CN116324056A - Cut-resistant polyethylene yarn - Google Patents

Cut-resistant polyethylene yarn Download PDF

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Publication number
CN116324056A
CN116324056A CN202180065214.5A CN202180065214A CN116324056A CN 116324056 A CN116324056 A CN 116324056A CN 202180065214 A CN202180065214 A CN 202180065214A CN 116324056 A CN116324056 A CN 116324056A
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CN
China
Prior art keywords
cut
yarn
angular frequency
polyethylene yarn
polyethylene
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Pending
Application number
CN202180065214.5A
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Chinese (zh)
Inventor
李信镐
李英洙
金成龙
朴贞恩
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Kolon Industries Inc
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Kolon Industries Inc
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Publication of CN116324056A publication Critical patent/CN116324056A/en
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/08—Melt spinning methods
    • D01D5/098—Melt spinning methods with simultaneous stretching
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
    • D02G3/38—Threads in which fibres, filaments, or yarns are wound with other yarns or filaments, e.g. wrap yarns, i.e. strands of filaments or staple fibres are wrapped by a helically wound binder yarn
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/442—Cut or abrasion resistant yarns or threads
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/08—Interlacing constituent filaments without breakage thereof, e.g. by use of turbulent air streams
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D02J1/228—Stretching in two or more steps, with or without intermediate steps
    • 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
    • D04B1/22—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 specially adapted for knitting goods of particular configuration
    • D04B1/24—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 specially adapted for knitting goods of particular configuration wearing apparel
    • D04B1/28—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 specially adapted for knitting goods of particular configuration wearing apparel gloves
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04B—KNITTING
    • D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
    • D04B21/20—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes specially adapted for knitting articles of particular configuration
    • D04B21/207—Wearing apparel or garment blanks
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • D10B2321/0211—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene high-strength or high-molecular-weight polyethylene, e.g. ultra-high molecular weight polyethylene [UHMWPE]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/041—Gloves

Abstract

The present invention relates to a cut-resistant polyethylene yarn, and more particularly, to a cut-resistant polyethylene yarn capable of producing a product having excellent abrasion resistance while having excellent cut resistance, and capable of producing a fiber product which is practically applicable to high-risk industries and disaster sites.

Description

Cut-resistant polyethylene yarn
Technical Field
The present invention relates to a cut-resistant polyethylene yarn, and more particularly, to a cut-resistant polyethylene yarn capable of producing a product having excellent abrasion resistance while having excellent cut resistance.
Background
Workers working in high risk industrial fields such as metal and glass processing workshops, meat workshops, etc., or personnel working in security and disaster relief fields such as police, military personnel, or firemen, etc., wear cut-resistant gloves or clothing to protect the body from being injured by a murder or sharp cutting tool such as a knife.
Generally, as a means for providing cut resistance, products made of high-strength textile yarns such as aramid fibers have been developed, but the cut resistance is insufficient for use in high-risk sites. On the other hand, various products using wires have been developed, but they are practically impossible to apply to work sites where workers often use hands due to lack of flexibility.
In contrast, japanese laid-open patent No. 2002-180324 discloses a glove using polyethylene yarn having high elastic modulus and strength, but in practice, cutting resistance is insufficient for use in high-risk industrial sites, and thus there is a problem of low practicality.
Further, when a protective article is made of such polyethylene yarn developed only by enhancing strength, there is a disadvantage in that it is difficult to reuse it for a long period of time because the yarn tends to generate burrs.
Disclosure of Invention
Technical problem
The invention aims to provide a polyethylene yarn which can manufacture a product with excellent cutting resistance and improved wear resistance.
Technical proposal
In the graph of the change of the storage modulus (G') with the angular frequency (ω), the storage modulus is 10Pa to 100Pa when the angular frequency is 0.1rad/s, the storage modulus is 100Pa to 1000Pa when the angular frequency is 1rad/s, and the tan delta is 9 or more when the angular frequency is 0.1rad/s in the graph of the change of the tan delta with the angular frequency (ω).
In the cut resistant polyethylene yarn according to an embodiment of the present invention, in the graph of the variation of the loss modulus (G ") of polyethylene with the angular frequency (ω), the loss modulus may be 100Pa to 700Pa when the angular frequency is 0.1rad/s, and a point where the loss modulus is 1000Pa may occur in the interval of 0.25 to 0.5 rad/s.
In the cut resistant polyethylene yarn according to an embodiment of the present invention, in the graph of the change of the complex viscosity (η) of the polyethylene with the angular frequency (ω), the complex viscosity (η) may be 3000pa·s to 6000pa·s when the angular frequency is 0.1rad/s, and the average slope may be-1000 to-300 in the interval of the angular frequency of 0.1rad/s to 1 rad/s.
In the cut resistant polyethylene yarn of an embodiment of the present invention, the fineness may be 1 to 3 DPFs.
In the cut resistant polyethylene yarn according to an embodiment of the present invention, in the graph of the phase angle as a function of the complex shear modulus (G), the phase angle may be 75 ° to 90 ° when the complex shear modulus (G) is 350 to 1000 Pa.
In the cut-resistant polyethylene yarn of an embodiment of the present invention, the hairiness generation number may be 20EA/50,000m or less.
The present invention may be a cut-resistant fabric comprising the cut-resistant polyethylene yarn described above.
In a cut resistant fabric according to an embodiment of the present invention, according to ISO13997: the cut resistance of the cloth measured by 1999 standard may be 5.5N or more.
The invention relates to a protective article, which comprises the cut-resistant polyethylene cloth.
The protective article of an embodiment of the present invention may be a cut resistant glove.
Advantageous effects
The cut-resistant polyethylene yarn of the present invention has excellent cut resistance, and thus, can produce fiber products that are practically applicable to high-risk industries and disaster sites.
In addition, the cut-resistant polyethylene yarn of the present invention can produce a product having high abrasion resistance.
Drawings
Fig. 1-5 are graphs of rheological measurements of cut-resistant polyethylene yarns according to an embodiment of the invention.
Detailed Description
Unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art, and in the following description and drawings, descriptions of well-known functions and constructions that unnecessarily obscure the gist of the present invention are omitted.
In addition, as used herein, the singular forms may be intended to include the plural forms unless the context clearly indicates otherwise.
In the present application, unless otherwise specifically indicated, the unit used is, for example,% or ratio, by weight or parts by weight, and unless otherwise defined, the term "wt% means the weight% of any component in the overall composition.
In addition, the numerical ranges used in the present application include a lower limit value, an upper limit value, and all values within the range, increments reasonably derived from the form and width of the defined range, all values doubly defined, and all possible combinations of upper and lower limits of the numerical ranges defined in different forms from each other. In this application, unless otherwise defined, values outside the range of values that may result from rounding off based on experimental error or values are also included within the range of values defined.
The terms "comprising," "including," and "having," are intended to be inclusive and open-ended in that sense as defined by the terms "comprising," "including," "having," or "characterized by," and not to exclude additional elements, materials, or processes not listed.
Cutting resistance refers to the durability of cutting by a blade or an object having a sharp portion like a blade, and workers working in industrial fields with a high risk such as metal and glass processing workshops, meat workshops, or people working in security and disaster relief fields such as police, soldiers, or firemen wear cutting resistance gloves or clothing to protect the body from being injured by a murder or sharp cutting tool such as a knife.
Although a cut-resistant fiber product using a polyethylene yarn having a high elastic modulus and strength has been developed in the past, the cut-resistant fiber product is not sufficiently cut-resistant to be used in an industrial site with a high risk, and therefore has a disadvantage of low practicality.
In addition, the polyethylene yarn developed by only enhancing strength has low abrasion resistance and is liable to generate burrs, and thus is difficult to reuse for a long period of time.
In view of the above, the applicant of the present application has conducted intensive studies for developing a polyethylene yarn excellent in cut resistance and abrasion resistance, and as a result, has found that a yarn having a specific rheology can produce a product excellent in cut resistance and also excellent in abrasion resistance, and has conducted intensive studies on this, leading to completion of the present invention.
In the present application, polyethylene yarn means monofilaments and multifilaments produced by spinning, drawing, and other steps using polyethylene chips as a raw material. As an example, the polyethylene yarn may comprise 40 to 500 filaments having a denier of 1 to 3, respectively, and the total denier may be 100 to 1,000.
In this application, rheology refers to storage modulus (G'), loss modulus (G "), tan delta, complex viscosity (eta), and phase angle (°), where rheology may be measured using DHR-2 (TA instruments) unless otherwise defined. The geometries used in the measurements were plate-plate (parallel plate; PP), and the storage modulus (G'), loss modulus (G "), tan δ, complex viscosity (η), and phase angle were measured as a function of angular frequency. Unless otherwise defined, the rheological measurements can be carried out under nitrogen atmosphere at a temperature of 250 ℃ and can be measured with a measurement specification (Sample Dimension) of 25mm diameter, 1.0mm Gap point and 10% deformation.
In the graph of change of the storage modulus (G') with the angular frequency (ω), the storage modulus may be 10Pa to 100Pa when the angular frequency is 0.1rad/s, 100Pa to 1000Pa when the angular frequency is 1rad/s, and tan δ may be 9 or more when the angular frequency (ω) is 0.1 rad/s. The polyethylene yarn can produce products with excellent cutting resistance and excellent wear resistance.
The cut resistance of a product comprising the polyethylene yarn of the present invention is determined not only by the strength of the polyethylene yarn, but also by the slip characteristics (slip) of the polyethylene yarn, i.e. the characteristics of a sharp tool such as a blade that is not caught by the yarn when passing over the polyethylene yarn but slides along the surface, and the rolling (rolling) characteristics of the yarn, i.e. the characteristics of a sharp tool such as a blade that is twisted or curled about the longitudinal axis of the yarn when passing over the yarn.
The polyethylene yarn of the present invention has the above-described ranges in the graph of the change in storage modulus and tan δ with angular frequency, and therefore, can produce a product having excellent sliding characteristics and rolling characteristics and exhibiting excellent cut resistance.
Specifically, in the graph of the storage modulus (G') as a function of angular frequency (ω), the storage modulus may be 20Pa to 80Pa, more specifically 30Pa to 50Pa, when the angular frequency is 0.1 rad/s. At this time, the storage modulus may have a positive (+) slope on average. Specifically, the slope of positive (+) can be uniformly maintained in the range of 0.1rad/s to 1000rad/s in angular frequency. Yarns having such physical properties can exhibit sufficient elasticity to be cut resistant and have excellent strength. Specifically, in the graph of the change of the storage modulus with the angular frequency, when the values of the angular frequency (ω) and the loss modulus (G ") are converted into logarithmic values, the average slope of the storage modulus (log G') may be 0.9 to 1.6, specifically 1.1 to 1.5, in the interval where the angular frequency (log ω) is 0 to 1 rad/s.
When the storage modulus is more than the above range, strength is improved, but Stiffness (Stiffness) is also improved, and thus, when woven or knitted into a cloth, it becomes stiff, making it difficult to process into a desired product, and causing discomfort to the wearer of the product.
At this time, in the graph in which tan δ varies with angular frequency (ω), tan δ may have a slope of minus (-) on average, more specifically, may have a slope of minus (-) on average in the interval of 0.1rad/s to 1000 rad/s. That is, in the graph of tan δ variation with angular frequency (ω) of the polyethylene yarn of the present invention, a slope value having a large absolute value is provided, and unlike other various polyethylenes, an inflection point is not formed. This means that such polyethylene yarns exhibit a higher tackiness compared to their elasticity. In particular, it means that entanglement or gelation between the polymer chains can be easily oriented in the flow direction even under low shear stress, and therefore, entanglement or gelation between the polymer chains is practically not present in the polyethylene yarn. With this rheology, there is virtually no or little gel in the yarn, and thus hairiness can be prevented from forming upon stretching.
In this case, in the graph in which tan δ varies with angular frequency (ω) of the yarn, when the angular frequency is 0.1rad/s, tan δ may be 9 or more and less than 15, specifically 9 to 12, but is not limited thereto.
the angular frequency at which the tan delta value is 1 may be 200 to 500rad/s, in particular 250 to 400rad/s. Since the angular frequency interval at the tan delta value of 1 is large, the tackiness is more advantageous than polyethylene yarns commonly used in the art, and thus, there is little entanglement between polyethylene polymer chains and the alignment of polymer chains is excellent. Since the yarns have excellent alignment between polymer chains, a cloth having more excellent sliding properties and rolling properties can be produced. The cloth made of the yarn has excellent cutting resistance, and can prevent the cloth from being damaged due to pilling (pilling) phenomenon caused by the repeated application of external force by a blade and a sharp object.
In the graph of the variation of the loss modulus (G') with angular frequency (ω) of the polyethylene yarn, the loss modulus may be between 100Pa and 700Pa, in particular between 200Pa and 500Pa, at an angular frequency of 0.1rad/s and 0.5rad/s, and points of loss modulus of 1000Pa may occur.
In the graph of the change in the loss modulus with the angular frequency, when the values of the angular frequency (ω) and the loss modulus (G ") are converted into logarithmic values, the average slope of the loss modulus (log G") may be 0.75 to 0.9 in the range of 0 to 1 rad/s.
In the graph in which the complex viscosity (η) varies with the angular frequency (ω), the complex viscosity (η) may be 3000pa.s to 6000pa.s, specifically 3700pa.s to 5000pa.s, and the average slope may be-1000 to-300, specifically-800 to-500, in the range of 0.1rad/s to 1rad/s, when the angular frequency is 0.1 rad/s.
In the graph of the phase angle (°) as a function of the complex shear modulus (G), the phase angle may be 60 ° to 90 °, specifically 75 ° to 90 °, when the complex shear modulus (G) is 350 to 1000 Pa.
The present invention has the loss modulus and complex viscosity as described above, and therefore, can have a melt viscosity that is easy to perform melt spinning, and can suppress defects caused by the spinning process.
The weight average molecular weight (Mw) of the polyethylene yarns of the invention may be in the range of 80,000g/mol to 180,000g/mol, specifically 100,000g/mol to 170,000g/mol, more specifically 120,000g/mol to 160,000g/mol.
In addition, the polyethylene yarn may have a density of 0.941 to 0.965g/cm 3 And the crystallinity may be 55% to 85%, preferably 60% to 85%.
In addition, the polyethylene yarn may have a polydispersity index (Polydispersity Index; PDI) of greater than 5 and less than 9. The polydispersity index (PDI) is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and may also be referred to as the molecular weight distribution index (MWD). When the PDI is less than 5, a relatively narrow molecular weight distribution may result in poor flowability and reduced processability at the time of melt extrusion, thereby causing yarn breakage due to uneven discharge in the spinning process. Conversely, when the PDI is greater than 9, the broad molecular weight distribution improves melt flowability and processability at the time of melt extrusion, but contains an excessive amount of low molecular weight polyethylene, and thus, the tensile strength of the finally obtained polyethylene yarn is lowered.
The polyethylene yarn of the invention may have a tensile strength of 3.5 to 8.5g/de, a tensile modulus of 15 to 80g/de and an elongation at break of 14 to 55%. When the tensile strength is more than 8.5g/de, or the tensile modulus is more than 80g/de, or the elongation at break is less than 14%, not only is the polyethylene yarn not good in weaving property, but also the cloth manufactured therefrom is excessively stiff, which may cause users to feel uncomfortable. Conversely, when the tensile strength is less than 3.5g/de, or the tensile modulus is less than 15g/de, or the elongation at break is more than 55%, the cloth manufactured from such polyethylene yarn may be caused to generate a hairball when the user continuously uses the cloth.
The polyethylene yarn of the present invention may have a circular (circular) cross section or a shaped (non-circular) cross section, but preferably has a circular cross section for excellent sliding characteristics.
In addition, the polyethylene yarn of the present invention may have a strength of 11g/d or more, specifically 13g/d or more, so that a product manufactured using the yarn has a cut resistance index of 5 or more.
The method for producing the yarn of the present invention may be any method known in the art for producing a yarn using polyethylene. As a specific example, the method may include the steps of: melting the polyethylene slices to obtain a polyethylene melt; extruding a polyethylene melt through a spinneret plate having a plurality of spinneret orifices; cooling a plurality of filaments formed from a polyethylene melt as it is discharged from a plurality of orifices; bundling the cooled plurality of filaments to form a multifilament yarn; stretching the multifilament at a total stretching ratio of 5-20 times and performing heat setting; and winding the drawn multifilament yarn. In this case, the stretching step may be performed in a multi-stage stretching manner, and the relaxation rate at the last stretching in the multi-stage stretching may be 3% to 8% or less, but is not limited thereto. The relaxation rate at the time of the last stretching refers to the relaxation rate at the time of the last stretching performed before winding after stretching.
The polyethylene melt may be conveyed by a screw in an extruder to a spinneret having a plurality of orifices and then extruded through the plurality of orifices. The number of the plurality of orifices of the spinneret may be set according to the single denier (Denier Per Filament; DPF) and total denier of the yarn to be produced. As a specific example, to produce a yarn having a total denier of 1 to 3DPF and 100 to 1,000 denier, the spinneret may have 40 to 500 spinneret orifices.
The melting step in the extruder and the extrusion step using the spinneret may be performed at 150 to 315 ℃, preferably 250 to 315 ℃, more preferably 260 to 290 ℃. When the spinning temperature is lower than 150 ℃, the low spinning temperature cannot uniformly melt the polyethylene chips (melting), so that spinning is difficult. Conversely, when the spinning temperature is higher than 315 ℃, thermal decomposition of polyethylene is caused, and it is difficult to exhibit high strength.
The cooling of the plurality of filaments may be performed by air cooling. For example, the cooling of the filaments may be performed at 15 to 40℃using cooling air having an air speed of 0.2 to 1 m/sec. When the cooled temperature is lower than 15 ℃, supercooling results in insufficient elongation, so that breakage may occur during the subsequent drawing, and when the cooled temperature is higher than 40 ℃, uneven solidification may result in increased fineness deviation between filaments, so that breakage may occur during the drawing.
A oiling process (oiling process) of supplying oil to the cooled plurality of filaments using an Oil Roller (OR) OR an oil jet (oil jet) may be further performed before forming the multifilament yarn. The finish providing step may also be performed by metering in (MO) means.
In addition, the interlacing process using the interlacing device may be further performed before the multifilament yarn is wound by the winding machine, so as to improve bundling and weaving properties of the polyethylene yarn.
The polyethylene yarn produced by this method can be knitted or woven into a cloth having cut resistance.
Specifically, the polyethylene cloth of the present invention may be knitted from a core spun yarn (covered yarn). The core spun yarn may be any yarn including the polyethylene yarn of the present invention, and may include, as a specific example, the polyethylene yarn of the present invention, a polyurethane yarn (for example, spandex; spandex) which surrounds the polyethylene yarn in a spiral shape, and a polyamide yarn (for example, nylon 6 or nylon 66 yarn) which surrounds the polyethylene yarn in a spiral shape. The polyamide yarns may be replaced with polyester yarns (e.g., PET yarns) depending on the characteristics of the target product.
In this case, the weight of the polyethylene yarn may be 45% to 85% of the total weight of the core-spun yarn, the weight of the polyurethane yarn may be 5% to 30% of the total weight of the core-spun yarn, and the weight of the polyamide or polyester yarn may be 5% to 30% of the total weight of the core-spun yarn, but is not limited thereto.
On the other hand, the cloth of the present invention may have a weight per unit area (i.e., areal density) of 150 to 800g/m 2 Is a woven or knitted fabric of (c). When the surface density of the cloth is less than 150g/m 2 In the case of a cloth, the consistency of the cloth is insufficient, and a plurality of voids are present in the cloth, which may reduce the cutting resistance of the cloth. In contrast, when the areal density of the cloth is greater than 800g/m 2 Too dense a cloth structure results in a cloth that is too stiff, can create problems with the feel experienced by the user, and high weight can cause problems in use.
Such cloth can be processed into products requiring excellent cut resistance. The product may be all existing fibre products, preferably protective gloves or garments, which provide a protective function to the human body.
The protective article of the present invention has excellent Cut Resistance (Cut Resistance) of 5gf or less, more preferably 2 to 5gf, while having a Cut Load (Cut Load) of 5.5N or more, more preferably 6 to 9N, and exhibits excellent wearing feeling.
Hereinafter, the present invention will be described in more detail with reference to examples. The following examples are merely references for the detailed description of the present invention, and the present invention is not limited thereto but can be implemented in various forms.
In addition, unless defined otherwise, all technical and scientific terms have the same meaning as commonly understood by one of ordinary skill in the art. In this application, the terminology used for the purpose of description is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The unit of the additive not specifically described in the specification may be weight%.
[ measurement of yarn rheology ]
Rheological properties were measured using DHR-2 (TA Instrument; TA Instrument), the geometry used in the measurement being plate-plate (parallel plate; PP), and storage modulus (G'), loss modulus (G "), tan δ, complex viscosity (η), and phase angle (°) as a function of angular frequency were measured. The measurement was performed under a nitrogen atmosphere at 250℃and in a Sample size (Sample Dimension) having a diameter of 25mm, a Gap point of 1.0mm and a deformation ratio of 10%.
Fig. 1 to 5 show graphs of rheological measurements of example 1 and comparative example 1.
Specifically, fig. 1 shows the measurement results of the storage modulus (G') of example 1 and comparative example 1, fig. 2 shows the measurement result of the loss modulus (g″), fig. 3 shows the measurement result of tan δ, fig. 4 shows the measurement result of complex viscosity (η), and fig. 5 shows the measurement result of phase angle (°).
[ measurement of physical Properties of protective glove ]
* Cut Resistance (Cut Resistance)
According to ISO13997: the 1999 standard measures the cut resistance of protective gloves.
* Stiffness (Stiffness) (gf)
Samples were cut from the palm portion of the protective glove (transverse: 60mm, longitudinal: 60 mm) and then measured for stiffness according to ASTM D885/D885M-10a (2014) section38 (section 38). The measuring device is as follows.
( i) Constant speed elongation type tensile tester (model: INSTRON 3343) (CRE-typeTensile Testing Machine; model: INSTRON 3343 )
(ii) Loading Cell, 2KN [200kgf ]
(iii) Sample Holder (specification Holder): sample Holder as defined in section38.4.3 (section 38.4.3)
(iv) Sample depressor (Specimen Depressor): sample depressor (Specimen Depressor) defined in section 38.4.4 (section 38.4.4)
Specifically, the sample was placed in the middle of a sample Holder (specification Holder) with the glove outside of the sample facing upward and the glove inside facing downward, so that the side adjacent to the fingers of the glove and the opposite side (i.e., the side adjacent to the wrist of the glove) were directly supported by the sample Holder (specification Holder). The sample is kept flat rather than curved. At this time, the distance between the sample support portion (Specimen supporting part) of the sample Holder (Specification Holder) and the pressing portion (pressing part) of the sample presser (Specimen Depressor) was 5mm. Next, with the sample presser (Specimen Depressor) stationary in this state, the sample Holder (specification Holder) was raised to 15mm, and the maximum strength was measured.
* Wear resistance evaluation
The abrasion resistance of the protective glove was measured according to ASTM-D3884 standard. The evaluation instrument used was a martindale abrasion tester. At this time, the rubbing cloth used was 320Cw of sandpaper, and the applied load was 500g.
Example 1 ]
A polyethylene multifilament interlaced yarn comprising 240 filaments and having a total denier of 400 was produced.
Specifically, polyethylene pellets are fed into an extruder and melted. The polyethylene melt was extruded through a spinneret having 240 orifices. The filaments discharged from the plurality of orifices of the spinneret and molded are cooled in a cooling section, and then bundled into multifilaments by a bundling machine. Next, the multifilament is stretched and heat-set in the stretching section.
The stretching step was performed in a multistage stretching manner, and the relaxation rate at the last stretching in the multistage stretching was 8%. Next, the drawn multifilament yarn was passed through 6.0kgf/cm in a interlacing device 2 Is interleaved and then wound by a winder. The winding tension was 0.6g/d.
The rheology of the yarns produced was measured and is shown in table 1 and figures 1 to 5. The density, weight average molecular weight, and PDI of the yarn produced were measured and are shown in table 2.
Next, 140 denier polyurethane yarns (Spandex) and 140 denier nylon yarns were spirally wound around the yarns of examples 1 to 3 and comparative examples 1 to 3, thereby producing core-spun yarns. The weight of the polyethylene yarn is 60% of the total weight of the core-spun yarn, and the weight of the polyurethane yarn and the weight of the nylon yarn are respectively 20% of the total weight of the core-spun yarn. Knitting the covering yarn into protective gloves.
Physical properties of the manufactured protective glove were measured and are shown in table 3.
Table:
Figure BDA0004141077010000111
table 2:
Figure BDA0004141077010000121
< examples 2 to 3 and comparative examples 1 to 3>
A protective glove was manufactured in the same manner as in example 1, except that polyethylene yarns satisfying the physical properties shown in tables 1 and 2 were used in example 1.
Table 3:
Figure BDA0004141077010000122
from table 3, it can be confirmed that the protective glove of the examples manufactured using the polyethylene fiber of the present invention has both excellent cut resistance and excellent abrasion resistance, and has low stiffness, and thus can have improved wearing feeling as compared with the comparative examples. The present invention has been described above with reference to a plurality of specific matters and limited embodiments and drawings, but this is only for aiding in a more complete understanding of the present invention, and the present invention is not limited to the above-described embodiments, and various modifications and variations can be made by those skilled in the art based on this description.
The inventive idea is therefore not limited to the embodiments described, but the appended claims and their equivalents or equivalent variants fall within the scope of the inventive idea.

Claims (10)

1. A cut-resistant polyethylene yarn is characterized in that,
in the graph of the change of the storage modulus (G') with the angular frequency (ω), the storage modulus is 10Pa to 100Pa when the angular frequency is 0.1rad/s, the storage modulus is 100Pa to 1000Pa when the angular frequency is 1rad/s,
in the graph in which tan delta varies with angular frequency (ω), when the angular frequency is 0.1rad/s, tan delta is 9 or more.
2. The cut resistant polyethylene yarn of claim 1 wherein,
in the graph of the variation of the loss modulus (G') with angular frequency (ω) of the polyethylene yarn, the loss modulus is 100Pa to 700Pa when the angular frequency is 0.1rad/s, and a point of the loss modulus of 1000Pa occurs in the interval of 0.25 to 0.5 rad/s.
3. The cut resistant polyethylene yarn of claim 1 wherein,
in the graph of the change of complex viscosity (eta) with angular frequency (omega), when the angular frequency is 0.1rad/s, the complex viscosity is 3000 Pa.s-6000 Pa.s, and the average slope is-1000 to-300 in the interval of 0.1 rad/s-1 rad/s.
4. The cut resistant polyethylene yarn of claim 1 wherein,
the titer of the polyethylene yarn is 1-3 DPF.
5. The cut resistant polyethylene yarn of claim 1 wherein,
in the graph of the phase angle of the polyethylene yarn as a function of the complex shear modulus (G), the phase angle is 75 ° to 90 ° when the complex shear modulus (G) is 350 to 1000 Pa.
6. The cut resistant polyethylene yarn of claim 1 wherein,
the hairiness generation number of the polyethylene yarn is below 20EA/50,000 m.
7. A cutting-resistant cloth is characterized in that,
a cut resistant polyethylene yarn comprising any one of claims 1 to 6.
8. The cut resistant fabric of claim 7, wherein the fabric comprises,
according to ISO13997: the cut resistance of the cloth measured by 1999 standard is 5.5N or more.
9. A protective article is characterized in that,
a cut resistant fabric comprising the cut resistant fabric of claim 7.
10. The protective article of claim 9, wherein the protective article comprises,
the protective articles are cut-resistant gloves.
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