WO2008063298A2 - Spinnerets for making cut-resistant yarns - Google Patents
Spinnerets for making cut-resistant yarns Download PDFInfo
- Publication number
- WO2008063298A2 WO2008063298A2 PCT/US2007/021617 US2007021617W WO2008063298A2 WO 2008063298 A2 WO2008063298 A2 WO 2008063298A2 US 2007021617 W US2007021617 W US 2007021617W WO 2008063298 A2 WO2008063298 A2 WO 2008063298A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- filaments
- spinneret
- extrusion holes
- yarn
- diameter
- Prior art date
Links
- 238000001125 extrusion Methods 0.000 claims description 31
- 229920003235 aromatic polyamide Polymers 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 27
- 239000004760 aramid Substances 0.000 description 23
- 238000000034 method Methods 0.000 description 17
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910052715 tantalum Inorganic materials 0.000 description 6
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 6
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 6
- 150000001805 chlorine compounds Chemical class 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 238000010791 quenching Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 238000002360 preparation method Methods 0.000 description 4
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- 239000010948 rhodium Substances 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 230000001112 coagulating effect Effects 0.000 description 3
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- 239000000203 mixture Substances 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920002577 polybenzoxazole Polymers 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
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- 238000005096 rolling process Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
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- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001080 W alloy Inorganic materials 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
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- 239000000806 elastomer Substances 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- XGZGDYQRJKMWNM-UHFFFAOYSA-N tantalum tungsten Chemical compound [Ta][W][Ta] XGZGDYQRJKMWNM-UHFFFAOYSA-N 0.000 description 2
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical compound C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 1
- ZZPLGBZOTXYEQS-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C(Cl)=C1Cl ZZPLGBZOTXYEQS-UHFFFAOYSA-N 0.000 description 1
- AZUHIVLOSAPWDM-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)-1h-imidazole Chemical compound C1=CNC(C=2NC=CN=2)=N1 AZUHIVLOSAPWDM-UHFFFAOYSA-N 0.000 description 1
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- 229920000784 Nomex Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
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- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 238000004621 scanning probe microscopy Methods 0.000 description 1
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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
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D4/00—Spinnerette packs; Cleaning thereof
- D01D4/02—Spinnerettes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/082—Melt spinning methods of mixed yarn
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
-
- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/442—Cut or abrasion resistant yarns or threads
Definitions
- the present invention relates to the field of spinnerets for spinning of synthetic fibres, in particular for making continuous filament yarns having mixtures of filaments of different deniers.
- Cut-resistant yarns are used for making fabrics which resist abrasion, cutting, tearing, penetration and puncture. Such fabrics can be used to manufacture protective garments for workers in various industries working with abrasive materials or sharp objects, as well as for police and military personnel requiring protection against stabbing implements and projectiles.
- Cut-resistant yarns can be made from glass, mineral fibres, steel, but increasingly, synthetic polymer fibres are being employed, because they provide excellent cut-resistance, while offering a weight advantage, and a look and feel in the finished fabric that is similar if not identical to regular fabric.
- Polymers that are used for cut-resistant yarns include, for example, polyamides (e.g. p- and m-aramids), polyolefins (e.g. polyethylene), and polyazoles (e.g. PBO), and PIPD (poly-diimidazol pyridinylene dihydroxy phenylene, "M5").
- Yarns made from synthetic polymer fibres are made using various spinning processes, all of which involve the use of a spinneret having multiple small openings, through which a concentrated solution or suspension of the polymer (or molten polymer) is sprayed or extruded. After extrusion, the polymer solidifies (and consolidates) into filaments, which are then spun into a multifilament yarn.
- U.S. Patent No. 4,078,034 discloses a method called "air gap spinning" in which a solution of an aromatic polyamide is extruded from a spinneret into an air gap (approximately 9 mm) before passing into a coagulating bath.
- air gap spinning in which a solution of an aromatic polyamide is extruded from a spinneret into an air gap (approximately 9 mm) before passing into a coagulating bath.
- the solution consists of 15-25% by weight p-aramid in concentrated H 2 SO 4
- the coagulating solution contains ⁇ 20 wt% aqueous H 2 SO 4 , at a temperature which is adjusted to below 35 0 C for this quenching step.
- a concentrated solution of m-aramid in an amide solvent such as N,N-dimethylacetamide (DMA) is extruded from a spinneret into an aqueous coagulation bath.
- DMA N,N-dimethylacetamide
- the holes in the spinneret head are chosen to produce filaments of the desired number and diameter.
- Filaments can be extended in air or gas before solidification (often referred to as "spin-stretch"), and/or in a liquid during the quenching/solidification process, and in many products by drawing after the filaments have been initially quenched or solidified. Drawing the filaments will reduce the average diameter.
- Multiple filaments are spun together to produce a yarn having a final linear density that is a sum of the linear density of each of the filaments.
- the inventors have found that if filaments having different deniers are spun together into a single yarn, the resulting yarn has excellent cut- and abrasion-resistance.
- the invention provides a yarn, comprising: a first plurality of continuous filaments, each of the first plurality of filaments having an average diameter in the range of at or about 2 to 25 (preferably 4 to 10) microns/filament; at least a second plurality of continuous filaments, each of the second plurality of filaments having an average diameter greater than the average diameter of the first plurality of filaments, and in the range of at or about 10 to 40 (preferably 10 to 32) microns/filament; and the first and second plurality of filaments being made of the same polymer selected from the group consisting of an aromatic polyamide, a polyolefin (preferably having a molecular weight above at or about 1 million Da, such as an UHMWPE), M5, and an aromatic polyazole.
- a first plurality of continuous filaments each of the first plurality of filaments having an average diameter in the range of at or about 2 to 25 (preferably 4 to 10) microns/filament
- at least a second plurality of continuous filaments each of the
- the invention provides a yarn, comprising: a first filament, having an average diameter in the range of at or about 4 to 25 microns; a second filament, having an average diameter greater than the average diameter of the first filament, and in the range of at or about 15 to 40 microns/filament; and a plurality of filaments having average diameters distributed between the average diameter of the first filament and the average diameter of the second filament; wherein all of the filaments are made of the same polymer selected from the group consisting of an aromatic polyamide, a polyolefin (preferably having a molecular weight above at or about 1 million Da, such as an UHMWPE), M5, and an aromatic polyazole.
- a first filament having an average diameter in the range of at or about 4 to 25 microns
- a second filament having an average diameter greater than the average diameter of the first filament, and in the range of at or about 15 to 40 microns/filament
- a plurality of filaments having average diameters distributed between the average diameter of the first filament and the average
- the invention provides a yarn, comprising: a first plurality of continuous filaments, each of the first plurality of filaments having a first nominal linear density in the range of 0.25 to 1.25 denier/filament; at least a second plurality of continuous filaments, each of the second plurality of filaments having a second nominal linear density greater than the first nominal linear density and in the range of 1.25 to 6 denier/filament; and the first and second plurality of filaments being made of the same polymer selected from the group consisting of an aromatic polyamide, a polyolefin (preferably having a molecular weight of at least 1 million Da), M5, and an aromatic polyazole.
- the invention provides a cut-resistant fabric comprising the yarn of the invention.
- the invention provides a cut-resistant garment made using the cut-resistant fabric of the invention.
- the invention provides a method for making a cut- resistant yarn, comprising the step of: extruding a polymer selected from an aromatic polyamide, a polyolefin (preferably having a molecular weight of at least 1 million Da), M5, and an aromatic polyazole from a spinneret comprising extrusion holes of a first average diameter and of a second average diameter, wherein the first and second average diameters differ by a factor of at least 1.2.
- the invention provides a spinneret for making a cut-resistant yarn, the spinneret comprising extrusion holes of a first, smaller average diameter and of a second, larger average diameter, wherein the first and second average diameters differ by a factor of at least 1.2.
- Figure 1 is a schematic diagram of a process for making yarn of the present invention.
- FIGS 2A-D illustrate spinnerets with various capillary patterns in accordance with the present invention.
- Figure 3 illustrates one embodiment of a spinneret pack.
- Figure 4 shows a spinneret according to the invention as used in the Example.
- UHMWPE ultra-high molecular weight polyethylene
- M5 polypyridobisimidazole, represented by the formula: dpf: denier per filament
- filament is defined as a relatively flexible, macroscopically homogeneous body having a high ratio of length to width across its cross-sectional area perpendicular to its length.
- the filament cross section can be any shape, but is typically circular.
- the term “fibre” is used interchangeably with the term “filament”.
- Diameter in reference to a filament is the diameter of the smallest circle that can be drawn to circumscribe the entire cross-section of the filament. In reference to a hole in a spinneret, it refers to the smallest circle that can be drawn to circumscribe the hole.
- capillary and "extrusion hole” are used interchangeably to mean the holes through which polymer is extruded in the formation of filaments.
- the yarns produced from the spinnerets of the invention having mixed average diameter filaments, show increased cut- and abrasion- resistance, as compared to conventional yarns comprising filaments of a single average diameter. It is believed that the mixed diameter arrangement has excellent cut- and abrasion-resistance for two main reasons:
- the inventors have chosen to refer to these yarns as being made of filaments having different average diameters.
- the expression "average diameter” can be replaced with the expression “linear density” for an alternate definition of the yarns. It is equally possible to refer to the yarns as being made up of filaments having different linear densities.
- the yarns may be referred to as “mixed filament yarns", “mixed denier yarns” and/or “mixed dtex yarns”.
- average diameter of a filament can be converted to linear density approximately as shown below:
- the yarns made with the spinnerets of the present invention may be made with filaments made from any polymer that produces a high-strength fibre, including, for example, polyamides, polyolefins, polyazoles, and mixtures of these.
- polyamide polyamide
- aramid is preferred.
- aramid is meant a polyamide wherein at least 85% of the amide (-CONH-) linkages are attached directly to two aromatic rings.
- Suitable aramid fibres are described in Man-Made Fibres - Science and Technology, Volume 2, Section titled Fibre-Forming Aromatic Polyamides, page 297, W. Black et al., lnterscience Publishers, 1968.
- Aramid fibres and their production are, also, disclosed in U.S. Patents 4,172,938; 3,869,429; 3,819,587; 3,673, 143; 3,354,127; and 3,094,511.
- the preferred aramid is a para-aramid.
- the preferred para-aramid is poly(p-phenylene terephthalamide) which is called PPD-T.
- PPD-T is meant the homopolymer resulting from mole-for-mole polymerization of p- phenylene diamine and terephthaloyl chloride and, also, copolymers resulting from incorporation of small amounts of other diamines with the p- phenylene diamine and of small amounts of other diacid chlorides with the terephthaloyl chloride.
- PPD-T means copolymers resulting from incorporation of other aromatic diamines and other aromatic diacid chlorides such as, for example, 2,6-naphthaloyl chloride or chloro- or dichloroterephthaloyl chloride or 3,4'-diaminodiphenylether.
- Additives can be used with the aramid and it has been found that up to as much as 10 percent or more, by weight, of other polymeric material can be blended with the aramid.
- Copolymers can be used having as much as 10 percent or more of other diamine substituted for the diamine of the aramid or as much as 10 percent or more of other diacid chloride substituted for the diacid chloride or the aramid.
- polyethylene is meant a predominantly linear polyethylene material of preferably more than one million molecular weight that may contain minor amounts of chain branching or comonomers not exceeding 5 modifying units per 100 main chain carbon atoms, and that may also contain admixed therewith not more than about 50 weight percent of one or more polymeric additives such as alkene-1 -polymers, in particular low density polyethylene, propylene, and the like, or low molecular weight additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated.
- polymeric additives such as alkene-1 -polymers, in particular low density polyethylene, propylene, and the like, or low molecular weight additives such as anti-oxidants, lubricants, ultra-violet screening agents, colorants and the like which are commonly incorporated.
- ECPE extended chain polyethylene
- UHMWPE ultra high molecular weight polyethylene
- Preparation of polyethylene fibers is discussed in U.S. Patents 4,478,083, 4,228,118, 4,276,348 and Japanese Patents 60-047,922, 64-008,732.
- High molecular weight linear polyolefin fibres are commercially available.
- Preparation of polyolefin fibres is discussed in U.S. 4,457,985.
- suitable polyazoles are polybenzazoles, polypyridazoles and polyoxadiaoles.
- suitable polyazoles include homopolymers and, also, copolymers. Additives can be used with the polyazoles and up to as much as 10 percent, by weight, of other polymeric material can be blended with the polyazoles. Also copolymers can be used having as much as 10 percent or more of other monomer substituted for a monomer of the polyazoles.
- Suitable polyazole homopolymers and copolymers can be made by known procedures, such as those described in U.S. Patents 4,533,693 (to Wolfe et al. on Aug. 6, 1985), 4,703, 103 (to Wolfe et al. on Oct.
- Preferred polybenzazoles are polyzimidazoles, polybenxothiazoles, and polybenzoxazoles. If the polybenzazole is a polyzimidazoles, preferably it is poly[5,5'-bi-1 H-benzimidazole]-2,2'-diyl-1 ,3-phenylene which is called PBI. If the polybenzazole is a polybenxothiazole, preferably it is a polybenxobisthiazole and more preferably it is poly(benxo[1 ,2-d:4,5-d']bisthiazole-2,6-diyl-1 ,4-phene which is called PBT.
- the polybenzazole is a polybenzoxazole, preferably it is a polybenzobisoxazole and more preferably it is poly(benzo[1 ,2-d:4,5- d']bisoxazole-2,6-diyl-1 ,4-phenylene which is called PBO.
- Preferred polypyridazoles are rigid rod polypyridobisazoles including poly(pyridobisimidazole), poly(pyridobisthiazole), and poly(pyridobisozazole).
- the preferred poly(pyridobisozazole) is poly(1 ,4- (2,5-dihydroxy)phenylene-2,6-pyrido[2,3-d:5,6-d']bisimidazole which is called M5.
- Suitable polypyridobisazoles can be made by known procedures, such as those described in U.S. Patent 5,674,969.
- Preferred polyoxadiaoles include polyoxadizaole homopolymers and copolymers in which at least 50% on a molar basis of the chemical units between coupling functional groups are cyclic aromatic or heterocyclic aromatic ring units.
- a preferred polyoxadizaole is Oxalon®.
- mixed dtex yarns can be made by "off-line assembly", that is, the different denier filaments can be assembled after spinning, a continuous filament yarn produced by direct spinning (i.e. using a spinneret having different size holes to produce directly a yarn having mixed dtex filaments) is preferred. Off-line assembly is less preferred than direct spinning since it can lead to segregation of the filaments of different diameters, resulting in a non-homogeneous yarn which has less resistance to attacking forces.
- the continuous filament mixed diameter yarns are made using a spinneret having holes of different diameters. Holes of smaller diameter will yield lower diameter filaments, and holes of larger diameter will yield larger diameter filaments.
- the arrangement of the larger holes with respect to the smaller holes in the spinneret is not of particular importance, however, it is advantageous to have smaller diameter filaments sandwiched between larger diameter filaments, as this maximizes rolling action of the filaments.
- the arrangement of holes in the spinneret is in the form of concentric circles, the whole forming a large circular array of holes. The holes toward the centre of the array are the smaller diameter holes, and those towards the circumference of the array are the larger diameter holes. Examples of different kinds of spinneret hole arrangements are shown in Figures 2A-E and 4.
- the arrangement shown in Figure 4 has filaments arranged in concentric order from the centre as follows: medium capillaries then small ones then medium again and finally large capillaries at the periphery. This provides a very stable yarn in terms of segregation and stability during processing. The smaller filaments are "squeezed" in the two layers of larger ones. The pressure distribution in this configuration is more favorable to spinning without dripping.
- the cross-section of the filaments used in mixed dtex yarns may be, for example, circular, elliptical, multi-lobed, "star-shaped” (refers to an irregular shape having a plurality of arms coming off a central body), and trapezoidal.
- the holes in the spinneret are chosen according to the desired filament diameter and cross-section.
- the "linear density" of the filament is determined by the rate (mass/time) at which polymer is extruded through a spinneret hole vs. the rate (speed, or linear distance/time) at which the filament is produced.
- the size (diameter) of the filament is a function of the polymer density and the fiber "linear density”.
- the number of holes in a spinneret (or section of a spinneret) is determined by the number of filaments desired in the final fiber bundle ("linear density" of which is the sum of the individual filaments contained therein).
- the size and shape of each hole in the spinneret is influenced by the pressure-drop, shear, spin-stretch, and orientation needed to produce the desired filament diameter.
- the smaller holes have a diameter of between at or about 35-65 microns, more preferably at or about 50 microns, and the larger holes have a diameter between at or about 60 to 90 microns, more preferably at or about 64 microns.
- the ratio between the diameter of the larger holes to that of the smaller holes is at or about 1.2 to at or about 3, more preferably at or about 1.3 to 2.5.
- a spinneret may be used, for example, in which the holes are in the following ranges: smallest 35 to 65 microns (preferably 45-55 microns), medium 64-80 microns, largest 75 to 90 microns.
- the spinneret is made of material suited to the polymer or polymer solution or suspension that will be spun.
- preferred material are tantalum, tantalum-tungsten alloys, and gold-platinum(rhodium) alloys.
- Other materials which may be used include high grade stainless steels [i.e. with a high chromium (> 15 wt %) and/or nickel (> 30 wt %) content], such as Hastelloy® C-276, ceramics and nanostructures made with ceramics.
- p-Aramid spinnerets may also be made from mixed materials, such as pure tantalum clad on a tantalum-tungsten alloy.
- Materials other than tantalum can be used for the cladding layer so long as they have the required corrosion resistance and annealed yield strengths of less than 30,000 psi (2,110 kg/cm 2 ).
- suitable materials listed in order of increasing hardness, are gold, M- metal (90% gold/10% rhodium by weight), C-metal (69.5% gold/30% platinum/0.5% rhodium by weight), D-metal (59.9% gold/40.0% platinum/0.1 % rhenium by weight), and Z-metal (50.0% gold/49.0% platinum/1.0% rhodium by weight). The latter was substantially the same hardness as tantalum. Also suitable is a 75% gold/25% platinum alloy.
- the polymer is extruded, either as a solution, suspension or melt, through the spinneret, and the resulting filaments are spun into yarn and treated in a manner suitable for the particular polymer.
- a group of filaments may be classified as having the same average diameter if the deviation of the average diameter of any filament in the group from the average is less than at or about 0.4 micron.
- two sizes of filaments make up the yarn.
- the smaller filaments have an average diameter in the range of at or about 8 to 22 microns
- the larger filaments have an average diameter in the range of at or about 16 to 32 microns. Although these ranges overlap, it is understood that the smaller and larger filaments are chosen to have different average diameters, such that the average diameter of the smaller filaments is smaller than the average diameter of the larger filaments.
- included in the invention is a yarn having smaller filaments with average diameter of at or about 8 microns together with larger filaments having average diameter of at or about 16 microns, and a yarn having smaller filaments with average diameter of at or about 22 microns together with larger filaments having average diameter of at or about 32 microns.
- the smaller filaments In yarns consisting of two sizes of filaments, it is preferred that the smaller filaments not differ from the larger filaments by more than a factor of at or about 2, more preferably not more than a factor of at or about 1.5. If the filaments differ too much in size, segregation can occur, leading to nonhomogeneity and reduced cut-resistance.
- the ratio of the diameter of the larger filaments to the smaller filaments is at or about 1.3- 1.5.
- the second plurality of filaments make up from at or about 20 to 60% (by number) of the filaments in the yarn
- the first plurality of filaments i.e. smaller diameter
- the larger diameter filaments make up from at or about 45 to 55% (by number) of the filaments in the yarn
- the smaller diameter filaments make up from at or about 45 to 55% (by number) of the filaments in the yarn.
- three sizes of filaments make up the yarn.
- the smallest filaments have an average diameter in the range of at or about 4 to 10 microns (more preferably at or about 6 to 9 microns)
- the medium filaments have an average diameter in the range of at or about 10 to 13 microns
- the largest filaments have an average diameter in the range of at or about 14 to 18 microns.
- an advantageous result is obtained with a yarn made up of filaments having the following average diameters: 8, 12 and 16 microns.
- the ratio of the average diameter of smallest : medium : largest is at or about 2:6:8, more preferably at or about 2:3:4.
- the third plurality of filaments i.e. the largest
- the second plurality of filaments i.e. the medium
- the first plurality of filaments i.e. the smallest
- the yarn is made up of four, five, six or more sizes of filaments.
- the yarn consists of a largest filament or group of filaments (e.g. average diameter of at or about 15-40 microns) and a smallest filament or group of filaments (e.g. average diameter of at or about 4-25 microns) wherein the largest filament (or group of filaments) and the smallest filament (or group of filaments) have different average diameters, and a plurality of filaments having average diameters distributed between the average diameter of the largest filament and the smallest filament.
- very high packing densities > 90%
- the size of the holes in the spinneret influences the average diameter of the extruded filaments.
- the tension used to draw the filaments (drawing) also influences the average diameter of the filaments and the characteristics of the finished yarn. Drawing reduces the average diameter of the filaments.
- the ratio of the two speeds here referred to, is called spin-stretch in p-aramids in which the filament is set in the coagulation batch and drawing ratio when referring to a fiber such as UHMWPE which is extended substantially after the fiber is quenched.
- High drawing ratio achievable with UHMWPE can reach up to 50-100 times.
- p-aramid a typical spin- stretch ratio is approximately 2 to 14.
- the filaments making up the mixed dtex yarns may have a substantially circular cross-section.
- a circular cross-section maximizes the "rolling" of the filaments with respect to each other, thus maximizing cut- resistance.
- a circular cross-section also maximizes the packing density, also beneficial for cut-resistance.
- the cross- section of the filaments may be elliptical. It is also possible for the smaller filaments to be circular in cross-section and the large filaments to be elliptical in cross-section, or vice versa.
- the cross-section of the filaments is influenced by the shape of the holes in the spinneret, with round holes resulting in a circular cross-section, and elliptical holes resulting in an elliptical cross-section.
- m-aramid e.g. Nomex ®
- filaments typically have a two-lobe "dog-bone” shape when dry spun, or are multi-lobed, or "star shaped” when wet spun, since the skin is solidified before the solvent is extracted from the core, and the contracted area does not "fill" the perimeter.
- the yarn preferably has a tenacity of at or about 15 to 40 g/denier, more preferably at or about 25 to 35 g/denier.
- the yarn of the invention preferably has an elongation at break of at or about 1.5 to 15 %, more preferably at or about 2 to 4%.
- the yarn preferably has a modulus of elasticity of at or about 5 to 450 N/tex, more preferably at or about 50 to 400 N/tex.
- the yarn has a tenacity of at or about 25 to 35 g/denier, an elongation at break of from at or about 2 to 4%, and a modulus of elasticity of from at or about 50 to 400 N/tex.
- the number of filaments making up the yarn is not limited, and depends on the end-use, and the linear density required in the final yarn. Typical yarns comprise from 16 to 1500 total filaments. In a preferred embodiment, the total number of filaments in the yarn is 276, of which 45-55% (in number) are the smaller filaments and 45-55% (in number) are the larger filaments.
- yarns of the invention having a third plurality of filaments, with greater average diameter than the first and second plurality of filaments an example would be 276 total filaments in the yarn, with 25-50% (by number) being the smallest filaments, 25-50% (by number) being the medium filaments and 15-35% (by number) being the largest filaments.
- the multi-dtex yarn made from the spinnerets of the invention preferably has a maximum possible packing density of at or about 80 to 95%, more preferably at or about 90 to 95%.
- Cross section and packing density can be measured by immobilizing the fibre under a relatively small tension in an epoxy resin placed in a cylindrical mould perforated at the bottom to allow passage of the fibre flow of the resin.
- the molded sample is then cured at room temperature for 12 hours.
- the sample is then frozen in liquid nitrogen for one minute and a cut transverse to the fibre axis is made to realize image analysis and diameter measurement and void ratio evaluation under SEM microscope enlargement.
- the sample preparation used is well known for scanning microscopy except that polishing is avoided.
- Packing density is influenced by the relative diameters (i.e. linear density) of the filaments, and the ratio of the number of first plurality of filaments (i.e. smaller) to the number of the second plurality of filaments (i.e. larger).
- Yarns having a ratio of first plurality of filaments to second plurality of filaments of at or about 0.5 i.e. 50% by number smaller filaments and 50% by number larger filaments
- a large difference in average diameter between the filaments large:small at or about 2
- yarns made in the "continuous" embodiment also have high packing densities.
- the multi-dtex yarn is particularly suited to making cut-, abrasion- and penetration-resistant fabrics, having excellent comfort characteristics.
- Such fabrics may be made by braiding, knitting or weaving techniques known in the art.
- Fabrics made from the yarns of the invention may be used for making cut-, abrasion- and penetration-resistant garments, for example, gloves, footwear, coveralls, trousers and shirts, as well as parts of garments that require particular cut-, abrasion- and penetration- resistance, such as the palms of gloves, cuffs of trousers, coveralls or shirts.
- Such articles may be coated with various resins and elastomers.
- multi-dtex yarns may be incorporated in unidirectional protective structures, in which largely unidirectional (parallel) yarns are imbedded or partially imbedded in an immobilizing medium, such as a resin and elastomers.
- an immobilizing medium such as a resin and elastomers.
- Denier is determined according to ASTM D 1577 and is the linear density of a fibre as expressed as weight in grams of 9000 meters of fibre. The denier can be measured on a Vibroscope from Textechno of Kunststoff, Germany. Denier times (10/9) is equal to decitex (dtex).
- a yarn according to the invention was made using as polymer a batch solution preparation of poly-para-phenylene terephthalamide containing 4.5 kg of polymer. 18.6 kg of acid were pumped into a mixer and cooled to -22 0 C while being agitated to form a frozen slush in a nitrogen atmosphere (12). One-half to one-third of the polymer was initially added and mixed for ten minutes before the remaining amount of polymer was added. The jacket surrounding the mixer was then heated to 87 0 C (14). Once the solution had maintained that temperature for an hour and a half, the mixer agitator and the vacuum pump were shut off, and the mixer was pressurized to 1.7 bar (absolute) with nitrogen.
- a 5 cm 3 meter pump (16) was used to transfer the solution through a flow plate (22) and a screen pack (20), shown in Figure 3 at (18), to the spinning process, which operated at 460 m/min.
- a 276 hole spinneret (24), shown in Figure 4 was used to spin the yarn.
- the spinneret had 46 holes with a 76 ⁇ capillary diameter (24a), 115 holes with a 64 ⁇ capillary diameter (24b), 115 holes with a 51 ⁇ capillary diameter (24c), and the hole arrangement is shown in Figure 4.
- the filaments were spun through a 6 mm air gap (26) before entering a 3 0 C quench bath (28) water and passing through a quench jet (30) (6.4 mm diameter radial jet with a 0.2 mm gap).
- the jet and tray flows for the quench bath were set to 2.3 l/min. and 5.3 l/min. respectively.
- the yarn was quenched, it was conveyed to an acid wash of water (32). There were 30 wraps on a pair of 113 mm diameter rolls (34) with a centreline spacing of 445 mm.
- the water flow was 15 l/min. and the tension was between 0.7 and 1.0 g/denier (0.0.8 and 1.1 g/dtex).
- the yarn moved on to a further wash cabinet (36) where there were also 30 wraps on a pair of rolls with the same diameter and centreline spacing as the acid wash rolls
- the first half of the wash cabinet was a caustic wash (38) (consisting of sodium hydroxide solution), and the second half was a water wash (40)
- the strong and dilute caustic flows for the caustic wash were each 7 5 I/mm , and the tension was between 0 5 and 0 8 g/den ⁇ er (0 55 and 0 89 g/dtex)
- the yarn was then dried at 31 1 0 C with 34 wraps on a pair of 160 mm diameter rolls (42) with a centreline spacing of 257 mm
- a finish was applied (44) and it was wound on a packaging roll (46)
- the inventive sample was made from a yarn of 400 denier out of a spinneret as depicted in Figure 4, as follows
- the yarn was knitted to yield a sample of areal density of about 400 g/m 2
- control sample was made using yarn made exactly as specified above, but the spinneret had only one size hole and yielded only 1 5 dpf (about 12 micron in diameter) filaments
- the resulting yarn was 400 denier and consisted exclusively of 1 5 dpf filaments
- the yarn was knitted to yield a sample of areal density of about 400 g/m 2 Testing of the Mixed dtex Yarns Cut Resistance Abrasive Cut Procedure
- the abrasive cut testing procedure was based on the EN388.1994 1 current procedure, which was modified in terms of the weight force applied onto the circular blade, i.e. instead of a 5N equivalent force a 2.9N equivalent force was applied, thereby permitting an increased number of cut cycles, which promotes abrasion.
- Two layers of a rectangular shaped sample (approx. 80 by 100 mm), one on the top of the other, were tested simultaneously.
- a load of 2.9N instead of 5N was positioned in its dedicated position.
- the test specimen sat on a support covered by a conductive rubber.
- the horizontal movement of the circular rotating blade was 50 mm long.
- the resulting linear peripheral speed was 10 cm/s.
- the cut tester was equipped with an automated electro-conductive system, which detected cuts throughout the specimen.
- the blade sharpness was checked at the beginning and between each sample testing using a cotton standard fabric as per specification of EN388-1994 procedure.
- a cut level was computed, whereby a cut level between 0 to 5 was determined, 0 being the lowest achievable cut protection level, and 5 being the highest.
- the inventive sample required more than 300 cycles to cut through, whereas the control one made of 100% identical filaments required less than 150 cycles to cut through.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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JP2009532387A JP2010506063A (ja) | 2006-10-10 | 2007-10-09 | 耐切断性糸を製造するための紡糸口金 |
EP07867215A EP2074246A2 (en) | 2006-10-10 | 2007-10-09 | Spinnerets for making cut-resistant yarns |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US11/545,285 US20080095875A1 (en) | 2006-10-10 | 2006-10-10 | Spinnerets for making cut-resistant yarns |
US11/545,285 | 2006-10-10 |
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WO2008063298A2 true WO2008063298A2 (en) | 2008-05-29 |
WO2008063298A3 WO2008063298A3 (en) | 2009-02-12 |
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PCT/US2007/021617 WO2008063298A2 (en) | 2006-10-10 | 2007-10-09 | Spinnerets for making cut-resistant yarns |
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Cited By (1)
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US10293289B2 (en) | 2013-02-14 | 2019-05-21 | Nanopareil, Llc | Hybrid felts of electrospun nanofibers |
Families Citing this family (12)
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US7638193B1 (en) * | 2006-10-10 | 2009-12-29 | E. I. Du Pont De Nemours And Company | Cut-resistant yarns and method of manufacture |
KR20080074019A (ko) * | 2007-02-07 | 2008-08-12 | 주식회사 코오롱 | 관형 편물 및 그를 이용한 복합 중공사막 |
JP6105203B2 (ja) * | 2009-02-17 | 2017-03-29 | テイジン・アラミド・ビー.ブイ. | 芳香族ポリアミドからフィラメント糸を製造する方法 |
KR101410542B1 (ko) * | 2010-06-30 | 2014-06-20 | 코오롱인더스트리 주식회사 | 아라미드 섬유 및 그 제조방법 |
US10301746B2 (en) * | 2012-10-16 | 2019-05-28 | Avintiv Specialty Materials, Inc. | Multi-zone spinneret, apparatus and method for making filaments and nonwoven fabrics therefrom |
KR102034197B1 (ko) * | 2014-03-27 | 2019-10-18 | 코오롱인더스트리 주식회사 | 합성섬유 방사구금 |
KR101975889B1 (ko) * | 2014-06-13 | 2019-05-07 | 코오롱인더스트리 주식회사 | 합성섬유 방사구금 |
KR101975883B1 (ko) * | 2014-06-24 | 2019-05-07 | 코오롱인더스트리 주식회사 | 합성섬유 방사구금 |
DE102016009570A1 (de) * | 2016-08-05 | 2018-02-08 | Texticord Steinfort S.A. | Verstärkungsmaterial für Gummianordnungen, insbesondere in Form einer Reifencordkonstruktion und Verfahren zu seiner Herstellung |
CN106984097A (zh) * | 2017-05-24 | 2017-07-28 | 上海创治环境科技有限公司 | 一种多丝径纳米级pp熔喷过滤材料和用于制造该材料的喷丝板 |
WO2019103013A1 (ja) * | 2017-11-21 | 2019-05-31 | 旭化成株式会社 | ポリウレタン弾性繊維及びその巻糸体 |
JP7352946B2 (ja) * | 2019-09-05 | 2023-09-29 | ヤマシンフィルタ株式会社 | メルトブロー装置 |
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JPS5813714A (ja) * | 1981-07-14 | 1983-01-26 | Toho Rayon Co Ltd | 湿式紡糸用ノズル |
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BR0213601A (pt) * | 2001-09-28 | 2004-09-14 | Du Pont | Fio hétero-compósito, vestimenta, processo de fabricação de um fio hétero- compósito e processo de fabricação de um fio de polìmero sintético |
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-
2006
- 2006-10-10 US US11/545,285 patent/US20080095875A1/en not_active Abandoned
-
2007
- 2007-10-09 CN CNA2007800372055A patent/CN101522963A/zh active Pending
- 2007-10-09 KR KR1020097008796A patent/KR20090063271A/ko not_active Withdrawn
- 2007-10-09 JP JP2009532387A patent/JP2010506063A/ja active Pending
- 2007-10-09 WO PCT/US2007/021617 patent/WO2008063298A2/en active Application Filing
- 2007-10-09 EP EP07867215A patent/EP2074246A2/en not_active Withdrawn
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10293289B2 (en) | 2013-02-14 | 2019-05-21 | Nanopareil, Llc | Hybrid felts of electrospun nanofibers |
USRE49773E1 (en) | 2013-02-14 | 2024-01-02 | Nanopareil, Llc | Hybrid felts of electrospun nanofibers |
Also Published As
Publication number | Publication date |
---|---|
KR20090063271A (ko) | 2009-06-17 |
EP2074246A2 (en) | 2009-07-01 |
WO2008063298A3 (en) | 2009-02-12 |
JP2010506063A (ja) | 2010-02-25 |
US20080095875A1 (en) | 2008-04-24 |
CN101522963A (zh) | 2009-09-02 |
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