Ultra-high molecular weight polyethylene fiber containing hard fiber as well as preparation method and application of ultra-high molecular weight polyethylene fiber

Abstract

The invention relates to an ultra-high molecular weight polyethylene fiber containing hard fibers, and a manufacturing method and an application of the ultra-high molecular weight polyethylene fiber. According to the ultra-high molecular weight polyethylene fiber, the wearing comfort of a fabric can be improved, and meanwhile, the fabric can reach the cutting-resistant EN388-2003 standard level 5. The ultra-high molecular weight polyethylene fiber comprises ultra-high molecular weight polyethylene as a matrix, hard fibers dispersed in the matrix and optional hard particles dispersed in the matrix, the hard fibers have one or more necking sections, and the length of the hard fibers is 10-2000 [mu] m.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber manufacturing, and more specifically to an ultra-high molecular weight polyethylene fiber containing hard fibers, a manufacturing method thereof and an application thereof. Background Art

[0002] Ultra-high molecular weight polyethylene fiber (UHMWPE) is the fiber with the highest specific strength and specific modulus in the world. It is a fiber spun from polyethylene with a molecular weight of 1 million to 5 million. Ultra-high molecular weight polyethylene fiber is the fiber with the highest specific strength among the currently industrialized fiber materials. It has excellent properties such as high strength, high modulus, wear resistance, and chemical corrosion resistance. It is widely used in safety protection, military, aerospace, ocean, sports and other fields. With the continuous deepening of military-civilian integration, the application of ultra-high molecular weight polyethylene fiber in the civilian market has gradually increased, among which the civilian market dominated by anti-cut gloves has gradually occupied a dominant position. At present, the highest cutting grade of protective gloves made of commonly used ultra-high molecular weight polyethylene fibers is EN388-20016 standard level 3, which does not meet the needs of protection against cut hazards in actual working environments.

[0003] In order to improve the cut resistance level of gloves, a common method is to blend steel wire materials with ultra-high molecular weight polyethylene fibers to achieve ultra-high cut resistance. Although this method can improve the cut resistance of gloves, it cannot achieve compatibility between protective performance and comfort performance because the steel wire is relatively hard, difficult to wear and has poor comfort. At present, inorganic fillers are often added to fill and modify UHMWPE.

[0004] Patent CN1 04233497A provides a fiber with cut-resistant properties prepared by nanocrystalline silicon carbide and ultra-high molecular weight polyethylene. The method is to put nanocrystalline silicon carbide particles into a solvent, grind them repeatedly with a sand mill, and then put them into the solvent together with ultra-high molecular weight polyethylene, and mix them evenly with high-speed shearing and stirring in an emulsifier to obtain a fiber spinning mixture.

[0005] Patent CN1 01528998A discloses a composite yarn containing silk threads or fixed-length fibers, wherein 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 cutting resistance of the yarn.

[0006] Patent CN1 09610040A discloses pouring glass fiber into a first white oil and mixing to obtain a glass fiber premix, then mixing the glass fiber premix, an antioxidant and UHMWPE powder in a second white oil to obtain a spinning mixture, which is swollen and extruded to form a molten state, cooled to form a gel filament and obtain a composite fiber. Summary of the invention

[0007] The inventors of the present invention have found that when adding hard fibers to fill and modify UHMWPE, although the cut resistance coefficient of the gloves can be improved, the gloves feel hard to wear, and because the hard fibers are easily detached from the fiber matrix during the manufacturing process or use, it causes pollution to the production environment, or causes secondary damage such as itching and allergies to the user, and it is impossible to achieve the unity of protective performance and wearing comfort (especially wearing safety). In addition, the inventors of the present invention have also found that when adding hard particles to fill and modify UHMWPE, the effect of improving cut resistance is limited. For this reason, the inventors of the present invention have found through diligent research that these technical problems existing in the prior art can be solved by introducing neck-shrinking hard fibers into the ultra-high molecular weight polyethylene matrix, and in a preferred case, combining them with hard particles to form a specific composite structure. The present invention is completed 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, hard fibers dispersed in the matrix, and optionally hard particles dispersed in the matrix, wherein the hard fibers have one or more (preferably 1-10 or 2-4) necking segments (preferably pits), and the length of the hard fibers is 10-2000 μm (preferably 30-300 μm).

[0010] 2. The fiber described in any of the preceding or following aspects, wherein the content of the hard 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 hard particles is 0-20 parts by weight (preferably 0.5-5 parts by weight).

[0011] 3. The fiber described in any of the preceding or following aspects, wherein the Mohs hardness of the hard fiber is greater than the Mohs hardness of the ultra-high molecular weight polyethylene, and the Mohs hardness of the hard particles is greater than the Mohs hardness of the ultra-high molecular weight polyethylene.

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

[0013] 5. The fiber described in any of the preceding or following aspects, wherein the diameter of the necking section is less than 85% (preferably 40-70%) of the main diameter of the hard fiber, and the length of the necking section is 5-80% (preferably 10-50%) of the length of the hard fiber.

[0014] 6. The fiber described in any of the preceding or following aspects, wherein the hard fiber is a one-dimensional linear structure with a main 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 in any of the preceding or following aspects, wherein the necking section is a pit (preferably an etched pit), the average length of the pit 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).

[0016] 8. The fiber described in any of the preceding or following aspects, wherein the hard fibers are substantially uniformly dispersed in the matrix, or, there is substantially no agglomerated 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 (preferably greater than 5 μm).

[0017] 9. The fiber according to any one of the preceding or following aspects, wherein the hard fiber is selected from at least one of inorganic hard fibers and organic hard fibers, preferably at least one of inorganic hard fibers.

[0018] 10. The fiber described in any of the preceding or following aspects, 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 yew fiber.

[0019] 11. The fiber according to any one of the preceding or following aspects, wherein the average diameter of the hard particles is not greater than 20 μm (preferably 0.5-2 μm).

[0020] 12. The fiber according to any one of the preceding or following aspects, wherein the hard particles are selected from at least one of inorganic hard particles and organic hard particles, preferably at least one of inorganic hard particles.

[0021] 13. The fiber described in any of the above or the following aspects, 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 silicone micropowder, amino micropowder, polyacrylate micropowder, polylactic acid micropowder, and polytetrafluoroethylene micropowder.

[0022] 14. The fiber described in any of the preceding or following aspects, wherein the hard fiber and / or the hard particles have been subjected to surface chemical modification, such as surface chemical modification with a silane coupling agent.

[0023] 15. The fiber described in any of the preceding or following aspects, wherein the silane coupling agent is at least one selected from aminopropyltriethoxysilane, γ-(glycidyloxy)propyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

[0024] 16. The fiber described in any of the preceding or following aspects, wherein the hard fiber and / or the hard particles have been subjected to surface physical modification treatment, such as surface roughening treatment and / or surface polymer coating treatment.

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

[0026] 18. The fiber described in any of the preceding or following aspects, wherein at least a portion of the hard particles are attached (such as adsorbed) to at least one of the necking sections, preferably attached (such as adsorbed) inside at least one of the pits.

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

[0028] 1) optionally subjecting a hard fiber to a surface chemical modification treatment and / or a surface physical modification treatment to obtain a modified hard fiber, wherein the hard fiber has one or more (preferably 1-10 or 2-4) necking segments, and the length of the hard fiber is 10-2000 μm (preferably 30-300 μm),

[0029] 2) optionally performing surface chemical modification and / or surface physical modification on the hard particles to obtain modified hard particles,

[0030] 3) mixing the hard fiber or the modified hard fiber, the optional hard particles or the optional modified hard particles, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution,

[0031] 4) Spinning the spinning solution into the polyethylene fiber.

[0032] 20. The manufacturing method described in any of the preceding or following aspects, wherein before performing the step 1) or the step 2), it also includes a step of drying the hard fibers or the hard particles, and the drying includes: reducing pressure, a drying temperature of 80-200°C (preferably 90-120°C), and a drying time of 0.5-10h (preferably 1-4h).

[0033] 21. The manufacturing method described in any of the above or the following aspects, wherein before performing the step 1), it also includes a step of etching the hard fiber (such as strong acid etching) to form the necking section.

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

[0035] 23. The manufacturing method described in any of the preceding or subsequent aspects, wherein the surface physical modification treatment includes: surface coating with a polymer, the amount of the polymer (dry basis) is at most 50% wt% (preferably 5-10 wt%) of the weight of the hard fibers 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 in any of the preceding or following aspects, wherein relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the hard fiber or the modified hard fiber (calculated as hard fiber) is at most 50 parts by weight (preferably 3-10 parts by weight), the amount of the hard particles or the modified hard particles (calculated as hard 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 in any of the above or below aspects, wherein in step 3), the hard fibers or the modified hard fibers are first dry-mixed with the hard particles or the modified hard particles, and then the ultra-high molecular weight polyethylene is added for dry mixing, and then the obtained mixture is mixed with the solvent.

[0038] 26. The manufacturing method described in any of the above or the following aspects, wherein in step 4), the spinning comprises: a gel spinning method, a primary stretching ratio of the spinneret is 3-10, a super stretching temperature is 80-150°C, and a super stretching ratio is 6-20.

[0039] 27. The manufacturing method described in any of the above or the following aspects, wherein before performing step 4), it also includes a step of combing and orienting the spinning solution.

[0040] 28. A fabric comprising the ultra-high molecular weight polyethylene fiber described in any one of the preceding or following aspects or the ultra-high molecular weight polyethylene fiber produced by the production method described in any one of the preceding or following aspects.

[0041] 29. The fabric described in any one of the preceding or following aspects further comprises at least one other fiber selected from natural plant fibers, natural animal fibers, artificial regenerated fibers, synthetic fibers and inorganic fibers.

[0042] Technical Effects

[0043] The necked hard fiber of the present invention can generate an anchoring effect in the fiber matrix, and can be more stably present in the fiber matrix and not easily fall out, thereby effectively reducing secondary damage to the human body. In particular, during the fiber manufacturing process or the cutting process, the necked section structure can remain stable and not fall out.

[0044] The present invention introduces necked hard fibers into an ultra-high molecular weight polyethylene matrix, and in a preferred case, uses them in combination with hard particles to form a specific composite structure, i.e., a composite structure in which hard particles are attached to the surface of the necked hard fibers. This can increase the bonding between the hard fibers and the fiber matrix, thereby obtaining UHMWPE fibers with low shedding, high comfort, high strength, high toughness, and anti-cutting properties.

[0045] The ultra-high molecular weight polyethylene fiber of the invention can greatly improve the wearing comfort of the fabric, especially the wearing safety, and the fabric can reach level 5 of the cut resistance EN388-2003 standard. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 Schematic diagram of a necked hard fiber according to the present invention.

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

[0048] The specific embodiments of the present invention are described in detail below, but it should be pointed out that the protection scope of the present invention is not limited by 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 conventionally understood by those skilled in the art. In the event of a conflict, the definitions in this specification shall prevail.

[0050] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0051] In the context of this specification, by substantially it is meant a deviation of no more than 20%, preferably no more than 10%, 5% or 1%.

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

[0053] In the context of this specification, the agglomeration is measured as follows: a 10 cm long section is randomly cut from the fiber, the number of agglomerated structures is investigated under a laser microscope, and then scored according to the following criteria. The measurement is repeated 10 times and the average value is taken.

[0054] No reunion: 0,

[0055] Small amount of reunion: less than 2,

[0056] Medium reunion: 3-4,

[0057] Large gatherings: 5 or more.

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

[0059] In the context of this specification, the distance between two hard fibers or similar expressions means the distance between any point on one hard fiber and any point on another hard fiber.

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

[0061] In the context of this specification, there are no specific operating conditions, additives, etc., and 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 may be arbitrarily combined, and the technical solutions thus formed belong to 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, it relates to an ultra-high molecular weight polyethylene fiber. 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, hard fibers dispersed in the matrix, and optionally hard particles dispersed in the matrix. Here, the so-called hard means that the Mohs hardness of the hard fibers is greater than the Mohs hardness of the ultra-high molecular weight polyethylene, and the Mohs hardness of the hard particles is greater than the Mohs hardness of the ultra-high molecular weight polyethylene.

[0065] According to one embodiment of the present invention, the hard fiber has one or more (preferably 1-10 or 2-4) necking segments. Without the necking segment, the hard fiber surface is smooth and not easy to combine with the fiber, resulting in insufficient cutting resistance. If there are too many necking segments, the hard fiber structure is damaged, which is also likely to result in insufficient cutting resistance.

[0066] In the context of this specification, the so-called necking section refers to a section on a hard fiber, one end or both ends (preferably both ends) of the section has the main body diameter of the hard fiber, and the diameter of the middle section is smaller than the main body diameter. Here, the so-called main body diameter refers to the diameter of the hard fiber body (excluding the necking section). However, it should be emphasized that the necking section of the present invention is a diameter-reduced portion that is "actively" or "intentionally" introduced on the hard fiber. Therefore, changes in fiber diameter caused by the surface roughness of the hard fiber or the unevenness of the fiber diameter do not belong to the necking section referred to in the present invention. According to the present invention, there is no particular limitation on the method for forming the necking section, but as examples, bamboo-shaped and pit-shaped types can be cited.

[0067] According to one embodiment of the present invention, the diameter of the necking section is less than 85% (preferably 40-70%) of the main body diameter of the hard fiber, and the length of the necking section is 5-80% (preferably 10-50%) of the length of the hard fiber. If the necking section is too thin or too long, the performance of the hard fiber will be damaged, resulting in insufficient cutting resistance. If the necking section is too shallow or too short, the surface roughness of the hard fiber will be insufficient, resulting in poor bonding and impaired cutting resistance. In a preferred case, the necking section is a pit, and the average length of the pit 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, and any method conventionally known in the relevant technical field can be used to form the etched pit, but as an example, laser etching, acid etching, etc. can be cited. The edges of the etched pit are more irregular, and it is easier to increase the bonding force than the natural pit.

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

[0070] According to one embodiment of the present invention, the content of the hard 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). Too few hard particle components cannot form a composite structure and increase the bonding force. Too many hard particles increase the difficulty of spinning, damage the fiber quality, and make the cutting resistance effect 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 hard fiber is a one-dimensional linear structure, with a main body diameter of at most 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 hard fibers are substantially uniformly dispersed in the matrix. In other words, there is substantially no agglomeration structure of the hard fibers in the matrix. As a quantitative indicator, the minimum distance between any two adjacent hard fibers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm). In the context of this specification, the so-called agglomeration structure refers to a composite structure formed by entanglement or interweaving of multiple hard fibers. According to the present invention, when hard fibers form an agglomeration structure in the fiber matrix, the uniformity of the polyethylene fiber linear density may be reduced, affecting the 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 yarrow fiber.

[0078] According to one embodiment of the present invention, the average diameter of the hard particles is no 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 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 micropowder, amino micropowder, polyacrylate micropowder, polylactic acid micropowder and polytetrafluoroethylene micropowder.

[0082] According to one embodiment of the present invention, the hard fiber is subjected to surface chemical modification, such as surface chemical modification with a silane coupling agent. If the hard fiber surface is not modified, it will not be well combined with the fiber matrix, resulting in insufficient cutting resistance.

[0083] According to one embodiment of the present invention, the hard particles are treated with surface chemical modification, such as surface chemical modification with a silane coupling agent. If the surface of the hard particles is not modified, the hard particles will not be well combined with the fiber matrix, resulting in insufficient cutting resistance.

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

[0085] According to one embodiment of the present invention, the hard fibers and / or the hard 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 rubbers, preferably selected from at least one of cellulose esters, olefin polymers (polyvinyl acetate, polyvinyl alcohol, perchlorethylene, polyisobutylene, etc.), polyesters, polyethers, polyamides, polyacrylates, a-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) to at least one of the necking sections, or preferably at least a portion of the hard particles are attached (e.g., adsorbed) inside at least one of the pits to form a composite structure of necking hard fiber surfaces with hard particles attached. According to the present invention, there is no particular limitation on the method for forming the composite structure, such as adsorption, adhesion, etc.

[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, it also relates to a method for manufacturing an ultra-high molecular weight polyethylene fiber. According to the present invention, the manufacturing method can be used to manufacture the ultra-high molecular weight polyethylene fiber of the present invention as described above. For this reason, the contents not described or expanded in detail in this document for the manufacturing method can be directly applied to the contents given in the previous text of this specification for the ultra-high molecular weight polyethylene fiber, and will not be repeated here.

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

[0091] 1) optionally subjecting the hard fibers to surface chemical modification and / or surface physical modification to obtain modified hard fibers,

[0092] 2) optionally performing surface chemical modification and / or surface physical modification on the hard particles to obtain modified hard particles,

[0093] 3) mixing the hard fiber or the modified hard fiber, the optional hard particles or the optional modified hard particles, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution,

[0094] 4) Spinning the spinning solution 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 fibers or the hard particles is also included, and the drying includes: reducing pressure, a drying temperature of 80-200°C (preferably 90-120°C), and a drying time of 0.5-10h (preferably 1-4h).

[0096] According to one embodiment of the present invention, before performing step 1), the hard fiber is further etched (e.g., acid etching) to form a necking section. The acid etching may be performed by any conventional method known in the art, particularly spraying with 98% sulfuric acid mist for 3-20 minutes, washing and drying for standby use.

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

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

[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 hard fiber or the modified hard fiber (calculated as hard fiber) is at most 50 parts by weight (preferably 3-10 parts by weight), the amount of the hard particles or the modified hard particles (calculated as hard 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 hard fiber or the modified hard fiber is first dry-mixed with the hard particles or the modified hard particles, and then the ultra-high molecular weight polyethylene is added for dry mixing, and then the obtained mixture is mixed with the solvent. If dry mixing is not performed, the hard particles and the hard fiber cannot be adsorbed and combined together to form a composite structural additive.

[0101] According to one embodiment of the present invention, in step 4), the spinning adopts a gel spinning method, including swelling at 60-120°C for 1-3h, dissolving by screw shearing, the dissolving temperature is 180-250°C, extruding the spinning gel, and then spinning through a spinneret. Preferably, under the condition of keeping warm at 100-200°C, flowing through a carder, the hard fibers are oriented and arranged in the direction of the spinning solution flow. In addition, the primary stretching ratio of the spinneret is 3-10, the super stretching temperature is 80-150°C, and the super stretching 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, non-woven fabrics, and non-woven fabrics, and its cut resistance reaches level 5 of EN388-2016 standard.

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

[0104] Example

[0105] The present invention is further described in detail below using examples, but the present invention is not limited to these examples.

[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 hard fibers are steel fibers, and the hard 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 necking sections, the diameter of the necking section is 60% of the body diameter of the steel fiber, and the length is 30% of the steel fiber. The necking section is a sulfuric acid etched pit 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-(glycidyl ether oxygen) propyl trimethoxy silane.

[0109] In this embodiment, the average diameter of the glass microbead particles is 1 μm, and the surface is treated with γ-(glycidyloxy)propyltrimethoxysilane.

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

[0111] In this embodiment, 10 cm of ultra-high molecular weight polyethylene fiber was observed with a laser microscope and it was found that the steel fibers were basically evenly dispersed in the matrix, no agglomeration structure of the steel fibers was observed in the matrix, and the minimum distance between any two adjacent steel fibers in the matrix was greater than 100 μm. In addition, laser microscope observation also found that most of the glass beads were attached to the inside of the pits, and only a small part was freely dispersed in the matrix.

[0112] In this embodiment, after measurement, the single fiber fineness of the ultra-high molecular weight polyethylene fiber is 2.9 dtex.

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

[0114] The steel fiber is sprayed with 98% sulfuric acid mist for 10 minutes to form a necked steel fiber. The steel fiber and glass microspheres are dried, and the drying conditions include: reduced pressure, drying temperature of 105°C, and drying time of 2 hours. The steel fiber and glass microspheres are treated with silane coupling agent respectively, and the amount of silane coupling agent is 2wt%, the treatment temperature is 80°C, and the treatment time is 25 minutes, respectively, to obtain modified steel fiber and modified glass microspheres. Relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of modified steel fiber (in terms of hard fiber) is 7 parts by weight, the amount of modified glass microspheres is 1 part by weight, and the amount of solvent decalin is 1000 parts by weight. The modified steel fiber and the modified glass microspheres are first dry-mixed, and then the full amount of ultra-high molecular weight polyethylene is added for dry mixing, and then the obtained mixture is mixed with the full amount of solvent to obtain a spinning solution. The gel spinning method includes swelling at 9°C for 2h, dissolving by screw shearing, the dissolving temperature is 180-250°C, extruding the spinning gel, and then spinning through a spinneret. Under the condition of keeping warm at 100-200°C, the steel fiber flows through a carder to orient the steel fiber in the direction of the spinning solution flow. In addition, the primary stretching ratio of the spinneret is 9, the super stretching temperature is 145°C, and the super stretching ratio is 10.

[0115] The ultra-high molecular weight polyethylene fibers were coated with spandex and then knitted into gloves on a 13-needle glove loom for the EN388-2016 cut resistance test.

[0116] Example 2

[0117] Compared with Example 1, the number of steel fiber necking sections is 8-10. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.9 dtex.

[0118] Example 3

[0119] Compared with Example 1, the diameter of the necking section is 30% of the main body diameter of the hard fiber, and the length of the necking section is 5% of the length of the hard fiber. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0120] Example 4

[0121] Compared with Example 1, the diameter of the necking section is 80% of the main body diameter of the hard fiber, and the length of the necking section is 60% of the length of the hard fiber. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 1.9 dtex.

[0122] Example 5

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

[0124] Example 6

[0125] Compared with Example 1, no glass microbeads are used. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 1.7 dtex.

[0126] Example 7

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

[0128] Example 8

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

[0130] Example 9

[0131] Compared with Example 1, the average diameter of the glass microbead particles is 5 μm. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0132] Example 10

[0133] Compared with Example 1, the steel fiber and the glass microbeads are not surface treated. The single filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 1.9 dtex.

[0134] Embodiment 11

[0135] Compared with Example 1, the surfaces of the steel fibers and glass microbeads are coated with polymethyl acrylate. The single filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0136] Example 12

[0137] Compared with Example 1, the steel fiber and the glass microbeads are not pre-dry mixed. The single filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex, and basically no attachment structure is observed.

[0138] Comparative Example 1

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

[0140] Comparative Example 2

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

[0142] Comparative Example 3

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

[0144] Comparative Example 4

[0145] The fiber is commercially available LY25 ultra-high molecular weight polyethylene fiber, which does not contain hard fibers and hard particles. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of 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, hard fibers dispersed in the matrix, and optionally hard particles dispersed in the matrix, wherein the hard fibers have one or more (preferably 1-10 or 2-4) necking segments (preferably pits), and the length of the hard fibers is 10-2000 μm (preferably 30-300 μm).

2. The fiber of claim 1, wherein the content of the hard fiber is at most 50 parts by weight (preferably 3-10 parts by weight) and the content of the hard particles is 0-20 parts by weight (preferably 0.5-5 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene.

3. The fiber of claim 1, wherein the diameter of the necking section is less than 85% (preferably 40-70%) of the main body diameter of the hard fiber, and the length of the necking section is 5-80% (preferably 10-50%) of the length of the hard fiber.

4. The fiber of claim 1, 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).

5. The fiber of claim 1, 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).

6. The fiber of claim 1, wherein the hard fibers are substantially uniformly dispersed in the matrix, or, there is substantially no agglomerated 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 (preferably greater than 5 μm).

7. The fiber of claim 1, wherein 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.

8. The fiber of claim 7, 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 yew fiber.

9. The fiber of claim 1, wherein the hard particles have an average diameter of no greater than 20 μm (preferably 0.5-2 μm).

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

11. The fiber of claim 10, 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 micropowders, amino micropowders, polyacrylate micropowders, polylactic acid micropowders, and polytetrafluoroethylene micropowders.

12. The fiber of claim 1, wherein at least a portion of the hard particles are attached (e.g., adsorbed) to at least one of the necking sections, preferably attached (e.g., adsorbed) inside at least one of the pits.

13. A method for producing ultra-high molecular weight polyethylene fiber, comprising the following steps: 1) optionally subjecting a hard fiber to a surface chemical modification treatment and / or a surface physical modification treatment to obtain a modified hard fiber, wherein the hard fiber has one or more (preferably 1-10 or 2-4) necking segments, and the length of the hard fiber is 10-2000 μm (preferably 30-300 μm), 2) optionally performing surface chemical modification and / or surface physical modification on the hard particles to obtain modified hard particles, 3) mixing the hard fiber or the modified hard fiber, the optional hard particles or the optional modified hard particles, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution, 4) Spinning the spinning solution into the polyethylene fiber.

14. The manufacturing method according to claim 13, wherein before performing step 1) or step 2), it further comprises a step of drying the hard fibers or the hard particles, wherein the drying comprises: Reduce pressure, the drying temperature is 80-200°C (preferably 90-120°C), and the drying time is 0.5-10h (preferably 1-4h).

15. The manufacturing method according to claim 13, wherein before performing the step 1), it further comprises the step of etching the hard fiber (such as strong acid etching) to form the necking section.

16. The manufacturing method according to claim 13, wherein relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the hard fiber or the modified hard fiber (calculated as hard fiber) is at most 50 parts by weight (preferably 3-10 parts by weight), the amount of the hard particles or the modified hard particles (calculated as hard 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).

17. The manufacturing method according to claim 13, wherein in step 3), the hard fiber or the modified hard fiber is first dry-mixed with the hard particles or the modified hard particles, and then the ultra-high molecular weight polyethylene is added for dry mixing, and then the obtained mixture is mixed with the solvent.

18. The manufacturing method of claim 13, wherein in step 4), the spinning comprises: In the gel spinning method, the primary stretching ratio of the spinneret is 3-10, the super stretching temperature is 80-150°C, and the super stretching ratio is 6-20.

19. 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 13.

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