An ultra-high molecular weight polyethylene fiber comprising a multi-branched filler and a fibrous filler, a method for manufacturing the same, and applications thereof

Abstract

The present invention relates to an ultra-high molecular weight polyethylene fiber comprising a multi-branched filler and a fibrous filler, a manufacturing method thereof, and an application thereof. The ultra-high molecular weight polyethylene fiber of the present invention can greatly improve the comfort of a fabric, while the fabric can achieve a 5th level of the anti-cutting EN388-2016 standard. The ultra-high molecular weight polyethylene fiber of the present invention comprises an ultra-high molecular weight polyethylene as a matrix, a multi-branched filler dispersed in the matrix, and a fibrous filler dispersed in the matrix, wherein the multi-branched filler has a plurality of dendritic protrusions in its structure, and an agglomerated structure between the fibrous filler and the multi-branched filler is substantially absent in the matrix.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber manufacturing, and more particularly to an ultra-high molecular weight polyethylene fiber containing a multi-branched filler and a fibrous filler, a manufacturing method thereof, and applications thereof. Background Art

[0002] Ultra-high molecular weight polyethylene fiber (UHMWPE) is currently 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 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, marine, 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 mainly composed of cut-resistant gloves has gradually occupied a dominant position. At present, the highest cut level of protective gloves made of commonly used ultra-high molecular weight polyethylene fiber is EN388-2016 standard level 3, which does not meet the needs of cut hazard protection in actual working environments.

[0003] To improve the cut resistance of gloves, a common method is to blend steel wire with ultra-high molecular weight polyethylene fibers to achieve ultra-high cut resistance. While this method can improve the gloves' cut resistance, the relatively stiff steel wire makes it difficult to wear and provides poor comfort, preventing the glove from achieving both protective and comfortable performance. Currently, inorganic fillers are commonly added to modify UHMWPE.

[0004] Patent CN104233497A provides a method for preparing cut-resistant fibers using 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, then adding them to the solvent along with ultra-high molecular weight polyethylene. The mixture is then mixed uniformly in an emulsifier using high-speed shearing and stirring to obtain a fiber spinning mixture.

[0005] Patent CN101528998A discloses a composite yarn containing silk threads 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 cutting resistance of the yarn.

[0006] Patent CN109610040A discloses pouring glass fiber into a first white oil and mixing it 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, and cooled to form a gel yarn to produce a composite fiber. Summary of the Invention

[0007] The inventors of the present invention have discovered that while adding fibrous fillers to UHMWPE for filling and modification can improve the cut resistance coefficient of gloves, the gloves feel stiff when worn. Furthermore, since the fibrous fillers easily escape from the fiber matrix during the manufacturing process or use, this can pollute the production environment or cause secondary damage to the user, such as itching and allergies, making it impossible to achieve a balance between protective performance and wearing comfort (particularly wearing safety). To this end, the inventors of the present invention, through diligent research, have discovered that by adding fibrous fillers (such as hard staple fibers) and multi-branched fillers (such as whiskers) as a bicomponent to an ultra-high molecular weight polyethylene matrix, the hard staple fibers can compensate for the brittle fracture of the whiskers, while the whiskers can compensate for the easy escape of the hard staple fibers. The combination of the two facilitates uniform dispersion, resulting in a UHMWPE fiber with low shedding, high comfort, high strength and toughness, cut resistance, and high uniformity (low linear density deviation). The present 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, a multi-branched filler (such as whiskers) dispersed in the matrix, and a fibrous filler dispersed in the matrix (hereinafter sometimes multi-branched filler and fibrous filler are collectively referred to as filler), wherein the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) branched protrusions in its structure, and there is basically no agglomeration structure between the fibrous filler and the multi-branched filler in the matrix.

[0010] 2. The fiber described in any of the preceding or following aspects, wherein the content of the multi-branched filler is at most 15 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 fibrous filler is at most 15 parts by weight (preferably 3-10 parts by weight).

[0011] 3. The fiber according to any one of the preceding or following aspects, wherein the filler has a Mohs hardness greater than that of the ultra-high molecular weight polyethylene.

[0012] 4. The fiber according to any one of the preceding or following 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 above or below aspects, wherein the multiple dendrites are the same or different from each other, and the length (from the root) is independently 5-2000 μm (preferably 10-300 μm), and the diameter (root) is independently at most 10 μm (preferably 0.05-3 μm).

[0014] 6. The fiber described in any of the preceding or following aspects, wherein the multi-branched filler is substantially uniformly dispersed in the matrix, or, there is substantially no agglomerated structure of the multi-branched filler in the matrix, or, the minimum distance between any two adjacent multi-branched fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0015] 7. The fiber according to any one of the preceding or following aspects, wherein the fibrous filler is substantially uniformly dispersed in the matrix, or substantially no agglomerated structure of the fibrous filler exists in the matrix.

[0016] 8. The fiber according to any one of the preceding or following aspects, wherein the minimum distance between any two adjacent fibrous fillers 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 minimum distance between the multi-branched filler and any adjacent fibrous filler in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0018] 10. The fiber according to any one of the preceding or following aspects, wherein the multi-branched filler is selected from at least one of inorganic compound whiskers and organic compound whiskers, preferably at least one of inorganic compound whiskers.

[0019] 11. The fiber described in any of the above or following aspects, wherein the inorganic compound is at least one selected from inorganic oxygen-containing compounds, preferably at least one selected from metal oxides, metal hydroxides and metal oxyacids, in particular at least one selected from metal oxyacids, specifically such as at least one selected from silicon carbide, silicon nitride, aluminum oxide, zinc oxide, magnesium oxide, calcium carbonate, basic magnesium sulfate, aluminum borate, magnesium borate, potassium titanate and calcium sulfate; or, the organic compound is at least one selected from organic polymers, preferably at least one selected from cellulose, polyester, polyamide, poly 4-hydroxybenzoate (PHB).

[0020] 12. The fiber of any preceding or following aspect, wherein the fibrous filler is a one-dimensional linear structure having a length of 1-2000 μm (preferably 50-200 μm), a diameter of up to 40 μm (preferably 1-20 μm), and an aspect ratio of at least 1 (preferably 3-100).

[0021] 13. The fiber according to any one of the preceding or following aspects, wherein the fibrous filler is selected from at least one of inorganic hard short fibers and organic hard short fibers, preferably at least one of inorganic hard short fibers.

[0022] 14. The fiber described in any of the above or the following aspects, wherein the inorganic hard short fiber is selected from at least one of metal fiber, glass fiber, ceramic fiber, mineral fiber, and basalt fiber, or the organic hard short 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.

[0023] 15. The fiber according to any one of the preceding or following aspects, wherein the multi-branched filler and / or the fibrous filler has been subjected to surface chemical modification, such as surface chemical modification with a silane coupling agent.

[0024] 16. The fiber according to any one 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.

[0025] 17. The fiber according to any one of the preceding or following aspects, wherein the multi-branched filler and / or the fibrous filler has undergone surface physical modification, such as surface roughening treatment and / or surface polymer coating treatment.

[0026] 18. 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.

[0027] 19. The fiber according to any one of the preceding or following aspects, wherein the angle between any two adjacent dendrites is greater than 5° (preferably 30°-90°).

[0028] 20. The polyethylene fiber according to any one of the preceding or following aspects, wherein the linear density deviation rate of a single fiber in the longitudinal direction is at most 50% (preferably at most 15%).

[0029] 21. A method for producing ultra-high molecular weight polyethylene fiber, comprising the following steps:

[0030] 1) optionally subjecting a multi-branched filler (such as whiskers) to a surface chemical modification and / or surface physical modification to obtain a modified multi-branched filler, wherein the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) dendrites in its structure,

[0031] 2) optionally performing a surface chemical modification and / or surface physical modification on the fibrous filler to obtain a modified fibrous filler,

[0032] 3) mixing the multi-branched filler or the modified multi-branched filler, the fibrous filler or the modified fibrous filler, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution,

[0033] 4) spinning the spinning solution into the polyethylene fiber.

[0034] 22. The manufacturing method described in any of the preceding or following aspects, wherein before performing step 1) or step 2), it also includes a step of drying the multi-branched filler or the fibrous filler, 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).

[0035] 23. The manufacturing method described in any of the above or following aspects, wherein 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 multi-branched filler or the fibrous filler, the treatment temperature is 40-100°C (preferably 70-90°C), and the treatment time is 1-120min (preferably 5-30min).

[0036] 24. The manufacturing method described in any of the above or following aspects, wherein the surface physical modification treatment includes: using a polymer for surface coating, the amount of the polymer used (dry basis) is at least 1% wt% (preferably 5-10 wt%) of the weight of the multi-branched filler or the fibrous filler, 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).

[0037] 25. 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 multi-branched filler or the modified multi-branched filler (calculated as multi-branched filler) is at most 50 parts by weight (preferably 5-15 parts by weight), the amount of the fibrous filler or the modified fibrous filler (calculated as fibrous filler) is at most 50 parts by weight (preferably 3-10 parts by weight), and the amount of the solvent is at least 500 parts by weight (preferably 1000-2000 parts by weight).

[0038] 26. The manufacturing method according to any one of the preceding or following aspects, wherein step 3) comprises:

[0039] 3-1) mixing the multi-branched filler or the modified multi-branched filler with a portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture A,

[0040] 3-2) mixing the fibrous filler or the modified fibrous filler with the remaining portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture B,

[0041] 3-3) mixing the mixture A and the mixture B,

[0042] The solvent is added to one or more of these steps at once or in batches. Preferably, a portion of the solvent (such as 10-90 wt% or 40-60 wt% of the total amount) is added in step 3-1), and the rest of the solvent is added in step 3-2).

[0043] 27. The manufacturing method according to any of the preceding or following aspects, wherein in step 4), the spinning comprises: a gel spinning method, a spinneret primary stretching ratio of 3-10, a super stretching temperature of 80-150°C, and a super stretching ratio of 6-20.

[0044] 28. The manufacturing method described in any of the above or following aspects, wherein before performing step 4), it also includes a step of combing and orienting the spinning solution.

[0045] 29. 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.

[0046] 30. The fabric according to any one of the preceding or following aspects, further comprising at least one other fiber selected from the group consisting of natural plant fibers, natural animal fibers, artificial regenerated fibers, synthetic fibers and inorganic fibers.

[0047] Technical Effects

[0048] The multi-branched filler of the present invention can create an anchoring effect within the fiber matrix, allowing it to remain more stably within the fiber matrix and resist dislodging, thereby effectively reducing secondary damage to the human body. In particular, during the fiber manufacturing process or cutting process, the multi-branched filler's branched protrusions can remain stable and prevent dislodging or rolling. Furthermore, the multi-branched filler's branched protrusions can simultaneously bridge both sides of a crack, preventing crack expansion, thereby achieving high strength, high toughness, and cut-resistant properties.

[0049] The present application can greatly improve the wearing comfort of the fabric, especially the wearing safety, and the fabric can reach the 5th level of the anti-cutting EN388-2003 standard.

[0050] The UHMWPE fiber of the present application can greatly improve the wearing comfort of the fabric, especially the wearing safety, and the fabric can reach the 5th level of the anti-cutting EN388-2003 standard. BRIEF DESCRIPTION OF DRAWINGS

[0051] Figure 1 A schematic diagram of the dispersion of the multi-branch filler and the fibrous filler in the polyethylene matrix according to the present application. Figure 1 In the diagram, H1 represents the length of the branch (from the root), H2 represents the length of the fibrous filler, and L represents the minimum distance between the multi-branch filler and the adjacent fibrous filler. DETAILED DESCRIPTION

[0052] The specific embodiments of the present application are described in detail below, but it should be noted that the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims of the appendix.

[0053] All publications, patent applications, patents and other references mentioned in this specification are hereby incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification will control.

[0054] When the present specification uses the phrase "known to those skilled in the art", "prior art", or similar phrases, the objects derived by the phrase cover those commonly used in the art at the time of the present application, but also include those which are not commonly used at present, but will be recognized as suitable for similar purposes in the art.

[0055] In the context of the present specification, "substantially" means a deviation of no more than 20%, preferably no more than 10%, 5% or 1%.

[0056] In the context of the present specification, the exfoliation of the filler from the fiber matrix is characterized by the degree of material exfoliation from the fiber during the fiber manufacturing process.

[0057] In the context of the present specification, the agglomeration is measured as follows: a 10 cm length is randomly cut from the fiber, the number of agglomerations is investigated under a laser microscope, and then scored according to the following criteria. The measurement is repeated 10 times, and the average is taken.

[0058] No agglomeration: 0,

[0059] Few agglomerations: 2 or less,

[0060] Moderate agglomeration: 3-4,

[0061] Heavy agglomeration: 5 or more.

[0062] In the context of the present specification, the linear density deviation rate is measured according to GB / T 14343.

[0063] In the context of the present specification, the distance between two fillers or similar expressions means the distance between any point on one filler and any point on the other filler.

[0064] In the present specification, all percentages, parts, ratios, etc. mentioned are by weight, and pressures are gauge pressures, unless otherwise specified.

[0065] In the context of the present specification, no specific operating conditions and additives, etc. are directly applicable to those known in the art, and are not particularly limited.

[0066] In the context of the present specification, any two or more embodiments of the present application can be combined arbitrarily, and the technical solutions formed thereby are part of the original disclosure of the present specification and also fall within the protection scope of the present application.

[0067] According to one embodiment of the present application, an ultrahigh molecular weight polyethylene fiber is provided. The ultrahigh molecular weight polyethylene fiber is generally a monofilament or a filament.

[0068] According to one embodiment of the present application, the ultrahigh molecular weight polyethylene fiber comprises ultrahigh molecular weight polyethylene as a matrix, a multi-branched filler (such as a whisker) dispersed in the matrix, and a fibrous filler dispersed in the matrix. Only branched fillers are added, and because branched fillers are irregular, they are easy to cross and bridge during dispersion, resulting in uneven dispersion, causing the local weight of the fiber to increase, the linear density deviation rate to be too large, the fiber to be uneven, and the cutting resistance to be insufficient. After adding fibrous fillers, it is beneficial to disperse the fillers in the axial direction of the fiber, making the fiber more uniform.

[0069] According to the present invention, the multi-branched filler (especially whiskers) and the fibrous filler can be directly purchased from the market or manufactured according to conventional methods known in the relevant technical field, and there is no particular limitation except for the relevant content below.

[0070] According to the present invention, the multi-branched filler and the fibrous filler are sometimes collectively referred to as a filler. Furthermore, the multi-branched filler has a Mohs hardness greater than that of the ultra-high molecular weight polyethylene, and the fibrous filler has a Mohs hardness greater than that of the ultra-high molecular weight polyethylene. Therefore, both fillers are hard fillers.

[0071] According to one embodiment of the present invention, the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) branch-like protrusions in its structure. When the number of branch-like protrusions is too large, the multi-branched filler generates a local mass concentration point in the fiber matrix, and the linear density uniformity of the ultra-high molecular weight polyethylene fiber along the length direction is too poor (the linear density deviation rate is too large), which may have an adverse effect on the processing performance, and the cut resistance may be insufficient. In addition, when the number of branch-like protrusions is too small, the risk of the multi-branched filler escaping from the fiber matrix increases, and the cut resistance may be insufficient.

[0072] According to one embodiment of the present invention, the content of the multi-branched filler is at most 15 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene. When the content of the multi-branched filler is too low, the cut resistance of the fiber may be insufficient. In addition, when the content of the multi-branched filler is too high, the multi-branched filler easily forms an agglomerated structure in the fiber matrix, which may result in an unnecessary and significant increase in the fiber modulus, affecting the wearing comfort.

[0073] According to one embodiment of the present invention, the content of the fibrous filler is at most 15 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene. If the content of the fibrous filler is too low, the cut resistance of the fiber may be insufficient. In addition, if the content of the fibrous filler is too high, the fibrous filler may agglomerate in the fiber matrix, which may cause the fiber linear density uniformity to deteriorate, affecting wearing comfort.

[0074] 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).

[0075] According to one embodiment of the present invention, the multiple dendrites are identical or different from each other, and the length (calculated from the root) is independently 5-2000 μm (preferably 10-300 μm). When the length of the dendrites is too small, the cut resistance of the fiber may be insufficient, and the risk of the multi-branched filler escaping from the fiber matrix increases. In addition, when the length of the dendrites is too large, the multi-branched filler produces a local mass concentration point in the fiber matrix, and the linear density uniformity of the ultra-high molecular weight polyethylene fiber along the length direction is too poor, which may have an adverse effect on the processing performance, and the cut resistance may be insufficient. Moreover, when the length of the dendrites is too large, the multi-branched filler easily forms an agglomerated structure in the fiber matrix, which may cause the fiber linear density uniformity to deteriorate, affecting wearing comfort.

[0076] According to one embodiment of the present invention, the plurality of dendrites are identical to or different from each other, and each independently has a diameter (root) of at most 10 μm (preferably 0.05-3 μm).

[0077] According to one embodiment of the present invention, there is substantially no agglomerate structure between the fibrous filler and the multi-branched filler in the matrix. In the context of this specification, the so-called agglomerate structure refers to a composite structure formed by entanglement or interweaving of multiple fillers (such as between the multi-branched fillers, between the fibrous fillers, or between the multi-branched fillers and the fibrous fillers). According to the present invention, when fillers form agglomerate structures in a fiber matrix, the uniformity of the fiber linear density may deteriorate, affecting wearing comfort.

[0078] According to one embodiment of the present invention, the multi-branched filler is substantially uniformly dispersed in the matrix. In other words, substantially no agglomerates of the multi-branched filler are present in the matrix. As a quantitative indicator, the minimum distance between any two adjacent multi-branched fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0079] According to one embodiment of the present invention, the fibrous filler is substantially uniformly dispersed in the matrix. In other words, substantially no agglomerates of the fibrous filler are present in the matrix. As a quantitative indicator, the minimum distance between any two adjacent fibrous fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0080] According to one embodiment of the present invention, as a quantitative index of the agglomerated structure, the minimum distance between the multi-branched filler and any adjacent fibrous filler in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0081] According to one embodiment of the present application, the multi-branched filler is selected from at least one of inorganic compound whiskers and organic compound whiskers, preferably at least one of inorganic compound whiskers.

[0082] According to one embodiment of the present application, the inorganic compound is at least one selected from inorganic oxygen-containing compounds, preferably at least one selected from metal oxides, metal hydroxides and metal oxygen-containing acid salts, in particular at least one selected from metal oxygen-containing acid salts, such as at least one selected from silicon carbide, silicon nitride, aluminum oxide, zinc oxide, magnesium oxide, calcium carbonate, basic magnesium sulfate, aluminum borate, magnesium borate, potassium titanate and calcium sulfate.

[0083] According to one embodiment of the present application, the organic compound is at least one selected from organic polymers, preferably at least one selected from cellulose, polyester, polyamide, poly-4-hydroxybenzoate (PHB).

[0084] According to one embodiment of the present application, the fibrous filler has a one-dimensional linear structure with a length of 1-2000 μm (preferably 50-200 μm). If the length of the fibrous filler is too small, the cut resistance of the fiber can be insufficient. In addition, if the length of the fibrous filler is too large, the fibrous filler can easily form agglomerated structures in the fiber matrix, which can result in poor uniformity of the fiber and affect the wearing comfort.

[0085] According to one embodiment of the present application, the fibrous filler has a diameter of at most 40 μm (preferably 1-20 μm) and an aspect ratio of at least 1 (preferably 3-100).

[0086] According to one embodiment of the present application, the fibrous filler is at least one selected from inorganic hard short fibers and organic hard short fibers, preferably at least one selected from inorganic hard short fibers.

[0087] According to one embodiment of the present application, the inorganic hard short fiber is at least one selected from metal fibers, glass fibers, ceramic fibers, mineral fibers, basalt fibers.

[0088] According to one embodiment of the present application, the organic hard short fiber is at least one selected from carbon fibers, aramid fibers, aramid copolymer fibers, heterocyclic polyamide fibers, graphite fibers, silicon carbide fibers, wood fibers, bamboo fibers, sisal fibers, yehi fibers.

[0089] According to one embodiment of the present application, the multi-branched filler is subjected to surface chemical modification treatment, such as surface chemical modification treatment with silane coupling agents. If not subjected to surface chemical modification treatment, the anchoring effect of the multi-branched filler to the fiber matrix can be poor, the risk of the multi-branched filler detaching from the fiber matrix is increased, and the cut resistance can be insufficient.

[0090] According to one embodiment of the present application, the fibrous filler is subjected to a surface chemical modification treatment, such as a surface chemical modification treatment with a silane coupling agent. Without a surface chemical modification treatment, the anchoring effect of the fibrous filler to the fibrous matrix can be poor, the risk of the fibrous filler being detached from the fibrous matrix can be increased, and the cut resistance can be insufficient.

[0091] According to one embodiment of the present application, the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, γ-(glycidoxy)propyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

[0092] According to one embodiment of the present application, the multi-branched filler is subjected to a surface physical modification treatment, such as a surface roughening treatment and / or a surface polymer coating treatment.

[0093] According to one embodiment of the present application, the fibrous filler is subjected to a surface physical modification treatment, such as a surface roughening treatment and / or a surface polymer coating treatment.

[0094] According to one embodiment of the present application, the polymer is selected from at least one of a thermoplastic polymer, a thermosetting polymer, and a rubber, and is preferably selected from at least one of a cellulose ester, a vinyl polymer (polyvinyl acetate, polyvinyl alcohol, polyvinylidene chloride, polyisobutylene, etc.), a polyester, a polyether, a polyamide, a polyacrylate, an a-cyanoacrylate, a polyvinyl acetal, an ethylene-vinyl acetate copolymer, and an isocyanate.

[0095] According to one embodiment of the present application, the included angle between any two adjacent branch protrusions is greater than 5° (and preferably 30° to 90°). When the included angle is too small, the fibrous matrix can not sufficiently infiltrate the multi-branched filler, the risk of the multi-branched filler being detached from the fibrous matrix can be increased, and the cut resistance can be insufficient. In addition, when the included angle is too large, the anchoring effect of the multi-branched filler to the fibrous matrix can be poor, the risk of the multi-branched filler being detached from the fibrous matrix can be increased, and the cut resistance can be insufficient.

[0096] According to one embodiment of the present application, the linear density deviation rate of the polyethylene fiber in the length direction of a single fiber is at most 50% (and preferably at most 15%). When the linear density deviation is too large, the fiber uniformity is poor, and the cut resistance can be insufficient.

[0097] According to one embodiment of the present application, the single fiber fineness of the fiber is at least 0.5 dtex (and preferably 0.9 to 5 dtex, and most preferably 1 to 3 dtex).

[0098] According to one embodiment of the present application, it also relates to a method for manufacturing the ultra-high molecular weight polyethylene fiber. According to the present application, the manufacturing method can be used for manufacturing the ultra-high molecular weight polyethylene fiber of the present application as previously described. For this purpose, the content not described or expanded in detail herein for the manufacturing method can directly apply the content given in the foregoing of the present specification for the ultra-high molecular weight polyethylene fiber, which will not be repeated here.

[0099] According to one embodiment of the present application, the method for manufacturing the ultra-high molecular weight polyethylene fiber comprises the following steps:

[0100] 1) optionally performing surface chemical modification treatment and / or surface physical modification treatment on the multi-branched filler (such as whisker) to obtain modified multi-branched filler,

[0101] 2) optionally performing surface chemical modification treatment and / or surface physical modification treatment on the fibrous filler to obtain modified fibrous filler,

[0102] 3) mixing the multi-branched filler or the modified multi-branched filler, the fibrous filler or the modified fibrous filler, ultra-high molecular weight polyethylene and solvent to obtain a spinning solution,

[0103] 4) spinning the spinning solution into the polyethylene fiber.

[0104] According to one embodiment of the present application, before performing the step 1) or the step 2), it further comprises a step of drying the multi-branched filler or the fibrous filler.

[0105] According to one embodiment of the present application, the drying comprises: reducing pressure, drying temperature is 80-200℃ (preferably 90-120℃), drying time is 0.5-10h (preferably 1-4h).

[0106] According to one embodiment of the present application, the surface chemical modification treatment comprises: using silane coupling agent, the amount of the silane coupling agent is 0.8-5wt% (preferably 1-3wt%) of the weight of the multi-branched filler or the fibrous filler, the treatment temperature is 40-100℃ (preferably 70-90℃), the treatment time is 1-120min (preferably 5-30min).

[0107] According to one embodiment of the present application, the surface physical modification treatment comprises: using polymer for surface coating, the amount (dry basis) of the polymer is at least 1wt% (preferably 5-10wt%) of the weight of the multi-branched filler or the fibrous filler, the treatment temperature is at least 30℃ (preferably 40-60℃), the treatment time is at least 1min (preferably 5-10min).

[0108] 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 multi-branched filler or the modified multi-branched filler (calculated as multi-branched filler) is at most 50 parts by weight (preferably 5-15 parts by weight), the amount of the fibrous filler or the modified fibrous filler (calculated as fibrous filler) is at most 50 parts by weight (preferably 3-10 parts by weight), and the amount of the solvent is at least 500 parts by weight (preferably 1000-2000 parts by weight).

[0109] According to one embodiment of the present invention, step 3) includes:

[0110] 3-1) mixing the multi-branched filler or the modified multi-branched filler with a portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture A,

[0111] 3-2) mixing the fibrous filler or the modified fibrous filler with the remaining portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture B,

[0112] 3-3) Mixing the mixture A and the mixture B.

[0113] According to this embodiment of the present invention, batch premixing allows the filler and UHMWPE powder to be adsorbed and aggregated in appropriate amounts. Branched or fibrous fillers embed themselves in depressions on the UHMWPE surface, maintaining a certain degree of adhesion and forming a morphological feature similar to that of wrapped sugar balls. Without premixing, the branched fillers tend to intersect and bridge, forming agglomerates. The fibrous fillers also tend to intersect, forming a spherical structure. Especially since both have a higher density than the UHMWPE, they tend to stratify within the system, resulting in material blockage and poor fiber cut resistance.

[0114] According to one embodiment of the present invention, the solvent is added to one or more of these steps at one time or in batches. As a preferred embodiment, it is preferred to add a portion of the solvent (for example, 10-90wt% or 40-60wt% of the total amount) in step 3-1), and add the rest of the solvent in step 3-2). The purpose of adding the solvent is to wet the surface of the additive, increase fluidity and intermolecular forces, make the combination stronger and the mixing more uniform. If no solvent is added, the molecular repulsion between the materials will cause dust to be generated during the mixing process, the amount added will be reduced, and the cutting resistance effect will not be achieved. At the same time, unsafe factors such as dust explosion will be introduced.

[0115] According to one embodiment of the present invention, in step 4), the spinning is performed using a gel spinning method, 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, while maintaining the temperature at 100-200°C, the spinning solution is passed through a whisker comber to orient the whiskers in the direction of the spinning solution flow. In addition, the spinneret primary stretch ratio is 3-10, the super stretching temperature is 80-150°C, and the super stretching ratio is 6-20 (preferably 8-15).

[0116] 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 the EN388-2016 standard.

[0117] 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.

[0118] Example

[0119] The present invention is further described in detail below with reference to examples, but the present invention is not limited to these examples.

[0120] Example 1

[0121] The ultra-high molecular weight polyethylene fiber of this embodiment comprises ultra-high molecular weight polyethylene as a matrix, multi-branched fillers dispersed in the matrix, and fibrous fillers dispersed in the matrix.

[0122] In this embodiment, the multi-branched filler is a whisker, which is a 1:1 mixture of zinc oxide and calcium sulfate by mass. Its surface is treated with Y-(glycidyloxy)propyltrimethoxysilane and has 4-7 dendrites. The length of each dendrite (measured from the root) is between 100-250 μm, the diameter (root) is between 0.8-1.5 μm, and the angle between any two adjacent dendrites is between 45-55 degrees.

[0123] In this embodiment, the fibrous filler is glass fiber, the surface of which is treated with Y-(glycidyloxy)propyltrimethoxysilane, and the length is 150 μm and the aspect ratio is 10.

[0124] In this embodiment, the amount of whiskers is 7 parts by weight and the amount of glass fiber is 7 parts by weight relative to 100 parts by weight of ultra-high molecular weight polyethylene. The viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 4.5 million.

[0125] In this embodiment, 10 cm of ultra-high molecular weight polyethylene fiber was observed with a laser microscope and it was found that the whiskers and glass fibers were basically evenly dispersed in the matrix, no whiskers or glass fibers or agglomeration structures between the two were observed in the matrix, and the minimum distance between any two adjacent whiskers in the matrix was greater than 100 μm, and the minimum distance between the whiskers and adjacent glass fibers in the matrix was greater than 20 μm.

[0126] In this embodiment, after measurement, the single fiber fineness of the ultra-high molecular weight polyethylene fiber of this embodiment is 2.9 dtex.

[0127] The fiber manufacturing method of this embodiment includes the following steps:

[0128] 1) Modifying the whiskers with a silane coupling agent to obtain modified whiskers,

[0129] 2) Modifying the glass fiber with a silane coupling agent to obtain modified glass fiber,

[0130] 3) mixing the modified whiskers, modified glass fibers, ultra-high molecular weight polyethylene and solvent decalin to obtain a spinning solution,

[0131] 4) spinning the spinning solution into the polyethylene fiber.

[0132] Before the silane coupling agent treatment, the whiskers and glass fibers were dried separately at a drying temperature of 100° C. and a drying time of 3 h.

[0133] During the silane coupling agent treatment, the amount of the silane coupling agent used is 2 wt % of the weight of the whisker and the glass fiber, respectively. The treatment temperature is 80° C., and the treatment time is 20 min.

[0134] The mixing process includes 100 parts by weight of ultra-high molecular weight polyethylene (UHMWPE), 9 parts by weight of modified whiskers (calculated as whiskers), 9 parts by weight of modified glass fibers (calculated as glass fibers), and 1,500 parts by weight of solvent. The modified whiskers are first mixed with 50% by weight of UHMWPE and 50% by weight of solvent to obtain mixture A. The modified glass fibers are then mixed with 50% by weight of UHMWPE and 50% by weight of solvent to obtain mixture B. Finally, mixture A and mixture B are mixed. A gel spinning process is employed, with a spinneret primary draw ratio of 8, a super-drawing temperature of 145°C, and a super-drawing ratio of 10. The spinning solution is passed through a carding orientation zone before spinning.

[0135] Ultra-high molecular weight polyethylene fibers were coated with spandex and then knitted into gloves on a 13-gauge glove loom. The gloves were then tested for cut resistance according to EN388-2016.

[0136] Example 2

[0137] Compared with Example 1, the whiskers and glass fibers were not treated with a silane coupling agent. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example was 2.9 dtex.

[0138] Example 3

[0139] Compared with Example 1, the whiskers have 25-30 dendrites, each with a length (from the root) of 35-100 μm and a diameter (from the root) of 0.5-1.5 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0140] Example 4

[0141] Compared with Example 1, the whiskers have 2-3 dendrites, each with a length (from the root) of 150-250 μm and a diameter (from the root) of 0.8-1.2 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 1.9 dtex.

[0142] Example 5

[0143] Compared with Example 1, the amount of modified whiskers (calculated as whiskers) used is 20 parts by weight for 100 parts by weight of ultra-high molecular weight polyethylene. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.3 dtex.

[0144] Example 6

[0145] Compared with Example 1, the length of each dendrite (calculated from the root) is between 1200-1800 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.9 dtex.

[0146] Example 7

[0147] Compared with Example 1, the diameter (at the root) of each dendrite is between 18 and 25 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.2 dtex.

[0148] Example 8

[0149] Compared with Example 1, the length of the glass fiber is 1000 μm and the aspect ratio is 50. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0150] Example 9

[0151] Compared with Example 1, the angle between any two adjacent dendrites is between 130 and 150 degrees. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this embodiment is 2.5 dtex.

[0152] Example 10

[0153] Compared with Example 1, the angle between any two adjacent dendrites is between 5 and 20 degrees. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this embodiment is 2.3 dtex.

[0154] Example 11

[0155] Compared with Example 1, only the surface treatment of the whiskers and glass fibers was changed, and polyacrylate was used for coating. The single-filament fineness of the ultra-high molecular weight polyethylene fibers in this example was 2.5 dtex.

[0156] Example 12

[0157] Compared with Example 1, the super stretching ratio is 4. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 3.5 dtex.

[0158] Example 13

[0159] Compared with Example 1, no pre-mixing step is performed, and the modified whiskers and modified glass fibers are directly mixed with the entire amount of polyethylene powder and then added to the solvent. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.9 dtex.

[0160] Comparative Example 1

[0161] Compared with Example 1, only whiskers were added without glass fibers. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this comparative example was 2.5 dtex.

[0162] Comparative Example 2

[0163] Compared with Example 1, no whiskers were added, and only glass fibers were added. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this comparative example was 1.9 dtex.

[0164] Comparative Example 3

[0165] Compared with Example 1, the glass fibers were replaced with glass microbeads with a diameter of 1 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fibers in this comparative example was 1.9 dtex.

[0166] Comparative Example 4

[0167] The fiber is commercially available Lilun LY25 ultra-high molecular weight polyethylene fiber, which does not contain whiskers and glass fibers. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this comparative example is 1.2 dtex.

[0168]

[0169]

Claims

1. A method for producing ultra-high molecular weight polyethylene fiber, comprising the following steps: 1) subjecting a multi-branched filler to a surface chemical modification treatment with a silane coupling agent to obtain a modified multi-branched filler, wherein the multi-branched filler has 3-10 dendrites in its structure, wherein the multi-branched filler is selected from at least one inorganic compound whisker, the length of the plurality of dendrites from the root is independently 10-300 μm, the root diameter is independently 0.05-10 μm, the content of the multi-branched filler is 3-15 parts by weight relative to 100 parts by weight of the ultra-high molecular weight polyethylene, and the angle between any two adjacent dendrites is 30°-90°, 2) chemically modifying the surface of the fibrous filler with a silane coupling agent to obtain a modified fibrous filler, wherein the fibrous filler is selected from at least one inorganic hard short fiber, the fibrous filler has a one-dimensional linear structure, a length of 50-200 μm, a diameter of 1-40 μm, an aspect ratio of 3-100, and the content of the fibrous filler is 3-15 parts by weight relative to 100 parts by weight of the ultra-high molecular weight polyethylene. 3) mixing the modified multi-branched filler, the modified fibrous filler, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution, Wherein said step 3) comprises: 3-1) mixing the modified multi-branched filler with 10-90 wt% of the ultra-high molecular weight polyethylene to obtain a mixture A, 3-2) mixing the modified fibrous filler with the remaining portion of the ultra-high molecular weight polyethylene to obtain a mixture B, 3-3) mixing the mixture A and the mixture B, In step 3-1), 10-90 wt% of the solvent is added, and in step 3-2), the rest of the solvent is added. 4) Spinning the spinning solution into the polyethylene fiber, wherein the spinning comprises: a gel spinning method, a spinneret primary stretching ratio of 3-10, a super stretching temperature of 80-150° C., and a super stretching ratio of 6-20.

2. The manufacturing method according to claim 1, wherein before performing step 1) or step 2), the method further comprises a step of drying the multi-branched filler or the fibrous filler, wherein the drying comprises: Reduce pressure, the drying temperature is 80-200℃, and the drying time is 0.5-10h.

3. The manufacturing method according to claim 1, wherein in step 3-1), the modified multi-branched filler is mixed with 40-60 wt% of the ultra-high molecular weight polyethylene to obtain mixture A, or, in step 3-1), 40-60 wt% of the solvent is added to the mixture, and the rest of the solvent is added to the mixture in step 3-2).

4. The manufacturing method of claim 1, wherein the multi-branched filler has 3 to 8 dendrites in its structure.

5. The production method according to claim 1, wherein the content of the multi-branched filler is 3-10 parts by weight, and the content of the fibrous filler is 3-10 parts by weight relative to 100 parts by weight of the ultra-high molecular weight polyethylene.

6. The production method according to claim 1, wherein the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million. The manufacturing method according to claim 1 , wherein the root diameters of the plurality of dendrites are independently 0.05-3 μm.

8. The production method according to claim 1, wherein the inorganic compound is at least one selected from the group consisting of metal oxides, metal hydroxides, and metal oxyacid salts.

9. The production method according to claim 1, wherein the inorganic compound is at least one selected from the group consisting of silicon carbide, silicon nitride, aluminum oxide, zinc oxide, magnesium oxide, calcium carbonate, basic magnesium sulfate, aluminum borate, magnesium borate, potassium titanate, and calcium sulfate.

10. The manufacturing method according to claim 1, wherein the diameter of the fibrous filler is 1-20 μm.

11. The manufacturing method according to claim 1, wherein the inorganic hard short fibers are selected from at least one of metal fibers, glass fibers, ceramic fibers, and basalt fibers.

12. An ultra-high molecular weight polyethylene fiber obtained by the manufacturing method according to any one of claims 1 to 11, comprising the ultra-high molecular weight polyethylene as a matrix, the modified multi-branched filler dispersed in the matrix, and the modified fibrous filler dispersed in the matrix.

13. A fabric comprising the ultra-high molecular weight polyethylene fiber according to claim 12.

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