Impact-resistant protective clothing for mining

Abstract

The application discloses an impact-resistant mine protective clothing and belongs to the technical field of mine protective clothing. The mine protective clothing is provided with an impact-resistant protective layer, and the impact-resistant protective layer comprises alternately stacked and connected first and second functional layers. The outermost layer of the impact-resistant protective layer towards the outside of a wearer of the protective clothing is the first functional layer, the first functional layer is a composite material layer composed of aramid woven fabric and a second resin, the second resin is filled in the fiber gap of the aramid woven fabric as a continuous matrix and covers the fiber surface, the weaving raw material of the aramid woven fabric is aramid monofilament subjected to first resin impregnation pretreatment, the first and second resins are both thermosetting resins, the first resin comprises a first compound, the first compound contains a morpholine ring and is bonded in a crosslinking network of the first resin, and the second functional layer is a dynamic crosslinking polymer layer. Compared with the prior art, the application can not only resist impact and be hard, but also absorb impact force and reduce the risk of blunt injury of personnel.

Description

Technical Field

[0001] This invention relates to the field of mining protective clothing technology, and more specifically, to an impact-resistant mining protective clothing. Background Technology

[0002] To improve protective performance, existing technologies typically incorporate rigid protective layers into impact-resistant protective clothing, such as metal plates, metal mesh, rigid engineering plastics, and high-modulus fiber-reinforced composites. These rigid layers offer advantages in ballistic scenarios: upon impact from high-speed projectiles, the rigid layer absorbs energy through material crushing and fiber breakage, and its high modulus effectively blocks penetration. However, directly applying these impact-resistant rigid protective layers to blunt impact scenarios in mining presents the following fundamental drawbacks: Mining environments are complex, and underground workers face various risks of low- to medium-velocity blunt force impacts, such as falling rocks, coal block collapses, tool slippage, and equipment collisions. Unlike military bulletproof vests, which primarily protect against high-speed penetration, the core challenge of mining protective clothing is to minimize the risk of blunt force injury caused by impact forces being directly transmitted to the body through the hard layer, while preventing punctures.

[0003] However, the rigid layer itself hardly deforms upon impact, and the impact energy cannot be absorbed by the protective layer itself. Existing impact-resistant protective clothing only has a rigid layer without a buffering and energy-absorbing protective layer, and the impact force is directly transmitted to the body through the rigid layer. In practical applications, it has been found that even if the protective layer is not penetrated, the pressure transmitted to the body from its back is still sufficient to cause serious blunt force injuries such as rib fractures and internal organ rupture.

[0004] Therefore, how to provide a new type of impact-resistant protective clothing for mining that can both withstand impacts and absorb impact forces to reduce the risk of injury has become an urgent problem to be solved by those skilled in the art. Summary of the Invention

[0005] The purpose of this invention is to provide an impact-resistant mining protective suit to solve the aforementioned technical problems.

[0006] To achieve the above objectives, the present invention provides the following technical solution: An impact-resistant mining protective suit, comprising an impact-resistant protective layer, the impact-resistant protective layer including: The first and second functional layers are alternately stacked and connected; The outermost layer of the impact-resistant protective layer facing the wearer is the first functional layer. The first functional layer is a composite material layer composed of aramid woven fabric and second resin. The second resin serves as a continuous matrix, filling the fiber gaps of the aramid woven fabric and covering the fiber surface. The aramid woven fabric serves as a reinforcing skeleton, distributed in the second resin matrix. The weaving material of the aramid woven fabric is aramid monofilaments impregnated and pretreated with the first resin. Both the first and second resins are thermosetting resins. The first resin includes a first compound containing a morpholine ring. The first compound is bonded to the cross-linked network of the first / second resin. The second functional layer is a dynamically cross-linked polymer layer.

[0007] Optionally, the first resin is a modified epoxy resin, the first compound is selected from at least one of amino morpholine compounds, epoxy morpholine compounds, and mercapto morpholine compounds, and the second resin is an epoxy resin.

[0008] Optionally, the first compound is selected from at least one of 2-morpholinoethylamine, N-(3-aminopropyl)morpholine, N-glycidylmorpholine, and 4-(2-mercaptoethyl)morpholine.

[0009] Alternatively, the first compound may be only 2-morpholinoethylamine.

[0010] Optionally, the first resin may also include tris(hydroxymethyl)aminomethane.

[0011] Optionally, the dynamically crosslinked polymer layer is a dynamically urea-linked polyurethane layer, and its dynamic crosslinking system is a dynamically urea-linked polyurethane system.

[0012] Optionally, the dynamically crosslinked polymer layer is a dynamically disulfide-crosslinked polyacrylate layer, and its dynamic crosslinking system is a dynamically disulfide-crosslinked acrylate system.

[0013] Optionally, along the thickness direction, at least one second functional layer includes a third functional layer and a fourth functional layer stacked and connected, the third functional layer being close to the first functional layer and the fourth functional layer being far from the first functional layer, the third functional layer being stacked between the first functional layer and the fourth functional layer, the third functional layer being a dynamically disulfide-crosslinked polyacrylate layer and the fourth functional layer being a dynamically urea-crosslinked polyurethane layer.

[0014] The mining protective suit provided by this invention features an impact-resistant protective layer that provides rigid impact resistance through its outermost first functional layer. Energy is absorbed through material crushing of the thermosetting resin layer and breakage of the reinforcing aramid fibers, ensuring the suit's impact resistance and preventing penetration. While the first functional layer provides impact resistance, it also transmits the impact force perpendicular to the layer to its back side. This application has a second functional layer stacked and fixedly installed on the back side of the first functional layer. The impact force acts vertically on the dynamically cross-linked polymer layer, and the resulting stress preferentially concentrates on the reversible cross-linked bonds. The reversible bonds break, causing anisotropic slippage of the molecular chains. Energy is absorbed through internal friction between molecular chains, conformational changes in chain segments, and interfacial friction until the stress decreases and the dynamic bonds reconnect. Therefore, the second functional layer can convert the kinetic energy of the vertical impact force into frictional heat generated by the anisotropic slippage of its own molecular chains, providing energy absorption and buffering, reducing the force on the next first functional layer, lowering the impact on the wearer, and reducing the risk of blunt force trauma.

[0015] Compared to existing technologies, this application has alternating layers of a first functional layer and a second functional layer in its impact-resistant protective layer. The first functional layer provides rigid impact resistance, reducing the risk of the protective clothing being penetrated or torn, while the second functional layer absorbs impact force, reducing the risk of blunt force injuries to personnel. Detailed Implementation

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0017] This invention provides an impact-resistant mining protective suit. The suit includes an impact-resistant protective layer comprising alternating layers of a first functional layer and a second functional layer. Wherein: The outermost layer of the impact-resistant protective layer facing the wearer is the first functional layer. The first functional layer is a composite material layer composed of aramid woven fabric and a second resin. The second resin serves as a continuous matrix, filling the gaps between the fibers of the aramid woven fabric and covering the fiber surface. The aramid woven fabric serves as a reinforcing skeleton distributed in the second resin matrix. The weaving material of the aramid woven fabric is aramid monofilaments impregnated and pretreated with the first resin. Both the first and second resins are thermosetting resins. The first resin includes a first compound containing a morpholine ring and is bonded to the cross-linking network of the first and second resins. The second functional layer is a dynamically cross-linked polymer layer.

[0018] The mining protective suit provided by this invention features an impact-resistant protective layer that provides rigid impact resistance through its outermost first functional layer. Energy is absorbed through material crushing of the thermosetting resin layer and breakage of the reinforcing aramid fibers, ensuring the suit's impact resistance and preventing penetration. While the first functional layer provides impact resistance, it also transmits the impact force perpendicular to the layer to its back side. This application has a second functional layer stacked and fixedly installed on the back side of the first functional layer. The impact force acts vertically on the dynamically cross-linked polymer layer, and the resulting stress preferentially concentrates on the reversible cross-linked bonds. The reversible bonds break, causing anisotropic slippage of the molecular chains. Energy is absorbed through internal friction between molecular chains, conformational changes in chain segments, and interfacial friction until the stress decreases and the dynamic bonds reconnect. Therefore, the second functional layer can convert the kinetic energy of the vertical impact force into frictional heat generated by the anisotropic slippage of its own molecular chains, providing energy absorption and buffering, reducing the force on the next first functional layer, lowering the impact on the wearer, and reducing the risk of blunt force trauma.

[0019] Compared to existing technologies, this application has alternating layers of a first functional layer and a second functional layer in its impact-resistant protective layer. The first functional layer provides rigid impact resistance, reducing the risk of the protective clothing being penetrated or torn, while the second functional layer absorbs impact force, reducing the risk of blunt force injuries to personnel.

[0020] In one possible implementation, the first resin is a modified epoxy resin, and the first compound is selected from at least one of amino-based morpholine compounds, epoxy-based morpholine compounds, and mercapto-based morpholine compounds. The second resin is an epoxy resin.

[0021] If the first compound contains aminomorpholine compounds or epoxymorpholine compounds, or if the first resin contains compounds such as trihydroxymethylaminomethane that spontaneously undergo ring-opening reactions with the epoxy resin prepolymer at room temperature, all process steps (including but not limited to impregnation pretreatment of aramid yarn bundles, twisting, weaving, and impregnation of aramid braided fabrics in the second resin) must be performed at a low temperature (≤0℃) before the first functional layer needs to be cured and molded. If the first compound contains mercaptomorpholine compounds, and also contains compounds with tertiary amine groups such as 2-morpholinoethylamine, 3-morpholinopropylamine, and N-(3-aminopropyl)morpholine, and the content of tertiary amine groups in the first resin is sufficient, low-temperature treatment is sufficient; no additional catalyst is required, nor is heat treatment of the resin necessary during the curing process. If the first compound does not contain the aforementioned morpholine compounds with tertiary amine groups, or if the content is too low, 0.3-1 wt% (by mass percentage of the first resin) of an alkaline catalyst (tertiary amine or phosphine catalyst, such as tris(dimethylaminomethyl)phenol DMP-30, benzyldimethylamine BDMA, triphenylphosphine TPP, tributylphosphine TBP) needs to be added before curing, or the resin needs to be pretreated by heating (60-80°C) during the curing process to bond the mercaptomorpholine compound to the crosslinking network of the epoxy resin.

[0022] Optionally, the first compound is selected from at least one of 2-morpholinoethylamine, 3-morpholinopropylamine, N-(3-aminopropyl)morpholine, N-glycidylmorpholine, and 4-(2-mercaptoethyl)morpholine. The first compound is preferably 2-morpholinoethylamine.

[0023] In one possible implementation, the first resin also includes tris(hydroxymethyl)aminomethane.

[0024] In one possible implementation, the difference between the second resin and the first resin is that the first compound (or the first compound and tris(hydroxymethyl)aminomethane) in the first resin is replaced with a prepolymer. For resins where a curing agent was not originally required due to the first compound or tris(hydroxymethyl)aminomethane, a curing agent is added, such that the curing agent constitutes 10-20 wt% of the second resin system. For resins with mixed prepolymers, the weight ratio of each component in the replaced prepolymer is configured according to the weight ratio of each component in the original prepolymer composition of the first resin system.

[0025] In one possible implementation, the second resin is completely identical to the first resin.

[0026] In one possible implementation, the first resin comprises, by weight percentage: 65-75wt% bisphenol A type epoxy resin, preferably E-51 type / EPON 828 type epoxy resin; 10-15 wt% 2-morpholinoethylamine; 5-8 wt% Tris(hydroxymethyl)aminomethane; Acetone or butanone is used as the solvent.

[0027] The second resin is essentially the same as the first resin, except that 2-morpholinoethylamine and tris(hydroxymethyl)aminomethane are replaced with bisphenol A type epoxy resin, and a curing agent is added to the second resin system. The mass percentage of the curing agent in the second resin is 10-20 wt%. The curing agent can be isophorone diamine (IPDA) or diethylenetriamine (DETA).

[0028] Take a certain amount of aramid single yarn as a yarn bundle and fully impregnate it in the first resin at a low temperature (below 0℃); Under low temperature (below 0℃) conditions, take the impregnated aramid yarn bundle, use a squeeze roller to remove excess first resin, and twist, ply (optional) the aramid, and weave it into two-dimensional woven fabrics such as twill fabrics or three-dimensional woven fabrics such as 3D orthogonal weaving and 3D interlocking weaving. Several layers of two-dimensional woven fabrics are stacked and combined to form the aforementioned aramid woven fabric with a certain thickness, or the three-dimensional woven fabric is directly used as the aforementioned aramid woven fabric. Under low temperature (below 0℃) conditions, add curing agent to the second resin system pre-cooled to below 0℃, stir evenly, impregnate the aramid fabric in the second resin, and set a squeeze roller at the impregnation outlet to remove excess second resin, or impregnate by roller pressing.

[0029] Remove the impregnated aramid fabric and allow it to stand at room temperature to set. Surface treatment can be flexibly selected as needed to obtain the first functional layer.

[0030] The prepared first and second functional layers are taken in corresponding quantities, alternately stacked, and hot-pressed together to form an impact-resistant protective layer. This layer is then installed on the outer surface, inner surface, or interlayer of the mining protective suit to provide impact protection for the designed area. During the hot-pressing process, the second functional layer deforms due to heat, thereby tightly connecting itself with the first functional layers on both sides of the thickness direction.

[0031] Alternatively, in embodiments where all or part of the second functional layer includes a third and fourth functional layer, the prepared first functional layer, (uniform second functional layer), third functional layer, and fourth functional layer are sequentially stacked and then hot-pressed. During the hot-pressing process, the (uniform second functional layer), third functional layer, and fourth functional layer deform under heat, thereby tightly connecting themselves with the functional layers on both sides in the thickness direction. This application does not specifically limit the hot-pressing process conditions, as long as a stable connection is achieved.

[0032] In one possible implementation, the dynamically crosslinked polymer layer is a dynamically urea-linked polymer layer, preferably a dynamically urea-linked polyurethane layer, and its dynamic crosslinking system is a dynamically urea-linked polyurethane system. The first functional layer and the second functional layer are alternately stacked and hot-pressed together.

[0033] In one possible implementation, the dynamically crosslinked polymer layer is a dynamically disulfide-crosslinked polymer layer, preferably a dynamically disulfide-crosslinked polyacrylate layer, wherein the dynamic crosslinking system is a dynamically disulfide-crosslinked acrylate system. The first functional layer and the second functional layer are alternately laminated and hot-pressed together.

[0034] In one possible implementation, along the thickness direction, at least one second functional layer includes a third functional layer and a fourth functional layer stacked and connected. The third functional layer is close to the first functional layer, and the fourth functional layer is away from the first functional layer, with the third functional layer stacked between the first and fourth functional layers. The third functional layer is a dynamically disulfide-crosslinked polymer layer, preferably a dynamically disulfide-crosslinked polyacrylate layer; the fourth functional layer is a dynamically urea-crosslinked polymer layer, preferably a dynamically urea-crosslinked polyurethane layer.

[0035] In one possible implementation, the second / fourth functional layer is a dynamically disulfide-crosslinked polyacrylate layer, whose dynamically crosslinked system comprises, by weight percentage: 40-60wt% Methyl methacrylate (MMA); 30-50wt% butyl acrylate (BA); 5-10 wt% hydroxyethyl acrylate (HEA); 2-6 wt% bis(2-methacryloylthioethyl) disulfide DSDMA; 0.5-1wt% initiator.

[0036] Ethyl acetate or butanone can be used as solvents, and azobisisobutyronitrile can be selected as the initiator.

[0037] The process for preparing the second / fourth functional layer using the above dynamic crosslinking system is as follows: Add MMA, BA, HEA and DSDMA to the solvent in sequence, and stir until completely homogeneous for later use; Add an initiator before molding, stir quickly and evenly, and complete the coating within 5-10 minutes; The coating is applied to form a film, and the solvent is allowed to evaporate at room temperature for 10-20 minutes. The film is then placed in an oven at 50-60℃ for 30-60 minutes, and then heated to 60-80℃ for 4-8 hours. The film is then removed and allowed to cool naturally to room temperature to obtain the second / fourth functional layer.

[0038] In one possible implementation, the second / third functional layer is a dynamically crosslinked polyurethane layer with urea bonds, and its dynamically crosslinked system comprises, by mass percentage: 50-60wt% castor oil; 30-40wt% dicyclohexylmethane diisocyanate (HMDI); 5-10wt% N-(2-hydroxyethyl)piperazine HEP; 0.05-0.1wt% catalyst.

[0039] Ethyl acetate or tetrahydrofuran can be used as solvents, and dibutyltin dilaurate can be selected as the catalyst.

[0040] The process for preparing the second / third functional layer using the above dynamic crosslinking system is as follows: Add castor oil to the solvent and stir well; Add N-(2-hydroxyethyl)piperazine (HEP) to it and stir until well mixed; Add the catalyst and stir well before use; When molding is required, slowly add dicyclohexylmethane diisocyanate (HMDI) dropwise to the mixture while stirring rapidly to obtain a final mixture. The coating process is completed within 10-15 minutes. The mixture is coated into a film and left at room temperature for 2-4 hours to evaporate the solvent. Then, it is transferred to an oven and heat-treated at 60-80℃ for 8-10 hours. After that, it is taken out and allowed to cool naturally to room temperature to obtain the second / third functional layer.

[0041] In one possible implementation, the second / third functional layer is a dynamically crosslinked polymer layer with urea bonds, and its dynamically crosslinked system comprises, by mass percentage: 60-75 wt% polyetheramine PEA, preferably polyetheramine D-2000; 15-25wt% Toluene diisocyanate (TDI); 2-5wt% 2-(tert-butylamino)ethyl methacrylate (TBEMA); 3-8wt% adipic acid dihydrazide AD; N,N-dimethylformamide (DMF) was used as the solvent.

[0042] The process for preparing the second / third functional layer using this dynamic crosslinking system is as follows: Add polyetheramine to DMF and stir; Add adipic acid dihydrazide (AD) and TBEMA sequentially, and stir until homogeneous to obtain the first solution for later use; When molding is required, take out the first solution, slowly add toluene diisocyanate (TDI) dropwise while stirring rapidly to obtain the second solution, and complete the coating within 5-10 minutes; The second solution is quickly poured onto the molding substrate and coated into a uniform film using a coater. The film is left at room temperature for 2-4 hours to evaporate the solvent. Then, it is transferred to a dryer and cured at a preset temperature of 60-80°C for 6-8 hours to obtain the second / third functional layer.

[0043] To better illustrate the present invention, Embodiment 1 is provided as follows: The dynamic crosslinking system for preparing the first resin, the second resin, and the second functional layer is as follows: The first resin comprises, by weight percentage: 70wt% E-51 type epoxy resin; 12wt% 2-morpholinoethylamine; 8wt% Tris(hydroxymethyl)aminomethane; The remainder is acetone solvent.

[0044] The second resin comprises, by weight percentage: 79wt% E-51 type epoxy resin; 11wt% Isophorone diamine IPDA (curing agent not added at this time); The remainder is acetone solvent.

[0045] Take a certain amount of aramid single yarn as a yarn bundle and fully impregnate it in the first resin at a low temperature (-4℃); Under low temperature (-4℃) conditions, take the impregnated aramid yarn bundle, use a squeeze roller to remove excess first resin, twist and weave the aramid into a twill fabric, and stack 3 layers of twill fabric to form an aramid woven fabric. Under low temperature (-4℃) conditions, IPDA is added to the second resin system that has been pre-cooled to -4℃ and stirred evenly. The aramid fabric is then impregnated in the second resin. An extrusion roller is set at the impregnation outlet to remove excess second resin. The aramid fabric is then moved to room temperature and left to stand for 6 hours to form the first functional layer.

[0046] The second functional layer is a dynamically crosslinked polyurethane layer with urea bonds. By mass percentage, its dynamically crosslinked system includes: 55wt% Methyl methacrylate (MMA); 30wt% butyl acrylate (BA); 6wt% hydroxyethyl acrylate (HEA); 4wt% bis(2-methacryloylthioethyl) disulfide DSDMA; 0.8wt% azobisisobutyronitrile.

[0047] The others are ethyl acetate solvent.

[0048] The process for preparing the second functional layer using this dynamic crosslinking system is as follows: Add polyetheramine to DMF and stir; Add adipic acid dihydrazide (AD) and TBEMA sequentially, and stir until homogeneous to obtain the first solution for later use; When molding is required, take out the first solution, slowly add toluene diisocyanate (TDI) dropwise while stirring rapidly to obtain the second solution, and then immediately pour the second solution onto the molding substrate. Use a coater to coat it into a uniform film, place it at room temperature for 3 hours to evaporate the solvent, and then transfer it to a dryer to cure at a preset temperature of 70°C for 6 hours to obtain the second functional layer.

[0049] Take three of each of the prepared first and second functional layers, stack them alternately, and heat-press them together to form an impact-resistant protective layer, which is then installed in the interlayer of the mining protective clothing.

[0050] The tensile strength of the second functional layer of the first embodiment was measured and is shown in Table 1 below. The second functional layer was scratched to a depth of 50% of its thickness, and then left at room temperature for 24 hours. The tensile strength of the scratched layer is shown in Table 1 below.

[0051] The mechanical properties of the impact-resistant protective layer prepared in Example 1 were tested as follows: Referring to GB / T 2791-1995, using a T-type peel test with a sample width of 25 mm and a peeling speed of 50 mm / min, the interlaminar peel strength of the impact-resistant protective layer in Example 1 was measured to be 0.8 N / mm. Referring to GB / T 9341-2008, using a sample length of 80 mm, a span of 64 mm, and a loading speed of 2 mm / min, the three-point flexural strength of the impact-resistant protective layer in Example 1 was tested to be 48.5 MPa, and the flexural modulus was 5.2 GPa.

[0052] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely preferred examples and are not intended to limit the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the present invention as claimed. The scope of protection of the present invention is defined by the appended claims and their equivalents.

Claims

1. An impact-resistant mining protective suit, characterized in that, The mining protective suit is equipped with an impact-resistant protective layer, which includes: The first and second functional layers are alternately stacked and connected; The outermost layer of the impact-resistant protective layer facing the wearer is the first functional layer. The first functional layer is a composite material layer composed of aramid woven fabric and a second resin. The second resin serves as a continuous matrix, filling the fiber gaps of the aramid woven fabric and covering the fiber surface. The aramid woven fabric serves as a reinforcing skeleton distributed in the second resin matrix. The weaving material of the aramid woven fabric is aramid monofilament impregnated and pretreated with the first resin. Both the first and second resins are thermosetting resins. The first resin includes a first compound containing a morpholine ring, and the first compound is bonded to the cross-linking network of the first / second resin. The second functional layer is a dynamically cross-linked polymer layer.

2. The impact-resistant mining protective clothing according to claim 1, characterized in that, The first resin is a modified epoxy resin, the first compound is selected from at least one of amino morpholine compounds, epoxy morpholine compounds and mercapto morpholine compounds, and the second resin is an epoxy resin.

3. The impact-resistant mining protective clothing according to claim 2, characterized in that, The first compound is selected from at least one of 2-morpholinoethylamine, N-(3-aminopropyl)morpholine, N-glycidylmorpholine, and 4-(2-mercaptoethyl)morpholine.

4. The impact-resistant mining protective clothing according to claim 3, characterized in that, The first compound is only 2-morpholinoethylamine.

5. The impact-resistant mining protective clothing according to claim 2, characterized in that, The first resin also includes tris(hydroxymethyl)aminomethane.

6. The impact-resistant mining protective clothing according to claim 1, characterized in that, The dynamically cross-linked polymer layer is a dynamically urea-linked polyurethane layer, and its dynamic cross-linking system is a dynamically urea-linked polyurethane system.

7. The impact-resistant mining protective clothing according to claim 1, characterized in that, The dynamically cross-linked polymer layer is a dynamically disulfide-cross-linked polyacrylate layer, and its dynamic cross-linking system is a dynamically disulfide-cross-linked acrylate system.

8. The impact-resistant mining protective clothing according to claim 1, characterized in that, Along the thickness direction, at least one second functional layer includes a third functional layer and a fourth functional layer stacked and connected, wherein the third functional layer is close to the first functional layer and the fourth functional layer is far from the first functional layer, and the third functional layer is stacked between the first functional layer and the fourth functional layer. The third functional layer is a dynamically disulfide-crosslinked polyacrylate layer and the fourth functional layer is a dynamically urea-crosslinked polyurethane layer.

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