm and wherein the polymer has a number average molecular weight of at least about 20,000 and a molecular weight distribution of less the 4.0.
  • Figure 1 is a schematic view of an apparatus suitable in the process of flash spinning polymer into a plexifilamentary web and laying down the plexifilamentary web to form a nonwoven sheet:
  • Figure 2 is a fragmentary perspective view of the laydown of the plexifilamentary web in Figure 1 ;
  • Figure 3 is an enlarged cross sectional view of the letdown chamber and spin orifice in the apparatus in Figure 1 ; and Figure 4 is a schematic view of a small scale test system for making plexifilamentary yarn from polymer.
  • FIG. 1 a preferred system and process for flash spinning fibers and forming sheets is illustrated in Figures 1 and 2.
  • the basic system has been previously disclosed in U.S. Patent 3,860,369 to Brethauer et al., which is hereby incorporated by reference.
  • the process is conducted in a chamber 1 , sometimes referred to as a spin cell by those in the industry, which has a vapor-removal port 2 and an opening 3 through which non-woven sheet material produced in the process is removed.
  • Polymer solution or spin liquid
  • the pressure of the solution is greater than cloud-point pressure which is the lowest pressure at which the polymer is fully dissolved in the spin agent forming a homogeneous single phase mixture.
  • the single phase polymer solution passes through a letdown orifice 1 1 into a lower pressure (or letdown) chamber 12. In the lower pressure chamber 12, the solution separates into a two-phase liquid-liquid dispersion.
  • One phase of the dispersion is a spin agent-rich phase which comprises primarily spin agent and the other phase of the dispersion is a polymer-rich phase which contains most of the polymer.
  • This two phase liquid-liquid dispersion is forced through a spinneret 13 into an area of much lower pressure (preferably atmospheric pressure) where the spin agent evaporates very rapidly (flashes), and the polyolefin emerges from the spinneret as a yarn (or plexifilament) 20.
  • the yam 20 is stretched in a tunnel 14 and is directed to impact a rotating baffle 15.
  • the rotating baffle 15 has a shape that transforms the yarn 20 into a flat web 21 , which is about 5-15 cm wide, and separating the fibrils to open up the web 21.
  • the rotating baffle 15 further imparts a back and forth oscillating motion having sufficient amplitude to generate a wide back and forth swath.
  • the web 21 is laid down on a moving wire laydown belt 16 located about 50 cm below the spinneret 13, and as best seen in Figure 2, the back and forth oscillating motion is arranged to be generally across the belt 16 to form a sheet 22.
  • the web 21 is deflected by the baffle 15 on its way to the moving belt 16. It enters a corona charging zone between a stationary multi- needle ion gun 30 and a grounded rotating target plate 31.
  • the multi-needle ion gun 30 is charged to a DC potential by a suitable voltage source 36.
  • the charged web 21 is carried by a high velocity spin agent vapor stream through a diffuser consisting of two parts: a front section 32 and a back section 33. The diffuser controls the expansion of the web 21 and slows it down.
  • the back section 33 of the diffuser may be stationary and separate from target plate 31 , or it may be integral with it. In the case where the back section 33 and the target plate 31 are integral, they rotate together.
  • Figure 1 shows the target plate 31 and the back section 33 of the diffuser as a single unit.
  • Aspiration holes 34 and 35 are drilled in the back section 33 of the diffuser to assure adequate flow of gas between the moving web 21 and the diffuser back section 33 to prevent sticking of the moving web 21 to the diffuser back section 33.
  • the moving belt 16 is grounded through roll 17 so that the charged web 21 is electrostatically attracted to the belt 16 and held in place thereon.
  • Overlapping web swaths collected on the moving belt 16 and held there by electrostatic forces are formed into a sheet 22 with a thickness controlled by the belt speed.
  • the sheet 22 is compressed between belt 16 and consolidation roll 18 into a structure having sufficient strength to be handled outside the chamber 1 and then collected outside the chamber 1 on a windup roll 23.
  • Flash-spun nonwoven sheets made by a process similar to the foregoing process are sold as Tyvek® spunbonded olefin sheets for air infiltration barriers in construction applications, as packaging such as air express envelopes, as medical packaging, as banners, and for protective apparel and other uses.
  • Tyvek® spunbonded olefin is quite strong and lightweight with small interstices between the fibers to allow moisture vapor and air to permeate the sheet but limit passage of liquid water.
  • Tyvek® spunbonded olefin is of considerable interest and importance for its various end uses. It should go without saying that it is always desirable to improve the properties of flash- spun products as long as there is not a sacrifice of other important properties. As described in many prior patent applications on flash spinning, a myriad of variations have been disclosed that lead to variations in properties of flash-spun fabrics.
  • Tyvek® spunbonded olefin sheet One particular important set of properties of Tyvek® spunbonded olefin sheet are tensile strength, elongation and toughness.
  • Tyvek® spunbonded olefin has considerable tensile strength especially considering that it is made of high density polyethylene. Flash spinning tends to provide highly oriented polymer in the plexifilaments. While flash spinning provides good tensile properties, improved tensile properties as well as considerable elongation and toughness would be appreciated in the market place.
  • Elongation is a measure of the amount the product stretches before it breaks.
  • Work to Break (WTB) relates to both the elongation and tensile strength. The WTB is the area under the stress-strain curve. Toughness is the WTB normalized for the basis weight.
  • DuPont has relied solely upon high density polyethylene for all commercial operations in its Tyvek business and, indeed, the polyethylene used was specified from specific sources with very tight specifications. Recently, however, DuPont has begun to add post consumer recycled high density polyethylene to virgin polymer. The post consumer recycle is primarily from recycled milk jugs. Considerable engineering has gone into the system and process to accommodate the recycled materials, and the company is quite proud of this accomplishment.
  • the polymers that can be used for this invention include ethylene homo-polymers and copolymers, and blends of ethylene homo-polymers and copolymers. These polymers can be prepared by using either Ziegler-Natta type catalysts or single site catalysts.
  • the polymers which are particularly useful for this invention are high density polyethylene (HDPE) made from ethylene homo-polymers or ethylene copolymers containing a relatively small amount of polymerized co-monomer units.
  • HDPE high density polyethylene
  • Alpha olefins such as propylene, butene, hexene and octene are commonly used as a co-monomer for commercially available high density polyethylene copolymers.
  • polyethylene shall mean a polymer comprised entirely or nearly entirely of ethylene monomer with no more than to a small portion of co-monomer units polymerized therein.
  • High density polyethylene shall mean polyethylene having a density greater than about 0.935 g/cc.
  • the shape of the spin orifice 14 of particular interest is the length to diameter ratio. Referring to Figure 3, the spin orifice has a length identified by the letter / and a diameter identified by the letter d. The ratio of the length to diameter "l/d" for the standard arrangement has historically been about one.
  • the polymer concentration has little effect on elongation and tensile strength.
  • the length to diameter ratio of the spin orifice 14 is sufficiently extended so that it is much longer than its diameter, the elongation of the flash-spun material can be substantially modified by adjustment of the ratio of polymer to spin agent in the homogeneous mixture being fed to the spin cell 10.
  • the combination of spin orifice configuration, solution concentration and narrow molecular weight distribution polymer combine to provide considerably higher elongation and tensile properties.
  • Example cases were prepared to illustrate the effects of changing the above described variables. However, it should be noted that other process conditions must be modified to be able to spin well fibrillated yarns which provide suitable sheets and sheet properties. In some situations, the amount of polymer available to test was not enough to make sheets.
  • a small scale test device shown in Figure 4 is used to make flash-spun fiber which can be tested and compared to polymer samples made into both fiber and sheet.
  • the device 40 comprises a block 41 which includes a primary cylinder chamber 44 and second cylinder chamber 45. Measured quantities of polymer and spin agent are provided into the primary cylinder chamber 44 through a suitable access such as port 48. The polymer and spin agent are directed back and forth between the primary cylinder chamber 44 and the second cylinder chamber 45 through passage 50 which includes a static mixer element 51. Pressurized fluid from a hydraulic pump 54 via hydraulic valve 55 and hydraulic lines 56 and 57 causes pistons 64 and 65 to move the polymer and spin agent between the two chambers 44 and 45. The mixture is heated to a predetermined temperature and the pressure is monitored at sensor 67 until the polymer and spin agent are adequately mixed. The hydraulic system is then operated to direct the solution into the primary cylinder chamber 44 whereupon the valve 55 is closed to lock the secondary piston 65 closest to the passage 50. The hydraulic valve 55 is also closed to preclude hydraulic fluid from passing from line 56 back into the pump 54.
  • the spin solution now in the primary chamber 44 is spun through a valve 71 using an accumulator 74 to maintain relatively constant spin pressure.
  • the accumulator 74 includes a relatively large cylinder 75
  • Hydraulic fluid preferably water
  • pressurized gas fills the space inside cylinder 75 on the other side of the piston 76.
  • the pressurized gas provided through a gas line 78 from a suitable source is controlled to create a nearly constant accumulator pressure during the spin which lasts a few seconds.
  • the accumulator pressure is monitored at sensor 79.
  • residence time does not have too much effect on fiber morphology and/or properties as long as it is greater than about 0.1 second but less than about 10 seconds.
  • the valve between the spin cell and the accumulator is opened, the pressure inside the spin cell drops immediately from the mixing pressure to the accumulator pressure.
  • the spin cell pressure drops again when the spinneret orifice 71 is opened because of the pressure drop in the line 82.
  • the pressure measured during spinning just before the spinneret with a pressure transducer using a computer is entered as the spin pressure in the examples. It is usually lower than the set accumulator pressure by about 100 to 200 psi.
  • the quality of the two phase dispersion in the spin cell depends on both the accumulator pressure and the actual spin pressure, and the time at those pressures.
  • the accumulator pressure is set at a pressure higher than the cloud point pressure.
  • the quality of the two phase dispersion in the spin cell will be determined primarily by the spin pressure reached after the spinneret orifice is opened.
  • There are a number of tests and other measured parameters such as the tensile strength, break elongation, and toughness on yarn and sheets. Several measurements, tests and test methods are described hereafter to provide a brief description of a number of the tests and measured parameters.
  • Weight average molecular weight and number average molecular weight were determined by gel permeation chromatography (GPC).
  • GPC analyses were performed on a Waters 150-C chromatograph equipped with three Polymer Labs Mixed B columns and a Viscotek viscosity detector.
  • the solvent used to prepare the polymer solutions and also used as the mobile phase is 1 ,2,4-trichlorobenzene.
  • Solution preparation and analysis are done at 140 C. The system is calibrated against a series of narrow distribution polystyrenes.
  • Melt index is measured according to ASTM D1238-90A, which is hereby incorporated by reference, at a temperature of 190° C with a 2.16 kg weight and is expressed in units of g/10 minutes.
  • Surface area for flash-spun polyethylene typically is in the range of 10 to 50 ⁇ r/gm. This is considerably higher than other fiber spinning technologies and provides the high opacity typically desired in nonwoven sheet products.
  • the surface area of the plexifilamentary film- fibril strand is measured by the BET nitrogen absorption method of S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc, V. 60 p 309-319 (1938), which is hereby incorporated by reference, and is reported as m 2 /g. While surface area was not measured for the samples discussed below, based on visual observations by experienced personnel, it can be reported that all test below were within the typical surface area range for flash-spun polyethylene of 10 to 50 m 2 /gm.
  • Denier of the flash-spun strand is determined as follows: One 90 cm long strand of yam is cut, and a weight of 100 grams is hung on one end of the yam for 3 minutes to remove bends and waviness. From the long single yam strand, five 18 cm individual pieces are cut, and denier is determined for each piece.
  • Tenacity, elongation and toughness of the strand are determined with an Instron tensile-testing machine.
  • the strands are conditioned and tested at 70 F and 65 % relative humidity.
  • the strands are then twisted to 10 turns per inch and mounted in the jaws of the Instron Tester.
  • a two-inch gauge length is used with an elongation rate of 2 inches per minute.
  • the tenacity at break is recorded in grams per denier (gpd).
  • the elongation at break is recorded as a percentage of the two-inch gauge length of the sample.
  • Toughness is a measure of the work required to break the sample divided by the denier of the sample and is recorded in gpd.
  • Modulus corresponds to the slope of the stress/strain curve and is expressed in units of gpd-
  • Basis weight is determined by ASTM D3776, which is hereby incorporated by reference, and is reported in oz/yd 2 (g/m 2 ). The basis weights reported for the examples below are each based on an average of at least six measurements made on the sheet.
  • Delamination strength of a sheet sample is measured using a constant rate of extension tensile testing machine such as an Instron table model tester.
  • a 1.0 in. (2.54 cm) by 8.0 in. (20.32 cm) sample is delaminated approximately 1.25 in. (3.18 cm) by inserting a pick into the cross-section of the sample to initiate a separation and delamination by hand.
  • the delaminated sample faces are mounted in the clamps of the tester which are set 1.0 in. (2.54 cm) apart.
  • the tester is started and run at a cross-head speed of 5.0 in./min. (12.7 cm/min.).
  • the computer starts picking up force readings after the slack is removed in about 0.5 in. of crosshead travel.
  • the sample is delaminated for about 6 in. (15.24 cm) during which 3000 force readings are taken and averaged.
  • the average delamination strength is the average force divided by the sample width and is expressed in units of lbs/in (N/cm).
  • the test generally follows the method of ASTM D2724-87, which is hereby incorporated by reference.
  • the delamination strength values reported for the examples below are each based on an average of at least six measurements made on the sheet. Opacity
  • Opacity is measured according to TAPPI T-519 om-86, which is hereby incorporated by reference.
  • the opacity is the reflectance from a single sheet against a black background compared to the reflectance from a white background standard and is expressed as a percent.
  • the opacity values reported for the examples below are each based on an average of at least six measurements made on the sheet.
  • the elongation at 13.34 Newtons (3 lb) load and the elongation at break were recorded as a percent of the original sample length.
  • the Work-to-Break (WTB) which is the area under the stress-strain curve, was normalized by dividing by the sample basis weight and the sample width and is reported as toughness in lb-yd 2 /oz (N-m 2 /g).
  • Elmendorf Tear Elmendorf tear strength is measured according to ASTM D 1424, which is hereby incorporated by reference. The Elmendorf tear values are reported for the examples below.
  • the spin agent comprises 68% normal pentane and 32% cyclopentane. Focusing on flash-spun yam properties the following examples were run in the twin cell system 40 with the following properties:
  • Example S-Bla plexifilamentary polyethylene was flash spun from a solution consisting of 18.1% of linear high density polyethylene and 81.9% of a spin agent consisting of 32% cyclopentane and 68% normal pentane.
  • the polyethylene had a melt index of 0.73 g/10 minutes (@ 190°C with a 2.16 kg weight), a melt flow ratio ⁇ MI(@ 190°C with a 2.16 kg weight)/MI (@190°C with a 21.6 kg weight) ⁇ of 34, and a density of 0.96 g/cc.
  • the polyethylene was obtained from Lyondell Petrochemical Company of Houston, Texas under the tradename ALATHON® .
  • ALATHON® is currently a registered trademark of Lyondell Petrochemical Company.
  • the solution was prepared in a continuous mixing unit and delivered at a temperature of 185°C, and a pressure of about 13.8 MPa (2000 psi) through a heated transfer line to an array of six spinning positions. Each spinning position has a pressure letdown chamber where the solution pressure was dropped to about 7.0 MPa ( 1010 psi).
  • the solution was discharged from each letdown chamber to a region maintained near atmospheric pressure and at a temperature of about 50°C through a 0.871 mm(0.0343 in) spin orifice having a length to diameter of about 0.9.
  • the flow rate of solution through each orifice was about 136 kg/hr (299 lbs/hr).
  • the solution was flash spun into plexifilamentary film-fibrils that were laid down onto a moving belt, consolidated, collected as a loosely consolidated sheet on a take-up roll as described above.
  • the sheet was bonded on a Palmer bonder by passing the sheet between a moving belt and a rotating heated smooth metal drum with a diameter of about five feet.
  • the drum is heated with pressurized steam and the bonding temperature is controlled by adjusting the pressure of the steam inside the drum.
  • the pressurized steam heats the bonding surface of the drum to approximately 133 to 141 °C.
  • the pressure of the steam is used to adjust the temperature of the drum according to the degree of bonding desired.
  • the bonded sheet has the opacity, delamination and other properties as set forth in the following Table as Example S-B 1 a. Examples S-B 1 b through C-Sheet were created manner similar to S-Bl a with differences as noted.
  • properties of the sheet vary as the bonding temperature is changed by adjusting the bonder steam pressure. Normally, delamination strength increases and opacity decreases as bonding temperature is increased.
  • the bonding temperature required to attain a specified level of delamination strength or opacity depends on the polymer and spinning conditions used to make the unbonded precursor sheet. In order to make meaningful comparisons among samples, each of the sheet samples below were bonded over a range of temperatures yielding delamination strength values both less than and greater than 0.35 lb/in, and the properties at 0.35 lb/in delamination strength were then estimated using linear regression.
  • flash spinning narrow molecular weight distribution polyethylene yields improved qualities, especially in tensile strength, elongation and toughness. Additional improvements in elongation may also be attained by changes in the spin orifice geometry and in the spin concentration. Notably, each of these changes, polymer and spin conditions, improve the properties of the product independently of the other. In other words, each can be adjusted individually to improve the properties and both can be adjusted together to improve them the most.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Nonwoven Fabrics (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

La présente invention a trait à des améliorations importantes apportées aux propriétés de traction, d'élongation et de ténacité de fibres filées éclair et de nappes non tissées constituées à partir de fibres filées éclair. Cette invention se réfère à des propriétés améliorées de fibres et de nappes comportant du polyéthylène à répartition étroite des poids moléculaires, et à d'autres améliorations lorsque celui-ci est combiné avec des aspects du procédé.
PCT/US1997/014513 1996-08-19 1997-08-19 Polymere file eclair WO1998007906A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP51087398A JP2001521585A (ja) 1996-08-19 1997-08-19 フラッシュ紡糸ポリマー
CA002260881A CA2260881A1 (fr) 1996-08-19 1997-08-19 Polymere file eclair
EP97937308A EP0917599A1 (fr) 1996-08-19 1997-08-19 Polymere file eclair

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US69928196A 1996-08-19 1996-08-19
US08/699,281 1996-08-19
US82526797A 1997-03-27 1997-03-27
US08/825,267 1997-03-27

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WO1998007906A1 true WO1998007906A1 (fr) 1998-02-26

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KR (1) KR20000068238A (fr)
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WO (1) WO1998007906A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1338692A1 (fr) * 2002-02-22 2003-08-27 E.I. DU PONT DE NEMOURS & COMPANY, INC. Nontissé plus résistant et plus doux
US7140292B2 (en) 2000-06-16 2006-11-28 The Quaker Oats Company Device, system and method for fluid additive injection into a viscous fluid food stream
WO2008001926A2 (fr) * 2006-06-27 2008-01-03 Sumitomo Chemical Company, Limited Composition de résine destinée à un filament, filament associé et procédé de production de ce filament
US7511115B2 (en) 2006-06-23 2009-03-31 Korea Institute Of Science & Technology Method of preparing biodegradable polyester polymer material in the form of filament and sheet using compressed gas
WO2015195898A1 (fr) * 2014-06-18 2015-12-23 E. I. Du Pont De Nemours And Company Feuilles plexifilamentaires
EP3199556A4 (fr) * 2014-12-10 2018-03-14 LG Chem, Ltd. Granulé de polyoléfine pour préparer une fibre, et fibre le comprenant
CN114687069A (zh) * 2020-12-30 2022-07-01 浙江青昀新材料科技有限公司 一种多功能聚合物无纺布及其织物
CN114763634A (zh) * 2020-12-30 2022-07-19 浙江青昀新材料科技有限公司 一种闪蒸纺制的薄片材料

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100063213A1 (en) * 2008-09-05 2010-03-11 Fredrickson Glenn H Gel-processed polyolefin compositions

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217452A (en) * 1969-02-04 1970-12-31 Celanese Corp Articles for absorbing liquid body discharges and materials therefor
US4554207A (en) * 1984-12-10 1985-11-19 E. I. Du Pont De Nemours And Company Stretched-and-bonded polyethylene plexifilamentary nonwoven sheet
US5250237A (en) * 1992-05-11 1993-10-05 E. I. Du Pont De Nemours And Company Alcohol-based spin liquids for flash-spinning polymeric plexifilaments
US5543454A (en) * 1993-08-10 1996-08-06 Ube Industries, Ltd. Reinforced polypropylene resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1217452A (en) * 1969-02-04 1970-12-31 Celanese Corp Articles for absorbing liquid body discharges and materials therefor
US4554207A (en) * 1984-12-10 1985-11-19 E. I. Du Pont De Nemours And Company Stretched-and-bonded polyethylene plexifilamentary nonwoven sheet
US5250237A (en) * 1992-05-11 1993-10-05 E. I. Du Pont De Nemours And Company Alcohol-based spin liquids for flash-spinning polymeric plexifilaments
US5543454A (en) * 1993-08-10 1996-08-06 Ube Industries, Ltd. Reinforced polypropylene resin composition

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7140292B2 (en) 2000-06-16 2006-11-28 The Quaker Oats Company Device, system and method for fluid additive injection into a viscous fluid food stream
EP1338692A1 (fr) * 2002-02-22 2003-08-27 E.I. DU PONT DE NEMOURS & COMPANY, INC. Nontissé plus résistant et plus doux
US7511115B2 (en) 2006-06-23 2009-03-31 Korea Institute Of Science & Technology Method of preparing biodegradable polyester polymer material in the form of filament and sheet using compressed gas
WO2008001926A2 (fr) * 2006-06-27 2008-01-03 Sumitomo Chemical Company, Limited Composition de résine destinée à un filament, filament associé et procédé de production de ce filament
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CN101466780B (zh) * 2006-06-27 2012-05-30 住友化学株式会社 适用于长丝的树脂组合物、长丝和生产长丝的方法
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CN106794660A (zh) * 2014-06-18 2017-05-31 纳幕尔杜邦公司 丛丝片材
EP3199556A4 (fr) * 2014-12-10 2018-03-14 LG Chem, Ltd. Granulé de polyoléfine pour préparer une fibre, et fibre le comprenant
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CN114763634A (zh) * 2020-12-30 2022-07-19 浙江青昀新材料科技有限公司 一种闪蒸纺制的薄片材料
CN114687069B (zh) * 2020-12-30 2023-06-20 江苏青昀新材料有限公司 一种多功能聚合物无纺布及其织物
CN114763634B (zh) * 2020-12-30 2023-09-05 江苏青昀新材料有限公司 一种闪蒸纺制的薄片材料

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CA2260881A1 (fr) 1998-02-26
KR20000068238A (ko) 2000-11-25
JP2001521585A (ja) 2001-11-06

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