High performance cut resistant glove composite and method of making

Abstract

The application discloses a high-performance anti-cutting glove composite material and a preparation method thereof, and belongs to the technical field of functional composite materials. The composite material comprises a fiber base material layer, an intelligent response impregnated layer, a primer layer and a topcoat layer. The fiber base material layer is woven into a glove blank body by anti-cutting fiber yarns; the intelligent response impregnated layer comprises a shear thickening fluid, which is in a low-viscosity liquid state to keep soft in a static state, and the viscosity of the shear thickening fluid increases instantaneously to realize liquid-solid phase transition when subjected to a shear impact; the primer layer comprises a first polymer matrix and micron-sized hard particles that are surface-modified; and the topcoat layer comprises a second polymer matrix and nanometer-sized fillers that are surface-modified. Through the synergy of the intelligent response of the shear thickening fluid and the gradient coating structure, normal softness and comfort are realized, automatic reinforcement protection is realized when subjected to an impact, the anti-cutting grade can reach above ANSIA6, and meanwhile, excellent wear resistance, oil resistance and wearing comfort are simultaneously achieved.

Description

Technical Field

[0001] This application relates to the field of functional composite materials technology, and in particular to a high-performance cut-resistant glove composite material with intelligent response characteristics and its preparation method. Background Technology

[0002] Cut-resistant gloves are critical personal protective equipment in high-risk industries such as machining, glass manufacturing, and metal assembly. With the improvement of industrial safety standards, the market has placed higher demands on cut-resistant gloves: they must have a high level of cut protection (such as ANSI / ISEA105A5-A9 level), while remaining soft, lightweight, and comfortable to wear, and also possessing multi-functional properties such as abrasion resistance, oil resistance, and slip resistance.

[0003] Existing technologies mainly employ the following approaches to improve cut resistance: ① blending stainless steel wire or glass fiber into high-strength fibers (UHMWPE, aramid); ② impregnating the glove surface with coatings such as nitrile rubber and polyurethane and adding hard particles (silicon carbide, corundum); ③ using a multi-layer composite weaving structure.

[0004] However, these solutions present significant technical contradictions: while adding metal wires or glass fibers can improve cut resistance, it results in stiff gloves and a strong itchy sensation; hard particle coatings, while increasing abrasion and cut resistance, significantly reduce hand dexterity. Conventional impregnated coatings have low bonding strength with inert fiber surfaces such as UHMWPE, and the coating is prone to peeling off under repeated friction or stretching, leading to a sharp decline in protective performance. Traditional composite materials have fixed mechanical properties and cannot adaptively adjust stiffness according to the magnitude of external force. Under low external force, excessively hard materials affect operational sensitivity, while under high external force, the protective response is lag. Summary of the Invention

[0005] A high-performance cut-resistant glove composite material includes a fiber substrate layer, a smart-responsive impregnation layer, a base layer, and a top layer. The fiber substrate layer is woven from cut-resistant fiber yarns to form the glove blank. The smart-responsive impregnation layer is formed on the fiber surface and within the internal voids of the fiber substrate layer, containing a shear-thickening fluid. This shear-thickening fluid is formed by dispersing nano-silica or nano-alumina in polyethylene glycol or ethylene glycol, and its viscosity increases sharply upon shear impact, achieving a liquid-solid phase transition. The base layer is composited on the surface of the fiber substrate layer and includes a first polymer matrix and micron-sized hard particles modified with a first surface treatment agent. The top layer is composited on the surface of the base layer and includes a second polymer matrix and nano-sized fillers modified with a second surface treatment agent. The shear-thickening fluid is a low-viscosity liquid in a static state, keeping the glove soft; upon cutting or impact, it instantly transforms into a high-viscosity solid, working synergistically with the base layer and top layer to resist external puncture.

[0006] By employing the above technical solution, shear-thickening fluid (STF) endows composite materials with intelligent responsive characteristics: under static or low-speed deformation, the nanoparticles in the STF are in a disordered dispersed state, the fluid viscosity is low, the fibers can slide freely, and the glove is as soft as ordinary fabric; when subjected to cutting or high-speed impact, the shear rate increases sharply, the nanoparticles collide with each other to form "particle clusters," the fluid viscosity increases by several orders of magnitude instantaneously, transforming into a near-solid state, hindering the advancement of the cutting edge. At the same time, the micron-sized hard particles in the base layer form a rigid skeleton, directly resisting the sharp edge; the nano-sized fillers in the top layer fill the micropores of the coating and toughen it. The synergistic effect of the three-layer structure realizes an adaptive mechanism in which the protective performance is enhanced by external impact, fundamentally solving the contradiction of traditional cut-resistant gloves being "either too hard or not protective at all."

[0007] Furthermore, the base layer also disperses shear-thickening fluid microcapsules, the wall material of which is urea-formaldehyde resin or melamine-formaldehyde resin, the core material of which is the same shear-thickening fluid, the microcapsule particle size is 10μm~100μm, and the addition amount is 3wt%~15wt% of the total mass of the base layer.

[0008] By employing the above technical solution, microcapsules pre-encapsulate shear-thickening fluid within the base layer. When the coating is subjected to external impact or abrasion, the microcapsules rupture, releasing the shear-thickening fluid. This process not only creates localized thickening and repair in the damaged area but also replenishes the overall STF content, extending the glove's lifespan. Simultaneously, the microcapsules themselves possess a certain degree of compressibility and resilience, allowing them to deform and store energy under pressure, thus improving wearing comfort.

[0009] Furthermore, the hardness of the base layer is greater than that of the top layer, and the particle sizes of the first surface treatment agent modified micron-sized hard particles in the base layer and the second surface treatment agent modified nano-sized fillers in the top layer are distributed in a stepped manner: the average particle size of the hard particles is 5μm~50μm, the average particle size of the nano-sized fillers is 20nm~200nm, and the particle size ratio of the two is 50:1 to 1000:1, forming a multi-scale synergistic reinforcement effect from large particle cut resistance to small particle toughening.

[0010] By adopting the above technical solutions, the design of hardness and particle size gradients achieves a smooth transition in mechanical properties: the topcoat layer is softer with fine nano-sized fillers, resulting in a smooth contact surface with the skin; the basecoat layer is harder with coarser micron-sized particles, providing core cut resistance. When the particle size ratio is above 50:1, large and small particles do not interfere with each other, and small particles can fill the gaps between large particles, forming a dense packing structure, significantly improving the overall density of the coating and crack propagation resistance. The multi-scale reinforcement effect enables the composite material to dissipate energy simultaneously at multiple scales from macro to micro when subjected to cutting, greatly improving the cut resistance level.

[0011] Furthermore, the cut-resistant fiber yarn is at least one of ultra-high molecular weight polyethylene fiber, para-aramid fiber, glass fiber, and basalt fiber, and the fiber substrate layer is pretreated by plasma or chemical etching before being impregnated with shear thickening fluid to introduce hydroxyl, carboxyl, or amino active groups on the fiber surface to enhance the chemical bonding with the shear thickening fluid and the base layer.

[0012] By employing the above technical solution, plasma etching generates microscopic roughness and polar functional groups on the fiber surface, breaking through the technical bottleneck of difficult bonding of inert fibers such as UHMWPE. The active groups can form hydrogen bonds or covalent bonds with the polyethylene glycol terminal hydroxyl groups in the STF and the polymer matrix of the base layer, increasing the interfacial bonding strength by more than 50%, effectively preventing coating peeling during use and extending the overall lifespan of the gloves.

[0013] Furthermore, the first polymer matrix in the base layer is thermoplastic polyurethane or nitrile rubber, and the micron-sized hard particles are silicon carbide, alumina, corundum, or boron carbide; the second polymer matrix in the top layer is thermoplastic polyurethane or nitrile rubber, and the nano-sized filler is nano-silica, nano-alumina, carbon nanotubes, or graphene.

[0014] By adopting the above technical solutions, TPU or nitrile rubber with good wear resistance and elasticity is selected as the matrix to ensure the flexibility and adhesion of the coating. Micron-sized hard particles provide a direct cutting barrier, while nano-sized fillers inhibit crack propagation through interface toughening and pinning effects. Carbon nanotubes or graphene can also endow the coating with electrical conductivity and antistatic properties.

[0015] A method for preparing the above-mentioned high-performance cut-resistant glove composite material includes steps S1 to S5, as detailed in the claims.

[0016] By employing the above technical solution, fibers are first activated through plasma pretreatment, then impregnated with STF to form a smart responsive layer; micron-sized hard particles and STF microcapsules are added to the base layer; and nano-sized fillers are added to the top layer. The gradient impregnation method ensures chemical matching and physical bonding between layers, avoiding delamination. Control of curing temperature and time guarantees optimal polymer crosslinking.

[0017] In step S1, an external electric or magnetic field can be applied to orient the nanoparticles, forming an anisotropic reinforcement network. The protective effect is optimal when the cutting direction is perpendicular to the alignment direction.

[0018] The selection of the first and second surface treatment agents enables the formation of chemical bonds between the particles or fillers and the polymer matrix, improving dispersibility and interfacial strength.

[0019] Interface activation treatment (UV irradiation or plasma etching) generates free radicals on the surface of the base coat, inducing chemical cross-linking with the top coat and further improving interlayer adhesion.

[0020] Technical solution of dependent claim 10 Furthermore, the composite material has a triple protection mechanism, as detailed in claim 10.

[0021] By adopting the above technical solution, the triple protection mechanism plays a role in different stages of the cutting process: the first layer, STF, instantly solidifies and consumes the initial impact energy; the second layer, a hard particle layer, blocks the cutting edge; and the third layer, a nanofiller layer, prevents crack penetration. The three layers work together to achieve a protection level of ANSI 6 or higher, while maintaining a softness close to that of ordinary cotton gloves under normal conditions. Beneficial effects

[0022] In summary, this application includes at least one of the following beneficial effects: 1. By introducing shear-thickening fluid intelligent response materials, the protective performance of cut-resistant gloves is adaptively enhanced with external impact. They are soft like cotton when static and harden instantly when impacted, breaking the technical contradiction between protection and comfort.

[0023] 2. The gradient coating structure of the base layer (micron-sized hard particles + STF microcapsules) and the top layer (nanofillers), as well as the hardness gradient and particle size gradient design, form a multi-scale synergistic enhancement effect, and the cut resistance level can reach ANSIA 6 or above.

[0024] 3. By introducing active functional groups on the fiber surface through plasma pretreatment, the interfacial bonding strength between STF and coating and inert fibers (such as UHMWPE) is significantly improved, solving the industry problem of easy coating peeling.

[0025] 4. Introducing shear-thickening fluid microcapsules into the coating provides self-healing capabilities for damaged areas, extending the lifespan of the gloves.

[0026] 5. By inducing the directional alignment of nanoparticles through an external electric / magnetic field and promoting interlayer chemical cross-linking through interface activation treatment, the anisotropic mechanical properties and overall durability of the composite material were further optimized. Attached Figure Description

[0027] Figure 1 This is a process flow diagram of the preparation method according to an embodiment of this application. Detailed Implementation

[0028] The present application will now be described in detail with reference to the accompanying drawings and embodiments. It should be noted that, unless otherwise specified, the embodiments and features described in the embodiments of the present application can be combined with each other.

[0029] Raw materials and equipment - Fiber substrate: UHMWPE fiber (DuPont, fineness 400D) knitted into glove blank, 13-gauge.

[0030] - Shear-thickening fluid: Nano-silica (particle size 12nm) is dispersed in PEG200 at a mass fraction of 20% and then ball-milled.

[0031] - Microcapsules: prepared by in-situ polymerization, with urea-formaldehyde resin as the wall material and the same STF as above as the core material, with an average particle size of 45 μm.

[0032] - Base layer: TPU resin (Lubrizol, hardness 85A) dissolved in DMF, with added silicon carbide micro powder (average particle size 25μm) modified with silane coupling agent KH570 and STF microcapsules.

[0033] - Topcoat layer: TPU resin (hardness 70A) dissolved in DMF, with added nano-silica (average particle size 40nm) treated with end-amino modifier.

[0034] - Plasma treatment instrument (atmospheric pressure dielectric barrier discharge), power 500W, processing time 2min.

[0035] Preparation method (general process, such as...) Figure 1 (As shown) S1: The UHMWPE glove preform is treated in an atmospheric pressure plasma treatment instrument (N2 atmosphere, power 500W, 2min), then immersed in STF dispersion, vacuum-assisted infiltration for 10min, removed, glued, and dried in a 60℃ vacuum drying oven for 4h to form a smart response impregnation layer.

[0036] S2: Prepare the base coat impregnation solution: TPU:DMF=15:85 (mass ratio), stir to dissolve, then add modified silicon carbide (20% of the dry weight of the base coat) and STF microcapsules (10% of the dry weight of the base coat), and continue stirring for 30 minutes.

[0037] S3: Immerse the glove blank treated in step S1 into the base adhesive solution for 15 minutes, remove it and rotate to drip the adhesive, dry it in an oven at 80°C for 30 minutes, and then cure it at 120°C for 2 hours to form the base adhesive layer.

[0038] S4: Prepare the surface adhesive layer impregnation solution: TPU (70A):DMF=15:85, add modified nano silica (accounting for 5% of the dry weight of the surface adhesive), and ultrasonically disperse for 30 minutes.

[0039] S5: Immerse the glove blank with the base adhesive layer into the top adhesive solution for 10 minutes, remove it, drip the adhesive, dry it at 80℃ for 30 minutes, and then cure it at 120℃ for 1 hour to obtain the product.

[0040] Formulations and process parameters of Examples 1-10 and Comparative Examples 1-6 Table 1. Formulations and process parameters of the examples and comparative examples. Note: "Yes" for STF impregnation layer indicates that step S1 is performed; "No" indicates that this step is omitted. The hardness of the base coat and top coat is determined by the TPU grade.

[0041] Performance testing methods and standards - Cut resistance rating: Tested 5 times and averaged according to ANSI / ISEA105-2016 standard using TDM-100 cut tester.

[0042] - Static flexibility: The cantilever beam method (ASTM D1388) is used, and the value is expressed as bending length (cm). The smaller the value, the more flexible the material.

[0043] - Coating peel strength: According to ASTM D903, peel the coating from the substrate at 180° and test the maximum force (N / cm).

[0044] - Wear mass loss: according to ASTM D3884 (H-18 wheel, 500g load, 500 rpm), weight loss (mg).

[0045] - Oil resistance: The sample was immersed in IRM903 oil at 70℃ for 24 hours, and the mass change rate (%) was tested.

[0046] - Subjective evaluation of glove usage flexibility: 5 testers operated standard screws while wearing gloves and rated them on a scale of 1-5 (5 being the best).

[0047] Performance test results Table 2 Performance test results of the examples and comparative examples Data Analysis and Discussion 1. The core role of the STF intelligent response layer Comparing Example 1 (with STF layer) and Example 9 (without STF layer): the cut resistance rating decreased from A6 to A4, and the bending length decreased from 6.2 cm to 5.5 cm (increased flexibility but decreased protection). This indicates that while the STF layer does provide low resistance when static (Example 9 is more flexible), it loses its ability to dynamically enhance protection. Example 1, with its instantaneous STF curing upon cutting, contributed approximately two ratings to the improvement. Comparative Example 1 (conventional hard coating, without STF) only achieved an A4 rating, further validating the synergistic value of the STF.

[0048] 2. Synergistic effect of hard particles in the base layer and STF microcapsules Example 3 increased the hard particles to 25% and microcapsules to 15%, achieving a cut resistance rating of A7, but the bending length increased (7.0 cm), and the feel became harder. Example 4 reduced the hard particles to 15% / 5%, lowering the rating to A5, but improving softness. Example 8 had no microcapsules, achieving a rating of A5, but with increased wear mass loss (68 vs 45 mg), indicating that the microcapsules release STF during wear, possessing self-healing capabilities and extending the effective lifespan of the coating.

[0049] 3. Interface enhancement through plasma pretreatment Example 7, omitting plasma treatment, showed a sharp drop in peel strength from 12.5 N / cm to 5.2 N / cm, with increased wear mass loss (78 mg). This indicates that the coating adhesion is extremely poor when the inert UHMWPE fibers are not activated, directly leading to unstable protective performance (grade A5, but the actual coating is prone to peeling). Example 1 demonstrates that introducing active groups through plasma improves peel strength by 140%, which is key to ensuring the durability of the composite material.

[0050] 4. The rationality of the design of gradient hardness and particle size gradient Comparative Example 3 (with the same surface and bottom hardness, both 85A) and Comparative Example 4 (hard surface, soft bottom) have cut resistance ratings of A5 and A4, respectively, and large bending lengths (7.0-7.5cm) and low flexibility scores (2.5-2.8). This indicates that violating the gradient principle of "soft outside, hard inside" leads to stress concentration at the interface, resulting in either excessive overall hardness (poor flexibility) or insufficient protection. Example 1 (soft surface, hard bottom) performed best: protection A6, flexibility 4.0. In terms of particle size gradient, the ratio of micron-sized SiC to nano-sized SiO2 is approximately 625:1, forming a close packing. Comparative Example 5 is not oriented but has comparable performance, indicating that oriented arrangement is not necessary but helps with anisotropic optimization.

[0051] 5. Overall optimal formula Example 1 achieved the best balance between cut resistance (A6), softness (6.2 cm), peel strength (12.5 N / cm), abrasion resistance (45 mg), oil resistance (3.2%), and flexibility (4.0). Example 5 also achieved A6 by using nano-alumina, demonstrating the effectiveness of different nanofillers. In Example 6, when the nanofiller content was increased to 8%, abrasion decreased but the feel became slightly harder.

[0052] 6. Comparison with existing technologies Comparative Example 2 (pure TPU coating) has a cut resistance of only A2, while Comparative Example 1 (traditional hard particle coating) has an A4 and low peel strength. The embodiments of this invention generally achieve A5-A7, and the bending length is close to that of pure TPU (around 6.0), truly achieving a breakthrough in "high protection and high comfort".

[0053] Summary of Implementation Principles The implementation principle of the high-performance cut-resistant glove composite material in this application embodiment is as follows: Active groups such as hydroxyl groups are introduced onto the surface of UHMWPE fibers through plasma pretreatment, enhancing the chemical bonding with the shear-thickening fluid (STF) and subsequent TPU coating. In a static state, the STF impregnation layer exhibits disordered dispersion of nanoparticles, resulting in a soft glove. Upon impact with a cut, the shear rate surges, causing nanoparticles to aggregate and form clusters, instantly increasing the fluid viscosity by several orders of magnitude, consuming cutting energy and hindering the cutting edge. Micron-sized silicon carbide particles in the base layer form a rigid framework, directly resisting cutting; simultaneously, the dispersed STF microcapsules rupture and release STF when the coating wears down, repairing localized damage. Nano-silica in the top layer fills voids, toughens the coating, and utilizes its surface-active functional groups to covalently bond with the TPU matrix. The three-layer structure, with its hardness and particle size gradients from flexible to rigid, achieves multi-scale energy dissipation, enabling the composite material to automatically strengthen its protection against cutting impacts while maintaining everyday wearing comfort, resulting in significantly superior overall performance compared to existing technologies.

[0054] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A high-performance cut-resistant glove composite material, characterized in that, include: The fiber substrate layer is made of cut-resistant fiber yarn woven into the glove blank; A smart response impregnation layer is formed on the fiber surface and in the internal voids of the fiber substrate layer. The smart response impregnation layer contains a shear thickening fluid, which is formed by dispersing nano-silica or nano-alumina in polyethylene glycol or ethylene glycol. When subjected to shear impact, the viscosity increases sharply to achieve a liquid-solid phase change. The base layer, laminated to the surface of the fiber substrate layer, comprises a first polymer matrix and micron-sized hard particles modified by a first surface treatment agent; The topcoat layer, laminated to the surface of the basecoat layer, comprises a second polymer matrix and nanoscale fillers modified by a second surface treatment agent; The shear-thickening fluid is a low-viscosity liquid when static, keeping the glove soft; when subjected to cutting or impact, it instantly transforms into a high-viscosity solid, working in conjunction with the base and top layers to resist external punctures.

2. The high-performance cut-resistant glove composite material according to claim 1, characterized in that, The base layer also contains shear-thickening fluid microcapsules. The wall material of the microcapsules is urea-formaldehyde resin or melamine-formaldehyde resin, and the core material is the same shear-thickening fluid. The microcapsule particle size is 10μm~100μm, and the amount added is 3wt%~15wt% of the total mass of the base layer.

3. The high-performance cut-resistant glove composite material according to claim 1, characterized in that, The hardness of the base layer is greater than that of the top layer, and the particle sizes of the first surface treatment agent modified micron-sized hard particles in the base layer and the second surface treatment agent modified nano-sized fillers in the top layer are distributed in a stepped manner: the average particle size of the hard particles is 5μm~50μm, the average particle size of the nano-sized fillers is 20nm~200nm, and the particle size ratio of the two is 50:1 to 1000:1, forming a multi-scale synergistic reinforcement effect from large particles to cut resistance to small particles to toughen the surface.

4. The high-performance cut-resistant glove composite material according to claim 1, characterized in that, The cut-resistant fiber yarn is at least one of ultra-high molecular weight polyethylene fiber, para-aramid fiber, glass fiber, and basalt fiber, and the fiber substrate layer is pretreated by plasma or chemical etching before being impregnated with shear thickening fluid to introduce hydroxyl, carboxyl, or amino active groups on the fiber surface to enhance the chemical bonding with the shear thickening fluid and the base layer.

5. The high-performance cut-resistant glove composite material according to claim 1, characterized in that, The first polymer matrix in the base layer is thermoplastic polyurethane or nitrile rubber, and the micron-sized hard particles are silicon carbide, alumina, corundum, or boron carbide; the second polymer matrix in the top layer is thermoplastic polyurethane or nitrile rubber, and the nano-sized filler is nano-silica, nano-alumina, carbon nanotubes, or graphene.

6. A method for preparing a high-performance cut-resistant glove composite material as described in any one of claims 1 to 5, characterized in that, Includes the following steps: Step S1: Perform plasma pretreatment on the glove blank, and then impregnate it with shear thickening fluid under vacuum or normal pressure to allow the shear thickening fluid to penetrate evenly into the fiber interior and surface, and then dry it at low temperature to form a smart response impregnation layer. Step S2: Prepare the base layer impregnation solution: Dissolve the first polymer matrix in an organic solvent, add micron-sized hard particles modified by the first surface treatment agent and shear-thickening fluid microcapsules, and stir evenly; Step S3: Immerse the glove blank treated in step S1 into the impregnation solution of the base adhesive layer. After the immersion treatment, remove the glove, apply adhesive, and cure to form the base adhesive layer. Step S4: Prepare the surface adhesive layer impregnation solution: Dissolve the second polymer matrix in an organic solvent, add the nano-sized filler modified by the second surface treatment agent, and stir evenly; Step S5: Immerse the glove blank with the base adhesive layer into the top adhesive layer impregnation solution. After the immersion treatment, remove the glove, apply adhesive, and cure to form the top adhesive layer, thereby obtaining a high-performance cut-resistant glove composite material.

7. The preparation method according to claim 6, characterized in that, After impregnating the fiber with shear-thickening fluid in step S1, the nano-silica or nano-alumina is further oriented on the fiber surface by applying an external electric or magnetic field to form an anisotropic reinforcing network.

8. The preparation method according to claim 6, characterized in that, The first surface treatment agent is a silane coupling agent or a titanate coupling agent, and the second surface treatment agent is a terminal amino or terminal epoxy functional group modifier, which grafts active functional groups onto the surface of the nanoscale filler and forms covalent bonds with the polymer matrix.

9. The preparation method according to claim 6, characterized in that, It also includes an interface activation treatment after the base coat is formed and before the top coat is impregnated. The interface activation treatment is to generate free radicals on the surface of the base coat by ultraviolet irradiation or plasma etching, which induces chemical cross-linking with the top coat.

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