uniformly filled yarn

Abstract

This invention relates to uniformly filled yarns, wherein the filler ratio χ in the yarn is greater than 0.004 times the UHMWPE present in the multifilament yarn, i.e., and wherein the toughness (TEN, in cN / dtex) of the filled multifilament yarn is or the toughness of the filled monofilament in the yarn is. The invention also relates to a method of manufacturing said multifilament yarn and articles comprising said multifilament yarn.

Description

[0001] This application is a divisional application of Chinese patent application 201880045684.3 (PCT / EP2018 / 069134) filed on July 13, 2018. Technical Field

[0002] This invention relates to a filled multifilament yarn comprising: UHMWPE with an intrinsic viscosity of up to 20 dL / g, and filler with a number-average diameter of up to 20 μm, wherein the filler is used in an amount such that the ratio (χ) of the filler mass to the total mass of UHMWPE and filler is between 0.02 and 0.50. Furthermore, this invention relates to a method for producing the filled multifilament yarn. This invention also relates to the use of the filled multifilament yarn in various applications. Background Technology

[0003] Such filled multifilament yarns are known, for example, from documents WO2008046476 and WO2013149990. These documents disclose yarns with high cut resistance, comprising a hard component with a Mohs hardness of at least 2.5, which consists of multiple hard fibers with an average diameter of up to 25 μm. However, the cut-resistant yarns in these documents exhibit low strength efficiency based on the IV of the UHMWPE used, resulting in the toughness of the filled multifilament yarn being significantly affected by the increased filler content. Existing yarns may have limited strength efficiency and are limited to small amounts of filler. Summary of the Invention

[0004] Therefore, an object of the present invention is to provide a filled multifilament yarn that does not have the aforementioned defects. In particular, an object of the present invention is to provide a filled multifilament yarn having improved strength efficiency and / or an increased filler content at comparable efficiency.

[0005] This objective is achieved by the filled multifilament yarn according to the invention, wherein the filler ratio χ in the yarn is greater than that of UHMWPE present in the multifilament yarn. 0.004 times, that is Furthermore, the tensile strength (TEN, in cN / dtex) of the filled multifilament yarn is...

[0006] The advantages of the yarns of the present invention are that, with similar strength efficiency, higher filler content can be achieved, thereby providing the filled multifilament yarns with further improved cut resistance or other properties provided by the filler present in the yarn, such as colorability, color strength, and density. The yarns of the present invention also have improved mechanical and physical properties. Furthermore, it has been surprisingly found that the yarns of the present invention exhibit improved operability, particularly at increased speeds, such as during coating processes or in processes involving yarn winding and / or high-speed yarn transport. It has been observed that, during the manufacture and processing of the yarns into articles, the filled multifilament yarns according to the present invention limit or prevent filament breakage and subsequent yarn breakage and / or reduce dust emissions, thus avoiding quality problems and downtime during production.

[0007] In the context of this invention, multifilament yarn, or simply yarn, is understood to refer to an elongated body comprising multiple, i.e., at least two, preferably at least five fibers. Hereinafter, a fiber is understood to be an elongated body whose length dimension is much larger than its transverse dimensions (e.g., width and thickness). The term "fiber" includes monofilaments, ribbons, strips, or bands, etc., and can have a regular or irregular cross-section. Fibers can have a continuous length, referred to in the art as filaments; or a discontinuous length, referred to in the art as constant-length fibers.

[0008] This invention relates to a filled multifilament yarn comprising:

[0009] -Intrinsic viscosity UHMWPE,

[0010] - Packing material with a number-average diameter of up to 20 μm, used in such quantities that the ratio (χ) of the packing mass to the total mass of UHMWPE and packing is between 0.02 and 0.50.

[0011] - Wherein, the tenacity (ten, in cN / dtex) of the filled monofilament in the filled multifilament yarn is: The preferred toughness of the filled monofilament is The tensile strength (TEN) of a filled multifilament yarn containing filled monofilaments can be... The filled multifilament yarns also exhibit improved strength efficiency and / or, at comparable efficiency, increased filler content, thereby providing further improved cut resistance or other properties, such as colorfastness, color strength, and density. Furthermore, the yarns exhibit improved workability, particularly at increased speeds, such as during coating processes or processes involving yarn winding and / or high-speed yarn transport. It has been observed that, during the manufacture and processing of the yarns into articles, the filled multifilament yarns according to the invention limit or prevent filament breakage and subsequent yarn breakage and / or reduce dust emissions, thus avoiding quality problems and downtime during production.

[0012] The filled multifilament yarn of the present invention comprises yarns having a certain intrinsic viscosity. UHMWPE. In this document, UHMWPE is understood as polyethylene with an intrinsic viscosity (IV) of at least 5 dL / g measured in a solution of decahydronaphthalene at 135°C. Preferably, the IV of UHMWPE is at least 6 dL / g, more preferably at least 7 dL / g, and most preferably at least 8 dL / g. Preferably, the IV is at most 20 dL / g, more preferably at most 18 dL / g, even more preferably at most 16 dL / g, and most preferably at most 14 dL / g.

[0013] The filled multifilament yarn according to the invention preferably contains 2.0 wt% to 50 wt%, more preferably 4.0 wt% to 40 wt%, even more preferably 5.0 wt% to 35 wt%, and even more preferably 6.0 wt% to 30 wt% of filler, the content being based on the total weight of the filler and UHMWPE present in the fibers of the multifilament yarn. The amount of filler can alternatively be expressed as a filler ratio χ, which is the ratio of the mass of the filler to the total mass of UHMWPE and filler present in the fibers of the multifilament yarn. Consistent with the above, the ratio χ is 0.02 to 0.50, preferably 0.04 to 0.40, even more preferably 0.05 to 0.35, and even more preferably 0.06 to 0.30.

[0014] An important aspect of this invention is the discovery that when the levels of UHMWPE and filler are carefully selected during the manufacturing process, particularly the amount of filler used in the method, such that the filler ratio (χ) is at least equal to the intrinsic viscosity of the UH used in the method,... 0.003 times, in other words Yes, it can improve the strength efficiency of UHMWPE-filled multifilament yarns. The amount of filler used in this method is substantially the same as the amount of filler in the final product (e.g., in the yarn or article). Preferably, the levels of filler and UHMWPE should be such that... More Even better Optimal Selection It was observed that the relationship between the filler ratio used in the spinning process and the intrinsic viscosity (IV) of UHMWPE unexpectedly led to a higher strength efficiency of the UHMWPE used. Filled multifilament yarns were obtained, enabling the stable production of multifilament yarns at higher filler levels, significantly higher than those described in the prior art. There is no particular limitation on the upper limit of the relationship between the intrinsic viscosity of UHMWPE used in the spinning process and the filler ratio, but the filler content and the intrinsic viscosity of UHMWPE... Should make Preferred

[0015] Careful selection of filler content and UHMWPE can provide improved strength efficiency for yarns. Strength (or toughness) efficiency should be understood herein as the strength (toughness, TEN, in cN / dtex) obtained by the multifilament yarn or the strength (ten, cN / dtex) obtained by the monofilament in the multifilament yarn divided by the intrinsic viscosity of the UHMWPE present in said yarn or monofilament. Expressed as ratios in other forms or For unfilled yarns, this efficiency typically ranges from 0.5 to 1.5, with higher efficiency being an indicator of a more optimized production process. (See Table 1 and...) Figure 1 The data shows that the presence of fillers during the production process significantly affects (i.e. reduces) strength efficiency.

[0016] The present invention now describes a multifilament yarn and method that unexpectedly outperforms the relationship between strength efficiency and filler content, i.e., the strength (toughness) obtained with varying filler content. The multifilament yarn has the following formula: Or rewritten as like Figure 1 As shown by the dashed line. Preferably, the toughness of the filled multifilament yarn is such that... More And the optimal choice exist Figure 1 The middle part is also represented by a broken line. The invention also describes the tensile strength (ten, in cN / dtex) of the filled monofilament in the filled multifilament yarn such that... The multifilament yarn containing this monofilament and the method of preparing the yarn also unexpectedly outperformed the relationship between strength efficiency and filler content, i.e., the strength (strength) obtained at different filler contents.

[0017] During the manufacturing process of the yarn of this invention, UHMWPE undergoes a combination of thermal, mechanical, and chemical degradation, resulting in a decrease in the intrinsic viscosity of UHMWPE. Therefore, the intrinsic viscosity of UHMWPE present in the yarn of this invention is... The intrinsic viscosity is different from and lower than that of UHMWPE supplied to the manufacturing process. Experiments have shown that the reduction in IV during the manufacturing process ranges from 25% to 40%, but this depends on various parameters such as polymer concentration, filler content, solvent type, and processing temperature. Therefore, in one embodiment of the invention, the multifilament yarn contains a certain amount of filler (χ) and has a certain intrinsic viscosity. UHMWPE makes Preferably, the level of the packing and the IV of the UHMWPE should be such that More preferably Even better The optimal choice makes

[0018] Further observation shows that the filled multifilament yarn according to the present invention can exhibit improved yarn property uniformity, particularly with smaller variations in fineness of individual filaments, smaller variations in toughness of individual filaments, and / or smaller variations in yarn toughness along the yarn length.

[0019] Therefore, a preferred embodiment of the present invention is a multifilament yarn according to the present invention, wherein the coefficient of variation of the linear density (dpf) between the (single) filaments of the yarn (hereinafter referred to as...) () up to 12%, of which yarn The linear density value x corresponding to 10 representative lengths is determined using Equation 1, where each length corresponds to a filament from a different random sample of the yarn.

[0020]

[0021] Where x i It is the linear density of any one of the 10 representative lengths studied, and It is the average linear density over n = 10 measured linear densities of n = 10 representative lengths. Preferably, the yarn of the present invention Less than 10%, more preferably less than 8%. This reduction... The filled multifilament yarn is obtained, for example, by the method of the present invention as described below.

[0022] Another preferred embodiment of the present invention is a multifilament yarn, wherein the coefficient of variation of the tenacity (ten) between the (single) filaments of the yarn (hereinafter referred to as...) () up to 12%, of which yarn The toughness value y is determined by Equation 2, corresponding to 10 representative lengths, where each length corresponds to a filament from a different random sample of the yarn.

[0023]

[0024] Where y i It is the toughness of any one of the 10 representative lengths studied, and It is the average toughness over n=10 measured toughness values ​​across n=10 representative lengths. Preferably, the yarn of the present invention... Less than 10%, more preferably less than 8%. This has a reduced... The filled multifilament yarn is obtained, for example, by the method of the present invention as described below.

[0025] Another preferred embodiment of the present invention is a multifilament yarn, wherein the coefficient of variation of the tensile strength (TEN) of the multifilament yarn (hereinafter referred to as...) The percentage is at most 1.0%, of which The yarn tenacity value z, corresponding to five representative yarn lengths randomly sampled from the multifilament yarn, is determined using Equation 3.

[0026]

[0027] Where z i It is the yarn tenacity of any one of the five representative yarn lengths studied, and It is the average yarn toughness over n=5 measured toughness values ​​for n=5 representative yarn lengths. Preferably, the yarn of the present invention... Less than 0.8%, more preferably less than 0.6%. This results in a reduction... The filled multifilament yarn of the value is obtained, for example, by the method of the present invention as described below. This embodiment of the invention is described by commonly reported methods. The value is used to demonstrate the commercial significance of the invention and to prove the consistency of the production process.

[0028] In the above embodiments, the representative yarn length and the representative filament length of a single filament should be understood as the length of yarn or filament from the same production period, i.e., a sample of several hundred meters during or after the production process, rather than the length spread throughout the entire (commercial) production operation. Therefore, the representative filament length of the yarn is a sample selected from a specific portion of the yarn, rather than randomly selected from different yarn portions, let alone samples selected from different yarn portions throughout the production process.

[0029] In the context of this invention, filler is understood as a component that is immiscible with UHMWPE and is substantially solid under the processing conditions of UHMWPE multifilament yarn. Such filler can affect one or more properties of the yarn, such as its density, cut resistance, color, abrasion resistance, etc. The filler may comprise or consist of particles made of a material with a hardness greater than that of a molded article measured without filler, and may be organic or inorganic. If the filler is organic, it is preferably a polymer with a melting temperature of at least 150°C, preferably at least 200°C. Preferably, the material is inorganic. In the context of this invention, inorganic material should be understood as material that has substantially no covalently bonded carbon atoms, and therefore does not include any organic materials, such as hydrocarbons, especially polymeric materials. In particular, inorganic material refers to compounds including metals, metal oxides, clays, silicates, silicates, or mixtures thereof, but also includes carbides, carbonates, cyanides, and allotropes of carbon, such as diamond, graphite, graphene, fullerenes, and carbon nanotubes. The use of fillers containing inorganic materials provides optimized secondary properties to multifilament yarns, such as abrasion resistance and cut resistance. Preferably, the inorganic materials are glass fibers, mineral fibers, metal fibers, or carbon fibers.

[0030] Preferably, the material used to produce the filler has a Mohs hardness of at least 2.5, more preferably at least 4, and most preferably at least 6. Useful materials include, but are not limited to, metals, metal oxides (e.g., alumina), metal carbides (e.g., tungsten carbide), metal nitrides, metal sulfides, metal silicates, metal silicides, metal sulfates, metal phosphates, and metal borides. Other examples include silicon dioxide and silicon carbide. Combinations of other ceramic materials and the above-mentioned materials may also be used.

[0031] The particle size, particle size distribution, particle diameter, and dosage of fillers are all important parameters for optimizing yarn properties (such as cut resistance) while obtaining uniform multifilament yarn. Fillers in granular form can be used, while powder is generally suitable. For particles without other sizes significantly larger than the particle itself, such as spherical or cubic particles, the average particle size is substantially equal to the average particle diameter, or simply diameter. In the context of this invention, unless otherwise stated, the average value is an exponential (or numerical) average. For substantially elliptical particles, such as elongated or non-spherical or anisotropic materials (e.g., needles, fibrils, or fibers), the particle size can refer to the average length dimension (L) along the long axis of the particle, while the average particle diameter, or simply diameter herein, refers to the average diameter of a cross-section perpendicular to the length direction of the elliptical shape. In cases where the cross-section of the particle is not circular, the average diameter (D) is determined by the following formula: D = 1.15 * A 1 / 2 , where A is the cross-sectional area of ​​the particle.

[0032] The appropriate particle size, diameter, and / or length depends on the process and the fineness of the multifilament yarn. However, the particles should be small enough to pass through the spinneret orifice. Sufficiently small particle sizes and diameters can be selected to avoid a significant decrease in fiber tensile properties. Particle size and diameter can have a log-normal distribution.

[0033] The average diameter of the filler is at most 20 μm, preferably at most 16 μm, and even more preferably at most 12 μm. A lower average filler diameter leads to increased yarn uniformity and fewer surface defects on the filament. A larger filler diameter results in processing difficulties and deterioration of mechanical strength.

[0034] Preferably, the average diameter of the filler is at least 0.01 μm, more preferably at least 0.1 μm, even more preferably 1 μm, and most preferably at least 3 μm. Fillers with a larger average diameter can result in optimized molding steps in the method of the present invention.

[0035] Preferably, the average diameter of the packing is at least 0.01 μm and at most 20 μm; more preferably, the average diameter of the packing is at least 0.1 μm and at most 20 μm; even more preferably, the average diameter of the packing is at least 1 μm and at most 20 μm; most preferably, the average diameter of the packing is at least 3 μm and at most 20 μm; even more preferably, the average diameter of the packing is at least 3 μm and at most 16 μm; and even more preferably, the average diameter of the packing is at least 3 μm and at most 12 μm.

[0036] Preferably, the average length (L) of the filler is at most 10,000 μm, more preferably at most 5,000 μm, and most preferably at most 3,000 μm. It has also been observed that when the average length of the filler is at most 1,000 μm, more preferably at most 750 μm, and most preferably at most 650 μm, the articles of the present invention, particularly gloves containing the filled multifilament yarn of the present invention, exhibit good flexibility. Preferably, the average length of the rigid fiber is at least 50 μm, more preferably at least 100 μm, most preferably at least 150 μm, and even more preferably at least 200 μm.

[0037] The filler present in the filled multifilament yarn can be particles with an aspect ratio (L / D) of about 1. The filler present in the filled multifilament yarn can be in the form of fibers with an aspect ratio (L / D) of at least 3, preferably at least 5, even more preferably at least 10, and more preferably at least 20. The filler in the multifilament yarn can comprise particles and / or fibers or be composed of particles and / or fibers.

[0038] Any filler known in the art can be used. Suitable fillers are commercially available, such as those used in the embodiment section of this invention. The fillers added to HPPE fibers and the methods of adding fillers to HPPE fibers are well known to those skilled in the art, and are described, for example, in documents WO9918156A1 (incorporated herein by reference), WO2008046476 (incorporated herein by reference), and WO2013149990 (incorporated herein by reference).

[0039] The aspect ratio of a filler is the ratio of its length (L) to its diameter (D). The average diameter and aspect ratio of the filler can be determined using any method known in the art, such as SEM images. To measure the diameter, an SEM image of the filler can be taken, for example, by scattering the fibers as is on a surface and measuring the diameter at 100 randomly selected locations, then calculating the arithmetic mean of the 100 values. For the aspect ratio, an SEM image of the filler (e.g., fibers) can be taken, and the length of the filler (e.g., fibers) can be measured, for example, fibers appearing on or beneath the surface of HPPE fibers. It is preferable to use backscattered electrons to create the SEM image, thus providing better contrast between the fibers and the HPPE fiber surface.

[0040] The filler can be continuous or spun fibers, particularly spun fibers. Suitable examples of spun fibers are glass or mineral fibers, which can be spun using spin spinning techniques well known to those skilled in the art. The fibers can be made into continuous filaments, which are then milled into much shorter fibers. This milling process can reduce the aspect ratio of at least a portion of the fiber. Alternatively, discontinuous filaments can be produced, for example by jet spinning, optionally followed by milling and used in the multifilament yarns of the present invention. During the production of multifilament yarns, the fibers may undergo a reduction in aspect ratio.

[0041] Carbon fibers can be used as fillers. Most preferably, carbon fibers with a diameter between 3 and 10 μm are used, more preferably between 4 and 6 μm. Articles containing carbon fibers exhibit improved electrical conductivity and are able to dissipate static electricity.

[0042] The filaments in the filled multifilament yarn, also known as monofilaments, may have a linear density of up to 20 dtex, preferably up to 15 dtex, and most preferably up to 10 dtex, because articles containing such filaments are very soft, thus providing a high level of comfort for the wearer. The fineness of the filaments is preferably at least 1 dtex, more preferably at least 2 dtex.

[0043] There is no particular limitation on the fineness of the filled multifilament yarn. For practical reasons, the fineness of the multifilament yarn can be up to 10,000 dtex, preferably up to 6,000 dtex, more preferably up to 3,000 dtex. Preferably, the fineness of the yarn is in the range of 50 to 10,000 dtex, more preferably in the range of 100 to 6,000 dtex, and most preferably in the range of 200 to 3,000 dtex, even more preferably in the range of 220 to 800 dtex, and even more preferably in the range of 100 to 2,000 dtex.

[0044] The filled multifilament yarn of the present invention is preferably high-performance polyethylene (HPPE) yarn, and preferably the tensile strength of the multifilament yarn is at least 5.0 cN / dtex, more preferably at least 7.5 cN / dtex, even more preferably at least 10.0 cN / dtex, more preferably at least 12.5 cN / dtex, even more preferably at least 15.0 cN / dtex, and most preferably at least 20.0 cN / dtex.

[0045] In the context of this invention, UHMWPE can be linear or branched, with linear polyethylene being preferred. Linear polyethylene should be understood herein to mean polyethylene having less than one side chain per 100 carbon atoms, preferably less than one side chain per 300 carbon atoms, wherein the side chain or branch typically contains at least 10 carbon atoms. The side chain can be suitably measured by FTIR. Linear polyethylene may further comprise up to 5 mol% of one or more other olefins that can be copolymerized therewith, such as propylene, 1-butene, 1-pentene, 4-methylpentene, 1-hexene, and / or 1-octene.

[0046] The filled multifilament yarns of the present invention can have higher filler levels and optimized strength efficiency, which is beneficial to the quality of articles made from said yarns. Therefore, one embodiment of the invention relates to articles comprising the filled multifilament yarns of the present invention. Articles comprising the yarns of the present invention may be, but are not limited to, products selected from: fishing lines, fishing nets, ground nets, cargo nets, curtains, kite lines, dental floss, tennis racket strings, canvas, woven fabrics, nonwoven fabrics, webbing, battery separators, medical devices, capacitors, pressure vessels, hoses, umbilical cables, automotive equipment, power transmission belts, building materials, cut-resistant articles, puncture-resistant articles, cut-resistant articles, protective gloves, composite sports equipment, skis, helmets, kayaks, canoes, bicycles and boat hulls, speaker cones, high-performance electrical insulation, radomes, sails, and geotextiles.

[0047] Fabrics containing the filled multifilament yarns according to the invention can be produced by knitting, weaving, or other methods using conventional equipment. Nonwoven fabrics can also be produced. The cut resistance of fabrics containing the yarns according to the invention can be 20% higher than that of the same fabric produced from unfilled yarns, as measured by the Ashland CutProtection Performance Test. Preferably, the cut resistance of the fabric is increased by at least 50%, more preferably by at least 100%, and even more preferably by at least 150%.

[0048] The filled multifilament yarn according to the invention is suitable for all kinds of products, such as clothing used to protect people working in the meat, metal, and timber industries from cuts. Good examples of such clothing include gloves, aprons, trousers, sleeves, and arm warmers. Other possible applications include truck side curtains and tarpaulins, soft-sided luggage, commercial linings, air cargo container curtains, and fire hose protective sleeves. Surprisingly, the yarn according to the invention is particularly suitable for use in stab-resistant products, such as those protecting against knife or ice pick stabs. An example of such a product is a police life-saving vest.

[0049] Preferably, in this type of structure, the yarn of the present invention is located on the side of the structure that is struck first by a sharp object that may be used as the initial target of the attack.

[0050] Filled multifilament yarns can be obtained by a variety of methods known in the art, such as melt spinning or gel spinning processes as described herein. Gel spinning processes are described in various publications, including EP0205960 A, EP 0213208 A1, US 4413110, GB2042414A, EP 0200547 B1, EP 0472114 B1, WO01 / 73173A1, and Advanced Fiber Spinning Technology, Ed.T. Nakajima, Woodhead Publ. Ltd (1994), ISBN 1-855-73182-7, and the references cited therein. Gel spinning is understood to include at least the following steps: spinning multifilaments from a solution of ultra-high molecular weight polyethylene in a spinning solvent; cooling the resulting filaments to form gel filaments; removing at least a portion of the spinning solvent from the gel filaments; and stretching the filaments in at least one stretching step before, during, and / or after the removal of the spinning solvent.

[0051] In the process according to the invention, any known solvent suitable for gel spinning of UHMWPE can be used; such solvents are referred to below as spinning solvents. Suitable examples of spinning solvents include aliphatic and alicyclic hydrocarbons, such as octane, nonane, decane, and paraffin, including their isomers; petroleum fractions; mineral oils; kerosene; aromatic hydrocarbons, such as toluene, xylene, and naphthalene, including their hydrogenated derivatives, such as decahydronaphthalene and tetrahydronaphthalene; halogenated hydrocarbons, such as monochlorobenzene; and cycloalkanes or cycloalkenes, such as carene, fluorene, camphene, menthol, dipentene, naphthalene, acenaphtalene, methylcyclopentadiene, tricyclodecane, 1,2,4,5-tetramethyl-1,4-cyclohexadiene, fluorenone, benzodihydroindane, tetramethyl-p-benzoquinone, ethyl fluorene, fluoranthene, and naphthenone. The gel spinning of UHMWPE can also be performed using combinations of spinning solvents listed above; for simplicity, these solvent combinations are also referred to as spinning solvents. We have found that the process of the present invention is particularly advantageous for relatively volatile solvents, such as decahydronaphthalene, tetrahydronaphthalene, and several kerosene fractions. In the most preferred embodiment, decahydronaphthalene is selected as the solvent. The spinning solvent can be removed by evaporation, extraction, or a combination of evaporation and extraction.

[0052] The present invention also relates to a method for preparing filled multifilament yarn according to the present invention, comprising the following steps:

[0053] a) Provide intrinsic viscosity UHMWPE concentrations of less than 24 dL / g, preferably less than 20 dL / g,

[0054] b) Provide fillers with an average diameter of up to 20 μm.

[0055] c) Prepare a solution of the UHMWPE in a solvent, the solution containing the filler in an amount such that the ratio (χ) of the filler mass to the total mass of UHMWPE and filler is between 0.02 and 0.50.

[0056] d) The solution obtained in step c) is spun through a porous template to form a filled multifilament yarn containing solvent.

[0057] e) Before, during, or after stretching the filled yarn to a total draw ratio of at least 20, remove at least part of the solvent from the filled yarn of step d).

[0058] To obtain the filled multifilament yarn, wherein the amount of filler is selected such that...

[0059] The selection of UHMWPE, filler, and ratio χ is preferably based on a previously preferred embodiment of the UHMWPE, filler, and ratio used to define the embodiments of the filled multifilament yarn of the present invention. Therefore, a preferred embodiment of the method of the present invention selects the ratio (χ) of the filler mass to the total mass of UHMWPE and filler as 0.04 to 0.40, or other ranges and levels described above. Another preferred embodiment of the method of the present invention selects the filler ratio χ and UHMWPE such that... Or within the preferred limitations provided above.

[0060] Standard equipment can be used for this process, preferably a twin-screw extruder, wherein the polymer is dissolved in a solvent in the first part, and fibers are fed into the extruder through a separate feed opening at the end of the first part.

[0061] Alternatively, the yarn obtained by the above method can be converted into fixed-length fibers and then these fixed-length fibers can be processed into yarn.

[0062] Furthermore, the scope of this invention also covers so-called composite yarns and products containing such yarns. Such composite yarns, for example, contain one or more monofilaments comprising filaments and / or fibers of a fixed length containing filler, and one or more additional monofilaments or yarns, wires, or filaments of glass, metal, or ceramic.

[0063] In the method for preparing filled multifilament yarn, the stretching, preferably uniaxial stretching, of the yarn can be performed using methods known in the art. Such methods include extrusion stretching and tensile stretching on suitable stretching units. To obtain increased mechanical tensile strength and stiffness, stretching can be performed in multiple steps. The first stretching step typically includes stretching to an elongation factor (also referred to as the tensile factor) of at least 1.5, preferably at least 3.0. Multi-step stretching typically yields an elongation factor of 9 for stretching temperatures up to 120°C, 25 for stretching temperatures up to 140°C, and 50 for stretching temperatures up to and above 150°C. An elongation factor of about 50 or greater can be achieved through multi-step stretching at elevated temperatures. This results in filled multifilament yarns with toughnesses ranging from 5.0 cN / dtex to 30 cN / dtex and higher. Specifically, for ultra-high molecular weight polyethylene yarns, strengths of 1.5 GPa to 1.8 GPa and higher can be obtained. The individual stretch ratios in the liquid phase, gel phase, and solid phase can be combined to express the total stretch ratio.

[0064] The filled multifilament yarn according to the invention may further comprise other fibers, which may be in the form of filaments and / or fixed-length fibers that differ from the filled filaments described herein, for example, in composition and / or shape, such as non-polymer fibers, such as glass fibers, carbon fibers, basalt fibers, metal wires or threads; and / or natural fibers, such as cotton, bamboo; and / or polymer fibers, such as polyamide fibers (e.g., nylon fibers), elastic fibers (e.g., elastic fibers), polyester fibers; and / or mixtures of these other fibers, which may be present in any proportion. Attached Figure Description

[0065] Figure 1 The relationship between strength (toughness) and filler content is shown. Detailed Implementation

[0066] The invention will be further explained through the following examples and comparative experiments, but first, methods for determining the various parameters that can be used to define the invention are described below.

[0067] method

[0068] • Yarn linear density: The fineness of the yarn is measured by weighing 100 meters of yarn. The dtex of the yarn is obtained by dividing the weight (in milligrams) by 10.

[0069] IV: The intrinsic viscosity of UHMWPE was determined according to method ASTM-D1601 / 2004. The test conditions were: dissolution time in decahydronaphthalene at 135°C for 16 hours, using 2 g / L DBPC as an antioxidant. The viscosity at zero concentration was obtained by extrapolating the viscosities measured at different concentrations.

[0070] • Tensile properties (TEN) of yarn: Toughness and modulus of multifilament yarn were defined and measured according to ASTM D885M, using fibers with a nominal rated length of 500 mm, a crosshead speed of 50% / min, and an Instron 2714 clamp (Fibre Grip D5618C). The modulus was determined as a gradient between 0.3% and 1% strain based on the measured stress-strain curve. To calculate the modulus and strength, the measured tensile force was divided by the fineness.

[0071] • Tensile properties of filaments (ten): According to the procedure of ISO 5079:1995, using fibers with a nominal rated length of 50 mm, a crosshead speed of 25 mm / min, and... A pneumatic clamp with a standard jaw surface (4*4mm) was used to define and determine the toughness of a monofilament using a Textechno's Favimat (test instrument number 37074, purchased from Textechno Herbert Stein GmbH & Co. KG, Monchengladbach, Germany). The filament was preloaded at 0.04 cN / dtex at a speed of 25 mm / min. To calculate the toughness, the measured tensile force was divided by the linear density (fineness) of the filament.

[0072] • Linear density: The linear density of the monofilament was determined according to ASTM D1577-01 on a semi-automatic microprocessor-controlled tensile testing machine (Favimat, tester number 37074, purchased from Textechno Herbert Stein GmbH & Co. KG, Monchengladbach, Germany). A representative length of monofilament was cut from the monofilament with a sharp blade and sandwiched between two small pieces of paper (4×4mm) using a... The two (4×4×2mm) jaw surfaces are manufactured together. This length is sufficient to ensure proper mounting of the monofilament, approximately 70mm.

[0073] As described above, the linear density of the monofilament length between the clamps was determined by a vibrometer by following the routine implemented in the tester software and described in the tester manual. During the measurement, the distance between the clamps was maintained at 50 mm, and the monofilament was tensioned at 0.6 cN / dtex at a speed of 2 mm / min.

[0074] • The number of alkene branches per thousand carbon atoms was determined by FTIR on a 2 mm thick pressed film, and quantification at 1375 cm⁻¹ was performed using a calibration curve based on NMR measurements. -1 The amount absorbed at the site, as in, for example, EP 0269151, particularly page 4.

[0075] • The average length and average diameter were measured using the CottonscopeHD analysis system.

[0076] • Dust emissions (based on the total amount of yarn treated, the amount of filler released during treatment, g / kg yarn) during the yarn online / treatment stage are determined as follows: during the yarn online / treatment stage, white paper is placed under the sample, and the amount of dust collected over 20 minutes is measured.

[0077] • The filler content (wt%) in the yarn was determined as the weight difference between the initial weight of the yarn and the weight of the yarn remaining after burning the polymer in the yarn (measured by weighing the ash content obtained after combustion). Combustion was carried out by heating the yarn at a temperature of 700°C.

[0078] • After weaving a fabric with 380 or 260 grams of the corresponding 440 or 220 dtex yarn per square meter, determine the cut resistance according to ISO 13997-1999.

[0079] Example

[0080] Comparative experiments A and B (CE A and CE B)

[0081] For comparative experiments CE A-1, CE A-2, and CE A-3, type A yarn was produced according to the method of Example 1 of WO2013149990: wherein... UHMWPE of 27.0 dL / g was dry-blended with 7 wt%, 10 wt%, and 15 wt% of mineral fibrils (number-average diameter 7.4 μm, average length 70 μm, Mohs hardness 3.5) sold under the trade name CF10ELS by Lapinus, NL, and then dissolved in decahydronaphthalene to achieve a total solids content (i.e., total content of polymer and filler) of 9 wt%. The resulting solution was fed into a twin-screw extruder with a 25 mm screw diameter and equipped with a gear pump. The solution was heated to 180 °C in this manner. The solution was pumped through a spinneret with 64 orifices, each 1 mm in diameter. The resulting filaments were drawn to a total maximum draw factor in the range of 170-200 and dried in a hot air furnace. After drying, the filaments were bundled into yarns and wound onto bobbins. The CE A-1 of the fiber was measured. It is 22.2 dL / g.

[0082] As described regarding yarn A, type B yarn is obtained, the difference being that... UHMWPE of 22.0 dL / g was used, and different levels of mineral fibers were employed. Filaments were obtained by stretching with a total factor ranging from 180 to 210. Fiber CE B-2 The measured value was 15.0 dL / g.

[0083] Subsequently, tensile measurements were performed on yarns A and B. Table 1 provides detailed information on the fiber composition, processing, and properties of yarns CE A and CE B.

[0084] Table 1

[0085]

[0086] Example 1 (Ex.1)

[0087] Yarns Ex 1-1 and 1-2 were obtained as described in yarn A, differing in that they used UHMWPE with an IV of 17.0 dL / g and fillers of 14.3 wt% and 6.5 wt%, respectively. Filaments were obtained by stretching with a total factor in the range of 200 to 210. The polymer IV in the obtained yarns was 11.3 dL / g.

[0088] Example 2 (Ex.2)

[0089] Yarns 2-1 and 2-2 were obtained using the same method as that used for yarn CE B, except that 35 and 35.2% by weight of filler were used, respectively. The draw ratios were 200-210, respectively. The polymer IV in the final yarns was 15.0 dL / g.

[0090] Example 3 (Ex.3)

[0091] Yarns 3-1 and 3-2 were obtained using the same method as that used for yarn CE B, except that a different type of filler was used. Morgan AW03 Alphawool filler grade (number-average diameter 3.9 μm, average length 70 μm, Mohs hardness 9) was used; yarn 3-1 used 15 wt% filler, and yarn 3-2 used 25 wt% filler. The draw ratios were 206-209, respectively. The final yarns had a polymer IV of 14.2 dL / g.

[0092] Table 2

[0093]

[0094] The coefficients of variation for yarn samples CE B-2 and Ex 1-2 have been measured. The results are reported in Table 3.

[0095] Table 3

[0096]

Claims

1. A filled multifilament yarn comprising: - intrinsic viscosity of UHMWPE, - a filler having a number average diameter of at least 1 pm and at most 20 pm and an aspect ratio of at least 3, in an amount such that the ratio χ of the mass of the filler to the total mass of the UHMWPE and the filler is between 0.04 and 0.50, - wherein The tenacity TEN of the filled multifilament yarn in cN / dtex is 2. A filled multifilament yarn comprising: - intrinsic viscosity of UHMWPE, - fillers having a number average diameter of at least 1 μm and at most 20 μm and an aspect ratio of at least 3, in an amount such that the ratio χ of the mass of the fillers to the total mass of UHMWPE and fillers is between 0.04 and 0.50, wherein, the tenacity of the filled monofilament in the filled multifilament yarn in cN / dtex is 3. The filled multifilament yarn according to claim 1 or 2, wherein the ratio χ of the mass of the filler to the total mass of the UHMWPE and the filler is between 0.05 and 0.

40.

4. The filled multifilament yarn according to claim 3, wherein, the ratio χ of the mass of the filler to the total mass of the UHMWPE and the filler is between 0.06 and 0.

30.

5. The filled multifilament yarn according to claim 1 or 2, wherein, 6. The filled multifilament yarn according to claim 1 or 2, wherein, The tenacity of the yarn is at least 5.0 cN / dtex.

7. The filled multifilament yarn according to claim 6, wherein, The tenacity of the yarn is between 5.0 cN / dtex and 30 cN / dtex.

8. The filled multifilament yarn according to claim 1 or 2, wherein, The average diameter of the filler is at least 3 pm.

9. The filled multifilament yarn according to claim 1 or 2, wherein, The average diameter of the filler is at most 16 pm.

10. The filled multifilament yarn according to claim 1 or 2, wherein, The aspect ratio of the filler is at least 5.

11. The filled multifilament yam according to claim 1 or 2, wherein, The aspect ratio of the filler is at least 10.

12. The filled multifilament yam according to claim 1 or 2, wherein, The average length of the filler is at most 1000 pm.

13. The filled multifilament yam according to claim 1 or 2, wherein, The filler comprises or consists of a material selected from the group comprising: a metal, a metal oxide, a clay, a silica, a silicate or mixtures thereof, a carbide, a carbonate, a cyanide and a carbon allotrope.

14. The filled multifilament yam according to claim 1 or 2, wherein, The filler comprises or consists of glass fibers, mineral fibers, metal fibers or carbon fibers.

15. The filled multifilament yam according to claim 1 or 2, wherein, The filler comprises or consists of mineral fibers.

16. The filled multifilament yam according to claim 1 or 2, wherein, The material used to produce the filler has a Mohs hardness of at least 2.

5.

17. The filled multifilament yam according to claim 1 or 2, wherein, The filaments in the filled multifilament yarn have a linear density of at most 10 dtex.

18. The filled multifilament yam according to claim 1 or 2, wherein, The filled multifilament yarn has a titre in the range of 50 to 800 dtex.

19. The filled multifilament yam according to claim 1 or 2, wherein, at most 18 dL / g.

20. The filled multifilament yam according to claim 1 or 2, wherein, at most 14 dL / g.

21. A process for the preparation of a filled multifilament yarn according to any of the preceding claims, comprising the steps of: a) providing an intrinsic viscosity UHMWPE of less than 20 dL / g, b) providing a filler having a diameter of at least 1 pm and at most 20 pm and an aspect ratio of at least 3, c) preparing a solution of the UHMWPE in a solvent, the solution comprising the filler in an amount such that the ratio χ of the mass of the filler to the total mass of the UHMWPE and the filler is between 0.04 and 0.50, d) spinning the solution obtained in step c) through a multi- hole die to form a filled multifilament yarn comprising the solvent, e) removing at least partially the solvent from the filled yarn of step d) before, during or after stretching the filled yarn at a total draw ratio of at least 20, to obtain the filled multifilament yarn, wherein the amount of the filler is selected so that 22. The method of claim 21, wherein, the ratio χ is between 0.05 and 0.

40.

23. The method of claim 21, wherein, the ratio χ is between 0.06 and 0.

30.

24. The method of claim 21, wherein, The average length of the filler is at most 1000 pm.

25. The method of claim 21, wherein, The filler comprises or consists of a material selected from the group comprising: a metal, a metal oxide, a clay, a silica, a silicate or mixtures thereof, a carbide, a carbonate, a cyanide and a carbon allotrope. The filler comprises or consists of glass fibers, mineral fibers, metal fibers or carbon fibers.

26. The method of claim 21, wherein, The filler comprises or consists of mineral fibers.

27. The method of claim 21, wherein, The material used to produce the filler has a Mohs hardness of at least 2.

5.

28. The method of claim 21, wherein, ​ 29. The method of claim 21, wherein, The filaments in the filled multifilament yarn have a linear density of at most 10 dtex.

30. The method of claim 21, wherein, 31. An article comprising the filled multifilament yarn of any one of claims 1 to 20.

32. The article of claim 31, wherein, The article is selected from the group consisting of fishing line, fishing net, ground net, cargo net, curtain, kite line, dental floss, tennis racket string, sailcloth, woven cloth, nonwoven cloth, braid, battery separator, medical device, capacitor, pressure vessel, hose, umbilical cable, automotive device, power transmission belt, construction material, cut resistant article, stab resistant article, cut and slash resistant article, protective glove, composite sports equipment, ski, helmet, kayak, canoe, bicycle and boat hull, loudspeaker cone, antenna radome, sail and geotextile.

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