EP3158114B1 - Nach dem flash-spinnverfahren hergestellten plexifilamentäre stränge und folien - Google Patents
Nach dem flash-spinnverfahren hergestellten plexifilamentäre stränge und folien Download PDFInfo
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- EP3158114B1 EP3158114B1 EP15753225.0A EP15753225A EP3158114B1 EP 3158114 B1 EP3158114 B1 EP 3158114B1 EP 15753225 A EP15753225 A EP 15753225A EP 3158114 B1 EP3158114 B1 EP 3158114B1
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- sheet
- fiber strand
- plexifilamentary
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- equal
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- 229920001474 Flashspun fabric Polymers 0.000 title description 3
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- 238000000034 method Methods 0.000 claims description 18
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- 239000005977 Ethylene Substances 0.000 claims description 5
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- 239000000463 material Substances 0.000 description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 25
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- 239000003795 chemical substances by application Substances 0.000 description 15
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- XJSRKJAHJGCPGC-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F XJSRKJAHJGCPGC-UHFFFAOYSA-N 0.000 description 6
- UYDBQWIWVMBDME-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane Chemical compound FC(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)F UYDBQWIWVMBDME-UHFFFAOYSA-N 0.000 description 6
- RIQRGMUSBYGDBL-UHFFFAOYSA-N 1,1,1,2,2,3,4,5,5,5-decafluoropentane Chemical compound FC(F)(F)C(F)C(F)C(F)(F)C(F)(F)F RIQRGMUSBYGDBL-UHFFFAOYSA-N 0.000 description 5
- 238000004049 embossing Methods 0.000 description 5
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- XADNQZFTMORUMO-UHFFFAOYSA-N cyclopentane;pentane Chemical compound CCCCC.C1CCCC1 XADNQZFTMORUMO-UHFFFAOYSA-N 0.000 description 3
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- DJXNLVJQMJNEMN-UHFFFAOYSA-N 2-[difluoro(methoxy)methyl]-1,1,1,2,3,3,3-heptafluoropropane Chemical compound COC(F)(F)C(F)(C(F)(F)F)C(F)(F)F DJXNLVJQMJNEMN-UHFFFAOYSA-N 0.000 description 2
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- OKIYQFLILPKULA-UHFFFAOYSA-N 1,1,1,2,2,3,3,4,4-nonafluoro-4-methoxybutane Chemical compound COC(F)(F)C(F)(F)C(F)(F)C(F)(F)F OKIYQFLILPKULA-UHFFFAOYSA-N 0.000 description 1
- FNUBKINEQIEODM-UHFFFAOYSA-N 3,3,4,4,5,5,5-heptafluoropentanal Chemical compound FC(F)(F)C(F)(F)C(F)(F)CC=O FNUBKINEQIEODM-UHFFFAOYSA-N 0.000 description 1
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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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
- D01D5/11—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
Definitions
- This invention relates to flash-spun plexifilamentary sheets, fabrics, or fiber webs suited for protective apparel, air filtration, and other end use applications.
- Protective apparel includes coveralls, gowns, smocks and other garments whose purpose is either to protect a wearer against exposure to something in the wearer's surroundings, or to protect the wearer's surroundings against being contaminated by the wearer.
- Examples of protective apparel include suits worn in microelectronics manufacturing cleanrooms, medical suits and gowns, dirty job coveralls, and suits worn for protection against liquids or particulates.
- the particular applications for which a protective garment is suitable depends upon the composition of the fabric or sheet material used to make the garment and the way that the pieces of fabric or sheet material are held together in the garment. For example, one type of fabric or sheet material may be excellent for use in hazardous chemical protection garments, while being too expensive or uncomfortable for use in medical garments. Another material may be lightweight and breathable enough for use in clean room suits, but not be durable enough for dirty job applications.
- the physical properties of a fabric or sheet material determine the protective apparel applications for which the material is suited. It has been found desirable for a wide variety of protective garment applications that the material used in making the protective garment provide good barrier protection against liquids such as body fluids, paints or sprays. It is also desirable that the material used in making protective apparel block the passage of fine dirt, dust and fiber particles. Another group of desirable properties for fabrics or sheet materials used in protective apparel is that the material have enough strength and tear resistance that apparel made using the sheet material not lose its integrity under anticipated working conditions. It is also important that fabrics and sheet materials used in protective garments transmit and dissipate both moisture and heat so as to permit a wearer to perform physical work while dressed in the garment without becoming excessively hot and sweaty.
- resiliency includes both elastic and plastic deformation as long as the material substantially recovers its original shape and essential properties after the stress gradient that is the cause of the crush has been removed.
- Bonding of fabrics to form garments may require fusion of the fabric material with other materials. Such fusion is easier with a material that has a reduced crystalline structure. What is needed therefore is a fabric with a high resilience, as evidenced by crush value, and a lower crystallinity than heretofore available so that bonding with other layers is enhanced. There are multiple situations where the deformation can occur while positioning or using the material of interest. It is then desirable that the material recovers its original shape and essential properties.
- US 7,179,413 describes a process for the preparation of plexifilamentary film-fibril strands of synthetic fiber-forming polymer comprising the steps of generating a spin fluid including among others trans-1,2-dichloroethylene and 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene and flash-spinning the spin fluid to form plexifilamentary film-fibril strands of the synthetic fiber-forming polymer.
- a spin fluid including among others trans-1,2-dichloroethylene and 3,3,4,4,5,5,6,6,6-nonafluoro-1 -hexene and flash-spinning the spin fluid to form plexifilamentary film-fibril strands of the synthetic fiber-forming polymer.
- WO 01/29295 A1 discloses a plexifilamentary sheet material useful in protective apparel and filtration media, which material is comprised of substantially continuous polyethylene plexifilamentary fiber strands and has a Frazier Permeability, normalized to 1.0 oz/yd 2 basis weight, of at least 2 cfm/ft 2 .
- the present invention is directed to a flash-spun plexifilamentary fiber strand having a total crystallinity index of less than or equal to 55%, the fiber strand having a BET surface area of less than 12 m 2 /g, a crush value of greater than or equal to 0.9 mm/g, wherein said fiber strand comprises predominantly fibers formed from homopolymers of ethylene.
- the fiber strand comprises predominantly fibers formed from polyethylene said fibers having a total crystallinity index of less than 52%.
- the fiber strand of the invention may further have a monoclinic and orthorhombic structure as determined by an X-ray analysis as described herein, and a crystallinity index of the monoclinic structures is equal or higher than 1 %.
- any of the embodiments disclosed here of plexifilamentary fiber strands may be consolidated into a sheet structure. This sheet structure may then be optionally thermally or mechanically bonded.
- the invention is directed to a multilayer structure comprising a multiplicity of two or more consolidated sheets.
- a multilayered structure of the invention may further comprise a multiplicity of two or more sheets wherein at least one sheet is a polyethylene sheet comprising the plexifilamentary structure of any of the embodiments described herein.
- the plexifilamentary structure may be a consolidated sheet made of a fiber strand according to any of the embodiments described herein.
- the plexifilamentary sheet or sheets may be thermally consolidated.
- polymer as used herein, generally includes but is not limited to, homopolymers, copolymers (such as for example, block, graft, random and alternating copolymers), terpolymers, etc. and blends and modifications thereof. Furthermore, unless otherwise specifically limited, the term “polymer” shall include all possible geometrical configurations of the material. These configurations include, but are not limited to isotactic, syndiotactic and random symmetries.
- polyethylene as used herein is intended to encompass not only homopolymers of ethylene, but also copolymers wherein at least 85% of the recurring units are ethylene units.
- nonwoven fabric, sheet or web means a structure of individual fibers or threads that are positioned in a random manner to form a planar material without an identifiable pattern, such a pattern, for example, as would be seen in a knitted fabric. Individual fibers that may organize themselves locally in some preferential ways or directions are still considered as positioned in a random manner for the purposes of this definition.
- machine direction is the long direction within the plane of a sheet, i.e., the direction in which the sheet is produced.
- the “cross direction” is the direction within the plane of the sheet that is perpendicular to the machine direction.
- plexifilamentary as used herein, means a three-dimensional integral network of a multitude of thin, ribbon-like, film-fibril elements of random length and with a median fibril width of less than about 25 microns.
- the film-fibril elements are generally coextensively aligned with the longitudinal axis of the structure and they intermittently unite and separate at irregular intervals in various places throughout the length, width and thickness of the structure to form a continuous three-dimensional network.
- spin fluid refers to the total composition that is spun using the spinning apparatus described herein.
- Spin fluid includes polymer and spin agent.
- spin agent refers to the solvent or mixture of solvents and any additives, solubility aids and blends therewith that is used to initially dissolve the polymer to form the spin fluid.
- multilayered structure is meant a composite structure that contains layers of distinct materials layered and optionally bonded in a face to face arrangement over at least a portion of their faces.
- the multilayered structure of the invention is directed to a multiplicity of two or more sheets wherein at least one sheet is a polyethylene sheet comprising any plexifilamentary structure as described herein.
- the present invention is directed to a flash-spun plexifilamentary fiber strand having a total crystallinity index of less than or equal to 55%, the fiber strand having a BET surface area of less than 12 m 2 /g, a crush value of greater than or equal to 0.9 mm/g, wherein the fiber strand comprises predominantly fibers formed from homopolymers of ethylene.
- the fiber strand comprises predominantly fibers formed from polyethylene said fibers having a total crystallinity index of less than 52%.
- the fiber strand of the invention may further have a monoclinic and orthorhombic structure as determined by an X-ray analysis as described herein, and a crystallinity index of the monoclinic structures is equal or higher than 1%.
- any of the embodiments disclosed here of plexifilamentary fiber strands may be consolidated into a sheet structure. This sheet structure may then be optionally thermally or mechanically bonded.
- the invention is directed to a multilayer structure comprising a multiplicity of two or more consolidated sheets.
- a multilayered structure of the invention may further comprise a multiplicity of two or more sheets wherein at least one sheet is a polyethylene sheet comprising the plexifilamentary structure of any of the embodiments described herein.
- the plexifilamentary structure may be a consolidated sheet made of a fiber strand according to any of the embodiments described herein.
- the plexifilamentary sheet or sheets may be thermally consolidated.
- the general flash-spinning apparatus chosen for illustration of the present invention is similar to that disclosed in U.S. Pat. No. 3,860,369 to Brethauer et al. , which is hereby incorporated by reference.
- a system and process for flash-spinning a fiber-forming polymer is fully described in U.S. Pat. No. 3,860,369 , and is shown in FIG. 1 .
- the flash-spinning process is normally conducted in a chamber 10, sometimes referred to as a spin cell, which has a spin agent removal port 11 and an opening 12 through which non-woven sheet material produced in the process is removed.
- a spin fluid comprising a mixture of polymer and spin agent, is provided through a pressurized supply conduit 13 to a spinning orifice 14.
- chamber 16 may act as a pressure letdown chamber wherein a reduction in pressure causes phase separation of the spin fluid, as is disclosed in U.S. Pat. No. 3,227,794 to Anderson et al.
- a pressure sensor 22 may be provided for monitoring the pressure in the chamber 16.
- the spin fluid in chamber 16 next passes through spin orifice 14. It is believed that passage of the pressurized polymer and spin agent from the chamber 16 into the spin orifice generates an extensional flow near the approach of the orifice that helps to orient the polymer. When polymer and spin agent discharge from the orifice, the spin agent rapidly expands as a gas and leaves behind fibrillated plexifilamentary film-fibrils. The gas exits the chamber 10 through the port 11. Preferably, the gaseous spin agent is condensed for reuse in the spin fluid.
- the polymer strand 20 discharged from the spin orifice 14 is conventionally directed against a rotating deflector baffle 26.
- the rotating baffle 26 spreads the strand 20 into a more planar structure 24 that the baffle alternately directs to the left and right.
- the fiber strand is electrostatically charged so as to hold the fiber strand in a spread open configuration until the fiber strand 24 reaches a moving belt 32.
- the fiber strand 24 deposits on the belt 32 to form a batt 34.
- the belt is grounded to help ensure proper pinning of the charged fiber strand 24 on the belt.
- the fibrous batt 34 may be passed under a roller 31 that compresses the batt into a lightly consolidated sheet 35 formed with plexifilamentary film-fibril networks oriented in an overlapping multi-directional configuration.
- the sheet 35 exits the spin chamber 10 through the outlet 12 before being collected on a sheet collection roll 29.
- thermal consolidated or “thermally bonded” sheet is a sheet made by thermal consolidation of a web of the invention.
- Some examples of thermal bonding processes are through gas bonding, steam entanglement, ultra-sonic bonding, stretched bonding, hot calendaring, hot roll embossing, hot surface bonding.
- Thermal surface bonding can be performed by a process as described in U.S. Patent 3,532,589 to David for hard bonded surfaces.
- the plexifilamentary sheet passes subsequently over a heated drum - cooling drum - heating drum - cooling drum to thermally bond both sides of the material.
- the heating drum is kept at a temperature that would result in partial melting of the plexifilamentary structure to include the bonding of the sheet.
- the cooling drum has the purpose to reduce the temperature to a value where the sheet will not shrink nor distort when unrestrained.
- the sheet is slightly compressed by a flexible belt to have a controlled shrinkage.
- the plexifilamentary sheet may be bonded by means of embossing rolls and rubber coated back-up roll to bond one or two sides of the sheet.
- the embossing roll can be smooth or contain different patterns, for example, but not limited to those shown in the following references, namely a point pattern ( US 3,478,141 , US 6,610,390 US 2004/241399 A1 ), a rib pattern ( US2003/0032355 A1 ), a random pattern ( US 7,744,989 ) or different patterns ( US 5,964,742 ).
- the sheet may pass through one or multiple stations of an embossing roll with rubber coated back-up roll.
- the sheet before and after the pairs of embossing and back-up rolls the sheet may be in contact with pre-heat or cooling rolls as described in US 5,972,147 .
- the material may be softened, for example, a button breaking device as described in US 3,427,376 by Dempsey .
- the surface area of the plexifilamentary fiber strand product is a measure of the degree and fineness of fibrillation of the flash-spun product. Surface area 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 ) and is reported as square meter per gram (m 2 /g).
- Crush values represent the ability of the fiber strand to recover its initial shape after having been compressed. They were determined using the following procedure: Three plexifilamentary fiber strands of different sizes were pulled from a Reemay® sheet. The three samples weighed about one, two and three grams. The reported crush values are the averages of the values measured on the three samples. Each sample plexifilamentary strand was formed into a ball shape with minimum application of pressure to avoid crushing and the sample was then weighed in grams. A crush tester comprised of an acrylic sample holder and crusher was used to measure the crush value of each sample. The sample holder comprised a cylindrical section having an inner diameter of 2.22 inches (5.64 cm) and an outer diameter of 2.72 inches (6.91 cm).
- the center of the cylinder was located at the geometric center of a square base measuring 6.00 inches by 6.00 inches (15.24 cm by 15.24 cm).
- the second disk also had a thickness of 0.25 inches (0.64 cm) and a diameter of 2.20 inches (5.59 cm).
- the disks were sized slightly smaller than the inner diameter of the cylindrical sample holder in order to allow air to escape from the sample during crushing.
- the plexifilamentary samples were placed, one at a time, in the sample holder and a thin piece of paper having a diameter of about 2.2 inches (5.59 cm) was placed on top of the plexifilamentary sample prior to crushing.
- the plunger rod was then inserted into the cylindrical sample holder such that the first disk-shaped face contacted the piece of paper.
- the second disk served to maintain the axis of the plunger rod in alignment with the axis of the cylindrical sample holder.
- Each plexifilamentary strand sample was crushed by placing a 2 lb (0.91 kg) weight on the plunger rod.
- the crush height (mm) was obtained by measuring the height of the sample from the bottom of the cylindrical sample holder to the bottom of the crusher. The plunger and weight were removed from the sample after approximately 2 minutes, leaving the piece of paper in place to facilitate measurement of the restored height of the sample. Each sample was allowed to recover approximately 2 minutes and the restored height (mm) of the sample was obtained by measuring the height of the paper from the center of each of the four sides of the sample holder and averaging the measurements.
- the crush value (mm/g) is calculated by subtracting the average crush height from the average restored height and dividing by the average of the weights of the samples. The crush value is a measure of how much the sample recovers its original size after being crushed, with higher values indicating greater recovery of original sample height.
- the crystallinity index of the polyethylene was measured using X-ray analysis according to the following procedure.
- a diffractometer in reflection ⁇ - ⁇ Bragg-Brentano geometry was fitted with a Cu-K ⁇ x-ray tube source with wavelength of 1.54 ⁇ and a 1-dimensional detector. Samples were mounted horizontally on a flat holder at the center of the diffractometer and normal to the scattering vector; during the measurement the sample rotated on this plane.
- the method used for the determination of crystallinity index was based on the ratio the scattering intensity of the crystalline regions to the total intensity as described in S.L. Aggarwal, G.P. Tilley, Determination of crystallinity in polyethylene by X-Ray diffractometer, Journal of Polymer Science, Vol. 18, pp. 17-26, 1955 .
- the analysis reported in this publication only considers the case in which the orthorhombic phase is present. Additionally, the monoclinic phase may also be present, and in those cases we applied the procedure described below.
- CI orthorhombic I 110 + I 200 I 110 + I 200 + I 100 + I amorphous
- CI monoclinic I 100 I 110 + I 200 + I 100 + I amorphous
- FIG. 2 is an illustration of the X-ray signals obtained using the X-ray analysis of polyethylene with monoclinic and orthorhombic crystal structure.
- the various crystalline phases are differentiated by the peak profiles, and, the related apex positions and the heights.
- the flash spun plexifilamentary webs are generated on a 1 gallon experimental flash spinning unit.
- the 1 gallon capacity flash spinning apparatus employed herein is a larger version of the 50 cc unit that is described in U.S. Patent 5.147,586 .
- the apparatus consisted of two high-pressure cylindrical chambers, each equipped with a piston that had been adapted to apply pressure to the contents of the chamber through a hydraulic pump.
- the cylinders each had an internal capacity of 1 gallon.
- the cylinders were connected to each other to one end by channel with a static mixer.
- the pistons were driven by high pressure oil supplied by a hydraulic system.
- the output of one of the cylinders was attached to a chamber that had a spinneret assembly at the other end.
- the two cylinders are heated to a temperature similar to the desired spin temperature.
- the polymer is charged into one cylinder. Subsequently a vacuum is pulled on the cylinders.
- the spin agent is added by a high pressure pump in order to give the desired polymer concentration.
- the polymer and spin agent were then heated to the desired mixing temperature as measured by a type J thermocouple and held typically at that temperature between 60 and 120 minutes. During heating the pistons were used to alternatively establish a differential pressure between the two cylinders. This action repeatedly forced the polymer and spin agent through the mixing channel from one cylinder to the other to provide mixing and to effect formation of a spin fluid. After mixing and just prior to spinning, the contents were placed completely in one cylinder by moving the other piston to the top of its cylinder.
- a valve is opened to direct the spin fluid to the chamber opening of the spinneret.
- the flash spun plexifilamentary web is directed by a baffle onto a moving Reemay®-covered belt in a nitrogen-purged stainless steel enclosure to collect the plexifilamentary web.
- Dichloromethane is a technical grade purity from Brenntag Northeast, 81 W. Huller Lane, Reading, PA 19605, United states and used as received. Dichloromethane has CAS Nr. 75-09-2 . Dichloromethane is also known as methylene chloride.
- 2,3-dihydrodecafluoropentane is a hydrofluorocarbon with CAS Nr. 138495-42-8 obtained from E.I. DuPont de Nemours and Company, 1007 Market Street, Wilmington DE, United States and used as received.
- Trans-1,2-dichloroethylene is purchased from Diversified CPC International Inc. 24338 W. Durkee Rd. Channahon IL 60410-9719, United States and used as received. Trans-1,2-dichloroethylene is also known to as trans-1,2-dichloroethene and has CAS Nr. 156-60-5
- HFE 7100 is a commercial grade hydrofluoroether known under the tradename NovecTM 7100 from 3MTM purchased from 3M Center, Building 224-3N-11, St. Paul MN 55144-1000.
- NovecTM 7100 is a mixture of methyl nonafluoroisobutylether, CAS Nr. 163702-08-7 with a contribution of 20 - 80 wt% and methyl nonafluorobutylether, CAS Nr. 163702-07-6 , with a contribution of 20 - 80 wt%.
- the purity of NovecTM 7100 is 99.5% and used as received.
- 1H-perfluorohexane (1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane) is a hydrofluorocarbon with CAS Nr. 355-37-3 .
- 1H-perfluorohexane is purchased from Fluoryx Inc., 1933 Davis St. Ste. 294, San Leandro, CA 94577, United States. 1H-perfluorohexane has a purity above 98% and used as received.
- 1H,6H-perfluorohexane (1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane) is a hydrofluorocarbon with CAS Nr. 336-07-2 .
- 1H,6H-perfluorohexane is purchased from Exfluor Research Corporation, 2350 Double Creek Dr., Round Rock, TX,78664, United States.
- 1H,6H-perfluorohexane has a purity level of about 95% and used as received.
- the examples 1 and 2 and the comparative examples were spun from a high density polyethylene having a melt index of 2.35 g/10 min (measured according to EN ISO 1133 at 190° C. and 5 kg load), and 24.5 g/10 min (measured according to EN ISO 1133 at 190° C. and 21.6 kg load) a density of 0.96 g/cm 3 (measured according to EN ISO 1183).
- Examples 3 to 6 are spun from a high density polyethylene having a melt index of 0.74 g/10 min (measured according to ASTM D 1238 at 190°C and 2.16 kg load) and 29.6 g/10 min (measured according to ASTM D 1238 at 190°C and 21.6 kg load) and density of 0.95 g/cm 3 .
- the sheet of the invention resulted from a flash spinning process conducted from an upstream pressure letdown chamber of at least 15 cm 3 and a discharge pressure of 70 bar gauge minimum, yielding a fiber of 200 to 400 denier.
- Table 1 summarizes spinning conditions for the examples and table 2 the properties obtained for the examples.
- Table 1 Case spin fluid spin condition spinagent media composition PE temperature pressure 1 2 wt%/wt% wt% °C barg 1 DCM 2,3-dihydrodecafluoropentane 80.0/20.0 10 181.5 77.4 2 DCM 2,3-dihydrodecafluoropentane 80.0/20.0 12 193.8 91.3 3 DCM 1H-perfluorohexane 80.0/20.0 12 193.4 97.9 4 DCM 1H,6H-perfluorohexane 77.5/22.5 10 195.3 74.0 5 DCM HFE 7100 75.0/25.0 8 192.1 129.5 6 trans-1,2-DCE 2,3-dihydrodecafluoropentane 77.5/22.5 10 186.6 70.9 7 trans-1,2-DCE HFE 7100 75.0/25.0 8 189.2 79.4 8 DCM HFE 7100 75.0/25.0 10 192.5 127.5
- Table 3 summarizes spinning conditions for the comparative examples and table 4 the properties obtained for the comparative examples.
- Table 3 spin fluid spin condition spinagent media composition PE temperature pressure Case 1 2 wt%/wt% wt% °C barg A n-pentane cyclopentane 75.0/25.0 20 199.6 99.0 B n-pentane cyclopentane 75.0/25.0 20 179.3 69.4 C n-pentane cyclopentane 75.0/25.0 20 211.0 113.2
- Table 4 fiber property crystallinity index BET crush monoclinic CI monoclinic orthorhombic CI orthorhombic total CI total Case m 2 /g mm/g % % % A 14.0 1.0 0.2 61.7 61.9 B 23.1 0.6 1.0 56.7 57.7 C 4.7 2.6 0.3 65.3 65.6
- a BET surface area of less than or equal to 12 m 2 /g, a crush value of greater than or equal to 0.9 mm/g, and a crystallinity index of less than or equal to 55% which is the set of properties that meet the invention objectives, is only reachable under the conditions of spinning and with the compositions described in the examples. None of the comparative examples meet the invention desired set of properties.
- Total crystallinity index ( CI total ) vs BET plots in fig. 3 for the comparative examples A through C made with hydrocarbon spin agent are shown by the black diamonds in the figure and show a drop in CI total with BET.
- Fig. 4 shows the crush values as a function of the total crystallinity index.
- cases A through C shown as black diamonds, the crush increases with increasing total crystallinity index, whereas for the examples 1-8, open diamonds, crush values above 0.9 mm/gram correspond to a crystallinity index below 55%.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Nonwoven Fabrics (AREA)
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Claims (9)
- Nach dem Flash-Spinnverfahren hergestellter plexifilamentärer Faserstrang umfassend Fasern, die einen Gesamtkristallinitätsindex von weniger als oder gleich 55 % aufweisen, wobei der nach dem Flash-Spinnverfahren hergestellte plexifilamentäre Faserstrang einen BET-Oberflächenbereich von weniger als oder gleich 12 m2/g, einen Knitterwert von mehr als oder gleich 0,9 mm/g aufweist, wobei der Faserstrang hauptsächlich Fasern umfasst, die aus Homopolymeren von Ethylen gebildet sind und wobei alle Parameterwerte den jeweiligen Verfahren entsprechend bestimmt werden, auf die in der Beschreibung Bezug genommen wird.
- Nach dem Flash-Spinnverfahren hergestellter plexifilamentärer Faserstrang nach Anspruch 1, wobei der Faserstrang hauptsächlich Fasern umfasst, die aus Polyethylen hoher Dichte gebildet sind.
- Faserstrang nach Anspruch 1 oder 2, wobei die Fasern einen Gesamtkristallinitätsindex von weniger als oder gleich 52 % aufweisen.
- Faserstrang nach den Ansprüchen 1, 2 oder 3, wobei die Fasern eine monokline und orthorhombische Struktur, wie durch Röntgenstrahlcharakterisierung bestimmt, aufweisen und ein Kristallinitätsindex der monoklinen Strukturen gleich oder höher als 1 % ist.
- Konsolidierte Platte, die aus einem Faserstrang nach einem der Ansprüche 1 bis 4 hergestellt ist.
- Mehrschichtstruktur umfassend eine Mehrzahl von zwei oder mehr Platten, wobei mindestens eine Platte eine Platte nach Anspruch 5 ist.
- Thermisch oder mechanisch konsolidierte Platte, die aus einem Faserstrang nach einem der Ansprüche 1 bis 4 hergestellt ist.
- Mehrschichtstruktur umfassend eine Mehrzahl von zwei oder mehr Platten, wobei mindestens eine Platte eine Platte nach Anspruch 7 ist.
- Verwendung einer konsolidierten Platte nach Anspruch 5 oder Mehrschichtstruktur nach Ansprüche 6 oder 8 zur Herstellung von Schutzkleidung.
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US201462013827P | 2014-06-18 | 2014-06-18 | |
US201514742768A | 2015-06-18 | 2015-06-18 | |
US14/796,350 US10329692B2 (en) | 2015-07-10 | 2015-07-10 | Flash spun plexifilamentary strands and sheets |
PCT/US2015/040566 WO2015196217A1 (en) | 2014-06-18 | 2015-07-15 | Flash spun plexifilamentary strands and sheets |
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EP (1) | EP3158114B1 (de) |
JP (1) | JP6722596B2 (de) |
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US11261543B2 (en) * | 2015-06-11 | 2022-03-01 | Dupont Safety & Construction, Inc. | Flash spinning process |
CN113262605A (zh) * | 2020-11-30 | 2021-08-17 | 浙江青昀新材料科技有限公司 | 一种聚乙烯薄片材料 |
CN115403842A (zh) * | 2021-05-27 | 2022-11-29 | 江苏青昀新材料科技有限公司 | 一种可印刷性的聚合物薄片及应用 |
CN114150439A (zh) * | 2021-11-29 | 2022-03-08 | 厦门当盛新材料有限公司 | 闪蒸纺丝丝束网的牵伸装置及闪蒸纺丝设备 |
CN115142142B (zh) * | 2022-06-24 | 2024-01-12 | 厦门当盛新材料有限公司 | 一种喷头及设有该喷头的闪蒸纺丝设备 |
CN115341342B (zh) * | 2022-08-24 | 2024-05-07 | 厦门当盛新材料有限公司 | 多喷孔喷头、闪纺设备和闪纺方法 |
CN115976738A (zh) * | 2023-01-04 | 2023-04-18 | 烟台民士达特种纸业股份有限公司 | 一种伸直链晶型无纺布及其制造方法和应用 |
CN116288762B (zh) * | 2023-03-07 | 2024-09-24 | 东华大学 | 一种均一连续的微纳米纤维超临界纺丝装置 |
CN116005282A (zh) * | 2023-03-07 | 2023-04-25 | 东华大学 | 一种均一连续的微纳米纤维超临界纺丝方法 |
CN117449037B (zh) * | 2023-12-26 | 2024-03-15 | 江苏青昀新材料有限公司 | 一种闪纺膜材及其制造方法 |
CN117779355B (zh) * | 2024-02-28 | 2024-05-24 | 江苏青昀新材料有限公司 | 一种闪纺膜材及其制造方法 |
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BE625998A (de) * | 1960-11-08 | 1900-01-01 | ||
US3081519A (en) | 1962-01-31 | 1963-03-19 | Fibrillated strand | |
NL300881A (de) | 1962-11-23 | |||
US3532589A (en) | 1965-04-12 | 1970-10-06 | Du Pont | Differentially bonded non-woven sheet |
US3478141A (en) | 1966-08-29 | 1969-11-11 | Du Pont | Process for treating film-fibril sheets |
US3427376A (en) | 1966-09-27 | 1969-02-11 | Du Pont | Softening nonwoven fabrics |
JPS5018083B1 (de) * | 1968-10-14 | 1975-06-26 | ||
US3655498A (en) * | 1970-09-11 | 1972-04-11 | Du Pont | Plexifilamentary structures prepared from non-crystalline synthetic organic polymers |
FR2112639A5 (de) * | 1970-11-03 | 1972-06-23 | Du Pont | |
US3860369A (en) | 1972-11-02 | 1975-01-14 | Du Pont | Apparatus for making non-woven fibrous sheet |
JPS5128731B1 (de) * | 1973-12-28 | 1976-08-20 | ||
US5147586A (en) | 1991-02-22 | 1992-09-15 | E. I. Du Pont De Nemours And Company | Flash-spinning polymeric plexifilaments |
US5786284A (en) * | 1993-04-08 | 1998-07-28 | Unitika, Ltd. | Filament having plexifilamentary structure, nonwoven fabric comprising said filament and their production |
US6096421A (en) * | 1996-01-11 | 2000-08-01 | E. I. Du Pont De Nemours And Company | Plexifilamentary strand of blended polymers |
JP2000510198A (ja) | 1996-04-23 | 2000-08-08 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | 接合されたポリオレフィンシート |
US5964742A (en) | 1997-09-15 | 1999-10-12 | Kimberly-Clark Worldwide, Inc. | Nonwoven bonding patterns producing fabrics with improved strength and abrasion resistance |
US6610390B1 (en) | 1999-08-13 | 2003-08-26 | First Quality Nonwovens, Inc. | Nonwoven with non-symmetrical bonding configuration |
US7179413B1 (en) * | 1999-08-20 | 2007-02-20 | E. I. Du Pont De Nemours And Company | Flash-spinning process and solution |
CN1221688C (zh) * | 1999-10-18 | 2005-10-05 | 纳幕尔杜邦公司 | 闪蒸纺制的薄片材料 |
US20030032355A1 (en) | 2001-02-27 | 2003-02-13 | Guckert Joseph R. | Tougher, softer nonwoven sheet product |
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JP2015503680A (ja) * | 2011-12-21 | 2015-02-02 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | 断熱バットおよび複合材 |
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WO2015196217A1 (en) | 2015-12-23 |
EP3158114A1 (de) | 2017-04-26 |
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