Cut-resistant filled elongated body

Abstract

To provide a lengthy body for limiting or even preventing the formation of dust during the processing of a yarn into an article and / or the processing of the article, and to provide a method for manufacturing the lengthy body.SOLUTION: The present invention relates to a lengthy body comprising: i) high- performance polyethylene fibers comprising a hard component, the hard component having a Mohs hardness of at least 2.5, and ii) a polymeric resin, wherein the polymeric resin is a homopolymer of ethylene or propylene or is a copolymer of ethylene and / or propylene, wherein the polymeric resin has a density as measured according to ISO1183-2004 in the range from 860 to 970 kg / m3, a melting temperature in the range from 40 to 140°C and a heat of fusion of at least 5 J / g.SELECTED DRAWING: None

Description

Detailed Description of the Invention

[0001] The present invention relates to an elongated body comprising high performance polyethylene fibers (HPPE) containing a rigid component, the rigid component having a Mohs hardness of at least 2.5. Furthermore, the present invention is directed to a method for producing said elongated body. The present invention also relates to the use of the elongated body in various applications.

[0002] Such elongated bodies are already known, for example, from document WO2008046476. This document discloses a yarn with high cut resistance, which comprises a hard component with a Mohs hardness of at least 2.5, the hard component being a plurality of hard fibers with an average diameter of at most 25 microns. However, the cut-resistant yarn disclosed in this document loses the hard component, which leads to a large amount of dust formation during the manufacturing process of the yarn and / or during further processing into different products, for example knitting to make gloves. This can lead to higher hardware wear and failure, as well as processing difficulties.

[0003] It is therefore an object of the present invention to provide a length which limits or even prevents dust formation during the processing of yarns into articles and also during the processing of articles, which length can be produced at low cost, is environmentally friendly and at the same time exhibits high cut resistance and versatility for coloring and dyeing.

[0004] This object is achieved by an elongated body according to the invention, which comprises: i) high performance polyethylene (HPPE) fibres comprising a hard component, the hard component having a Mohs hardness of at least 2.5; and ii) a polymeric resin, which is a homopolymer of ethylene or propylene or a copolymer of ethylene and / or propylene, the polymeric resin having a hardness of 860 to 970 kg / m, measured according to ISO 1183-2004. 3 and a polymer resin having a density in the range of 100 to 200° C., a melting temperature in the range of 40 to 140° C., and a heat of fusion of at least 5 J / g.

[0005] Surprisingly, it has been observed that the elongated bodies according to the invention limit or even prevent dust formation during processing of yarns containing filled fibers, thus avoiding hardware failures and processing-related damage. Furthermore, the elongated bodies according to the invention may be easier to process with materials of different chemical compositions, for example by treatment with coloring, dyeing and "grip coating", and thus can be applied in different applications. Furthermore, the tendency for fiberization of the elongated bodies with added polymer resin according to the invention is lower than a comparable elongated body without a coating. Thus, less occurrence of microfibril clusters occurs on the processing equipment, for example the guiding eye or the axle over which the body extends. Furthermore, the elongated bodies according to the invention, and the process for producing the elongated bodies, may allow easier addition of additional functionality, for example coloring and dyeing.

[0006] By fibre is understood herein an elongated body, the length dimension of which is much greater than the transverse dimensions of width and thickness. Thus, the term fibre includes filaments, strips, bands, tapes etc., with regular or irregular cross-section. A fibre may have a continuous length, known in the art as a filament or continuous filament, or a non-continuous length, known in the art as a staple fibre. A yarn for the purposes of the present invention is an elongated body containing many individual fibres. By individual fibre is understood herein the fibre itself. Preferably, the HPPE fibre of the present invention is an HPPE tape, HPPE filament or HPPE staple fibre.

[0007] HPPE fibres comprising a hard component in an elongated body according to the invention, wherein the hard component has a Mohs hardness of at least 2.5, may also be referred to herein as filled fibres of HPPE-based fibres or filled HPPE fibres. The material in the hard component may have a Mohs hardness of at least 3, preferably at least 3.5, more preferably at least 4, most preferably at least 6. The hard component in the HPPE fibre is preferably distributed, more preferably uniformly distributed, within the body of the HPPE fibre.

[0008] By elongated body is herein understood an elongated body, in particular an elongated body comprising filled fibers and polymer resins, the elongated body having a length dimension of the elongated body that is much greater than the transverse dimensions of width and thickness. Thus, the term elongated body includes, but is not limited to, fibers, monofilaments, multifilament yarns, staple fiber yarns, tapes, strips, films, strands, cables, cords, ropes, ribbons, hoses, tubes, etc. Preferably, said length dimension is at least 10 times, more preferably at least 20 times, even more preferably at least 50 times, and most preferably at least 100 times greater than the greater of the width or thickness dimension of the elongated body. Most preferably, the length is substantially continuous, for example several hundred meters. The cross-sectional shape of the elongated body may be circular or nearly circular, oval or rectangular in shape, whereby elongated bodies having a circular or nearly circular cross-section may be, but are not limited to, filaments, fibers, multifilament yarns, staple fiber yarns, strands, cables, cords, ropes, hoses or tubes, while elongated bodies having an oval to rectangular cross-section are commonly referred to as tapes, films, ribbons or strips.

[0009] The elongated body may consist of two or more threads of HPPE fibers, comprising a hard component with a Mohs hardness of at least 2.5, lying side by side without wrapping around each other. Such threads of said HPPE-based fibers that are not wrapped around may also be called bundles and may have various cross-sectional shapes, as detailed above. The HPPE-based fibers in the bundle are substantially oriented in a single direction, the length direction of the elongated body. Furthermore, the threads may consist of two or more wound HPPE-based fibers, generally called yarns. Some yarns may be arranged in the same or different directions, producing so-called composite bundles or strands, which may again be aggregated together or combined with other fiber arrangements to form complex fiber assemblies, for example ropes or ribbons. The arrangement of one fiber to another in the elongated body of the invention may be of different types, among which are parallel, laid, braided or woven fiber or yarn arrangements, or others that may be known to the skilled person.

[0010] The hard component in the filled HPPE fibres in the elongated body according to the invention may comprise or consist of a material having a higher hardness than the hardness of the HPPE fibres or body measured in the absence of the material. The hard component may comprise or consist of an organic and / or non-polymeric material. Preferably, the material contained in the hard component is a non-polymeric material.

[0011] "Non-polymeric material" is understood herein as a material that does not contain a polymer. An alternative definition of non-polymeric material used in the present invention is a material that does not essentially contain hydrogen atoms, i.e., a material that contains hydrogen atoms in an amount of less than 7% by weight, preferably less than 5% by weight, most preferably less than 1% by weight, based on the total weight of the non-polymeric fiber. In particular, non-polymeric material refers to a compound that includes metals, alloys, metal oxides, ceramic materials, crystalline materials, and / or mixtures thereof. Suitable metals include tungsten, copper, brass, bronze, aluminum, steel, iron, Monel, cobalt, titanium, magnesium, silver, molybdenum, tin and zinc, zirconia; metal oxides, including aluminum oxide, silicon oxide, titanium oxide, iron oxide, calcium oxide, magnesium oxide, potassium oxide, phosphorus oxide, manganese oxide, and / or combinations thereof; metal carbides, such as tungsten carbide; metal nitrides; metal sulfides; metal silicates; metal silicides; metal sulfates; metal phosphates; and metal borides; and / or mixtures thereof. Non-limiting examples of suitable crystalline minerals include baddeleyite, anhydrite, sclerotinite, chondroite, euclase, petalite, sapphire, spodumene, staurolite, clay, silica, silicates, silicon dioxide, carbides, such as silicon carbide, carbonates, cyanides, and / or mixtures thereof. Suitable ceramic materials include glass and alumina. Allotropes of carbon, such as diamond, graphite, graphene, fullerenes, carbon nanotubes, and / or mixtures thereof, can also be used as materials for the hard components. Preferably, the hard components include materials selected from the group consisting of glasses, minerals, such as materials containing metal oxides and metals. More preferably, the hard components may have a composition that is resorbable in vivo, such as when it is vitreous and preferably contains at most 40% Si by weight, and is harmless if it enters the human body in any way.

[0012] The rigid components may be used in any known shape, size, size distribution, diameter and / or length, as described, for example, in documents WO2013149990, WO2008046476, US5738940A and US5597649A, all of which are incorporated herein by reference. For example, particulate forms of rigid components may be used. For particles of substantially spherical shape, the average particle size is substantially equal to the average particle diameter. For particles of substantially oval shape, e.g., elongated or non-spherical or anisotropic shape, e.g., needles or fibers, the particle size may refer to the average length dimension (L) along the major axis of the particle, while the average particle diameter, or simply the diameter as may also be referred to herein, refers to the average diameter of the cross section perpendicular to the length direction of said oval shape. If the cross section of the particle is not circular, the average diameter (D) may be calculated according to the following formula: D=1.15. * A 1 / 2 where A is the cross-sectional area of ​​the particle.

[0013] Selection of the appropriate particle size, diameter and / or length of the hard component depends on the processing and dimensions of the HPPE-based fiber. For HPPE-based fibers produced by a spinning process, the hard component should be small enough to pass easily through the spinneret opening. The particle size and average diameter may be selected small enough to avoid too much deterioration of the fiber tensile properties. The particle size and average diameter may have a log-normal distribution.

[0014] Preferably, the average diameter (D) of the hard components is at most 50 microns, more preferably at most 30 microns, even more preferably at most 25 microns, even more preferably at most 15 microns, and most preferably at most 10 microns. Hard components with smaller average diameters, especially when prepared by extrusion, can result in more uniform articles and less surface defects in the articles obtained from the elongated bodies according to the invention. Larger average diameters result in more dust formation.

[0015] Preferably, the average diameter of the rigid components is at least 0.01 microns, more preferably at least 0.1 microns, even more preferably at least 1 micron, and most preferably at least 3 microns.

[0016] Preferably, the average length (L) of the hard components is at most 10000 microns, more preferably at most 5000 microns, and most preferably at most 3000 microns. It has also been observed that the articles of the invention, in particular gloves comprising the articles of the invention, exhibit good dexterity when the hard components are hard fibers having an average length of at most 1000 microns, more preferably at most 750 microns, and most preferably at most 650 microns. Preferably, said average length of said hard fibers is at least 50 microns, more preferably at least 100 microns, most preferably at least 150 microns, and even most preferably at least 200 microns.

[0017] The hard components present in the HPPE-based fibres may be hard particles which may have an aspect ratio L / D of about 1. The hard components present in the HPPE-based fibres may be in the form of hard fibres which may have an aspect ratio L / D of more than 1, preferably at least 3, preferably at least 5, even more preferably at least 10, more preferably more than 30. The hard components in the HPPE-based fibres may comprise or consist of hard particles and / or hard fibres.

[0018] Any hard component known in the art can be used.Suitable hard components are already commercially available, as also used in the examples section of the present invention.Hard components and methods of adding hard components to HPPE fibers are well known to those skilled in the art and are described, for example, in documents WO 9918156 A1, which is incorporated herein by reference, and WO 2008046476, which is incorporated herein by reference, and WO 2013149990, which is incorporated herein by reference.

[0019] The aspect ratio of the rigid components is the ratio between the length, i.e., average length (L), and the diameter, i.e., average diameter (D), of the rigid components. The average diameter and aspect ratio of the rigid components can be determined by any method known in the art, for example, by using SEM images. To measure the diameter, it is possible to make an SEM image of the rigid components, e.g., the rigid fibers themselves, spread on a surface, and measure the diameter at 100 randomly selected positions, and then calculate the arithmetic mean of the 100 values ​​thus obtained. For the aspect ratio, it is possible to make an SEM image of the rigid components, e.g., the rigid fibers, and measure the length of the rigid components, e.g., the rigid fibers, that appear at the surface of the HPPE fibers or that are just below the surface of the HPPE fibers. Preferably, the SEM image is made with backscattered electrons to achieve a better contrast between the rigid fibers and the surface of the HPPE fibers.

[0020] The hard components can be continuous or spun fibers, in particular spun fibers. Suitable examples of hard spun fibers are glass or mineral fibers, which can be spun by spinning techniques well known to those skilled in the art. It is possible to produce hard fibers as continuous filaments, which are subsequently ground into hard fibers of much shorter length. The grinding process can reduce the aspect ratio of at least a portion of the hard fibers. Alternatively, non-continuous filaments can be produced, for example, by jet spinning, optionally followed by grinding, and used in the elongated bodies of the invention. The hard fibers can be subjected to a reduction in their aspect ratio during the production process of the HPPE fibers.

[0021] Carbon fibers may be used as the rigid component. Most preferably, carbon fibers having a diameter of 3 to 10 microns, more preferably 4 to 6 microns, are used. Articles containing carbon fibers exhibit improved electrical conductivity and allow for the discharge of static electricity.

[0022] The HPPE-based fibres as filaments may have a linear density of at most 15 dtex, preferably at most 12 dtex, most preferably at most 10 dtex, since articles comprising such fibres are very flexible and achieve a high level of comfort for the person wearing the article. The HPPE-based fibres preferably have a titer of at least 5 dtex, more preferably at least 10 dtex. For practical reasons, the titer of these fibres may be at most 10000 dtex, preferably at most 5000 dtex, more preferably at most 3000 dtex. Preferably, the titer of said fibres is in the range of 100-10000, more preferably 500-6000, most preferably in the range of 1000-3000 dtex, even more preferably in the range of 220-1760 dtex or 220-725 dtex.

[0023] Preferably, the elongated body according to the present invention comprises: i) HPPE fibres consisting of a hard component, the hard component having a Mohs hardness of at least 2.5; and ii) a polymer resin, the polymer resin being a homopolymer of ethylene or propylene or a copolymer of ethylene and / or propylene, the polymer resin having a hardness of 860 to 970 kg / m2 measured according to ISO 1183-2004. 3 The composition comprises or consists of a polymer resin having a density in the range of 0.1 to 1.0 mm, a melting temperature in the range of 40 to 140° C., and a heat of fusion of at least 5 J / g.

[0024] The HPPE-based fibres in the elongated bodies according to the invention preferably contain from 0.1% to 45% by weight of hard constituents, preferably from 1% to 35% by weight, further preferably from 2% to 20% by weight, even more preferably from 2% to 7% by weight, based on the total weight of the HPPE-based fibres.

[0025] In the context of the present invention, high performance polyethylene (HPPE) fibers (without hard components) are understood to be fibers that comprise or consist of polyethylene having a tensile strength of at least 0.5 N / tex, more preferably at least 1 N / tex, even more preferably at least 1.5 N / tex, more preferably at least 1.8 N / tex, even more preferably at least 2.5 N / tex, most preferably at least 3.5 N / tex. Preferred polyethylenes are high molecular weight (HMWPE) or ultra-high molecular weight polyethylene (UHMWPE). Best results have been obtained when the high performance polyethylene fibers comprise ultra-high molecular weight polyethylene (UHMWPE) and have a tenacity of at least 2.0 N / tex, more preferably at least 3.0 N / tex. The tensile strength is measured by the method in the examples of the present invention.

[0026] HPPE fibres comprising a hard component having a Mohs hardness of at least 2.5 in an elongated body according to the invention may have a tensile strength of at least 0.5 N / tex, more preferably at least 1 N / tex, even more preferably at least 1.5 N / tex, more preferably at least 1.8 N / tex, even more preferably at least 2.5 N / tex and most preferably at least 3.5 N / tex.

[0027] Preferably, the elongated bodies of the present invention comprise HPPE fibers comprising high molecular weight polyethylene (HMWPE) or ultra-high molecular weight polyethylene (UHMWPE) or a combination thereof, and preferably the HPPE-based fibers consist essentially of HMWPE and / or UHMWPE and a rigid component. The inventors have observed the greatest effect on tenacity when using HMWPE and UHMWPE. These polymers are commercially available and methods for producing UHMWPE are well known in the art.

[0028] In the context of the present invention, the expression "consisting essentially of" has the meaning "may contain insignificant amounts of further species", where insignificant is at most 5% by weight, preferably at most 2% by weight, of said further species, or in other words "more than 95% by weight", preferably "more than 98% by weight" of HMWPE and / or UHMWPE.

[0029] In the context of the present invention, polyethylene (PE) can be linear or branched, whereby linear polyethylene is preferred. Linear polyethylene is understood herein to mean polyethylene with less than one side chain per 100 carbon atoms, preferably less than one side chain per 300 carbon atoms; the side chain or branch generally contains at least 10 carbon atoms. The side chains can be suitably measured by FTIR. Linear polyethylene can further contain up to 5 mol % of one or more other alkenes with which it is copolymerizable, such as propene, 1-butene, 1-pentene, 4-methylpentene, 1-hexene and / or 1-octene.

[0030] The PE is preferably of high molecular weight with an intrinsic viscosity (IV) of at least 2 dl / g; more preferably at least 4 dl / g, most preferably at least 8 dl / g. Such polyethylenes with an IV greater than 4 dl / g are also referred to as ultra-high molecular weight polyethylenes (UHMWPE). Intrinsic viscosity is a measure for molecular weight that can be more easily determined than actual molar mass parameters such as number average molecular weight and weight average molecular weight (Mn and Mw).

[0031] HPPE and HPPE-based fibers may be obtained by various processes known in the art, for example by a melt spinning process, a gel spinning process or a solid-state powder compaction process, as also described herein.

[0032] The process for the production of HPPE fibers and HPPE-based fibers can be a solid-state powder process that includes feeding polyethylene as a powder between a combination of endless belts, compression molding the polymer powder at a temperature below its melting point, rolling the resulting compression molded polymer, followed by solid-state stretching. Such a process is described, for example, in U.S. Pat. No. 5,091,133, which is incorporated herein by reference. If necessary, before feeding the polymer powder and compression molding, the polymer powder can be mixed with a suitable liquid compound having a boiling point above the melting point of said polymer. Compression molding can also be performed by temporarily holding the polymer powder between endless belts while conveying it. This can be done, for example, by providing press platens and / or rollers associated with the endless belts.

[0033] A preferred method for the production of HPPE fibers used in the present invention involves feeding polyethylene into an extruder, extruding a shaped article at a temperature above its melting point, and stretching the extruded fiber below its melting temperature. If necessary, before feeding the polymer into the extruder, the polymer may be mixed with a suitable liquid compound, for example to form a gel, which is preferably the case when, for example, ultra-high molecular weight polyethylene is used.

[0034] In a most preferred manner, the HPPE fibres used in the present invention are prepared by a gel spinning process. Suitable gel spinning processes are described, for example, in GB-A-2042414, GB-A-2051667, EP-A-0205960A and WO 01 / 73173 A1. Briefly, the gel spinning process comprises preparing a solution of polyethylene with a high intrinsic viscosity, extruding the solution at a temperature above the dissolution temperature into a solution-fiber, cooling the solution-fiber below the gelling temperature, thereby at least partially gelling the polyethylene solution of the fibre, and drawing the fibre before, during and / or after at least partial removal of the solvent.

[0035] In the described method of preparing HPPE fibers, drawing, preferably uniaxial drawing, of the produced fibers can be carried out by means known in the art. Such means include extrusion drawing and tensile drawing on a suitable drawing unit. To obtain increased mechanical tensile strength and stiffness, drawing can be carried out in multiple steps. For the preferred UHMWPE fibers, drawing is typically carried out uniaxially in several drawing steps. The first drawing step can for example include drawing to a stretch factor (also called draw ratio) of at least 1.5, preferably at least 3.0. Multiple drawing can typically result in stretch factors of up to 9 for drawing temperatures up to 120°C, stretch factors of up to 25 for drawing temperatures up to 140°C, and stretch factors of 50 or more for drawing temperatures up to and above 150°C. By multiple drawing at increasing temperatures, stretch factors of about 50 or more can be reached. This results in HPPE fibres, which may give tensile strengths of 1.5N / tex to 3N / tex or more for ultra high molecular weight polyethylene.

[0036] The HPPE-based fibers with hard components present in the elongated bodies according to the invention can be obtained by applying the same method as presented in this patent application for producing HPPE fibers, with the difference that the hard components are also added together with the HPPE polymer powder to form a mixture, which is then spun, preferably gel spun, as described herein for the HPPE fibers. For example, the document WO2008046476, incorporated herein by reference, describes in detail, for example, obtaining filled HPPE fibers by a) mixing HPPE polymer powder or polymer granules and the hard component, b) melting or dissolving the polymer while still mixing the polymer and the hard component, and c) spinning fibers from the mixture obtained in step b).

[0037] Preferably, the elongated body comprises a polymer resin ii), the polymer resin being present throughout the elongated body, e.g. impregnated within the elongated body, more preferably the polymer resin is coated on the elongated body, and most preferably the polymer resin is coated on the elongated body at the filament level.

[0038] Preferably, the polymer resin is in contact with the surface of the HPPE fibres comprising the hard component, more preferably the polymer resin has been applied as a coating on the surface of the HPPE fibres comprising the hard component, most preferably the polymer resin has been applied onto the HPPE fibres comprising the hard component as a coating obtained from an aqueous suspension. The elongated bodies exhibit very low or even no dust formation during processing.

[0039] More preferably, the elongated body comprises HPPE fibres comprising a hard component, the hard component having a Mohs hardness of at least 2.5, the HPPE fibres comprising a coating on a surface of the HPPE fibres, the coating comprising or consisting of a polymer resin, the polymer resin being a homopolymer of ethylene or propylene or a copolymer of ethylene and / or propylene, the polymer resin having a hardness of 860 to 970 kg / m measured according to ISO 1183-2004. 3 in the range of 0.1 to 100° C., a melting temperature in the range of 40 to 140° C., and a heat of fusion of at least 5 J / g.

[0040] The elongated body according to the invention may further comprise iii) other fibres different from the HPPE fibres or HPPE-based fibres, e.g. different in composition and / or shape, which may be in the form of filaments and / or staple fibres, e.g. non-polymeric fibres, e.g. glass fibres, carbon fibres, basalt fibres, metal wires or threads; and / or natural fibres, e.g. cotton; bamboo; and / or polymeric fibres, e.g. polyamide fibres, e.g. nylon fibres, elastic fibres, e.g. elastane fibres, polyester fibres; and / or mixtures of these other fibres, which may be present in any ratio. These other fibres may be wound around the HPPE-based fibres or other fibres, and / or the HPPE-based fibres may be wound around a core of metal wires. These other fibres as well as the construction of the HPPE-based fibres and other fibres are already known in the art, e.g. described in documents WO2008046476 and WO2010089410, which are incorporated herein by reference.

[0041] The elongated body according to the invention can be manufactured by any process known in the art. Preferably, the elongated body according to the invention is a) providing an HPPE fibre comprising or consisting of a hard component, the hard component having a Mohs hardness of at least 2.5; b) during or after step a), applying a solvent solution or an aqueous suspension of a polymer resin to the HPPE fibres comprising or consisting of the hard components of step a); c) at least partially drying the solvent solution or aqueous suspension of polymeric resin applied in step b); Upon completion of steps a), b) and c), obtaining an elongated body comprising filled fibers and polymer resin; d) before, during and / or after step c), optionally subjecting the elongated body of step b) to a temperature ranging from the melting temperature of the resin to 153° C. to at least partially melt the polymer resin; and e) before, during and / or after step d), optionally applying pressure and / or tension to the elongated body obtained in step c) to at least partially compact and / or stretch the elongated body. The method includes the steps of: The polymer resin is a homopolymer of ethylene or propylene, or a copolymer of ethylene and / or propylene, and the polymer resin has a modulus of elasticity of 860 to 970 kg / m, measured according to ISO 1183-2004. 3 in the range of 0.1 to 100° C., a melting temperature in the range of 40 to 140° C., and a heat of fusion of at least 5 J / g.

[0042] In one preferred process step of the present invention, an aqueous suspension is applied to HPPE-based fibers containing a rigid component, the rigid component having a Mohs hardness of at least 2.5. Such application of the suspension is performed before, during or after the fibers are assembled to form an elongated body. By aqueous suspension, it is understood that particles of polymeric resin are suspended in water, which acts as a non-solvent. The concentration of the polymeric resin can vary widely and is mainly limited by the ability to formulate a stable suspension of the resin in water. A typical range of concentration is 0.5-60% by weight of polymeric resin in water, the weight percentage being the weight of the polymeric resin in the total weight of the aqueous suspension. A preferred concentration is 1-40% by weight, more preferably 2-30% by weight, most preferably 3-20% by weight. Further preferred concentrations of the polymer resin in the dispersion are at least 1% by weight, 2% by weight, 3% by weight, 5% by weight, 10% by weight, 15% by weight, 20% by weight or 25% by weight, based on the total weight of the aqueous suspension, and at most 30% by weight, 40% by weight or 50% by weight, based on the total weight of the aqueous suspension. The suspension or solution may further comprise additives, such as ionic or non-ionic surfactants, tackifying resins, stabilizers, antioxidants, colorants or other additives that modify the properties of the suspension, the resin and / or the elongated bodies prepared.

[0043] The polymer resin present in the applied solution or suspension and finally in the elongated body of the invention is a homopolymer of ethylene or propylene, or a copolymer of ethylene and / or propylene (also called polyethylene, polypropylene or copolymers thereof, also called polyolefin resins in the context of the present invention), in other words the polymer resin is selected from the group consisting of homopolymers of ethylene, homopolymers of propylene, copolymers of ethylene and copolymers of propylene. It may include various forms of polyethylene, ethylene-propylene copolymers, other ethylene copolymers with comonomers such as 1-butene, isobutylene, and with heteroatom-containing monomers such as acrylic acid, methacrylic acid, vinyl acetate, maleic anhydride, ethyl acrylate, methyl acrylate; generally, α-olefin and cyclic olefin homopolymers and copolymers, or blends thereof. Preferably, the polymer resin is a copolymer of ethylene or propylene, which may contain as a comonomer one or more olefins having 2 to 12 C atoms, in particular ethylene, propylene, isobutene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, acrylic acid, methacrylic acid and vinyl acetate. In the absence of a comonomer in the polymer resin, a wide variety of polyethylenes or polypropylenes may be used, among which are high density polyethylene (HDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), low density polyethylene (LDPE), isotactic polypropylene, atactic polypropylene, syndiotactic polypropylene or blends thereof.

[0044] Furthermore, the polymer resin may be a functionalized polyethylene or polypropylene or copolymer thereof, or alternatively, the polymer resin may comprise a functionalized polymer. Such functionalized polymers are often referred to as functional copolymers or graft polymers, with grafting referring primarily to the chemical modification of the polymer backbone with ethylenically unsaturated monomers containing heteroatoms, while functional copolymers refer to the copolymerization of ethylene or propylene with ethylenically unsaturated monomers. Preferably, the ethylenically unsaturated monomers contain oxygen and / or nitrogen atoms. Most preferably, the ethylenically unsaturated monomers contain carboxylic acid groups or derivatives thereof, resulting in acylated polymers, in particular acetylated polyethylene or polypropylene. Preferably, the carboxylic acid reactant is selected from the group consisting of acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, and maleic acid, fumaric acid, and itaconic acid reactants. More preferably, ethylene acrylic acid (EAA) copolymers, such as the commercially available EAA copolymers sold under the trade name Michemprime®, are the polymer resins used. This is because the copolymer adheres to the HPPE fibres and also to the rigid components. The functionalised polymer typically comprises 1-10% by weight or more of a carboxylic acid reactant. The presence of such functionalisation in the resin may substantially increase the dispersibility of the resin and / or allow the reduction of further additives present for that purpose, e.g. surfactants. Preferably, the suspension is substantially free of additives that may act as a solvent for the polymeric resin. Such a suspension may also be referred to as solvent-free. A solvent is understood herein to be a liquid in which at room temperature the polymeric resin is soluble in an amount of more than 1% by weight, whereas a non-solvent is understood to be a liquid in which at room temperature the polymeric resin is soluble in an amount of less than 0.1% by weight.

[0045] Polymer resin: 860-970kg / m 3 , preferably 870 to 970 kg / m 3 , more preferably 875 to 920 kg / m 3 , and even more preferably 870 to 940 kg / m 3, and even more preferably 875 to 910 kg / m 3 The inventors have identified that polyolefin resins having a density within said preferred range provide an improved balance between the mechanical properties of the elongated bodies and the processability of the suspension, especially the dried suspension, during the process of the present invention.

[0046] The polymer resin is preferably a semi-crystalline polyolefin having a peak melting temperature in the range of 40-140°C and a heat of fusion of at least 5 J / g, measured by ASTM E793 and ASTM E794, taking into account a second heating curve at a heating rate of 10 K / min on a dry sample. Preferably, in the present invention, the polymer resin has a heat of fusion of at least 10 J / g, preferably at least 15 J / g, more preferably at least 20 J / g, even more preferably at least 30 J / g, and most preferably at least 50 J / g. The inventors surprisingly found that with increasing heat of fusion, the elongated bodies showed improved monofilament-like characteristics. Other than the theoretical maximum heat of fusion of about 300 J / g for fully crystalline polyethylene or polypropylene, the heat of fusion of the polymer resin is not particularly limited by the above values. The polymer resin is a semi-crystalline product having a peak melting temperature in a specific range.

[0047] Thus, a reasonable upper limit of the heat of fusion for the polymer resin is at most 200 J / g, preferably at most 150 J / g. Preferably, the peak melting temperature of the polymer resin is in the range of 50-130°C, preferably in the range of 60-120°C. Such preferred peak melting temperatures provide a more robust processing method for producing elongated bodies, in that conditions for drying and / or compaction of the elongated bodies do not require more attention while still producing elongated bodies with good properties. The polymer resin may have two or more peak melting temperatures. In such cases, at least one of the melting temperatures falls within the above range. The second and / or further peak melting temperatures of the polymer resin may fall within or outside the temperature range. This may be the case, for example, when the polymer resin is a blend of polymers.

[0048] Polymer resins may have elastic modulus that may vary over a wide range. For example, a low modulus resin with a modulus of about 50 MPa may provide a very flexible elongated body with good strength properties. For example, a high modulus resin with a modulus of about 500 MPa may provide an elongated body, such as a monofilament, with improved structural appearance. Each application may have an optimum modulus for the resin in relation to the specific demands during the use of the application. The modulus may be measured by the method of the Examples section of the present invention.

[0049] The application of the suspension of polymer resin to the HPPE fibers comprising the rigid components according to the invention may be carried out by methods known in the art and may depend, among other things, on the nature of the fibers, the concentration and the viscosity of the suspension when the suspension is applied to the fibers. The suspension may be applied, for example, to the loaded fibers by spraying, dipping, brushing, transfer rolling, etc., depending, among other things, on the intended amount of polymer resin present in the elongated body of the invention. The amount of suspension present in the body may vary widely depending on the intended use of the elongated body and can be adjusted by the method used, but also by the properties of the suspension. For some applications, a small amount of highly concentrated suspension is used to reduce the energy and the time required to dry the impregnated elongated body. For other applications, a low concentration of suspension may be advantageous, for example, to increase the wetting and impregnation speed by a low viscosity suspension. Finally, the concentration and amount of the aqueous suspension or solution should be selected to provide the elongated body with the required amount of polymer resin that may be present as a coating material to said body.

[0050] Once the polymer aqueous suspension or solvent solution has been applied to the HPPE fibres containing the rigid components, the assembly containing the coated filled fibres, preferably coated HPPE fibres containing the rigid components, is at least partially dried. Such a drying step involves the removal, e.g. evaporation, of at least a portion of the water or solvent present in the assembly. Preferably, most, more preferably essentially all of the solvent or water, optionally in combination with other components, is removed during the drying step. Drying, i.e. removal of water or solvent, may be carried out by methods known in the art. Typically, evaporation of the water or solvent involves increasing the temperature of the elongated body up to or above the boiling point of the water or solvent. The increase in temperature may be assisted or replaced by a reduction in pressure and / or combined with a continuous exchange of the surrounding atmosphere. Typical drying conditions are temperatures between 40 and 130°C, preferably between 50 and 120°C. Typical pressure during the drying process is atmospheric pressure.

[0051] The method of the invention may optionally include a step in which the HPPE-based fiber containing the polymeric resin is heated to a temperature ranging from the melting temperature of the polymeric resin to 153°C before, during and / or after partial drying of the aqueous suspension. Heating of the fiber may be performed by holding the fiber in an oven set at a heating temperature for a dwell time, subjecting the impregnated fiber to thermal radiation or by contacting the body with a heat carrier, e.g. a heated fluid, a heated gas stream or a heated surface. Preferably, the temperature is at least 2°C, preferably at least 5°C, most preferably at least 10°C above the peak melting temperature of the polymeric resin. The above temperature is at most 153°C, preferably at most 150°C, more preferably at most 145°C, most preferably at most 140°C to prevent deterioration of the (strength) properties of the fiber. The dwell time is preferably between 2 and 200 seconds, more preferably between 3 and 100 seconds, most preferably between 4 and 30 seconds. Preferably, the heating of the fibre and / or elongate body in this step overlaps with the drying step of the aqueous suspension, more preferably is coordinated with the drying step of the aqueous suspension. It may prove practical to subject the impregnated fibre to a temperature gradient, increasing the temperature from about room temperature to the maximum temperature of the heating step over a period of time, whereby the HPPE-based fibre undergoes a continuous process from drying of the suspension to at least partial melting of the polymer resin.

[0052] Preferably, the elongated body according to the present invention contains more than 65 wt.% UHMWPE, preferably more than 80 wt.% UHMWPE, most preferably more than 90 wt.% UHMWPE, the weight percentage being expressed as the mass of UHMWPE relative to the total mass of the elongated body.

[0053] The application of an aqueous polymer suspension, in which the polymer resin is present according to the above embodiments, provides a product with improved properties. The use of an aqueous suspension of polymer resin as a binder material for HPPE-based fibres, in which the polymer resin is a homopolymer of ethylene or propylene or a copolymer of ethylene and / or propylene, the polymer resin having a viscosity of 860-940 kg / m2 measured according to ISO 1183-2004, 3 a peak melting temperature in the range of 40-140° C., and a heat of fusion of at least 5 J / g) are therefore further embodiments of the present invention.

[0054] It is important that polyolefin resins soften or melt at higher temperatures. To date, such aqueous suspensions of polymer resins have not yet been applied in combination with HPPE-based fibers. Surprisingly, they achieve improved performance in a variety of products, especially those containing oriented UHMWPE-based fibers.

[0055] HPPE fibres coated with polymers having ethylene or propylene crystallinity are described in EP 0091547, whereby monofilament or multifilament fibres are treated at high temperature with a solution of the polymer in a hydrocarbon solvent at a concentration of up to 12 g / L. However, such hot solvent treatments may cause the fibres to contain residual amounts of the used hydrocarbon solvent, which adversely affect the fibre properties. Furthermore, the residual hydrocarbon solvent may have harmful effects on human health. Furthermore, treatment of HPPE fibres at high temperatures with a hydrocarbon solvent may affect the structural properties of the fibre, in particular by diffusion of the hydrocarbon solvent and / or polymer into the HPPE filaments. The fibre-polymer interface may be modified by partial etching and dissolution of the HPPE, which may affect, among other things, the interface and the bulk properties of the HPPE fibre. In contrast, the present method may be carried out at room temperature and uses a non-solvent for HPPE, i.e. water. Thus, fibres and lengths produced by the method of the present invention may involve better retention of the structural properties of the HPPE fibre. The fibers may also present a different surface structure, in particular a better differentiated HPPE-coating interface, compared to fibers treated with a hydrocarbon solvent at high temperature, because the hydrocarbon solvent and / or polymer cannot diffuse into the HPPE fiber. Furthermore, the process and products described in EP 0 091 547 are in hydrocarbon solution and are therefore limited by the amount of polymer applied to the HPPE fiber. The solutions are limited by their increasing viscosity and large amounts of polymer coating can only be applied by repeated coating operations.

[0056] The elongated bodies according to the invention can be colored using any method known in the art. The coloring process can be carried out, for example, by adding a colorant to the dispersion, according to WO2013120983, which is incorporated herein by reference. This can result in a durable coloring of the elongated bodies. A more versatile method can be to apply a dispersion of functionalized polyethylene, for example EAA, thus achieving a coating that is more compatible with the subsequent coloring process than uncoated HPPE fibers containing hard components. Suitable colorants for the present invention can be dyes or pigments known in the art. The dyes can be conventional ionic dyes, i.e. acid or basic dyes, also called reactive dyes, and disperse dyes. Acid dyes contain one or more acidic groups, for example -SO3H or salts thereof, for example -SO3Na. Common structural types of acid dyes are monoazo and anthraquinone dyes. Basic dyes contain basic groups, for example -N(CH3)2 or salts thereof, for example -NH(CH3)2Cl. Dyes are typically soluble in HPPE fibers containing hard components and can be applied after treatment of said fibers, whereas pigments are typically not soluble in HPPE fibers containing hard components and may need to be dispersed during spinning.

[0057] The present invention also relates to an elongated body obtained or obtainable by the method of the present invention, comprising: i) high performance polyethylene fibres comprising or consisting of a hard component, the hard component having a Mohs hardness of at least 2.5; and ii) a polymeric resin, the polymeric resin being a homopolymer of ethylene or propylene or a copolymer of ethylene and / or propylene, the polymeric resin having a hardness of at least 860 to 970 kg / m2 measured according to ISO 1183-2004. 3and a polymer resin having a density in the range of 0.1 to 1.0 mm, a melting temperature in the range of 40-140° C., and a heat of fusion of at least 5 J / g. Such elongated bodies are subject to the preferred embodiments and potential advantages as discussed above and below with respect to the method of the invention, while the preferred embodiments for the elongated bodies also have potential applications in reverse for the method of the invention.

[0058] The present invention further relates to an article comprising the elongated body according to the invention. The article may be selected from the group consisting of fishing lines and nets, ground nets, cargo nets and curtains, kite strings, dental floss, tennis racket strings, canvas, tent canvas, nonwovens, webbing, pressure vessels, hoses, umbilical cables, electrical, optical and signal cables, automotive equipment, building construction materials, cut and puncture resistant and cut resistant articles, apparel such as protective gloves, mittens, aprons, trousers, cuffs, sleeves, composite sports equipment, skis, helmets, kayaks, canoes, bicycle and boat hulls and spars, speaker cones, high performance electrical insulation, radomes, sails and geotextiles. Preferably, the article is an apparel such as a glove.

[0059] The present invention will be further illustrated by the following examples and comparative experiments, but first, the methods used in determining various parameters useful in defining the present invention are presented herein below.

[0060] [method] Dtex: The titer of a yarn or filament was measured by weighing 100 meters of yarn or filament, respectively. The dtex of a yarn or filament was calculated by dividing the weight (in milligrams) by 10. The heat of fusion and peak melting temperature were determined by standard DSC methods ASTM E794 and ASTM E793, respectively, at a heating rate of 10 K / min for the second heating curve and performed on dehydrated samples under nitrogen. · The density of polymer resin is measured according to ISO1183-2004. · IV: Intrinsic viscosity is determined by method ASTM D1601 (2004) in decalin at 135 °C, with a dissolution time of 16 hours and BHT (butylated hydroxytoluene) as antioxidant in an amount of 2 g / l solution, by extrapolating the viscosity as measured at zero concentration from different concentrations. Tensile properties of HPPE fibers: Tensile strength (or tenacity) and tensile modulus (or modulus) are defined and determined on multifilament yarns as specified in ASTM D885M, using a nominal gauge length of the fiber of 500 mm, a crosshead speed of 50% / min, and an Instron 2714 clamp of type "Fiber Grip D5618C". Based on the measured stress-strain curve, the modulus is determined as the slope from 0.3 to 1% strain. For the calculation of modulus and strength, the measured tensile force is divided by the titer as determined above; values ​​in GPa are 0.97 g / cm for HPPE. 3 The calculation is performed assuming a density of . Tensile properties of fibers having a tape-like geometry: Tensile strength, tensile modulus and elongation at break are defined and determined on a 2 mm wide tape at 25°C using a nominal gauge length of the tape of 440 mm, a crosshead speed of 50 mm / min as specified in ASTM D882. The tensile strength and tensile modulus at break of polyolefin resin were measured according to ISO527-2. The number of olefin branches per 1000 carbon atoms was determined by FTIR on 2 mm thick compression molded films by quantifying the absorption at 1375 cm-1 using a calibration curve based on NMR measurements, as for example in EP 0 269 151 (in particular pg. 4 thereof). ·SEM measurements were performed by using a Phenom XL table-top SEM micrograph. Dust formation was determined by knitting the samples and placing a white paper under the sample during the knitting process for 15 minutes. Cutting resistance determined by ISO13997-1999.

[0061] [material] Suspension A, purchased from Michelman under the trade name Michem® Prime 5931, is a 28 wt % water suspension of an acrylate modified polyolefin, i.e., an ethylene acrylic acid (EAA) copolymer, having a melting peak of 78° C. and a heat of fusion of 29 J / g.

[0062] [Example] [Comparative experiment 1 (CE1)] Yarn A obtained according to Example 1 of WO2013149990 was then knitted into a fabric (Fabric A) of 260 grams per square meter. The fabric was tested and the results are shown in Table 1.

[0063] [Example 1 (Ex.1)] The yarn A obtained according to Comparative Experiment 1 was then coated by immersion in a polyolefin suspension prepared by diluting the suspension A with 10 times the amount of water. The wet yarn was then fed into an oven having a length of 8.4 meters with an inlet speed of 5 m / s and an outlet speed of 6 m / s. The oven temperature was set at 130° C. The resulting dried yarn (Yarn B) contained 3.5% by weight of polyolefin resin and 96.5% by weight of fibrous material. Subsequently, the yarn B was knitted into a fabric (Fabric B) of 260 grams per square meter. The fabric was tested and the results are shown in Table 1.

[0064] [Table 1]

[0065] During the knitting process of yarn A, dust formation was observed to be visible as grey specks (Comparative Experiment 1), whereas no visible specks of dust were observed when knitting yarn B according to the invention for 15 minutes (Example 1). This can also be observed from the SEM images shown as Figure 1 (Yarn A of Comparative Experiment 1) and Figure 2 (Yarn B of Example 1). Figure 1 illustrates an SEM micrograph of a filament (i.e., a long body) containing hard fibers that are hardly connected to one filament in the absence of a polymer resin coating. The base UHMWPE filament runs from top to bottom at an angle of about 20 degrees with the vertical. The diameter of the filament in Figure 1 is about 30 microns (concluded from the scale bar at the bottom, which is 60 microns). FIG. 2 shows an SEM micrograph of a UHMWPE-based filament (elongated body according to the invention) with a hard fiber connected to one UHMWPE filament containing a coating, which can be seen as a small amount of meniscus-shaped solid between the hard fiber and the UHMWPE filament. The base UHMWPE filament extends mostly in the horizontal direction. The diameter of the filament in FIG. 2 is about 30 microns (concluded from the scale bar at the bottom, which is 50 microns). The polymer resin EAA coating is visible in FIG. 2, but it is surprising that such a small amount can prevent dust formation. Furthermore, it was observed that by introducing the polymer resin through the UHMWPE fiber containing the hard component, the tenacity of yarn B and the cut resistance of the fabric formed from yarn B were maintained at a high level. [Brief description of the drawings]

[0066] [Figure 1] FIG. 1 illustrates an SEM micrograph of a filament (ie, a length) containing stiff fibers that are largely not connected to one filament in the absence of a polymeric resin coating. [Diagram 2]FIG. 2 shows an SEM micrograph of a UHMWPE-based filament (elongated body according to the present invention) having a hard fiber connected to one UHMWPE filament containing a coating, which can be seen as a small amount of meniscus-shaped solid between the hard fiber and the UHMWPE filament.

Claims

1. A yarn having an aspect ratio (fiber length / fiber diameter) of 20 or more, i) filled polyethylene fibers formed from a polyethylene composition containing ultra-high molecular weight polyethylene and a hard component as a filler, the hard component comprising hard fibers having a Mohs hardness of at least 2.5, the aspect ratio L / D (average length / average diameter) of the hard fibers being 5 or greater, the average diameter (D) of the hard fibers being 1 micron or greater, and the tensile strength of the filled polyethylene fibers being at least 0.5 N / tex; and ii) A polymer resin, the polymer resin being a homopolymer of ethylene or propylene or a copolymer of ethylene and / or propylene, the polymer resin having a compressibility of 860 to 970 kg / m as measured according to ISO 1183-2004. ３ a melting temperature in the range of 40 to 140° C., and a heat of fusion of at least 5 J / g. Including, the polymer resin ii) is in contact with the surface of the filled polyethylene fibers i), the rigid components comprise carbon fibers, and the filled polyethylene fibers are filaments having a linear density of up to 15 dtex; Yarn.

2. The yarn of claim 1, wherein the carbon fibers have a diameter of 3 to 10 microns.

3. The yarn of claim 1, wherein the carbon fibers have a diameter of 4 to 6 microns.

4. The yarn of claim 1, wherein the aspect ratio L / D of the hard fibers is 10 or greater.

5. The yarn of claim 1, wherein the average length (L) of the hard fibers is at least 50 microns and at most 3000 microns.

6. The yarn of claim 1, wherein the average length (L) of the hard fibers is at least 50 microns and at most 750 microns.

7. The yarn of claim 1, wherein the average length (L) of the hard fibers is up to 650 microns.

8. A yarn described in any one of claims 1 to 7, wherein the filled polyethylene fibers are filaments having a linear density of up to 12 dtex.

9. The yarn of claim 1, wherein the filled polyethylene fibers are filaments having a linear density of up to 10 dtex.

10. The yarn of claim 1, wherein the hard fibers have an average diameter (D) of at least 3 microns and at most 25 microns.

11. The yarn of claim 1, wherein the hard fibers present in the filled polyethylene fibers have an aspect ratio L / D of greater than 30.

12. The yarn of claim 1, wherein the filled polyethylene fibers are continuous filaments or staple fibers.

13. The yarn of claim 1, wherein the filled polyethylene fibers are melt spun fibers or gel spun fibers.

14. The yarn of any one of claims 1 to 13, wherein the polymeric resin is a coating on the filled polyethylene fibers.

15. The yarn of claim 1, wherein the filled polyethylene fibers have a tensile strength of at least 1 N / tex.

16. The yarn of claim 1, wherein the filled polyethylene fibers have a tensile strength of at least 1.8 N / tex.

17. The yarn of any one of claims 1 to 16, wherein the filled polyethylene fibre consists essentially of the ultra-high molecular weight polyethylene (UHMWPE) and the hard component.

18. The yarn of claim 1, wherein the hard component has a Mohs hardness of at least 3.

5.

19. The yarn of claim 1, wherein the hard component has a Mohs hardness of at least 4.

0.

20. The yarn of any one of claims 1 to 19, wherein the amount of polymer resin in the yarn is from 1 to 20% by weight, said weight percentage being the weight of polymer resin relative to the total weight of the yarn.

21. A yarn as described in any one of claims 1 to 20, wherein the amount of polymer resin in the yarn is 2 to 10 weight percent, said weight percentage being the weight of polymer resin relative to the total weight of the yarn.

22. The density of the polymer resin is 870 to 930 kg / m ３ The yarn according to any one of claims 1 to 21, wherein the yarn viscosity is in the range of 23. The yarn of any one of claims 1 to 22, wherein the length dimension is at least 100 times greater than the greater of the width or thickness dimensions of the yarn.

24. The yarn of any one of claims 1 to 23, wherein the filled polyethylene fibers i) are coated with the polymer resin ii).

25. The yarn of claim 1, wherein the hard fibers are distributed within the filled polyethylene fibers.

26. The yarn of claim 1, wherein the polymer resin has a heat of fusion of at least 5 J / g and at most 200 J / g.

27. A method for producing the yarn according to any one of claims 1 to 26, comprising the steps of: a) providing a filled polyethylene fiber formed from a polyethylene composition containing ultra high molecular weight polyethylene and a hard component as a filler, said hard component comprising hard fibers having a Mohs hardness of at least 2.5, said hard fibers having an aspect ratio L / D (average length / average diameter) of 5 or more, said hard fibers having an average diameter (D) of 1 micron or more, said filled polyethylene fiber having a tensile strength of at least 0.5 N / tex, and said filled polyethylene fiber being a filament having a linear density of up to 15 dtex; b) during or after step a), applying a solution of a polymer resin in a solvent to the fibers of step a); c) at least partially removing said solvent of said solution applied in step b) to obtain, at the completion of steps a), b) and c), a yarn comprising filled polyethylene fibers; Including, The polymer resin is a homopolymer of ethylene or propylene, or a copolymer of ethylene and / or propylene, and the polymer resin has a modulus of elasticity of 860 to 970 kg / m as measured according to ISO 1183-2004. ３ a melting temperature in the range of 40-140° C., and a heat of fusion of at least 5 J / g.

28. The method of claim 27, wherein the filled polyethylene fibers consist essentially of the ultra-high molecular weight polyethylene (UHMWPE) and the rigid component.

29. The method of claim 27, wherein the heat of fusion of the polymer resin is up to 200 J / g.

30. A fabric comprising the yarn of any one of claims 1 to 26.

31. 31. An article of apparel comprising the fabric of claim 30.

32. 32. The article of apparel of claim 31, which is a glove.

33. An article comprising the yarn of any one of claims 1 to 26, the article being selected from the group consisting of fishing lines and nets, ground nets, cargo nets and curtains, kite string, dental floss, tennis racquet string, canvas, tent canvas, nonwoven fabrics, webbing, pressure vessels, hoses, umbilical cables, electrical cables, fiber optic cables, signal cables, automotive equipment, building and construction materials, cut-, puncture- and incision-resistant articles, apparel, composite sporting equipment, skis, helmets, kayak, canoe, bicycle and boat hulls and spars, speaker cones, high performance electrical insulators, radomes, sails and geotextiles.

34. The article of claim 33, wherein the article of clothing is a protective glove, a glove, an apron, pants, a cuff, or a sleeve.

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