An ultra-high molecular weight polyethylene fiber containing rigid fibers, its manufacturing method and its applications

Abstract

This invention relates to an ultra-high molecular weight polyethylene (UHMWPE) fiber comprising rigid fibers, its manufacturing method, and its applications. The UHMWPE fiber of this invention improves the wearing comfort of fabrics, while also achieving cut resistance level 5 according to EN388-2003 standard. The UHMWPE fiber of this invention comprises UHMWPE as a matrix, rigid fibers dispersed in the matrix, and optionally rigid particles dispersed in the matrix, wherein the rigid fibers have one or more necked sections, and the length of the rigid fibers is 10-2000 μm.

Description

Technical Field

[0001] This invention relates to the field of fiber manufacturing technology, and more specifically to an ultra-high molecular weight polyethylene fiber containing rigid fibers, its manufacturing method, and its applications. Background Technology

[0002] Ultra-high molecular weight polyethylene (UHMWPE) fiber is currently the fiber with the highest specific strength and specific modulus in the world. It is spun from polyethylene with a molecular weight of 1 million to 5 million. UHMWPE fiber is the highest specific strength fiber among industrialized fiber materials, possessing excellent high strength, high modulus, abrasion resistance, and chemical corrosion resistance. It is widely used in safety protection, military, aerospace, marine, and sports fields. With the deepening of military-civilian integration, the application of UHMWPE fiber in the civilian market is gradually increasing, with cut-resistant gloves gradually becoming dominant. Currently, the highest cut rating for protective gloves made of commonly used UHMWPE fiber is EN388-20016 standard Level 3, which is not suitable for the needs of actual working environments for cut hazard protection.

[0003] To improve the cut resistance of gloves, a common method is to blend steel wire with ultra-high molecular weight polyethylene (UHMWPE) fibers to achieve an ultra-high cut resistance rating. While this method improves the cut resistance of the gloves, the steel wire is relatively stiff, making them difficult to wear and uncomfortable, thus failing to achieve a balance between protective performance and comfort. Currently, the common practice is to modify UHMWPE by adding inorganic fillers.

[0004] Patent CN1 04233497A provides a method for preparing cut-resistant fibers from nanocrystalline silicon carbide and ultra-high molecular weight polyethylene. The method involves adding nanocrystalline silicon carbide particles to a solvent, repeatedly grinding them in a sand mill, and then adding them together with ultra-high molecular weight polyethylene into the solvent. The mixture is then thoroughly mixed using a high-speed shearing and stirring machine to obtain a fiber spinning solution.

[0005] Patent CN1 01528998A discloses a composite yarn containing filaments or fixed-length fibers. The fixed-length fibers used are short-cut hard fibers with a certain aspect ratio, including glass fibers, mineral fibers or metal fibers, which are used to improve the cut resistance of the yarn.

[0006] Patent CN1 09610040A discloses a method of mixing glass fiber with a first white oil to obtain a glass fiber premix, then mixing the glass fiber premix, antioxidant and UHMWPE powder in a second white oil to obtain a spinning mixture, which is then swelled, extruded and molten, cooled to form gel filaments and thus obtained composite fibers. Summary of the Invention

[0007] The inventors of this invention discovered that while adding rigid fibers to UHMWPE for filling modification can improve the cut resistance of gloves, the gloves feel stiff to wear. Furthermore, because the rigid fibers are prone to detaching from the fiber matrix during manufacturing or use, this can lead to environmental pollution or secondary harm to users, such as itching and allergies, failing to achieve a balance between protective performance and wearing comfort (especially wearing safety). Additionally, the inventors found that adding rigid particles to UHMWPE for filling modification has limited effect on improving cut resistance. Therefore, through diligent research, the inventors discovered that introducing necked rigid fibers into the ultra-high molecular weight polyethylene matrix, and preferably combining them with rigid particles to form a specific composite structure, can solve these technical problems of the prior art. This invention is based on this discovery.

[0008] Specifically, the present invention relates to the following aspects.

[0009] 1. An ultra-high molecular weight polyethylene fiber comprising ultra-high molecular weight polyethylene as a matrix, rigid fibers dispersed in the matrix, and optionally rigid particles dispersed in the matrix, wherein the rigid fibers have one or more (preferably 1-10 or 2-4) necked sections (preferably pits), and the length of the rigid fibers is 10-2000 μm (preferably 30-300 μm).

[0010] 2. The fiber described above or below, wherein the content of the rigid fiber is at most 50 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene, and the content of the rigid particles is 0-20 parts by weight (preferably 0.5-5 parts by weight).

[0011] 3. The fiber described above or below, wherein the Mohs hardness of the rigid fiber is greater than that of the ultra-high molecular weight polyethylene, and the Mohs hardness of the rigid particles is greater than that of the ultra-high molecular weight polyethylene.

[0012] 4. The fiber described above or below, wherein the ultra-high molecular weight polyethylene has a viscosity-average molecular weight of 1 million to 9 million (preferably 3 million to 5 million).

[0013] 5. The fiber described above or below, wherein the diameter of the necked section is less than 85% (preferably 40-70%) of the body diameter of the hard fiber, and the length of the necked section is 5-80% (preferably 10-50%) of the length of the hard fiber.

[0014] 6. The fiber described above or below, wherein the hard fiber is a one-dimensional linear structure with a body diameter of up to 20 μm (preferably 3-10 μm) and an aspect ratio of 3-1000 (preferably 5-50).

[0015] 7. The fiber described above or below, wherein the necked section is a pit (preferably an etched pit) having an average length of 0.01-100 μm (preferably 0.1-1 μm) and an average depth of at least 0.01 μm (preferably 0.1-3 μm).

[0016] 8. The fiber described above or below, wherein the hard fibers are substantially uniformly dispersed in the matrix, or the matrix is ​​substantially free of agglomeration of the hard fibers, or the minimum distance between any two adjacent hard fibers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0017] 9. The fiber described in any of the foregoing or hereinafter, wherein the hard fiber is selected from at least one of inorganic hard fibers and organic hard fibers, preferably from at least one of inorganic hard fibers.

[0018] 10. The fiber described above or below, wherein the inorganic hard fiber is selected from at least one of metal fiber, glass fiber, ceramic fiber, mineral fiber, and basalt fiber, or the organic hard fiber is selected from at least one of carbon fiber, aramid fiber, aromatic polyamide copolymer fiber, heterocyclic polyamide fiber, graphite fiber, silicon carbide fiber, wood fiber, bamboo fiber, sisal fiber, and kerosene fiber.

[0019] 11. The fiber described above or below, wherein the average diameter of the hard particles is not greater than 20 μm (preferably 0.5-2 μm).

[0020] 12. The fiber described in any of the foregoing or hereinafter, wherein the hard particles are selected from at least one of inorganic hard particles and organic hard particles, preferably from at least one of inorganic hard particles.

[0021] 13. The fiber described above or below, wherein the inorganic hard particles are selected from at least one of metal particles, glass particles, ceramic particles, mineral particles, vitrified microspheres, and fly ash, or the organic hard particles are selected from at least one of organosilicon micropowder, amino micropowder, polyacrylate micropowder, polylactic acid micropowder, and polytetrafluoroethylene micropowder.

[0022] 14. The fiber described in any of the foregoing or hereinafter, wherein the hard fiber and / or the hard particles have undergone surface chemical modification treatment, such as surface chemical modification treatment with a silane coupling agent.

[0023] 15. The fiber described above or below, wherein the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, γ-(glycidoxy)propyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

[0024] 16. The fiber described in any of the foregoing or hereinafter, wherein the hard fiber and / or the hard particles have undergone surface physical modification treatment, such as surface roughening treatment and / or surface polymer coating treatment.

[0025] 17. The fiber described in any of the foregoing or subsequent aspects, wherein the polymer is selected from at least one of thermoplastic polymers, thermosetting polymers and rubber, preferably selected from at least one of cellulose esters, olefin polymers (polyvinyl acetate, polyvinyl alcohol, chlorinated polyethylene, polyisobutylene, etc.), polyesters, polyethers, polyamides, polyacrylates, α-cyanoacrylates, polyvinyl acetals, ethylene-vinyl acetate copolymers and isocyanates.

[0026] 18. The fiber described above or below, wherein at least a portion of the hard particles are attached (e.g., adsorbed) to at least one of the necked sections, preferably attached (e.g., adsorbed) inside at least one of the recesses.

[0027] 19. A method for manufacturing ultra-high molecular weight polyethylene fiber, comprising the following steps:

[0028] 1) Optionally, the rigid fibers are subjected to surface chemical modification treatment and / or surface physical modification treatment to obtain modified rigid fibers, wherein the rigid fibers have one or more (preferably 1-10 or 2-4) necked segments, and the length of the rigid fibers is 10-2000 μm (preferably 30-300 μm).

[0029] 2) Optionally, perform surface chemical modification treatment and / or surface physical modification treatment on the hard particles to obtain modified hard particles.

[0030] 3) Mix the hard fibers or the modified hard fibers, optionally the hard particles or the modified hard particles, ultra-high molecular weight polyethylene, and a solvent to obtain a spinning solution.

[0031] 4) The spinning solution is spun into the polyethylene fiber.

[0032] 20. The manufacturing method described above or below, wherein before performing step 1) or step 2), the method further includes a step of drying the hard fiber or the hard particles, the drying comprising: reducing pressure, drying temperature of 80-200°C (preferably 90-120°C), and drying time of 0.5-10h (preferably 1-4h).

[0033] 21. The manufacturing method described above or below, wherein prior to step 1), the method further includes etching the rigid fiber (e.g., strong acid etching) to form the necked section.

[0034] 22. The manufacturing method described above or below, wherein the surface chemical modification treatment comprises: using a silane coupling agent, wherein the amount of the silane coupling agent is 0.8-5 wt% (preferably 1-3 wt%) of the weight of the rigid fiber or the rigid particles, the treatment temperature is 40-100°C (preferably 70-90°C), and the treatment time is 1-120 min (preferably 5-30 min).

[0035] 23. The manufacturing method described above or below, wherein the surface physical modification treatment comprises: surface coating with a polymer, wherein the amount of the polymer (dry basis) is up to 50% wt% (preferably 5-10 wt%) of the weight of the hard fiber or the hard particles, the treatment temperature is at least 30°C (preferably 40-60°C), and the treatment time is at least 1 min (preferably 5-10 min).

[0036] 24. The manufacturing method described above or below, wherein, relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the rigid fiber or the modified rigid fiber (based on rigid fiber) is at most 50 parts by weight (preferably 3-10 parts by weight), the amount of the rigid particles or the modified rigid particles (based on rigid particles) is 0-20 parts by weight (preferably 0.5-5 parts by weight), and the amount of the solvent is at least 500 parts by weight (preferably 1000-2000 parts by weight).

[0037] 25. The manufacturing method described above or below, wherein in step 3), the rigid fiber or the modified rigid fiber is first dry-mixed with the rigid particles or the modified rigid particles, and then the ultra-high molecular weight polyethylene is added for dry mixing, and then the resulting mixture is mixed with the solvent.

[0038] 26. The manufacturing method described above or below, wherein in step 4), the spinning includes: gel spinning, with a primary draw ratio of 3-10 at the spinneret, an over-drawing temperature of 80-150°C, and an over-drawing ratio of 6-20.

[0039] 27. The manufacturing method described above or below, wherein, prior to step 4), the method further includes a step of combing and orienting the spinning solution.

[0040] 28. A fabric comprising ultra-high molecular weight polyethylene fibers as described above or below, or ultra-high molecular weight polyethylene fibers manufactured by the manufacturing methods described above or below.

[0041] 29. The fabric described in any of the foregoing or hereinafter includes at least one other fiber selected from natural plant fibers, natural animal fibers, man-made regenerated fibers, synthetic fibers and inorganic fibers.

[0042] Technical effect

[0043] The necked rigid fiber of this invention can create an anchoring effect within the fiber matrix, allowing it to exist more stably within the fiber matrix and preventing it from easily detaching, thereby effectively reducing secondary harm to the human body. Especially during fiber manufacturing or cutting, the necked segment structure remains stable and does not detach.

[0044] This invention introduces necked rigid fibers into an ultra-high molecular weight polyethylene matrix, and in a preferred case, combines them with rigid particles to form a specific composite structure, namely a composite structure in which rigid particles are attached to the surface of the necked rigid fibers. This increases the bonding between the rigid fibers and the fiber matrix, resulting in UHMWPE fibers with low shedding, high comfort, high strength and toughness, and cut resistance.

[0045] The ultra-high molecular weight polyethylene fiber of this invention can greatly improve the wearing comfort of the fabric, especially the wearing safety, while the fabric can achieve level 5 of the EN388-2003 standard for cut resistance. Attached Figure Description

[0046] Figure 1 This is a schematic diagram of the necked rigid fiber according to the present invention.

[0047] exist Figure 1 In the diagram, L represents the length of the hard fiber, L1 and L2 represent the lengths of the two indentations respectively, D represents the diameter of the hard fiber (i.e., the diameter of the body), and D1 and D2 represent the depths of the two indentations respectively. Detailed Implementation

[0048] The specific embodiments of the present invention will be described in detail below. However, it should be noted that the scope of protection of the present invention is not limited to these specific embodiments, but is determined by the claims in the appendix.

[0049] All publications, patent applications, patents, and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings commonly understood by those skilled in the art. In case of conflict, the definitions in this specification shall prevail.

[0050] When this specification uses the prefixes “known to those skilled in the art,” “prior art,” or similar terms to derive materials, substances, methods, steps, apparatus, or components, the objects derived from such prefixes cover those commonly used in the art at the time of this application, but also include those that are not currently commonly used but will become generally recognized in the art as suitable for similar purposes.

[0051] In the context of this specification, "basically" means a deviation of no more than 20%, preferably no more than 10%, 5%, or 1%.

[0052] In the context of this specification, the extent to which filler is released from the fiber matrix is ​​characterized by the degree to which material is released from the fiber during the fiber manufacturing process.

[0053] In the context of this specification, aggregation was measured as follows: a 10cm segment was randomly cut from the fiber, the number of aggregated structures was investigated under a laser microscope, and then scored according to the following criteria. This measurement was repeated 10 times, and the average value was taken.

[0054] No family reunions: 0

[0055] Small group reunions: 2 or fewer

[0056] Medium-sized family reunification: 3-4

[0057] Large-scale reunions: 5 or more.

[0058] In the context of this specification, linear density deviation rate is measured according to GB / T 14343.

[0059] In the context of this specification, the term "distance between two rigid fibers" or a similar expression means the distance between any point on one rigid fiber and any point on the other rigid fiber.

[0060] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this instruction manual are based on weight, and the pressure is gauge pressure.

[0061] In the context of this specification, where no specific operating conditions or additives are specified, those known in the art are directly applicable without particular limitation.

[0062] In the context of this specification, any two or more embodiments of the present invention can be arbitrarily combined, and the resulting technical solutions are part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0063] According to one embodiment of the present invention, a type of ultra-high molecular weight polyethylene fiber is disclosed. The ultra-high molecular weight polyethylene fiber is generally a monofilament or a filament.

[0064] According to one embodiment of the present invention, the ultra-high molecular weight polyethylene fiber comprises ultra-high molecular weight polyethylene as a matrix, rigid fibers dispersed in the matrix, and optionally rigid particles dispersed in the matrix. Here, "rigid" means that the Mohs hardness of the rigid fibers is greater than that of the ultra-high molecular weight polyethylene, and that the Mohs hardness of the rigid particles is greater than that of the ultra-high molecular weight polyethylene.

[0065] According to one embodiment of the present invention, the rigid fiber has one or more (preferably 1-10 or 2-4) necked sections. Without necked sections, the rigid fiber surface is smooth, making it difficult to bond with other fibers and resulting in insufficient cut resistance. Too many necked sections damage the rigid fiber structure, also easily leading to insufficient cut resistance.

[0066] In the context of this specification, a necked section refers to a segment on a rigid fiber, wherein one or both ends (preferably both ends) of the segment have the body diameter of the rigid fiber, and the diameter of the middle segment is smaller than the body diameter. Here, the body diameter refers to the diameter of the rigid fiber body (excluding the necked section). However, it should be emphasized that the necked section of the present invention is a diameter reduction portion "actively" or "intentionally" introduced on the rigid fiber. Therefore, variations in fiber diameter caused by surface roughness of the rigid fiber or by non-uniformity of fiber diameter are not considered necked sections in the present invention. According to the present invention, there is no particular limitation on the method of forming the necked section, but examples such as bamboo-joint type and pitted type can be given.

[0067] According to one embodiment of the present invention, the diameter of the necked section is less than 85% (preferably 40-70%) of the body diameter of the rigid fiber, and the length of the necked section is 5-80% (preferably 10-50%) of the length of the rigid fiber. If the necked section is too thin or too long, the performance of the rigid fiber is impaired, resulting in insufficient cut resistance. If the necked section is too shallow or too short, the surface roughness of the rigid fiber is insufficient, causing poor bonding and impairing cut resistance. In a preferred embodiment, the necked section is a recess, and the average length of the recess is 0.01-100 μm (preferably 0.1-1 μm), and the average depth is at least 0.01 μm (preferably 0.1-3 μm).

[0068] According to one embodiment of the present invention, the pit is an etched pit. According to the present invention, there is no particular limitation on the method for forming the etched pit; any method conventionally known in the relevant technical field can be used. However, examples include laser etching and acid etching. Etched pits have more irregular edges and are more likely to increase adhesion than natural pits.

[0069] According to one embodiment of the present invention, the length of the rigid fiber is 10-2000 μm (preferably 30-300 μm). If the rigid fiber is too short, it will not achieve the effect of cut resistance; if the rigid fiber is too long, the spinning difficulty will increase, the fiber quality will be damaged, and the cut resistance will be insufficient.

[0070] According to one embodiment of the present invention, the content of the rigid fiber is at most 50 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene.

[0071] According to one embodiment of the present invention, the content of the hard particles is 0-20 parts by weight (preferably 0.5-5 parts by weight). If the hard particle component is too small, a composite structure cannot be formed, increasing the bonding force; if the hard particles are too large, the spinning difficulty increases, the fiber quality is damaged, and the cut resistance is insufficient.

[0072] According to one embodiment of the present invention, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million (preferably 3 million to 5 million).

[0073] According to one embodiment of the present invention, the rigid fiber is a one-dimensional linear structure with a body diameter of up to 10 μm (preferably 3-5 μm) and an aspect ratio of 3-1000 (preferably 5-50).

[0074] According to one embodiment of the present invention, the rigid fibers are substantially uniformly dispersed in the matrix. In other words, there is substantially no agglomeration of the rigid fibers in the matrix. As a quantitative indicator, the minimum distance between any two adjacent rigid fibers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm). In the context of this specification, an agglomeration refers to a composite structure formed by multiple rigid fibers entangled or interwoven together. According to the present invention, when rigid fibers form an agglomeration structure in the fiber matrix, it may lead to a decrease in the uniformity of the linear density of polyethylene fibers, affecting wearing comfort.

[0075] According to one embodiment of the present invention, the hard fiber is selected from at least one of inorganic hard fibers and organic hard fibers, preferably selected from at least one of inorganic hard fibers.

[0076] According to one embodiment of the present invention, the inorganic hard fiber is selected from at least one of metal fiber, glass fiber, ceramic fiber, mineral fiber, and basalt fiber.

[0077] According to one embodiment of the present invention, the organic hard fiber is selected from at least one of carbon fiber, aramid fiber, aromatic polyamide copolymer fiber, heterocyclic polyamide fiber, graphite fiber, silicon carbide fiber, wood fiber, bamboo fiber, sisal fiber, and kerosene fiber.

[0078] According to one embodiment of the present invention, the average diameter of the hard particles is not greater than 20 μm (preferably 0.5-2 μm).

[0079] According to one embodiment of the present invention, the hard particles are selected from at least one of inorganic hard particles and organic hard particles, preferably selected from at least one of inorganic hard particles.

[0080] According to one embodiment of the present invention, the inorganic hard particles are selected from at least one of metal particles, glass particles, ceramic particles, mineral particles, vitrified microspheres, and fly ash.

[0081] According to one embodiment of the present invention, the organic hard particles are selected from at least one of organosilicon micro powder, amino micro powder, polyacrylate micro powder, polylactic acid micro powder, and polytetrafluoroethylene micro powder.

[0082] According to one embodiment of the present invention, the rigid fiber undergoes surface chemical modification treatment, such as surface chemical modification treatment with a silane coupling agent. Without surface modification treatment, the rigid fiber does not bond well with the fiber matrix, resulting in insufficient cut resistance.

[0083] According to one embodiment of the present invention, the hard particles undergo surface chemical modification treatment, such as surface chemical modification treatment with a silane coupling agent. Without surface modification treatment, the hard particles do not bond well with the fiber matrix, resulting in insufficient cut resistance.

[0084] According to one embodiment of the present invention, the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, γ-(glycidoxy)propyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

[0085] According to one embodiment of the present invention, the rigid fibers and / or the rigid particles are subjected to surface physical modification treatment, such as surface roughening treatment and / or surface polymer coating treatment.

[0086] According to one embodiment of the present invention, the polymer is selected from at least one of thermoplastic polymers, thermosetting polymers and rubber, and preferably from at least one of cellulose esters, olefin polymers (polyvinyl acetate, polyvinyl alcohol, chlorinated polyethylene, polyisobutylene, etc.), polyesters, polyethers, polyamides, polyacrylates, α-cyanoacrylates, polyvinyl acetals, ethylene-vinyl acetate copolymers and isocyanates.

[0087] According to one embodiment of the present invention, at least a portion of the hard particles are attached (e.g., adsorbed) onto at least one of the necked sections, or preferably at least a portion of the hard particles are attached (e.g., adsorbed) into at least one of the recesses, to form a composite structure in which hard particles are attached to the surface of the necked hard fiber. According to the present invention, there are no particular limitations on the method for forming the composite structure; for example, adsorption, adhesion, etc., are also possible methods.

[0088] According to one embodiment of the present invention, the fiber has a single filament fineness of at least 0.5 dtex (preferably 0.9-5 dtex, most preferably 1-3 dtex).

[0089] According to one embodiment of the present invention, a method for manufacturing ultra-high molecular weight polyethylene (UHMWPE) fiber is also provided. According to the present invention, the manufacturing method can be used to manufacture the UHMWPE fiber as described above. Therefore, for any content of the manufacturing method not described or elaborated herein, the content given above in this specification regarding the UHMWPE fiber can be directly applied, and will not be repeated here.

[0090] According to one embodiment of the present invention, the method for manufacturing the ultra-high molecular weight polyethylene fiber includes the following steps:

[0091] 1) Optionally, perform surface chemical modification treatment and / or surface physical modification treatment on the hard fibers to obtain modified hard fibers.

[0092] 2) Optionally, perform surface chemical modification treatment and / or surface physical modification treatment on the hard particles to obtain modified hard particles.

[0093] 3) Mix the hard fibers or the modified hard fibers, optionally the hard particles or the modified hard particles, ultra-high molecular weight polyethylene, and a solvent to obtain a spinning solution.

[0094] 4) The spinning solution is spun into the polyethylene fiber.

[0095] According to one embodiment of the present invention, before performing step 1) or step 2), a step of drying the hard fiber or the hard particles is further included, wherein the drying includes: reducing pressure, drying temperature of 80-200°C (preferably 90-120°C), and drying time of 0.5-10h (preferably 1-4h).

[0096] According to one embodiment of the invention, prior to step 1), the rigid fiber is further etched (e.g., acid etching) to form a necked section. The acid etching can be performed using any method conventionally known in the art, particularly 98% sulfuric acid mist spraying for 3-20 minutes, followed by cleaning and drying.

[0097] According to one embodiment of the present invention, the surface chemical modification treatment includes: using a silane coupling agent, wherein the amount of the silane coupling agent is 0.8-5 wt% (preferably 1-3 wt%) of the weight of the hard fiber or the hard particles, the treatment temperature is 40-100°C (preferably 70-90°C), and the treatment time is 1-120 min (preferably 5-30 min).

[0098] According to one embodiment of the present invention, the surface physical modification treatment includes: surface coating with a polymer, wherein the amount of the polymer (dry basis) is up to 50% wt% (preferably 5-10 wt%) of the weight of the hard fiber or the hard particles, the treatment temperature is at least 30°C (preferably 40-60°C), and the treatment time is at least 1 min (preferably 5-10 min).

[0099] According to one embodiment of the present invention, relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the rigid fiber or the modified rigid fiber (based on rigid fiber) is at most 50 parts by weight (preferably 3-10 parts by weight), the amount of the rigid particles or the modified rigid particles (based on rigid particles) is 0-10 parts by weight (preferably 0.5-5 parts by weight), and the amount of the solvent is at least 500 parts by weight (preferably 1000-2000 parts by weight).

[0100] According to one embodiment of the present invention, preferably, in step 3), the rigid fiber or the modified rigid fiber is first dry-mixed with the rigid particles or the modified rigid particles, and then the ultra-high molecular weight polyethylene is added and dry-mixed again. The resulting mixture is then mixed with the solvent. Without dry mixing, the rigid particles and rigid fibers cannot be adsorbed and bonded together to form a composite additive structure.

[0101] According to one embodiment of the present invention, in step 4), the spinning is performed using gel spinning, including swelling at 60-120°C for 1-3 hours, dissolving by screw shearing at a dissolution temperature of 180-250°C, extruding the spinning gel, and then spinning through a spinneret. Preferably, the fibers are kept at 100-200°C and flow through a carder to orient the hard fibers in the direction of the spinning solution flow. Furthermore, the initial draw ratio of the spinneret is 3-10, the over-drawing temperature is 80-150°C, and the over-drawing ratio is 6-20 (preferably 8-15).

[0102] The ultra-high molecular weight polyethylene fiber of the present invention can be made into cut-resistant fabrics, including but not limited to at least one of woven fabrics, knitted fabrics, nonwoven fabrics, and non-woven fabrics, whose cut resistance reaches level 5 of EN388-2016 standard.

[0103] According to one embodiment of the present invention, the fabric further includes at least one other fiber selected from natural plant fibers, natural animal fibers, man-made regenerated fibers, synthetic fibers and inorganic fibers.

[0104] Example

[0105] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0106] Example 1

[0107] The ultra-high molecular weight polyethylene fiber of this embodiment comprises ultra-high molecular weight polyethylene as a matrix, steel fibers dispersed in the matrix, and glass microspheres dispersed in the matrix. The rigid fibers are steel fibers, and the rigid particles are glass microspheres.

[0108] In this embodiment, the steel fiber is a one-dimensional linear structure with a length of 200 μm, a body diameter of 4 μm, and an aspect ratio of 50. The steel fiber has 2-4 necked sections, each with a diameter 60% of the fiber's body diameter and a length 30% of the fiber's length. These necked sections are sulfuric acid-etched pits with an average length of 0.5 μm and an average depth of 2 μm. The surface of the steel fiber is treated with γ-(glycidoxy)propyltrimethoxysilane.

[0109] In this embodiment, the glass microspheres have an average diameter of 1 μm and their surface is treated with γ-(glycidoxy)propyltrimethoxysilane.

[0110] In this embodiment, relative to 100 parts by weight of ultra-high molecular weight polyethylene, the content of steel fiber is 7 parts by weight, the content of glass microspheres is 1 part by weight, and the viscosity-average molecular weight of ultra-high molecular weight polyethylene is 4.5 million.

[0111] In this embodiment, observation of 10cm of ultra-high molecular weight polyethylene fiber using a laser microscope revealed that the steel fibers were basically uniformly dispersed in the matrix, with no aggregated structures observed. Furthermore, the minimum distance between any two adjacent steel fibers in the matrix was greater than 100μm. Additionally, laser microscopy observation showed that the vast majority of glass microspheres were attached to the inside of the pits, with only a small portion freely dispersed in the matrix.

[0112] In this embodiment, the single filament fineness of the ultra-high molecular weight polyethylene fiber was measured to be 2.9 dtex.

[0113] The fiber manufacturing method in this embodiment is as follows.

[0114] Steel fibers were sprayed with 98% sulfuric acid mist for 10 minutes to form necked steel fibers. The steel fibers and glass microspheres were then dried under the following conditions: reduced pressure, drying temperature of 105°C, and drying time of 2 hours. The steel fibers and glass microspheres were then treated with silane coupling agents at 2 wt% each, at 80°C, and for 25 minutes, respectively, to obtain modified steel fibers and modified glass microspheres. The amount of modified steel fiber (based on rigid fiber) was 7 parts by weight, the amount of modified glass microspheres was 1 part by weight, and the amount of solvent decahydronaphthalene was 1000 parts by weight, relative to 100 parts by weight of the ultra-high molecular weight polyethylene. The modified steel fibers and modified glass microspheres were first dry-mixed, then the full amount of ultra-high molecular weight polyethylene was added and dry-mixed again. The resulting mixture was then mixed with the full amount of solvent to obtain the spinning solution. The gel spinning method is employed, including swelling at 9°C for 2 hours, shearing and dissolving via a screw at a temperature of 180-250°C, extruding the spinning gel, and then spinning through a spinneret. Under a holding temperature of 100-200°C, the fibers flow through a carder, orienting them according to the direction of the spinning solution flow. Furthermore, the initial draw ratio of the spinneret is 9, the super-drawing temperature is 145°C, and the super-draw ratio is 10.

[0115] Ultra-high molecular weight polyethylene fibers were coated with spandex and then woven into gloves on a 13-needle glove knitting machine for EN388-2016 cut resistance test.

[0116] Example 2

[0117] Compared to Example 1, the steel fiber has 8-10 necking segments. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 2.9 dtex.

[0118] Example 3

[0119] Compared to Example 1, the diameter of the necked section is 30% of the body diameter of the rigid fiber, and the length of the necked section is 5% of the length of the rigid fiber. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 2.5 dtex.

[0120] Example 4

[0121] Compared to Example 1, the diameter of the necked section is 80% of the body diameter of the rigid fiber, and the length of the necked section is 60% of the length of the rigid fiber. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 1.9 dtex.

[0122] Example 5

[0123] Compared to Example 1, the steel fiber length is 800 μm. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 2.5 dtex.

[0124] Example 6

[0125] Compared to Example 1, glass microspheres are not used. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 1.7 dtex.

[0126] Example 7

[0127] Compared to Example 1, the steel fiber content is 60 parts by weight. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 2.9 dtex.

[0128] Example 8

[0129] Compared to Example 1, the content of glass microspheres is 30 parts by weight. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 2.7 dtex.

[0130] Example 9

[0131] Compared to Example 1, the average diameter of the glass microspheres is 5 μm. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 2.5 dtex.

[0132] Example 10

[0133] Compared to Example 1, the steel fibers and glass microspheres were not surface-treated. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this example is 1.9 dtex.

[0134] Example 11

[0135] Compared to Example 1, the steel fibers and glass microspheres were coated with polymethyl methacrylate. The ultra-high molecular weight polyethylene fiber in this example has a single filament fineness of 2.5 dtex.

[0136] Example 12

[0137] Compared to Example 1, the steel fibers and glass microspheres were not pre-dry-blended. The ultra-high molecular weight polyethylene fibers in this example have a single filament fineness of 2.5 dtex, and virtually no adhesion structure is observed.

[0138] Comparative Example 1

[0139] Compared to Example 1, the steel fiber has no necking section. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this comparative example is 2.5 dtex.

[0140] Comparative Example 2

[0141] Compared to Example 1, the steel fiber length is 8 μm. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this comparative example is 2.5 dtex.

[0142] Comparative Example 3

[0143] Compared to Example 1, the steel fiber length is 2500 μm. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this comparative example is 2.7 dtex.

[0144] Comparative Example 4

[0145] The fiber used is commercially available Lilun LY25 ultra-high molecular weight polyethylene fiber, which does not contain hard fibers or hard particles. The monofilament fineness of the ultra-high molecular weight polyethylene fiber in this comparative example is 1.2 dtex.

[0146]

[0147]

Claims

1. An ultra-high molecular weight polyethylene fiber, comprising ultra-high molecular weight polyethylene as a matrix, rigid fibers dispersed in the matrix, and rigid particles dispersed in the matrix, wherein the rigid fibers have one or more necked sections, and the length of the rigid fibers is 10-2000 μm. Of the 100 parts by weight of ultra-high molecular weight polyethylene, the content of rigid fiber is at most 50 parts by weight, the content of rigid particles is 0-20 parts by weight, the length of the necked section is 10-50% of the length of the rigid fiber, and the diameter of the necked section is 40-70% of the body diameter of the rigid fiber. The rigid fibers and rigid particles are surface chemically modified with a silane coupling agent.

2. The fiber of claim 1, wherein the content of the rigid fiber is 3-10 parts by weight relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the content of the rigid particles is 0.5-5 parts by weight, and / or, the rigid fiber has 1-10 necking segments, and / or, the necking segments are pits.

3. The fiber of claim 1, wherein the hard fiber has 2-4 necking segments.

4. The fiber of claim 1, wherein the length of the hard fiber is 30-300 μm.

5. The fiber of claim 1, wherein the hard fiber is a one-dimensional linear structure with a body diameter of up to 20 μm and an aspect ratio of 3-1000.

6. The fiber of claim 1, wherein the diameter of the hard fiber body is 3-10 μm, and / or the aspect ratio of the hard fiber is 5-50.

7. The fiber of claim 1, wherein the necked section is a pit, the average length of which is 0.01-100 μm and the average depth is at least 0.01 μm.

8. The fiber of claim 7, wherein the necking section is an etched pit, and / or the average length of the pit is 0.1-1 μm, and / or the average depth of the pit is 0.1-3 μm.

9. The fiber of claim 1, wherein the hard fibers are uniformly dispersed in the matrix, or, there is no agglomeration structure of the hard fibers in the matrix, or, the minimum distance between any two adjacent hard fibers in the matrix is ​​greater than 0.1 μm.

10. The fiber of claim 1, wherein the minimum distance between any two adjacent hard fibers in the matrix is ​​greater than 5 μm.

11. The fiber of claim 1, wherein the hard fiber is selected from at least one of inorganic hard fibers and organic hard fibers.

12. The fiber of claim 11, wherein the inorganic hard fiber is selected from at least one of metal fiber, glass fiber, ceramic fiber, mineral fiber, and basalt fiber, or the organic hard fiber is selected from at least one of carbon fiber, aramid fiber, aromatic polyamide copolymer fiber, heterocyclic polyamide fiber, graphite fiber, silicon carbide fiber, wood fiber, bamboo fiber, sisal fiber, and kerosene fiber.

13. The fiber of claim 1, wherein the average diameter of the hard particles is not greater than 20 μm.

14. The fiber of claim 1, wherein the average diameter of the hard particles is 0.5-2 μm.

15. The fiber of claim 1, wherein the hard particles are selected from at least one of inorganic hard particles and organic hard particles.

16. The fiber of claim 15, wherein the inorganic hard particles are selected from at least one of metal particles, glass particles, ceramic particles, mineral particles, vitrified microspheres, and fly ash, or the organic hard particles are selected from at least one of organosilicon micropowder, amino micropowder, polyacrylate micropowder, polylactic acid micropowder, and polytetrafluoroethylene micropowder.

17. The fiber of claim 1, wherein at least a portion of the hard particles are attached to at least one of the necked sections.

18. The fiber of claim 17, wherein at least a portion of the hard particles are attached to at least one of the pits.

19. The fiber of claim 17 or 18, wherein the adhesion is adsorption.

20. A method for manufacturing ultra-high molecular weight polyethylene fiber as described in claim 1, comprising the following steps: 1) Surface chemical modification and / or surface physical modification treatment of rigid fibers to obtain modified rigid fibers, wherein the rigid fibers have one or more necked sections and the length of the rigid fibers is 10-2000 μm. 2) Surface chemical modification and / or surface physical modification treatments are applied to the hard particles to obtain modified hard particles. 3) Mix the modified hard fibers, the modified hard particles, ultra-high molecular weight polyethylene, and a solvent to obtain a spinning solution. 4) The spinning solution is spun into the polyethylene fiber. In step 3), the modified rigid fiber and the modified rigid particles are first dry-mixed, and then the ultra-high molecular weight polyethylene is added and dry-mixed. The resulting mixture is then mixed with the solvent.

21. The manufacturing method of claim 20, wherein the rigid fiber has 1-10 necked segments, and / or the length of the rigid fiber is 30-300 μm.

22. The manufacturing method of claim 20, wherein before performing step 1) or step 2), it further comprises a step of drying the rigid fiber or the rigid particles, the drying comprising: Reduce pressure, dry at 80-200℃, and dry for 0.5-10 hours.

23. The manufacturing method of claim 22, wherein the drying temperature is 90-120°C, and / or the drying time is 1-4 hours.

24. The manufacturing method of claim 20, wherein prior to performing step 1), it further comprises etching the rigid fiber to form the necked section.

25. The manufacturing method of claim 24, wherein the etching is a strong acid etching.

26. The manufacturing method of claim 20, wherein, relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the modified rigid fiber, calculated as rigid fiber, is at most 50 parts by weight, the amount of the modified rigid particles, calculated as rigid particles, is 0-20 parts by weight, and the amount of the solvent is at least 500 parts by weight.

27. The manufacturing method of claim 20, wherein, relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the modified rigid fiber, calculated as rigid fiber, is 3-10 parts by weight, and / or, the amount of the modified rigid particles, calculated as rigid particles, is 0.5-5 parts by weight, and / or, the amount of the solvent is 1000-2000 parts by weight.

28. The manufacturing method of claim 20, wherein in step 4), the spinning comprises: In gel spinning, the initial draw ratio of the spinneret is 3-10, the super-drawing temperature is 80-150℃, and the super-drawing ratio is 6-20.

29. A fabric comprising the ultra-high molecular weight polyethylene fiber of claim 1 or the ultra-high molecular weight polyethylene fiber manufactured by the manufacturing method of claim 20.

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