WO2018181309A1 - Polyethylene fiber and product using same - Google Patents

Polyethylene fiber and product using same Download PDF

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Publication number
WO2018181309A1
WO2018181309A1 PCT/JP2018/012428 JP2018012428W WO2018181309A1 WO 2018181309 A1 WO2018181309 A1 WO 2018181309A1 JP 2018012428 W JP2018012428 W JP 2018012428W WO 2018181309 A1 WO2018181309 A1 WO 2018181309A1
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WIPO (PCT)
Prior art keywords
polyethylene fiber
fiber
polyethylene
less
hard particles
Prior art date
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PCT/JP2018/012428
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French (fr)
Japanese (ja)
Inventor
優二 池田
佳史 丸岡
奥山　幸成
Original Assignee
東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2019509885A priority Critical patent/JP6996555B2/en
Publication of WO2018181309A1 publication Critical patent/WO2018181309A1/en

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Classifications

    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
    • D—TEXTILES; PAPER
    • D03—WEAVING
    • D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
    • D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
    • D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
    • D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
    • D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads

Definitions

  • the present invention relates to a polyethylene fiber excellent in cut resistance and a product containing the fiber.
  • JP 2004-019050 A Special table 2010-5007026 gazette Special table 2015-518528
  • Patent Documents 2 and 3 are used for melt spinning, there is a problem that the added hard fiber clogs the filtration filter in the spinning process, and the productivity is remarkably reduced.
  • an object of the present invention is to provide a novel polyethylene fiber having excellent cut resistance and high productivity, and a product using the fiber.
  • this invention consists of the following structures.
  • 3. The polyethylene fiber according to 1 or 2 above, wherein in the cut resistance evaluation according to EN 388, which is a European standard, the level of cut resistance when a fabric of 350 g / m 2 ⁇ 35 g / m 2 is 4 or more. 4).
  • a product comprising the polyethylene fiber according to any one of 1 to 3 above.
  • the polyethylene fiber of the present invention has an intrinsic viscosity [ ⁇ ] of 0.8 dL / g or more and less than 4.9 dL / g, preferably 1.0 dL / g or more and 4.0 dL / g or less, more preferably 1 It is not less than 2 dL / g and not more than 2.5 dL / g.
  • the intrinsic viscosity By setting the intrinsic viscosity to less than 4.9 dL / g, it becomes easy to produce yarn by melt spinning, and it is not necessary to produce yarn by so-called gel spinning. Therefore, it is advantageous in terms of suppressing the manufacturing cost and simplifying the work process. Furthermore, since no solvent is used during production, the impact on workers and the environment is small. In addition, since there is no residual solvent in the product fiber, there is no adverse effect of the solvent on the product user. Further, by setting the intrinsic viscosity to 0.8 dL / g or more, it is possible to reduce the number of structural defects in the fiber due to a decrease in molecular end groups of polyethylene. Therefore, the mechanical properties of the fiber such as strength and elastic modulus and cut resistance can be improved.
  • the preferred weight average molecular weight (Mw) of the polyethylene fiber according to the present invention is 50,000 to 600,000.
  • Mw weight average molecular weight
  • the Mw is 600,000 or less, yarn production by the melt spinning method is facilitated, and it is not necessary to produce yarn by so-called gel spinning or the like. Therefore, it is advantageous in terms of suppressing the manufacturing cost and simplifying the work process.
  • no solvent is used during production, the impact on workers and the environment is small.
  • there is no residual solvent in the product fiber there is no adverse effect of the solvent on the product user.
  • the repeating unit may be substantially ethylene, and the ethylene and a small amount of other monomers; for example, ⁇ -olefin, acrylic acid and its derivatives, methacrylic acid and its derivatives, vinylsilane and its It may be a copolymer with a derivative or the like.
  • these copolymers, or a copolymer of an ethylene homopolymer and the above copolymer, or a blend of an ethylene homopolymer and another homopolymer such as an ⁇ -olefin may be used.
  • inclusion of a short chain or long chain branch to some extent by using a copolymer with an ⁇ -olefin such as propylene and butene-1 is advantageous in producing the polyethylene fiber of the present invention, particularly in spinning and drawing. Since the above stability is provided, it is more preferable. However, if the content other than ethylene is excessively increased, it becomes a hindrance to stretching, so from the viewpoint of obtaining polyethylene fibers with high strength and high elastic modulus, the proportion of components other than ethylene in the total polyethylene fibers is the monomer.
  • the unit is preferably 0.2 mol% or less, more preferably 0.1 mol% or less.
  • the polyethylene in the present invention may be composed of ethylene alone.
  • the polyethylene fiber of the present invention contains a plurality of hard particles having an aspect ratio of less than 3.
  • the aspect ratio of the hard particles contained in the polyethylene fiber of the present invention may be less than 3, but is preferably 1 or more and 2 or less.
  • the aspect ratio of the hard particle represents a particle shape defined by a value calculated based on JIS 8900-1 (that is, in the microscopic image of the particle, (maximum major axis / width orthogonal to the maximum major axis)). Index).
  • JIS 8900-1 that is, in the microscopic image of the particle, (maximum major axis / width orthogonal to the maximum major axis)). Index).
  • the method for measuring the aspect ratio of the hard particles will be described in detail in the column of Examples described later. If the aspect ratio of the hard particles is 3 or more, there is a concern that the filtration filter is clogged during spinning and the productivity of the fiber is remarkably lowered, which is not preferable.
  • hard particles means those that are difficult to aggregate in a polymer (polyethylene fiber) such as silica and alumina. Therefore, examples of the main raw material of the hard particles contained in the polyethylene fiber of the present invention include silica and alumina, and among these, those made of silica are preferable.
  • the shape of the plurality of hard particles contained in the polyethylene fiber of the present invention is preferably true spherical or oblate.
  • the filtration filter is clogged at the time of spinning, and it is feared that the productivity of the fiber will be remarkably lowered.
  • the plurality of hard particles contained in the polyethylene fiber of the present invention may be used as they are, or those having a modified surface may be used.
  • a modified surface may be used.
  • dimethyl group, epoxy group, hexyl group, phenyl group, methacryl group, vinyl group, isocyanate group and the like can be applied.
  • the average particle diameter of the plurality of hard particles contained in the polyethylene fiber of the present invention is 3.0 ⁇ m or more, preferably 5.0 ⁇ m or more.
  • the average particle diameter of the hard particles is determined by measuring the major axis (maximum major axis) and minor axis (maximum minor axis) for each of the ten hard particles by the same method as the aspect ratio of the hard particles described later. The average particle diameter was calculated by calculating the average value of the total of the maximum short diameter (20).
  • the content of the plurality of hard particles contained in the entire polyethylene fiber of the present invention is 5% by mass or more, preferably 10% by mass or more and 30% by mass or less.
  • the content of the hard particles is less than 5% by mass, the contact frequency between the hard particles present in the fiber and the blade is low, and it is difficult to obtain the effect of improving cut resistance.
  • the hard particles When spinning the polyethylene fiber of the present invention, the hard particles may be used as a master batch kneaded with polyethylene in advance, or may be used alone.
  • the fiber diameter per single yarn is preferably 45 ⁇ m or less, and more preferably 37 ⁇ m or less.
  • the fiber diameter per single yarn can be calculated
  • the lower limit is not particularly limited from the above viewpoint, but in consideration of productivity and the like, it is preferably approximately 10 ⁇ m or more.
  • the polyethylene fiber of the present invention may contain an antioxidant, a lubricant, an antistatic agent, a peroxide, a pigment, a dye, a dispersant and the like as an additive in addition to the hard particles.
  • the average strength of the polyethylene fiber of the present invention is desirably 4 cN / dtex or more, and preferably 6 cN / dtex or more. When the average strength is less than 4 cN / dtex, the strength may be insufficient when an application product is manufactured.
  • the upper limit is not particularly limited from the above viewpoint, but in consideration of productivity such as spinnability, it is preferably about 50 cN / dtex or less.
  • the polyethylene fiber of the present invention may apply a core-sheath structure, or may have an irregular shape such as a star shape, a triangle shape, or a hollow shape.
  • a melt spinning method for example, a melt spinning method can be used.
  • the gel spinning method which is one of the methods for producing ultra-high molecular weight polyethylene fibers using a solvent, high-strength polyethylene fibers can be obtained. The impact on the health and environment of manufacturing workers, and the impact of solvents remaining in the fiber on the health of product users.
  • melt spinning method for the polyethylene fiber of the present invention.
  • the method for producing the polyethylene fiber of the present invention using the melt spinning method will be specifically described below.
  • the method of manufacturing the polyethylene fiber of this invention is not limited to the following processes and numerical values.
  • the pressure of the inert gas supplied into the extruder is preferably 0.001 MPa or more and 0.8 MPa or less, more preferably 0.05 MPa or more, 0.7 MPa or less, and further preferably 0.1 MPa or more. , 0.5 MPa or less is recommended.
  • it discharges with the discharge amount of 0.1 g / min or more from the spinning nozzle which has a diameter of 0.3 mm or more and 2.5 mm or less, preferably 0.5 mm or more and 1.5 mm or less.
  • the discharge linear velocity when discharging the molten resin from the spinning nozzle is preferably 10 cm / min or more and 120 cm / min or less.
  • a more preferable discharge linear velocity is 20 cm / min or more and 110 cm / min or less, and further preferably 30 cm / min or more and 100 cm / min or less.
  • the discharged yarn is cooled to 5 to 40 ° C. and then wound up at 50 m / min or more, and the obtained undrawn yarn is further obtained at a temperature not higher than the melting point of the undrawn yarn at least once.
  • Stretch. Specifically, the stretching process is preferably performed in two or more stages.
  • the initial drawing temperature is preferably less than the crystal dispersion temperature of the undrawn yarn, more preferably 80 ° C. or less, and even more preferably 75 ° C. or less.
  • the undrawn yarn is preferably drawn at a crystal dispersion temperature or higher and a melting point or lower, preferably 90 ° C. or higher and lower than the melting point.
  • the crystal dispersion temperature is a temperature measured by the following method.
  • the solid viscoelasticity is measured using a solid viscoelasticity measuring apparatus (TA Instruments, “DMA Q800”).
  • TA Universal Analysis for analysis of the measured solid viscoelastic modulus, “TA Universal Analysis” (manufactured by TA Instruments) is used.
  • the measurement start temperature is ⁇ 140 ° C.
  • the measurement end temperature is 140 ° C.
  • the rate of temperature rise is 1.0 ° C./min.
  • the strain amount is 0.04%
  • the initial load at the start of measurement is 0.05 cN / dtex.
  • the measurement frequency is 11 Hz.
  • the stretching ratio is preferably 6 times or more in total, more preferably 8 times or more, and further preferably 10 times or more. Moreover, it is preferable that a draw ratio is 30 times or less in total, More preferably, it is 25 times or less, More preferably, it is 20 times or less.
  • the first stage stretching ratio is preferably 1.05 times or more and 4.00 times or less, and the second stage stretching.
  • the magnification is preferably 2.5 times or more and 15 times or less.
  • a product using the polyethylene fiber of the present invention for example, a woven or knitted fabric, is suitably used as a cut resistant woven or knitted fabric, a glove, a vest and the like.
  • a glove is obtained by hanging the polyethylene fiber of the present invention on a knitting machine.
  • the polyethylene fiber of the present invention can be applied to a loom to obtain a fabric, which can be cut and sewn to form a glove.
  • the glove thus obtained can be used as a glove as it is, for example, but if necessary, a resin can be applied to impart anti-slip properties.
  • a resin can be applied to impart anti-slip properties.
  • the resin used here include urethane-based and ethylene-based resins, but are not particularly limited.
  • the polyethylene fiber of the present invention is excellent in cut resistance, as can be seen from the examples described later.
  • the level of cut resistance when a fabric of 350 g / m 2 ⁇ 35 g / m 2 is satisfied satisfies 4 or more. Therefore, the products using the polyethylene fiber of the present invention include tapes, ropes, nets, fishing lines, material protection covers, sheets, kite threads, bowstrings, sailcloths, in addition to the above-mentioned knitted and knitted fabrics such as gloves and vests It is suitably used as a curtain material.
  • the product using the polyethylene fiber of the present invention is not limited to these.
  • the polyethylene fiber of the present invention has high cut resistance
  • a material utilizing the cut resistance such as a fiber reinforced resin reinforcing material, a cement reinforcing material, a fiber reinforced rubber reinforcing material, or an environment change is assumed.
  • the polyethylene fiber of the present invention is not limited to these materials, and can be used as various materials.
  • Intrinsic viscosity [ ⁇ ] Intrinsic viscosity was measured using an Ubbelohde capillary viscosity tube using decalin heated to 135 ° C. as a solvent. Specifically, the specific viscosities of various dilute solutions were measured, and the intrinsic viscosity was determined from the extrapolation point to the origin of the straight line obtained by the least square approximation of the plot with respect to the concentration of the viscosity.
  • the fiber sample was divided or cut into approximately 5 mm lengths, 1% by mass of an antioxidant (Yoshinox BHT (registered trademark), manufactured by Yoshitomi Pharmaceutical) was added to the polymer, and the temperature was measured at 135 ° C for 4 hours.
  • the measurement solution was prepared by stirring and dissolving.
  • the aspect ratio of hard particles was determined by using SEM photographs.
  • the fiber sample was placed in a crucible, burned until it became ash and carbonaceous material, then placed in an electric furnace and heated above the decomposition temperature of polyethylene. When the carbonaceous material became completely ash, it was allowed to cool in a desiccator to obtain ash.
  • the aspect ratio was calculated by obtaining the average value.
  • grain has high hardness, it is thought that a shape does not change even if it heats.
  • Hard particle content was determined by using ash measurement based on JIS-2272.
  • a fiber sample (1.0 g) was placed in a crucible, burned until it became ash and carbonaceous material, then placed in an electric furnace and heated above the decomposition temperature of polyethylene. After the carbonaceous material was completely turned into ash, it was allowed to cool in a desiccator and the mass was measured to determine the ash content. Based on the mass ratio of the ash content to the total of the obtained ash content and the fiber content, the hard particle content was determined.
  • Cut resistance was measured based on the EN388 method, which is a European standard, using an apparatus of a coup tester (manufactured by SODMAT). Specifically, a cylindrical knitted fabric having a basis weight of 350 g / m 2 ⁇ 35 g / m 2 was produced using a circular knitting machine manufactured by Shima Seiki Seisakusho using each polyethylene fiber produced by the method described later. The index value of the obtained tubular knitted coup tester was calculated as follows to evaluate cut resistance.
  • an aluminum foil was provided on the sample stage of the above apparatus, and a knitted sample was placed thereon.
  • the circular blade provided in the apparatus was run on the sample while rotating in the direction opposite to the running direction.
  • the cut resistance test was completed by energizing the circular blade and the aluminum foil in contact with each other. While the circular blade was operating, the counter attached to the device counted and recorded the value.
  • a plain woven cotton fabric having a basis weight of about 200 g / m 2 was used as a blank, and the cut level of a knitted sample was evaluated.
  • the test was started from a blank, the blank test and the knitted sample test were alternately performed, the knitted sample was tested five times, and finally the sixth blank was tested to complete one set of tests.
  • Five sets of the above test were conducted, and the average index value (index value) of the five sets was used as a substitute evaluation for cut resistance. A higher index value means better cut resistance. In this embodiment, the index value level of 4 or higher was regarded as acceptable.
  • index value is calculated by the following formula.
  • A (count value of cotton cloth before sample test + count value of cotton cloth after sample test) / 2
  • Index value (sample count value + A) / A
  • the cutter used for the evaluation of cut resistance is ⁇ 45 mm for L-type rotary cutter manufactured by OLFA Corporation.
  • the material was SKS-7 tungsten steel, and the blade thickness was 0.3 mm.
  • the load applied at the time of the test was 3.14N (320 gf).
  • Example 1 A blend polymer was prepared by mixing 88% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.4 and an average particle diameter of 3 ⁇ m.
  • the aspect ratio of the hard particles was an average of 10 particles as described above, and the range thereof was 1.1 to 2.3.
  • This blend polymer was supplied to an extruder, melted at 280 ° C., and discharged from a spinneret having an orifice diameter of 0.8 mm and 30 H at a nozzle surface temperature of 288 ° C. at a single hole discharge rate of 0.32 g / min.
  • the discharged yarn was allowed to pass through a 10 cm warming section, and then cooled by quenching at 18 ° C. and 0.5 m / sec, and then wound into a cheese shape at a spinning speed of 200 m / min to obtain an undrawn yarn.
  • the undrawn yarn was wound three times between two drive rolls, then heated with hot air at 100 ° C. and wound up at the maximum draw ratio that could be stably drawn to obtain a drawn yarn.
  • the drawn yarns were combined so as to be 880 dtex ⁇ 88 dtex as a whole, and the polyethylene fiber of Example 1 was obtained. Using the obtained polyethylene fiber, a tubular knitted fabric was produced by the above-described method, and cut resistance was evaluated. These results are shown in Table 1. In the following examples and comparative examples including this example, the drawn yarns were combined so as to have a desired dtex.
  • Example 2 An undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 ⁇ m was used under the conditions of Example 1. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and cylindrical knitted fabric of Example 2 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
  • Example 3 In the conditions of Example 1, 95% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 5% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 ⁇ m are used.
  • An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 3 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
  • Example 4 An undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 15 ⁇ m was used under the conditions of Example 1. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 4 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
  • Example 5 An undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of alumina particles (hard particles) having an aspect ratio of 1.6 and an average particle diameter of 7 ⁇ m was used under the conditions of Example 1. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and tubular knitted fabric of Example 5 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
  • Example 1 Under the conditions of Example 1, 80% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 20% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 2 ⁇ m are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and cylindrical knitted fabric of Comparative Example 1 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
  • Example 2 Under the conditions of Example 1, a blend polymer was prepared using 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 17 ⁇ m. The yarn could not be obtained.
  • Example 3 (Comparative Example 3) In the conditions of Example 1, 97% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 3% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 ⁇ m are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and tubular knitted fabric of Comparative Example 3 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
  • Example 4 Under the conditions of Example 1, 88% by mass of polyethylene pellets having an intrinsic viscosity of 5.5 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 ⁇ m were mixed. Thus, a blend polymer was produced, but the polymer and hard particles were not mixed and an undrawn yarn could not be obtained.
  • Example 5 Under the conditions of Example 1, 88% by mass of polyethylene pellets having an intrinsic viscosity of 0.5 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 ⁇ m are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and cylindrical knitted fabric of Comparative Example 5 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
  • Example 6 (Comparative Example 6) Under the conditions of Example 1, a blend polymer was produced using 12% by mass of silica particles (hard particles) having an aspect ratio of 18 and an average particle diameter of 7 ⁇ m. However, clogging occurred during spinning, and undrawn yarn was Cann't get.
  • the polyethylene fibers of Examples 1 to 5 specifically, the intrinsic viscosity is 0.8 dL / g or more and less than 4.9 dL / g, the aspect ratio is less than 3, and the average particle diameter is 3
  • a cylindrical knitted fabric using polyethylene fibers containing a plurality of hard particles of 0.0 ⁇ m or more and 15.0 ⁇ m or less has a high index value, that is, a high level of cut resistance.
  • the comparison between Examples 1 to 5 and Comparative Examples 1 to 6 shows that the polyethylene fibers satisfying the requirements of the present invention are excellent in cut resistance.
  • the polyethylene fiber of the present invention has high cut resistance, it can be used for cut-resistant woven or knitted fabrics utilizing the cut resistance, such as gloves and vests.
  • the polyethylene fiber alone as a tape, rope, net, fishing line, material protective cover, sheet, kite thread, bowstring, sail cloth, curtain material, protective material, bulletproof material, medical suture, artificial tendon, artificial muscle It can be used for industrial materials such as fiber reinforced resin reinforcing materials, cement reinforcing materials, fiber reinforced rubber reinforcing materials, machine tool parts, battery separators, and chemical filters.
  • the polyethylene fiber of the present invention can exhibit excellent performance and can be widely applied, it can greatly contribute to the industry.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Knitting Of Fabric (AREA)

Abstract

Provided are a novel polyethylene fiber having excellent cut resistance, and a product including the polyethylene fiber. This polyethylene fiber comprises polyethylene having intrinsic viscosity [η] of at least 0.8 dL/g and no more than 4.9 dL/g, hard particles having an aspect ratio less than 3 and an average particle diameter of 3.0-15.0 μm being contained in an amount of 5 mass% of the polyethylene fiber.

Description

ポリエチレン繊維、およびそれを用いた製品Polyethylene fiber and products using the same
　本発明は、耐切創性に優れたポリエチレン繊維および該繊維を含む製品に関する。 The present invention relates to a polyethylene fiber excellent in cut resistance and a product containing the fiber.
　従来、天然繊維の綿や一般的な有機繊維が耐切創性素材として用いられてきた。また、それらの繊維などを編みあげた手袋が耐切創性を必要とする分野で多く用いられてきた。そこで耐切創性機能の付与として、アラミド繊維などの高強度繊維の紡績糸からなる編物や織物などが考案されてきた。しかしながら、これらは、毛抜けや耐久性の観点で不満が見受けられた。一方、別の手段として、金属繊維を有機繊維や天然繊維と合わせて用いることにより耐切創性を向上させる試みが行われている。しかしながら、金属繊維を合わせることにより、風合いが堅くなり、柔軟性が損なわれるという問題がある。 Conventionally, natural fiber cotton and general organic fibers have been used as cut resistant materials. In addition, gloves made of these fibers have been used in many fields that require cut resistance. Therefore, knitted fabrics and woven fabrics made of spun yarns of high-strength fibers such as aramid fibers have been devised to give cut resistance. However, these were unsatisfactory in terms of hair loss and durability. On the other hand, as another means, attempts have been made to improve cut resistance by using metal fibers in combination with organic fibers or natural fibers. However, by combining metal fibers, there is a problem that the texture becomes stiff and the flexibility is impaired.
　上記の問題を解決するため、重量平均分子量（Ｍｗ）、及び重量平均分子量と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）を規定した、耐切創性に優れるポリエチレン繊維の技術が知られている（例えば、特許文献１を参照）。 In order to solve the above problems, a technology of polyethylene fiber excellent in cut resistance, in which the weight average molecular weight (Mw) and the ratio of the weight average molecular weight to the number average molecular weight (Mn) (Mw / Mn) are defined, is known. (For example, refer to Patent Document 1).
　また、硬質繊維を含む糸により耐切創性に優れる超高分子量ポリエチレン繊維の技術が知られている（例えば、特許文献２および３を参照）。 Also, a technique of ultra high molecular weight polyethylene fiber that is excellent in cut resistance due to a yarn containing hard fibers is known (see, for example, Patent Documents 2 and 3).
特開２００４－０１９０５０号公報JP 2004-019050 A 特表２０１０－５０７０２６号公報Special table 2010-5007026 gazette 特表２０１５－５１８５２８号公報Special table 2015-518528
　しかし、近年安全意識の高まりから、従来よりも耐切創性の高い素材が求められている。また、特許文献２や３に開示の技術を溶融紡糸に利用すると、添加する硬質繊維が紡糸工程における濾過フィルターを目詰まりさせ、生産性を著しく低下させるという問題がある。 However, in recent years, materials with higher cut resistance than ever before have been demanded due to an increase in safety awareness. Further, when the techniques disclosed in Patent Documents 2 and 3 are used for melt spinning, there is a problem that the added hard fiber clogs the filtration filter in the spinning process, and the productivity is remarkably reduced.
　そこで、本発明は、かかる従来技術の課題を解決するためになされた。すなわち、本発明の目的は、優れた耐切創性を有し、生産性の高い新規なポリエチレン繊維、および該繊維を用いた製品を提供することにある。 Therefore, the present invention has been made to solve the problems of the prior art. That is, an object of the present invention is to provide a novel polyethylene fiber having excellent cut resistance and high productivity, and a product using the fiber.
　本発明者らは鋭意検討した結果、以下に示す手段により、上記課題を解決できることを見出し、本発明を完成するに到った。すなわち、本発明は、以下の構成からなる。 As a result of intensive studies, the present inventors have found that the above problems can be solved by the following means, and have completed the present invention. That is, this invention consists of the following structures.
１．極限粘度［η］が０．８ｄＬ／ｇ以上、４．９ｄＬ／ｇ未満のポリエチレンからなる繊維であり、アスペクト比が３未満であり、平均粒子径が３．０μｍ以上１５.０μｍ以下の硬質粒子を、ポリエチレン繊維中に５質量％以上含有することを特徴とするポリエチレン繊維。
２．上記硬質粒子は、シリカまたはアルミナである上記１に記載のポリエチレン繊維。
３．ヨーロッパ規格であるＥＮ３８８による耐切創性評価において、３５０ｇ／ｍ2±３５ｇ／ｍ2の布帛にした場合の耐切創性のレベルが４以上である上記１または２に記載のポリエチレン繊維。
４．上記１から３のいずれか１つに記載のポリエチレン繊維を含むことを特徴とする製品。 1. Hard particles having an intrinsic viscosity [η] of 0.8 dL / g or more and less than 4.9 dL / g of polyethylene, an aspect ratio of less than 3, and an average particle size of 3.0 μm or more and 15.0 μm or less Is contained in polyethylene fiber in an amount of 5% by mass or more.
2. 2. The polyethylene fiber according to 1 above, wherein the hard particles are silica or alumina.
3. 3. The polyethylene fiber according to 1 or 2 above, wherein in the cut resistance evaluation according to EN 388, which is a European standard, the level of cut resistance when a fabric of 350 g / m 2 ± 35 g / m 2 is 4 or more.
4). A product comprising the polyethylene fiber according to any one of 1 to 3 above.
　本発明により、優れた耐切創性を有し、生産性の高いポリエチレン繊維、および該繊維を用いた製品を提供することができる。 According to the present invention, it is possible to provide a polyethylene fiber having excellent cut resistance and high productivity, and a product using the fiber.
　以下、本発明を詳述する。
　本発明のポリエチレン繊維は、その極限粘度［η］が０．８ｄＬ／ｇ以上、４．９ｄＬ／ｇ未満であり、好ましくは１．０ｄＬ／ｇ以上、４．０ｄＬ／ｇ以下、更に好ましくは１．２ｄＬ／ｇ以上、２．５ｄＬ／ｇ以下である。 The present invention is described in detail below.
The polyethylene fiber of the present invention has an intrinsic viscosity [η] of 0.8 dL / g or more and less than 4.9 dL / g, preferably 1.0 dL / g or more and 4.0 dL / g or less, more preferably 1 It is not less than 2 dL / g and not more than 2.5 dL / g.
　極限粘度を４．９ｄＬ／ｇ未満とすることにより、溶融紡糸法での製糸が容易になり、いわゆるゲル紡糸等で製糸する必要がない。そのため、製造コストの抑制、作業工程の簡略化の点で優位である。さらに、製造時に溶剤を用いないため、作業者や環境への影響も小さい。また製品となった繊維中の残留溶剤も存在しないため製品使用者に対する溶媒の悪影響がない。また、極限粘度を０．８ｄＬ／ｇ以上とすることにより、ポリエチレンの分子末端基の減少により、繊維中の構造欠陥数を減少させることができる。そのため、強度や弾性率等の繊維の力学物性や耐切創性能を向上させることができる。 By setting the intrinsic viscosity to less than 4.9 dL / g, it becomes easy to produce yarn by melt spinning, and it is not necessary to produce yarn by so-called gel spinning. Therefore, it is advantageous in terms of suppressing the manufacturing cost and simplifying the work process. Furthermore, since no solvent is used during production, the impact on workers and the environment is small. In addition, since there is no residual solvent in the product fiber, there is no adverse effect of the solvent on the product user. Further, by setting the intrinsic viscosity to 0.8 dL / g or more, it is possible to reduce the number of structural defects in the fiber due to a decrease in molecular end groups of polyethylene. Therefore, the mechanical properties of the fiber such as strength and elastic modulus and cut resistance can be improved.
　また本発明に係るポリエチレン繊維の好ましい重量平均分子量（Ｍｗ）は５００００～６０００００である。Ｍｗを５００００以上とすることにより、ポリエチレンの分子末端基の減少により、繊維中の構造欠陥数を減少させることができる。そのため、強度や弾性率等の繊維の力学物性や耐切創性能が向上する。一方、Ｍｗを６０００００以下とすることにより、溶融紡糸法での製糸が容易になり、いわゆるゲル紡糸等で製糸する必要がない。そのため、製造コストの抑制、作業工程の簡略化の点で優位である。さらに、製造時に溶剤を用いないため、作業者や環境への影響も小さい。また製品となった繊維中の残留溶剤も存在しないため製品使用者に対する溶媒の悪影響がない。 Further, the preferred weight average molecular weight (Mw) of the polyethylene fiber according to the present invention is 50,000 to 600,000. By setting Mw to 50000 or more, the number of structural defects in the fiber can be reduced due to a decrease in molecular end groups of polyethylene. For this reason, the mechanical properties of the fiber such as strength and elastic modulus and the cut-resistant performance are improved. On the other hand, when the Mw is 600,000 or less, yarn production by the melt spinning method is facilitated, and it is not necessary to produce yarn by so-called gel spinning or the like. Therefore, it is advantageous in terms of suppressing the manufacturing cost and simplifying the work process. Furthermore, since no solvent is used during production, the impact on workers and the environment is small. In addition, since there is no residual solvent in the product fiber, there is no adverse effect of the solvent on the product user.
　また本発明におけるポリエチレンは、その繰り返し単位が実質的にエチレンであればよく、当該エチレンと、少量の他のモノマー；例えばα－オレフィン、アクリル酸及びその誘導体、メタクリル酸及びその誘導体、ビニルシラン及びその誘導体等との共重合体であってもよい。或は、これら共重合体同士、またはエチレン単独ポリマーと上記共重合体との共重合体、更にはエチレン単独ポリマーと他のα－オレフィン等のホモポリマーとのブレンド体であってもよい。特にプロピレン、ブテン－１などのα－オレフィンとの共重合体を用いて短鎖または長鎖の分岐をある程度含有させることは、本発明のポリエチレン繊維を製造する上で、特に紡糸・延伸における製糸上の安定性が付与されるため、より好ましい。しかしながら、エチレン以外の含有量が増え過ぎると逆に延伸の阻害要因となるため、高強度・高弾性率のポリエチレン繊維を得るという観点からは、ポリエチレン繊維全体に占めるエチレン以外の成分の比率はモノマー単位で好ましくは０．２ｍｏｌ％以下、より好ましくは０．１ｍｏｌ％以下である。もちろん、本発明におけるポリエチレンはエチレン単独で構成されていてもよい。 In the polyethylene of the present invention, the repeating unit may be substantially ethylene, and the ethylene and a small amount of other monomers; for example, α-olefin, acrylic acid and its derivatives, methacrylic acid and its derivatives, vinylsilane and its It may be a copolymer with a derivative or the like. Alternatively, these copolymers, or a copolymer of an ethylene homopolymer and the above copolymer, or a blend of an ethylene homopolymer and another homopolymer such as an α-olefin may be used. In particular, inclusion of a short chain or long chain branch to some extent by using a copolymer with an α-olefin such as propylene and butene-1 is advantageous in producing the polyethylene fiber of the present invention, particularly in spinning and drawing. Since the above stability is provided, it is more preferable. However, if the content other than ethylene is excessively increased, it becomes a hindrance to stretching, so from the viewpoint of obtaining polyethylene fibers with high strength and high elastic modulus, the proportion of components other than ethylene in the total polyethylene fibers is the monomer. The unit is preferably 0.2 mol% or less, more preferably 0.1 mol% or less. Of course, the polyethylene in the present invention may be composed of ethylene alone.
　本発明のポリエチレン繊維は、アスペクト比が３未満である複数の硬質粒子を含有している。本発明のポリエチレン繊維が含有する硬質粒子のアスペクト比は、３未満であればよいが、好ましくは１以上２以下である。ここで、硬質粒子のアスペクト比とは、ＪＩＳ８９００－１に基づいて算出される値（すなわち、粒子の顕微鏡像において、（最大長径／最大長径に直交する幅）で定義される粒子の形状を表す指数）である。硬質粒子のアスペクト比の測定方法は、後記する実施例の欄で詳述する。硬質粒子のアスペクト比が３以上になると、紡糸時に濾過フィルターが目詰まりし、繊維の生産性を著しく低下させることが懸念される為、好ましくない。 The polyethylene fiber of the present invention contains a plurality of hard particles having an aspect ratio of less than 3. The aspect ratio of the hard particles contained in the polyethylene fiber of the present invention may be less than 3, but is preferably 1 or more and 2 or less. Here, the aspect ratio of the hard particle represents a particle shape defined by a value calculated based on JIS 8900-1 (that is, in the microscopic image of the particle, (maximum major axis / width orthogonal to the maximum major axis)). Index). The method for measuring the aspect ratio of the hard particles will be described in detail in the column of Examples described later. If the aspect ratio of the hard particles is 3 or more, there is a concern that the filtration filter is clogged during spinning and the productivity of the fiber is remarkably lowered, which is not preferable.
　本発明において「硬質粒子」とは、シリカ、アルミナ等のようにポリマー（ポリエチレン繊維）中で凝集し難いものを意味する。よって、本発明のポリエチレン繊維が含有する硬質粒子の主たる原料としては、例えばシリカ、アルミナが挙げられ、なかでも、シリカからなるものが好ましい。 In the present invention, “hard particles” means those that are difficult to aggregate in a polymer (polyethylene fiber) such as silica and alumina. Therefore, examples of the main raw material of the hard particles contained in the polyethylene fiber of the present invention include silica and alumina, and among these, those made of silica are preferable.
　本発明のポリエチレン繊維が含有する複数の硬質粒子の形状は、真球状、扁球状であることが好ましい。硬質粒子が繊維状の場合、紡糸時に濾過フィルターが目詰まりし、繊維の生産性を著しく低下させることが懸念されるため、好ましくない。 The shape of the plurality of hard particles contained in the polyethylene fiber of the present invention is preferably true spherical or oblate. When the hard particles are fibrous, the filtration filter is clogged at the time of spinning, and it is feared that the productivity of the fiber will be remarkably lowered.
　本発明のポリエチレン繊維が含有する複数の硬質粒子は、そのまま用いてもよいし、表面を修飾したものを用いてもよい。表面修飾としては、ジメチル基、エポキシ基、ヘキシル基、フェニル基、メタクリル基、ビニル基、イソシアネート基等が適用できる。 The plurality of hard particles contained in the polyethylene fiber of the present invention may be used as they are, or those having a modified surface may be used. As the surface modification, dimethyl group, epoxy group, hexyl group, phenyl group, methacryl group, vinyl group, isocyanate group and the like can be applied.
　本発明のポリエチレン繊維が含有する複数の硬質粒子の平均粒子径は、３．０μｍ以上であり、好ましくは５.０μｍ以上である。硬質粒子の平均粒子径が１５.０μｍよりも大きくなると、紡糸時に濾過フィルターが目詰まりし、繊維の生産性を著しく低下させ、特に延伸性を大幅に低下させる。
　なお上記硬質粒子の平均粒子径は、後記する硬質粒子のアスペクト比と同様の方法により硬質粒子１０個のそれぞれについて長軸（最大長径）と短軸（最大短径）を測定し、最大長径と最大短径の合計（２０個）の平均値を求めることで、平均粒子径を算出した。 The average particle diameter of the plurality of hard particles contained in the polyethylene fiber of the present invention is 3.0 μm or more, preferably 5.0 μm or more. When the average particle diameter of the hard particles is larger than 15.0 μm, the filter is clogged during spinning, and the productivity of the fiber is remarkably lowered, and particularly the stretchability is greatly lowered.
The average particle diameter of the hard particles is determined by measuring the major axis (maximum major axis) and minor axis (maximum minor axis) for each of the ten hard particles by the same method as the aspect ratio of the hard particles described later. The average particle diameter was calculated by calculating the average value of the total of the maximum short diameter (20).
　本発明のポリエチレン繊維全体に含まれる上記複数の硬質粒子の含有量は、５質量％以上であり、好ましくは１０質量％以上３０質量％以下である。硬質粒子の含有量が５質量％未満であると、繊維中に存在する硬質粒子と刃の接触頻度が少なく、耐切創性を向上させる効果を得られ難い。 The content of the plurality of hard particles contained in the entire polyethylene fiber of the present invention is 5% by mass or more, preferably 10% by mass or more and 30% by mass or less. When the content of the hard particles is less than 5% by mass, the contact frequency between the hard particles present in the fiber and the blade is low, and it is difficult to obtain the effect of improving cut resistance.
　本発明のポリエチレン繊維を紡糸する際、硬質粒子は、事前にポリエチレンと混練したマスターバッチとして用いてもよいし、単体で用いてもよい。 When spinning the polyethylene fiber of the present invention, the hard particles may be used as a master batch kneaded with polyethylene in advance, or may be used alone.
　本発明のポリエチレン繊維は、単糸あたりの繊維径が４５μｍ以下であるのが好ましく、３７μｍ以下であるのがより好ましい。単糸あたりの繊維径が４５μｍよりも太くなると、織物または編物（織編物）に形成した際の風合いが堅くなり、柔軟性が損なわれる。なお、単糸あたりの繊維径は、例えば、ｄｔｅｘと繊維の比重より求める方法や、顕微鏡を用いて求める方法を用いることで求めることができる。その下限は、上記観点からは特に限定されないが、生産性などを考慮すると、おおむね１０μｍ以上であることが好ましい。 In the polyethylene fiber of the present invention, the fiber diameter per single yarn is preferably 45 μm or less, and more preferably 37 μm or less. When the fiber diameter per single yarn becomes thicker than 45 μm, the texture when formed into a woven fabric or a knitted fabric (woven fabric) becomes stiff and the flexibility is impaired. In addition, the fiber diameter per single yarn can be calculated | required by using the method calculated | required from the specific gravity of dtex and a fiber, and the method calculated | required using a microscope, for example. The lower limit is not particularly limited from the above viewpoint, but in consideration of productivity and the like, it is preferably approximately 10 μm or more.
　本発明のポリエチレン繊維は、上記硬質粒子以外に、添加剤として、酸化防止剤、滑剤、帯電防止剤、過酸化物、顔料、染料、分散剤等を含んでもいても良い。 The polyethylene fiber of the present invention may contain an antioxidant, a lubricant, an antistatic agent, a peroxide, a pigment, a dye, a dispersant and the like as an additive in addition to the hard particles.
　本発明のポリエチレン繊維の平均強度は、４ｃＮ／ｄｔｅｘ以上であることが望ましく、好ましくは、６ｃＮ／ｄｔｅｘ以上である。平均強度が４ｃＮ／ｄｔｅｘ未満の場合、応用製品を作製したとき、強度が不足する可能性がある。その上限は、上記観点からは特に限定されないが、紡糸性などの生産性を考慮すると、おおむね５０ｃＮ／ｄｔｅｘ以下であることが好ましい。 The average strength of the polyethylene fiber of the present invention is desirably 4 cN / dtex or more, and preferably 6 cN / dtex or more. When the average strength is less than 4 cN / dtex, the strength may be insufficient when an application product is manufactured. The upper limit is not particularly limited from the above viewpoint, but in consideration of productivity such as spinnability, it is preferably about 50 cN / dtex or less.
　本発明のポリエチレン繊維は、芯鞘構造を適用してもよく、また星形、三角や、中空等の異形の形状を有していてもよい。 The polyethylene fiber of the present invention may apply a core-sheath structure, or may have an irregular shape such as a star shape, a triangle shape, or a hollow shape.
　本発明のポリエチレン繊維を得る製造方法については、例えば、溶融紡糸法を用いることができる。ここで、例えば、溶剤を用いて行う超高分子量ポリエチレン繊維の製法の一つであるゲル紡糸法を用いると、高強度のポリエチレン繊維を得られるものの、生産性が低いばかりでなく、溶剤使用による製造作業者の健康や環境への影響、また繊維中に残留する溶剤が製品使用者の健康に与える影響が大きい。 For the production method for obtaining the polyethylene fiber of the present invention, for example, a melt spinning method can be used. Here, for example, by using the gel spinning method, which is one of the methods for producing ultra-high molecular weight polyethylene fibers using a solvent, high-strength polyethylene fibers can be obtained. The impact on the health and environment of manufacturing workers, and the impact of solvents remaining in the fiber on the health of product users.
　よって、本発明のポリエチレン繊維は溶融紡糸法を用いるのが好ましい。溶融紡糸法を用いて本発明のポリエチレン繊維を製造する方法について、具体的に以下に説明する。なお、本発明のポリエチレン繊維を製造する方法は、以下の工程や数値に限定されない。 Therefore, it is preferable to use the melt spinning method for the polyethylene fiber of the present invention. The method for producing the polyethylene fiber of the present invention using the melt spinning method will be specifically described below. In addition, the method of manufacturing the polyethylene fiber of this invention is not limited to the following processes and numerical values.
　上述したポリエチレン樹脂と粉末状態の硬質粒子とをブレンドし、押出機等を用いて、ポリエチレン樹脂の融点よりも例えば１０℃以上、好ましくは５０℃以上、更に好ましくは８０℃以上高い温度で溶融押出しをして、定量供給装置を用いてポリエチレン樹脂の融点より例えば８０℃、好ましくは１００℃以上高い温度で紡糸ノズル（紡糸口金）に供給する。この時、押出機内に供給する不活性ガスの圧力は、０．００１ＭＰａ以上、０．８ＭＰａ以下とするのが好ましく、より好ましくは０．０５ＭＰａ以上、０．７ＭＰａ以下、更に好ましくは０．１ＭＰａ以上、０．５ＭＰａ以下とすることが推奨される。その後、例えば直径０．３ｍｍ以上、２．５ｍｍ以下、好ましくは直径０．５ｍｍ以上、１．５ｍｍ以下を有する紡糸ノズルより０．１ｇ／ｍｉｎ以上の吐出量で吐出する。紡糸ノズルから溶融樹脂を吐出する際の吐出線速度は、１０ｃｍ／ｍｉｎ以上、１２０ｃｍ／ｍｉｎ以下とするのが好ましい。より好ましい吐出線速度は、２０ｃｍ／ｍｉｎ以上、１１０ｃｍ／ｍｉｎ以下であり、更に好ましくは３０ｃｍ／ｍｉｎ以上、１００ｃｍ／ｍｉｎ以下である。 Blending the above-mentioned polyethylene resin and powdered hard particles, and using an extruder or the like, melt extrusion at a temperature higher than the melting point of the polyethylene resin by, for example, 10 ° C or higher, preferably 50 ° C or higher, more preferably 80 ° C or higher. Then, it is supplied to the spinning nozzle (spinneret) at a temperature that is, for example, 80 ° C., preferably 100 ° C. or more higher than the melting point of the polyethylene resin, using a quantitative supply device. At this time, the pressure of the inert gas supplied into the extruder is preferably 0.001 MPa or more and 0.8 MPa or less, more preferably 0.05 MPa or more, 0.7 MPa or less, and further preferably 0.1 MPa or more. , 0.5 MPa or less is recommended. Then, for example, it discharges with the discharge amount of 0.1 g / min or more from the spinning nozzle which has a diameter of 0.3 mm or more and 2.5 mm or less, preferably 0.5 mm or more and 1.5 mm or less. The discharge linear velocity when discharging the molten resin from the spinning nozzle is preferably 10 cm / min or more and 120 cm / min or less. A more preferable discharge linear velocity is 20 cm / min or more and 110 cm / min or less, and further preferably 30 cm / min or more and 100 cm / min or less.
　次に、該吐出糸を５～４０℃まで冷却した後に５０ｍ／ｍｉｎ以上で巻き取り、更に得られた該未延伸糸を、少なくとも１回以上の回数で該未延伸糸の融点以下の温度で延伸する。具体的には、２段階以上に分けて延伸工程を行うことが好ましい。延伸の初期の温度は、上記未延伸糸の結晶分散温度未満が好ましく、より好ましくは８０℃以下、更に好ましくは７５℃以下である。次いで、上記未延伸糸の結晶分散温度以上、融点以下、好ましくは９０℃以上、融点未満で延伸するのが好ましい。 Next, the discharged yarn is cooled to 5 to 40 ° C. and then wound up at 50 m / min or more, and the obtained undrawn yarn is further obtained at a temperature not higher than the melting point of the undrawn yarn at least once. Stretch. Specifically, the stretching process is preferably performed in two or more stages. The initial drawing temperature is preferably less than the crystal dispersion temperature of the undrawn yarn, more preferably 80 ° C. or less, and even more preferably 75 ° C. or less. Next, the undrawn yarn is preferably drawn at a crystal dispersion temperature or higher and a melting point or lower, preferably 90 ° C. or higher and lower than the melting point.
　ここで結晶分散温度とは、以下の方法によって測定される温度である。
　まず固体粘弾性測定装置（Ｔ．Ａ．インスツルメント社製、「ＤＭＡ　Ｑ８００」）を用いて固体粘弾性率を測定する。測定した固体粘弾性率の解析には、「Ｔ．Ａ．Ｕｎｉｖｅｒｓａｌ　Ａｎａｌｙｓｉｓ」（Ｔ．Ａ．インスツルメント社製）を用いる。ここで測定開始温度を－１４０℃、測定終了温度を１４０℃、昇温速度を１．０℃／ｍｉｎとする。また、歪み量を０．０４％とし、測定開始時の初荷重０．０５ｃＮ／ｄｔｅｘとする。また、測定周波数を１１Ｈｚとする。次に、得られた固体粘弾性率に基づいて損失弾性率を計算し、温度分散を低温側より求め、損失弾性率の値を対数で縦軸に取り、横軸に温度を取ってプロットし、最も高温側に現れる損失弾性率のピーク値を結晶分散温度とする。 Here, the crystal dispersion temperature is a temperature measured by the following method.
First, the solid viscoelasticity is measured using a solid viscoelasticity measuring apparatus (TA Instruments, “DMA Q800”). For analysis of the measured solid viscoelastic modulus, “TA Universal Analysis” (manufactured by TA Instruments) is used. Here, the measurement start temperature is −140 ° C., the measurement end temperature is 140 ° C., and the rate of temperature rise is 1.0 ° C./min. The strain amount is 0.04%, and the initial load at the start of measurement is 0.05 cN / dtex. The measurement frequency is 11 Hz. Next, calculate the loss modulus based on the obtained solid viscoelastic modulus, obtain the temperature dispersion from the low temperature side, take the value of the loss modulus as a logarithm on the vertical axis, and plot the temperature on the horizontal axis. The peak value of the loss elastic modulus that appears on the highest temperature side is defined as the crystal dispersion temperature.
　延伸倍率は、合計で６倍以上とするのが好ましく、より好ましくは８倍以上であり、更に好ましくは１０倍以上である。また、延伸倍率は、合計で３０倍以下とするのが好ましく、より好ましくは２５倍以下であり、更に好ましくは２０倍以下である。なお、多段延伸を採用する場合、例えば、２段延伸を行う場合であれば、１段階目の延伸倍率は１．０５倍以上、４．００倍以下とするのが好ましく、２段階目の延伸倍率は２．５倍以上、１５倍以下とするのが好ましい。 The stretching ratio is preferably 6 times or more in total, more preferably 8 times or more, and further preferably 10 times or more. Moreover, it is preferable that a draw ratio is 30 times or less in total, More preferably, it is 25 times or less, More preferably, it is 20 times or less. When multi-stage stretching is adopted, for example, when two-stage stretching is performed, the first stage stretching ratio is preferably 1.05 times or more and 4.00 times or less, and the second stage stretching. The magnification is preferably 2.5 times or more and 15 times or less.
　本発明のポリエチレン繊維を使用した製品、例えば、織編物は、耐切創性織編物、手袋及びベスト等として好適に用いられる。例えば、手袋は、本発明のポリエチレン繊維を編み機に掛けることで得られる。もしくは、本発明のポリエチレン繊維を織り機に掛けて布帛を得、それを裁断、縫製して手袋とすることもできる。 A product using the polyethylene fiber of the present invention, for example, a woven or knitted fabric, is suitably used as a cut resistant woven or knitted fabric, a glove, a vest and the like. For example, a glove is obtained by hanging the polyethylene fiber of the present invention on a knitting machine. Alternatively, the polyethylene fiber of the present invention can be applied to a loom to obtain a fabric, which can be cut and sewn to form a glove.
　このようにして得られた手袋は、例えば、そのまま手袋として使用することもできるが、必要であれば滑り止め性を付与するために、樹脂を塗布することもできる。ここで用いられる樹脂は、例えば、ウレタン系やエチレン系などが挙げられるが、特に限定されるものではない。 The glove thus obtained can be used as a glove as it is, for example, but if necessary, a resin can be applied to impart anti-slip properties. Examples of the resin used here include urethane-based and ethylene-based resins, but are not particularly limited.
　本発明のポリエチレン繊維は、後述の実施例からも分かるように、耐切創性能に優れている。具体的には、ヨーロッパ規格であるＥＮ３８８による耐切創性評価において、３５０ｇ／ｍ2±３５ｇ／ｍ2の布帛にした場合の耐切創性のレベルが４以上を満足する。
　よって、本発明のポリエチレン繊維を使用した製品は、上記した手袋やベスト等の織編物以外にも、テープ、ロープ、ネット、釣糸、資材防護カバー、シート、カイト用糸、洋弓弦、セールクロス、幕材として好適に用いられる。もちろん、本発明のポリエチレン繊維を用いた製品はこれらに限定されない。 The polyethylene fiber of the present invention is excellent in cut resistance, as can be seen from the examples described later. Specifically, in the cut resistance evaluation according to the European standard EN388, the level of cut resistance when a fabric of 350 g / m 2 ± 35 g / m 2 is satisfied satisfies 4 or more.
Therefore, the products using the polyethylene fiber of the present invention include tapes, ropes, nets, fishing lines, material protection covers, sheets, kite threads, bowstrings, sailcloths, in addition to the above-mentioned knitted and knitted fabrics such as gloves and vests It is suitably used as a curtain material. Of course, the product using the polyethylene fiber of the present invention is not limited to these.
　また、本発明のポリエチレン繊維は、高い耐切創性を有するため、該耐切創性を活かした材料、例えば、繊維強化樹脂補強材、セメント補強材、繊維強化ゴム補強材、あるいは環境変化が想定される防護材、防弾材、医療用縫合糸、人工腱、人工筋肉、繊維強化樹脂補強材、セメント補強材、繊維強化ゴム補強材、工作機械部品、電池セパレーター、化学フィルターとして好適に用いられる。もちろん、本発明のポリエチレン繊維は、これらの材料に限定されず、様々な材料として用いることができる。 In addition, since the polyethylene fiber of the present invention has high cut resistance, a material utilizing the cut resistance, such as a fiber reinforced resin reinforcing material, a cement reinforcing material, a fiber reinforced rubber reinforcing material, or an environment change is assumed. Protective materials, bulletproof materials, medical sutures, artificial tendons, artificial muscles, fiber reinforced resin reinforcing materials, cement reinforcing materials, fiber reinforced rubber reinforcing materials, machine tool parts, battery separators, and chemical filters. Of course, the polyethylene fiber of the present invention is not limited to these materials, and can be used as various materials.
　本願は、２０１７年３月２９日に出願された日本国特許出願第２０１７－０６５３３１号に基づく優先権の利益を主張するものである。２０１７年３月２９日に出願された日本国特許出願第２０１７－０６５３３１号の明細書の全内容が、本願に参考のため援用される。 This application claims the benefit of priority based on Japanese Patent Application No. 2017-066531, filed on Mar. 29, 2017. The entire contents of the specification of Japanese Patent Application No. 2017-066531 filed on March 29, 2017 are incorporated herein by reference.
　以下に、実施例を例示し、本発明を具体的に説明する。しかし、本発明は下記実施例によって限定されるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and it is of course possible to carry out the invention with appropriate modifications within a range that can be adapted to the purpose described above and below. To be included in the scope.
　まず、後述の実施例および比較例で作製した繊維（繊維サンプル）およびそれを用いた筒編み物（編物サンプル）に対して行った特性値の測定及び評価について説明する。 First, measurement and evaluation of characteristic values performed on fibers (fiber samples) produced in Examples and Comparative Examples described later and cylindrical knittings (knitted samples) using the fibers will be described.
（１）極限粘度［η］
　極限粘度は、溶媒として１３５℃に加熱したデカリンを用い、ウベローデ型毛細粘度管を用いて測定した。具体的には、種々の希薄溶液の比粘度を測定し、その粘度の濃度に対するプロットの最小２乗近似で得られる直線の原点への外挿点より極限粘度を決定した。比粘度の測定に際し、繊維サンプルを約５ｍｍ長に分割または切断し、ポリマーに対して１質量％の酸化防止剤（ヨシノックスＢＨＴ（登録商標）、吉富製薬製）を添加し、１３５℃で４時間攪拌溶解して測定溶液を調整した。 (1) Intrinsic viscosity [η]
Intrinsic viscosity was measured using an Ubbelohde capillary viscosity tube using decalin heated to 135 ° C. as a solvent. Specifically, the specific viscosities of various dilute solutions were measured, and the intrinsic viscosity was determined from the extrapolation point to the origin of the straight line obtained by the least square approximation of the plot with respect to the concentration of the viscosity. When measuring the specific viscosity, the fiber sample was divided or cut into approximately 5 mm lengths, 1% by mass of an antioxidant (Yoshinox BHT (registered trademark), manufactured by Yoshitomi Pharmaceutical) was added to the polymer, and the temperature was measured at 135 ° C for 4 hours. The measurement solution was prepared by stirring and dissolving.
（２）硬質粒子のアスペクト比
　硬質粒子のアスペクト比は、ＳＥＭ写真を用いることによって求めた。繊維サンプルをるつぼの中に入れ、灰と炭素質物質になるまで燃焼をさせた後、電気炉に入れ、ポリエチレンの分解温度以上で加熱した。炭素質物質が完全に灰になったら、デシケータ中で放冷して灰分を得た。灰分のＳＥＭ写真を撮影し、無作為に選択した硬質粒子１０個のそれぞれについて、長軸（最大長径）および最大長径に直交する幅を測定し、最大長径を、最大長径に直交する幅で除して、その平均値を求めることで、アスペクト比を算出した。なお、硬質粒子は硬度が高い為、加熱しても形状が変化しないと考えられる。 (2) Aspect ratio of hard particles The aspect ratio of hard particles was determined by using SEM photographs. The fiber sample was placed in a crucible, burned until it became ash and carbonaceous material, then placed in an electric furnace and heated above the decomposition temperature of polyethylene. When the carbonaceous material became completely ash, it was allowed to cool in a desiccator to obtain ash. Take an SEM photo of ash and measure the long axis (maximum major axis) and the width perpendicular to the maximum major axis for each of 10 randomly selected hard particles, and divide the maximum major axis by the width orthogonal to the maximum major axis. The aspect ratio was calculated by obtaining the average value. In addition, since a hard particle | grain has high hardness, it is thought that a shape does not change even if it heats.
（３）硬質粒子の含有量
　硬質粒子の含有量は、ＪＩＳ－２２７２に基づき、灰分測定を用いることによって求めた。繊維サンプル１．０ｇをるつぼの中に入れ、灰と炭素質物質になるまで燃焼をさせた後、電気炉に入れ、ポリエチレンの分解温度以上で加熱した。炭素質物質が完全に灰になった後、デシケータ中で放冷して質量を測定し、灰分を求めた。得られた灰分量と上記繊維量の合計に対する灰分量の質量比率に基づき、硬質粒子の含有量を求めた。 (3) Hard particle content The hard particle content was determined by using ash measurement based on JIS-2272. A fiber sample (1.0 g) was placed in a crucible, burned until it became ash and carbonaceous material, then placed in an electric furnace and heated above the decomposition temperature of polyethylene. After the carbonaceous material was completely turned into ash, it was allowed to cool in a desiccator and the mass was measured to determine the ash content. Based on the mass ratio of the ash content to the total of the obtained ash content and the fiber content, the hard particle content was determined.
（４）耐切創性
　耐切創性は、クープテスター（ソドマット（ＳＯＤＭＡＴ）社製）の装置を用い、ヨーロッパ規格であるＥＮ３８８法に基づいて測定を行った。具体的には、後記する方法で作製した各ポリエチレン繊維を用い、島精機製作所社製の丸編み機を用いて、目付が３５０ｇ／ｍ2±３５ｇ／ｍ2の筒編み物を作製した。得られた筒編み物のクープテスターのインデックス値を以下のようにして算出して、耐切創性を評価した。 (4) Cut resistance The cut resistance was measured based on the EN388 method, which is a European standard, using an apparatus of a coup tester (manufactured by SODMAT). Specifically, a cylindrical knitted fabric having a basis weight of 350 g / m 2 ± 35 g / m 2 was produced using a circular knitting machine manufactured by Shima Seiki Seisakusho using each polyethylene fiber produced by the method described later. The index value of the obtained tubular knitted coup tester was calculated as follows to evaluate cut resistance.
　ここで、上記装置の試料台にはアルミ箔が設けられており、この上に編物サンプルを載置した。次いで、装置に備えられた円形の刃を、走行方向とは逆方向に回転させながら試料の上を走らせた。なお、編物サンプルが切断されると、円形刃とアルミ箔とが接触して通電することで、耐切創性試験が終了したことが検知された。円形刃が作動している間中、装置に取り付けられているカウンターがカウントを行うので、その数値を記録した。 Here, an aluminum foil was provided on the sample stage of the above apparatus, and a knitted sample was placed thereon. Next, the circular blade provided in the apparatus was run on the sample while rotating in the direction opposite to the running direction. When the knitted sample was cut, it was detected that the cut resistance test was completed by energizing the circular blade and the aluminum foil in contact with each other. While the circular blade was operating, the counter attached to the device counted and recorded the value.
　この試験では、目付け約２００ｇ／ｍ2の平織りの綿布をブランクとし、編物サンプルの切創レベルを評価した。ブランクからテストを開始し、ブランクのテストと編物サンプルのテストとを交互に行い、編物サンプルを５回テストし、最後に６回目のブランクをテストして、１セットの試験を終了した。以上の試験を５セット行い、５セットの平均のＩｎｄｅｘ値（インデックス値）を耐切創性の代用評価とした。インデックス値が高いほど、耐切創性に優れることを意味する。本実施例では、上記インデックス値のレベルが４以上を合格とした。 In this test, a plain woven cotton fabric having a basis weight of about 200 g / m 2 was used as a blank, and the cut level of a knitted sample was evaluated. The test was started from a blank, the blank test and the knitted sample test were alternately performed, the knitted sample was tested five times, and finally the sixth blank was tested to complete one set of tests. Five sets of the above test were conducted, and the average index value (index value) of the five sets was used as a substitute evaluation for cut resistance. A higher index value means better cut resistance. In this embodiment, the index value level of 4 or higher was regarded as acceptable.
　インデックス値は、次式により算出される。
　Ａ＝（サンプルテスト前の綿布のカウント値＋サンプルテスト後の綿布のカウント値）／２
　インデックス値＝（サンプルのカウント値＋Ａ）／Ａ The index value is calculated by the following formula.
A = (count value of cotton cloth before sample test + count value of cotton cloth after sample test) / 2
Index value = (sample count value + A) / A
　耐切創性の評価に使用したカッターは、ＯＬＦＡ株式会社製のロータリーカッターＬ型用φ４５ｍｍである。材質はＳＫＳ－７タングステン鋼であり、刃厚０．３ミリ厚であった。また、テスト時にかかる荷重は３．１４Ｎ（３２０ｇｆ）にして評価を行った。 The cutter used for the evaluation of cut resistance is φ45 mm for L-type rotary cutter manufactured by OLFA Corporation. The material was SKS-7 tungsten steel, and the blade thickness was 0.3 mm. Moreover, the load applied at the time of the test was 3.14N (320 gf).
（実施例１）
　極限粘度が１．９ｄＬ／ｇであるポリエチレンペレット８８質量％と、アスペクト比が１．４、平均粒子径が３μｍであるシリカ粒子（硬質粒子）１２質量％とを混ぜてブレンドポリマーを作製した。なお、硬質粒子のアスペクト比は、上記したように１０個の平均であり、その範囲は１．１から２．３であった。このブレンドポリマーを押出機に供給して２８０℃で溶融し、オリフィス径φ０．８ｍｍ、３０Ｈからなる紡糸口金からノズル面温度２８８℃にて単孔吐出量０．３２ｇ／ｍｉｎで吐出させた。 Example 1
A blend polymer was prepared by mixing 88% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.4 and an average particle diameter of 3 μm. The aspect ratio of the hard particles was an average of 10 particles as described above, and the range thereof was 1.1 to 2.3. This blend polymer was supplied to an extruder, melted at 280 ° C., and discharged from a spinneret having an orifice diameter of 0.8 mm and 30 H at a nozzle surface temperature of 288 ° C. at a single hole discharge rate of 0.32 g / min.
　吐出された糸条を１０ｃｍの保温区間通過させ、その後１８℃、０．５ｍ／ｓｅｃのクエンチで冷却後、紡糸速度２００ｍ／ｍｉｎでチーズ形状に捲き取り、未延伸糸を得た。次いで、上記の未延伸糸を２個の駆動ロール間で３倍、次いで１００℃の熱風で加熱して安定に延伸できる最大の延伸倍率にて巻き取って延伸糸を得た。延伸糸を全体として８８０ｄｔｅｘ±８８ｄｔｅｘとなるように合糸し、実施例１のポリエチレン繊維を得た。得られたポリエチレン繊維を用いて、上記方法により筒編み物を作製して耐切創性を評価した。これらの結果を表１に示す。なお、本実施例を含め以下の実施例及び比較例では、延伸糸を所望のｄｔｅｘとなるように合糸を行ったが、分繊を行う場合もある。 The discharged yarn was allowed to pass through a 10 cm warming section, and then cooled by quenching at 18 ° C. and 0.5 m / sec, and then wound into a cheese shape at a spinning speed of 200 m / min to obtain an undrawn yarn. Next, the undrawn yarn was wound three times between two drive rolls, then heated with hot air at 100 ° C. and wound up at the maximum draw ratio that could be stably drawn to obtain a drawn yarn. The drawn yarns were combined so as to be 880 dtex ± 88 dtex as a whole, and the polyethylene fiber of Example 1 was obtained. Using the obtained polyethylene fiber, a tubular knitted fabric was produced by the above-described method, and cut resistance was evaluated. These results are shown in Table 1. In the following examples and comparative examples including this example, the drawn yarns were combined so as to have a desired dtex.
（実施例２）
　実施例１の条件において、アスペクト比が１．５、平均粒子径が７μｍであるシリカ粒子（硬質粒子）１２質量％を用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、実施例２のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 (Example 2)
An undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 μm was used under the conditions of Example 1. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and cylindrical knitted fabric of Example 2 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
（実施例３）
　実施例１の条件において、極限粘度が１．９ｄＬ／ｇであるポリエチレンペレット９５質量％と、アスペクト比が１．５、平均粒子径が７μｍであるシリカ粒子（硬質粒子）５質量％とを用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、実施例３のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 (Example 3)
In the conditions of Example 1, 95% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 5% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 μm are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 3 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
（実施例４）
　実施例１の条件において、アスペクト比が１．５、平均粒子径が１５μｍであるシリカ粒子（硬質粒子）１２質量％を用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、実施例４のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 Example 4
An undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 15 μm was used under the conditions of Example 1. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and the tubular knitted fabric of Example 4 were obtained in the same manner as in Example 1, and the cut resistance was evaluated. These results are shown in Table 1.
（実施例５）
　実施例１の条件において、アスペクト比が１．６、平均粒子径が７μｍであるアルミナ粒子（硬質粒子）１２質量％を用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、実施例５のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 (Example 5)
An undrawn yarn was obtained in the same manner as in Example 1 except that 12% by mass of alumina particles (hard particles) having an aspect ratio of 1.6 and an average particle diameter of 7 μm was used under the conditions of Example 1. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and tubular knitted fabric of Example 5 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
（比較例１）
　実施例１の条件において、極限粘度が１．９ｄＬ／ｇであるポリエチレンペレット８０質量％と、アスペクト比が１．５、平均粒子径が２μｍであるシリカ粒子（硬質粒子）２０質量％とを用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、比較例１のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 (Comparative Example 1)
Under the conditions of Example 1, 80% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 20% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 2 μm are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and cylindrical knitted fabric of Comparative Example 1 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
（比較例２）
　実施例１の条件において、アスペクト比が１．５、平均粒子径が１７μｍであるシリカ粒子（硬質粒子）１２質量％を用いてブレンドポリマーを作製したが、紡糸時、詰まりが発生し、未延伸糸を得ることができなかった。 (Comparative Example 2)
Under the conditions of Example 1, a blend polymer was prepared using 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 17 μm. The yarn could not be obtained.
（比較例３）
　実施例１の条件において、極限粘度が１．９ｄＬ／ｇであるポリエチレンペレット９７質量％と、アスペクト比が１．５、平均粒子径が７μｍであるシリカ粒子（硬質粒子）３質量％とを用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、比較例３のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 (Comparative Example 3)
In the conditions of Example 1, 97% by mass of polyethylene pellets having an intrinsic viscosity of 1.9 dL / g and 3% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 μm are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and tubular knitted fabric of Comparative Example 3 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
（比較例４）
　実施例１の条件において、極限粘度が５．５ｄＬ／ｇであるポリエチレンペレット８８質量％と、アスペクト比が１．５、平均粒子径が７μｍであるシリカ粒子（硬質粒子）１２質量％とを混ぜてブレンドポリマーを作製したが、ポリマーと硬質粒子とが混ざり合わず未延伸糸が得られなかった。 (Comparative Example 4)
Under the conditions of Example 1, 88% by mass of polyethylene pellets having an intrinsic viscosity of 5.5 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 μm were mixed. Thus, a blend polymer was produced, but the polymer and hard particles were not mixed and an undrawn yarn could not be obtained.
（比較例５）
　実施例１の条件において、極限粘度が０．５ｄＬ／ｇであるポリエチレンペレット８８質量％と、アスペクト比が１．５、平均粒子径が７μｍであるシリカ粒子（硬質粒子）１２質量％とを用いた以外は、実施例１と同様にして未延伸糸を得た。得られた未延伸糸から実施例１と同様にして延伸糸を得た。得られた延伸糸から、実施例１と同様に、比較例５のポリエチレン繊維および筒編み物を得て耐切創性を評価した。これらの結果を表１に示す。 (Comparative Example 5)
Under the conditions of Example 1, 88% by mass of polyethylene pellets having an intrinsic viscosity of 0.5 dL / g and 12% by mass of silica particles (hard particles) having an aspect ratio of 1.5 and an average particle diameter of 7 μm are used. An undrawn yarn was obtained in the same manner as in Example 1 except that. From the obtained undrawn yarn, a drawn yarn was obtained in the same manner as in Example 1. From the obtained drawn yarn, the polyethylene fiber and cylindrical knitted fabric of Comparative Example 5 were obtained in the same manner as in Example 1, and cut resistance was evaluated. These results are shown in Table 1.
（比較例６）
　実施例１の条件において、アスペクト比が１８、平均粒子径が７μｍであるシリカ粒子（硬質粒子）１２質量％を用いてブレンドポリマーを作製したが、紡糸時、詰まりが発生し、未延伸糸を得ることができなかった。 (Comparative Example 6)
Under the conditions of Example 1, a blend polymer was produced using 12% by mass of silica particles (hard particles) having an aspect ratio of 18 and an average particle diameter of 7 μm. However, clogging occurred during spinning, and undrawn yarn was Couldn't get.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１から分かるように、実施例１～５のポリエチレン繊維；詳細には極限粘度が０．８ｄＬ／ｇ以上４．９ｄＬ／ｇ未満であり、アスペクト比が３未満であり、平均粒子径が３．０μｍ以上１５．０μｍ以下の複数の硬質粒子を含有するポリエチレン繊維を用いた筒編み物では、インデックス値が高く、つまり、耐切創性レベルが高い。このように、上記実施例１～５および比較例１～６の対比から、本発明の要件を満足するポリエチレン繊維は、耐切創性に優れた繊維であることがわかる。 As can be seen from Table 1, the polyethylene fibers of Examples 1 to 5; specifically, the intrinsic viscosity is 0.8 dL / g or more and less than 4.9 dL / g, the aspect ratio is less than 3, and the average particle diameter is 3 A cylindrical knitted fabric using polyethylene fibers containing a plurality of hard particles of 0.0 μm or more and 15.0 μm or less has a high index value, that is, a high level of cut resistance. Thus, the comparison between Examples 1 to 5 and Comparative Examples 1 to 6 shows that the polyethylene fibers satisfying the requirements of the present invention are excellent in cut resistance.
　以上、本発明の実施の形態および各実施例について説明したが、今回開示された実施の形態および各実施例はすべての点で例示であって制限的なものではない。本発明の範囲は特許請求の範囲によって示され、特許請求の範囲と均等の意味および範囲内での全ての変更が含まれる。 The embodiment and each example of the present invention have been described above, but the embodiment and each example disclosed this time are examples in all respects and are not restrictive. The scope of the present invention is defined by the terms of the claims, and includes meanings equivalent to the terms of the claims and all modifications within the scope.
　本発明のポリエチレン繊維は、高い耐切創性を有するため、該耐切創性を活かした耐切創性織編物、例えば手袋及びベスト等に利用可能である。また、該ポリエチレン繊維単独としてテープ、ロープ、ネット、釣糸、資材防護カバー、シート、カイト用糸、洋弓弦、セールクロス、幕材、防護材、防弾材、医療用縫合糸、人工腱、人工筋肉、繊維強化樹脂補強材、セメント補強材、繊維強化ゴム補強材、工作機械部品、電池セパレーター、化学フィルター等の産業用資材に利用可能である。このように、本発明のポリエチレン繊維は、優れた性能を発揮でき、幅広く応用できるため、産業界へ大きく寄与できる。 Since the polyethylene fiber of the present invention has high cut resistance, it can be used for cut-resistant woven or knitted fabrics utilizing the cut resistance, such as gloves and vests. In addition, the polyethylene fiber alone as a tape, rope, net, fishing line, material protective cover, sheet, kite thread, bowstring, sail cloth, curtain material, protective material, bulletproof material, medical suture, artificial tendon, artificial muscle It can be used for industrial materials such as fiber reinforced resin reinforcing materials, cement reinforcing materials, fiber reinforced rubber reinforcing materials, machine tool parts, battery separators, and chemical filters. Thus, since the polyethylene fiber of the present invention can exhibit excellent performance and can be widely applied, it can greatly contribute to the industry.

Claims (4)

  1. 　極限粘度［η］が０．８ｄＬ／ｇ以上、４．９ｄＬ／ｇ未満のポリエチレンからなる繊維であり、
    　アスペクト比が３未満であり、平均粒子径が３．０μｍ以上１５.０μｍ以下の硬質粒子を、ポリエチレン繊維中に５質量％以上含有することを特徴とするポリエチレン繊維。     Intrinsic viscosity [η] is a fiber made of polyethylene of 0.8 dL / g or more and less than 4.9 dL / g,
    A polyethylene fiber comprising 5% by mass or more of hard particles having an aspect ratio of less than 3 and an average particle diameter of 3.0 μm or more and 15.0 μm or less in polyethylene fiber.
  2. 　上記硬質粒子は、シリカまたはアルミナであることを特徴とする請求項１に記載のポリエチレン繊維。 2. The polyethylene fiber according to claim 1, wherein the hard particles are silica or alumina.
  3. 　ヨーロッパ規格であるＥＮ３８８による耐切創性評価において、３５０ｇ／ｍ2±３５ｇ／ｍ2の布帛にした場合の耐切創性のレベルが４以上であることを特徴とする請求項１または２に記載のポリエチレン繊維。 The cut resistance evaluation according to European standard EN388 is characterized in that the level of cut resistance when the fabric is 350 g / m 2 ± 35 g / m 2 is 4 or more. Polyethylene fiber.
  4. 　請求項１から３のいずれか１項に記載のポリエチレン繊維を含むことを特徴とする製品。 A product comprising the polyethylene fiber according to any one of claims 1 to 3.
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