CN110669331A - Inorganic particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet and preparation method and application thereof - Google Patents
Inorganic particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet and preparation method and application thereof Download PDFInfo
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
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Abstract
The invention relates to an inorganic particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet and a preparation method and application thereof. The resin sheet is a hard composite sheet body which is formed by pressing micron-scale inorganic particles into thermoplastic resin liquid under the action of high temperature and high pressure to be stacked and then curing the mixture at high temperature to form a uniform high-density stacked uniform structure. The preparation method comprises the steps of laying inorganic particles on the surface of molten resin at high temperature, then immersing the resin liquid under the pressure of a constant pressure flat plate, and loosening, uniformly and slowly settling and adjusting the resin liquid under the action of gravity; and keeping pressurizing and standing, removing bubbles, and finally cooling, curing and forming into the composite resin sheet. The resin sheet has high hardness and toughness and high anti-cutting performance, because the hard inorganic particles can perform collision barrier passivation and reverse cutting roughening on the puncture sharp device. Can be used as an individual protection dressing material for preventing terrorism and riot, fire fighting, explosion prevention, earthquake search and rescue and national defense and military.
Description
Technical Field
The invention relates to an individual stab-resistant and cut-resistant dressing material, belongs to the field of functional technical textiles, and particularly relates to a flexible, light and high-efficiency resin composite sheet for stab-resistant, cut-resistant and cut-resistant dressing and a preparation technology thereof.
Background
In rescue and escape such as terrorism prevention, riot prevention, fire fighting, sudden change accidents and the like in peace period, and in war or armed activities, specialized protective equipment is needed. The basic requirements of these installations are: high efficacy protective function and light weight, softness and no mobility disorder; the latter are becoming increasingly important and becoming increasingly light and soft. The control of firearms in China is relatively strict, and although the control of cutters also exists, the firearms are easy to acquire and carry about. Therefore, dressing in terrorism and riot control, in particular to a garment with the functions of puncture prevention, cutting, chopping and the like is basic equipment for ensuring the personal safety and the barrier-free action of rescue personnel. The stab-resistance is the most difficult of three functions of stab-resistance, cutting and chopping, and the highest protection function is required, so people mainly pay attention to the stab-resistance. The existing stab-resistant material mainly depends on hard metal to destroy a blade and a sharp blocking device, or uses hard non-metal materials to block and damage a cutter, or uses hard high polymer to extrude and rub to dissipate impact energy. Obviously, a metallic material "hard on hard" has a deficiency in weight; the 'soft to hard' high polymer also has the defects on the cutter baffle; inorganic hard materials, although advantageous in terms of hardness, are brittle and easily broken. How to combine the two is a field which is rarely related to people at present. Much of the research has focused on fabric coatings and resin sheet-to-fabric bonding techniques. With the current process technology and raw material properties, only a thickened laminate can be passedThe quality of the material and the substances is increased and the hardness of the material is selected to achieve the stab-resistant effect, which is a low-grade, initial stage. The best effect it can achieve at present is a fabric square meter weight of 6.67kg/m minimum with no apparent penetration (national standard) at 24 joules impact force2I.e. 2kg of vest with 0.3 square meter. The minimum weight is 3.33kg/m if the maximum exposure length allowed to penetrate is 7mm (European standard)2I.e. 1kg of vest with 0.3 square meter.
Many studies on the above-mentioned anti-cutting materials have been conducted at present, mainly focusing on the following ones.
The first is to form a stab-resistant layer using a thermosetting resin or a thermoplastic material to achieve a stab-resistant effect. For example, a method for using a thermoplastic resin coating on nonmetal bulletproof stab-resistant armor (patent publication No. CN201577566U), and adopting a fiber precise arrangement technology to arrange aramid non-woven fabric at 0 degree/90 degree to achieve the bulletproof effect; a bulletproof and stab-resistant vest (patent publication No. CN203657618U) is formed by hot-pressing and curing a protective sheet of aramid fiber cloth layer impregnated with resin, and has strong toughness and elasticity; an aramid fiber reinforced resin based stab-resistant composite material (patent publication No. CN102632665B) is formed by laminating sheets formed by impregnating aramid fiber fabrics with modified vinyl resin, wherein the sheets are independent from each other, and the hardness and the quality are reduced; ballistic and stab resistant composites (patent publication No. CN107580550A) provide a flexible stab resistant material consisting essentially of three zones forming a composite stab resistant material, wherein a second zone comprising a fabric and an elastomeric or thermoplastic resin serves as a primary stab resistant layer; the high-performance nonmetal stab-resistant sheet (patent publication No. CN105696357A) is prepared by mixing epoxy resin and acetone according to a certain proportion, then mixing the mixture with polyamide according to a certain mass ratio, coating the mixture on two sides of aramid fiber woven fabric, and carrying out mould pressing, drying and curing on the aramid fiber woven fabric, so that the stab-resistant performance becomes more stable, and the stab-resistant performance is relatively strong; the stab-resistant composite material and the preparation method thereof (patent publication No. CN101936684A) adopt high-performance fiber to form a reinforcement, a resin matrix compounded on the reinforcement is made into a single-layer composite material, and resin is independently used as a part of the composite stab-resistant material; the bulletproof and stab-resistant multi-purpose composite material prepared from the multi-layer non-woven fabric and the preparation method (patent publication number: US2013/0219600A1) adopt the non-woven fabric impregnated with resin or filled with the resin to prepare the stab-resistant material through multi-angle layering, and the lock of the non-woven fabric achieves the stab-resistant performance; the puncture-proof protective body with the telescopic function (patent publication No. CN107478095A) provides a puncture-proof structural layer consisting of base cloth and reinforced composite thermoplastic resin sheets, the groups are mutually overlapped in a ladder shape, and the puncture-proof layer has the telescopic function and can improve the protective performance, the softness and the air permeability; bulletproof and stab-resistant structures and protective clothing (patent publication No. CN206832131U) provide a stab-resistant and bulletproof material which comprises fiber layers, fiber layers and resin matrix composite layers, wherein the fiber layers and the fiber layers are arranged at 90 degrees, and the structure is light in weight and does not affect the comfort and flexibility of a wearer; a Z-shaped resin molding flexible stab-resistant fabric and a preparation method thereof (patent publication No. CN105544228B) obtain a Z-shaped resin condensate through a 3D printing technology or an injection molding technology, solidify the Z-shaped resin condensate on ready-made clothes fabric through hot melt adhesive powder, and then dry the Z-shaped resin condensate to obtain the Z-shaped resin molding flexible stab-resistant fabric, and the Z-shaped resin molding flexible stab-resistant fabric has the characteristics of light weight, comfort, flexibility and the like; a composite thermoplastic bulletproof and stab-resistant sheet (patent publication No. CN207180483U) is characterized in that a reinforced thermoplastic material is hot-melted and injection-molded on a bulletproof fiber assembly, through holes are punched in the bulletproof fiber assembly, and part of the reinforced thermoplastic material is hot-melted and infiltrated into the through holes to form a reverse reinforcement to form an integrated structure. The stab-resistant material impregnated or coated with resin described above is required to meet the stab-resistant requirements of the standard GA68-2008 police stab-resistant clothing, and requires a larger mass, a thicker number of layers, and a less flexible material, resulting in a heavy and inflexible wearing because of the presence of only a slightly stiff resin film, which is inefficient in stab-resistance. If the metal layer is directly plated, the metal layer cannot be thickened, so that the weight is increased and the metal layer is easy to crack; and secondly, the sheet is processed, the main function of puncture prevention is still resin, the hardness of the resin is limited, and the weight cannot be reduced as long as the thickness of the sheet is increased.
The second type is that high polymer containing inorganic particles is coated on the base fabric of the prior aramid fiber woven fabric and the like to form a puncture-proof layer so as to achieve the aim ofAnd (4) a stab-resistant effect. A stab-resistant material, a coating carrier used for the stab-resistant material, and clothes made of the material (patent publication No. EP0972169B1) achieve stab-resistant effect by adhering inorganic particle abrasive grains with the diameter of 0.1-3 mm on the surface of a fabric through polyurethane serving as an adhesive, and stab-resistant particles (patent publication No. US2004/0048536A1) can passivate the penetration depth of a cutter by adhering a certain amount of solid hard particle substances on the surface of a high-performance fiber fabric, wherein the thickness of the coating is 0.1-2 mm; in the puncture-proof composite material (patent publication number: US2007/0105471A1), the puncture-proof performance of the material is improved by coating inorganic particles on the surface of aramid fiber fabric; the composite stab-resistant fabric and the preparation method thereof (patent publication No. CN101125040A) adopt carborundum, silicon carbide and the like as reinforcing particles, polyurethane, epoxy resin and the like as binders, and the coating points with the interval of 2-20 mm and the arrangement thickness of 0.1-1 mm are arranged on the base cloth to prepare the composite stab-resistant fabric, and the texture is very soft and is suitable for processing various stab-resistant clothes; according to the bonding forming method (patent publication No. CN103791778B) of the flexible stab-resistant material and the stab-resistant body, thermoplastic particles or composite reinforced material particles produced by an injection molding process are filled in a mold with the thickness of 3-30 mm, the depth of a mold hole of 0.3-2 mm, the distance between the mold holes is 1-20 mm, and the gap between the mold holes is 0.2-2 mm, and then the flexible stab-resistant material is prepared by uniformly coating a binder or hot melt adhesive powder and curing and bonding the powder on base cloth; a composite bulletproof and stab-resistant material (patent publication No. CN206430639U/CN206648524U) is prepared by coating inorganic powder such as silicon carbide on aramid woven fabric with PU glue to form an inorganic dust coating stab-resistant fabric with a single layer surface density of 150-500 g/m2The number of layers is not more than 10, the weight is basically the lowest level in the existing stab-resistant material, and the inorganic coating stab-resistant cloth or ultrathin stab-resistant steel sheet is used as a stab-resistant layer, and the high-performance fiber woven cloth is used as a bulletproof layer to prepare the bulletproof stab-resistant composite material. A preparation method of a stab-resistant and cut-resistant flexible material (patent publication No. CN108058469A) further comprises the steps of coating an adhesive on the surfaces of fabrics, membrane materials, rubber materials or leather, then pasting organic macromolecules such as epoxy resin and the like or inorganic particles such as diamond, silicon carbide and the like to obtain a composite material, then carrying out hot pressing to obtain the stab-resistant and cut-resistant flexible material,the invention has the characteristics of simple process, low cost, light weight and the like; a flexible anti-slash and anti-stab protector (patent publication No. CN207180485U) is made by dividing a reinforced thermoplastic anti-stab sheet material arranged on a base fabric into a plurality of separated particles with flexible gaps, and combining the particles into a particle pattern with protrusions. Although the flexibility of the stab-resistant material formed by coating inorganic particles or adhering pure resin sheets on the surface of the base cloth is improved, the stab-resistant effect is not increased or even reduced. In addition, the former can cause the surface particles to fall off due to continuous friction in the using process, so that the anti-piercing performance is reduced, and great potential safety hazard is brought; meanwhile, because the fabric is too thin, the inorganic particle layer is easy to disintegrate and break holes to lose effectiveness, and the extrusion effect of the inorganic particles is basically lost after the cutter is penetrated, and the friction cutting effect is almost disappeared.
The third kind of stab-resistant material is made of traditional woven fabric, knitted fabric or non-woven fabric, and has stab-resistant performance by wrapping, clamping, superposing a hard or flexible shear thickening body or adding a reinforced structure. For example, a hard protective garment disclosed in a hard stab-resistant garment (patent publication No. CN207084185U), in which the inner layer is composed of a high impact polystyrene plate, a high impact polypropylene plate and a foam plastic layer, the inner layer is a detachable metal sheet, and the outer layer is provided with a buffer layer with copper and aluminum strips as reinforcing ribs as a main stab-resistant layer; a flexible stab-resistant fabric and a preparation method thereof (patent publication No. CN107650458A) are characterized in that buffering bulges are introduced to be repeatedly connected and form a wave shape, carbon fiber reinforced material stab-resistant blocks are elaborately layered, and then the fabric is cut, wrapped and sparsely quilted to obtain the flexible stab-resistant fabric; a flexible stab-resistant knitted fabric and a preparation process thereof (patent publication No. CN107587247A) disclose a stab-resistant material prepared by a special knitting process, which comprises floating threads and loop-forming tissues formed by six courses of stitches, and the stab-resistant fabric is prepared by repeated circulation; a preparation method of a soft and durable stab-resistant material (patent publication No. CN107815870A) introduces a shear thickening body to be fully mixed and compounded with a fabric, thereby improving the durability and the flexibility of the stab-resistant material; a flexible stab-resistant material and a preparation method thereof (patent publication No. CN107385676A) disclose a stab-resistant material which comprises a comfort layer 1, a core stab-resistant layer and a comfort layer; 2. the materials are sequentially laminated and then are solidified after being spun-laced to form the stab-resistant composite material. The outstanding disadvantages of the above types of stab-resistant materials are that the processing technology is too complex, the labor cost is high, the mass production is not easy, and when the reinforced material is fiber, the flexibility is improved to some extent, but the stab-resistant function is limited and easy to damage and the weight is increased; when the reinforced material is a metal grid, the flexibility is sharply reduced, the stab-resistant efficiency is related to the grid coarse mesh and the grid space thereof, and the reinforced material is a structure with the quality, the hardness and the flexibility in inverse proportion.
The fourth type of stab-resistant material is a stab-resistant material made of hard or soft materials. A flexible stab-resistant fabric (patent publication No. CN107212485A) uses resin sheets, fiber reinforced resin sheets or metal alloy sheets as protective modules, and achieves stab-resistant effect by gapless fit, greatly improves the flexibility of stab-resistant materials, but is mainly stab-resistant by metal sheets, so the weight is heavier. For example, the anti-stab material is prepared according to various bionics principles, the scale shell splicing type anti-stab clothes (patent publication No. CN108095222A) based on the hollow micro-eggshell is formed by horizontally arranging all anti-stab base plates prepared from plastic materials according to the arrangement layout of upper and lower layers by using the arrangement mode of overlapping the scale shells of animals, and a plurality of hollow semi-ellipsoid shells are arranged on the anti-stab body in a parallel and staggered way, so that the weight of the anti-stab material can be reduced, but the anti-stab effect is influenced by uneven overlapping; the scale-type stab-resistant chip and stab-resistant equipment (patent publication No. CN105403106A) made of the scale-type stab-resistant chip are designed by referring to the scale of crocodile based on the principle of bionics, comprise pyramid and columnar members with sector sections, can well disperse the puncture of sharp instruments such as cutters and the like, and are easy to cause gathering and puncture under the cutting action; the application and preparation method of the nanotube aggregate in the carbon nanotube impact-resistant material (patent publication number: WO2017128944(A1)) utilizes the hollow structure of the carbon nanotube to absorb a large amount of impact energy, the carbon nanotube is in macroscopically ordered and microscopically disordered states, and the optimal puncture-proof and explosion-proof effects are strived to be achieved, but the scale is too small, the rigidity of the material is insufficient, the puncture-proof performance is slightly increased, and the cost is increased; a stab-resistant garment (patent publication No. CN106858769A) based on carbon fiber plate splice blocks is made up of multiple carbon fiber plates, and a stab-resistant sheet made of CNC (computerized numerical control) plate with metal sheet through sewing and sealing. The main deficiency of the stab-resistant material prepared by the scheme is the problem of overlarge quality, and the preparation process is complicated, which is the same as the problem of the early artificial armature manufacturing.
In conclusion, the defects of heavy weight, rigidity and low efficacy of single damping still commonly exist in the existing hard or soft stab-resistant materials.
Disclosure of Invention
The invention aims to solve the problems that: how to strengthen the action mechanism of the collision barrier and the passivation sharp device of the composite resin sheet, in particular to adopt the same inorganic particle body to form a high-probability collision and barrier mechanism on the surface layer of the composite resin sheet and make the penetrating tip passivated rapidly to reduce the speed and consume energy. The idea behind this mechanism of action is therefore to select single crystal inorganic particles with a large surface area and to use a high-density structure on the surface that will flatten or flatten the inorganic particles on the resin surface. Therefore, the puncture-preventing mechanism of high-probability collision and blocking passivation is realized, and meanwhile, a reverse cutting mechanism with higher efficiency can be ensured, so that the high-probability collision, passivation and scraping effects are achieved. On the basis, aiming at the problems of heavy weight, poor flexibility and the like of the anti-stab materials in the market, the invention provides the anti-stab cutting thermoplastic resin sheet with closely-arranged collision barrier type inorganic particle surface layers, which has excellent anti-stab performance, light weight and thin thickness, and the preparation method and the application thereof.
In order to achieve the purpose, the invention provides an inorganic particle surface layer close-packed collision barrier type anti-cutting thermoplastic resin sheet, which is characterized in that inorganic particles with high heat and average particle size of 10-1000 mu m are pressed into molten thermoplastic resin liquid to form a two-layer structure or three-layer structure, and then the composite sheet body is formed after cooling and solidification; the surface layer of the two layered structures is a structural layer with the highest stacking density and most of inorganic particles are upward in a plane, and the inner layer is a high-density uniform stacking structural layer; in the three-layered structure, the surface layer is the highest stacking density, most of the inorganic particles are planar upward structural layers, the middle layer is a high-density uniform stacking structural layer, and the inner layer is a pure resin layer; the surface layer is a structural layer with the highest stacking density and most of inorganic particles facing upwards, so that a high-probability collision and blocking mechanism is formed, and the penetrating tips are quickly passivated to reduce the speed and consume energy; the inner layer or the middle layer is a high-density uniformly-distributed structural layer which plays roles of reversely cutting and passivating the sharp object and supporting inorganic particles on the surface layer.
When the anti-puncturing tool is used, the surface is the front surface, namely the structural layer with the highest stacking density and most inorganic particles facing upwards is punctured towards the tool, and the path is from high density to low density, so that the anti-puncturing tool is the most reasonable and efficient for manufacturing an anti-puncturing host machine in a collision separation mode, and the tool tip end can be passivated quickly to increase the puncturing resistance; meanwhile, if the inorganic particles deflect, the inorganic particles have larger rotation resistance. In this way, the flexible configuration of the sheet material structure is also exactly compatible, because the reverse deformation is large, the part corresponding to the resin as the main part can be exactly deformed without brittle fracture; the front deformation is small, the impact is large, corresponding to the part mainly made of inorganic particle rigid body, the collision and the blunting are just carried out to separate, the contact area can be enlarged, and the loss of energy consumption is increased. The resulting dense, planar, upward and perpendicular to the stab direction, surface layer of the particles is the most important condition for the collision barrier mechanism.
Preferably, the inorganic particles have an average particle size of 30 to 300 μm, i.e., a mesh number of about 150 to 15000 mesh; the filling mass fraction of the inorganic particles in the puncture-proof thermoplastic resin sheet is 40-55 wt%. Although 10-30 μm still belongs to the upper section size of micron; 300 to 500 μm still has a sub-millimeter size, but inorganic particles of 30 μm or less and 300 μm or more are not recommended because the impact barrier effect is drastically reduced by the inorganic particles of 30 μm or less; inorganic particles larger than 300 μm tend to cause excessive thickness of the entire resin sheet or easily crack.
Preferably, the inorganic particles include, but are not limited to, one or more of silicon carbide particles, boron nitride particles, or synthetic diamond particles.
Preferably, the thermoplastic resin includes, but is not limited to, one of polyester resin (PET), polycarbonate resin (PC), polypropylene resin (PP), polyethylene resin (PE), or polyamide resin (PA).
Preferably, the thickness of the inorganic particle surface layer close-packed collision barrier type anti-puncturing thermoplastic resin sheet is 0.2-2 mm.
The preparation method of the anti-piercing thermoplastic resin sheet with closely-arranged collision barrier type inorganic particle surface layers is characterized by comprising the following steps of:
(1) placing the thermoplastic resin powder or the film in a polytetrafluoroethylene template slot box, and softening and melting the thermoplastic resin powder or the film at high temperature; simultaneously heating the inorganic particles to 5-10 ℃ above the high temperature; the high temperature is 5-20 ℃ higher than the melting temperature of the used thermoplastic resin; the softening and melting means the fluidity of the thermoplastic resin liquid, the softening flow is lower than that of the melting, but the softening and melting can provide higher inorganic particle packing density and more surfaces of the inorganic particles parallel to the surface of the molded resin sheet to obtain a surface with higher collision probability; while melting provides better wetting and uniformity of the mound structure.
(2) Uniformly spreading hotter inorganic particles on the surface of the heat-softened molten thermoplastic resin in (1) until the required mass fraction is reached; or stopping the spreading of the inorganic particles until the volume occupied by the inorganic particles is less than or equal to the volume of the molten resin; the hotter inorganic particles are inorganic particles with the temperature 3-8 ℃ higher than the high temperature in the step (1); the volume occupied by the inorganic particles is less than that of the molten resin, which means that the formed softened and molten thermoplastic resin has a pure resin layer at the bottom; the volume occupied by the inorganic particles is equal to the volume of the molten resin, that is, the formed softened and molten thermoplastic resin is completely filled with the inorganic particles;
(3) slowly pressing and immersing the exposed inorganic particles into the softened and melted thermoplastic resin under the action of constant pressure;
(4) keeping the constant pressure and standing for 5-30 min, vacuumizing to remove bubbles, and gradually cooling and solidifying to obtain the inorganic particle surface layer close-packed collision barrier type anti-stab cutting thermoplastic resin sheet.
Preferably, the template slot box in the step (1) is a hexagonal, square or round flat template slot box made of polytetrafluoroethylene.
The present invention aims at making inorganic particle have higher temperature than that of softening and melting resin, and this makes inorganic particle and thermoplastic resin possess excellent wetting property, adhesion and soaking to reduce pressure and speed pressing, raise yield and save power consumption. Meanwhile, the temperature is matched with the melting temperature, so that the material is stopped immediately when entering, a stable stacking structure is formed, and the stacking density is improved. Therefore, the probability and the acting force of collision and reverse cutting on the stabbing objects are increased, and the aim of efficiently preventing stabbing and cutting is fulfilled.
The invention also provides application of the inorganic particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet in individual protection dressing materials for riot, fire fighting, explosion, earthquake search and rescue and national defense and military.
Compared with the prior art, the invention has the beneficial effects that:
(1) the density of the resin and the inorganic particles is far lower than that of metal, particularly hard metal, but the hardness of the inorganic particles is generally much higher than that of the hard metal and is 6-20 times higher than that of the hard metal. The quality of the resin sheet with the same puncture-proof effect can be reduced by times, and light puncture-proof, cutting, chopping and composite materials thereof are prepared;
(2) the surface layer of the inorganic particles can be densely arranged to reach a filling rate of 55-65 wt%, and the inorganic particles are mostly hexagonal or cubic single crystals with larger planes, so that larger barrier planes can be formed; and the edges and corners of the single crystal are sharp, the size is submicron scale, and the edges and corners are far smaller than the cutting edges or tips of common cutters. Meanwhile, the hardness of the inorganic particles is far harder than that of metal cutters comprising high-hardness metal, so that the inorganic particles can collide and passivate and reversely cut into the cutting edge of the cutter to form efficient collision barriers, passivate and roughen the piercing tip and the cutting edge.
(3) Due to the adoption of a thermoplastic mode, the toughness of the resin sheet is higher, the strength is stronger, the inorganic particles can be filled more uniformly, and even can be freely controlled to be layered, so that the efficient reverse cutting of a high-density layer to a cutter and the interlayer rapid blocking and decelerating are obtained;
(4) the preparation process is simple, the temperature can directly adjust the fluidity and the curing point of the thermoplastic resin, so the preparation period is shorter, and the industrialization can be directly carried out.
Drawings
FIG. 1 is a closely-spaced collision barrier type puncture resistant thermoplastic resin sheet with inorganic particle surface layers in a two-layer structure; wherein, 1-inorganic particles; 2-a thermoplastic resin; 3-the highest stacking density and most inorganic particles are structural layers with upward planes; 4-uniformly stacking the structural layer at high density;
FIG. 2 is a three-layer structure of inorganic particle surface layer closely packed collision barrier type anti-puncture thermoplastic resin sheet; wherein: 1-inorganic particles; 2-a thermoplastic resin; 3-the highest stacking density and most inorganic particles are structural layers with upward planes; 4-uniformly stacking the structural layer at high density; 5-pure resin layer.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
As shown in fig. 1-2, the preparation method of the inorganic particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet comprises the following steps:
(1) placing the thermoplastic resin powder or the film in a polytetrafluoroethylene template slot box, and softening and melting the thermoplastic resin powder or the film at high temperature; simultaneously heating the inorganic particles to 5-10 ℃ above the high temperature;
(2) uniformly spreading hotter inorganic particles on the surface of the heat-softened molten thermoplastic resin in (1) until the required mass fraction is reached; or stopping the spreading of the inorganic particles until the volume occupied by the inorganic particles is less than or equal to the volume of the molten resin;
(3) slowly pressing and immersing the exposed inorganic particles into the softened and melted thermoplastic resin under the action of constant pressure;
(4) keeping the constant pressure and standing for 5-30 minutes, vacuumizing to remove bubbles, and gradually cooling and solidifying to prepare the inorganic particle surface layer close-packed collision barrier type anti-puncture thermoplastic resin sheet with a two-layer structure or three-layer structure. The structure is shown in detail in fig. 1 or fig. 2.
The total surface density and the thickness of the prepared puncture-proof resin sheet are listed in a detailed table, the protection requirements are met according to the standard detection of GA68-2008 & lt & gt police puncture-proof clothes & gt of Ministry of public Security of China, and the total surface density required by the existing nonmetal puncture-proof material to reach the standard is higher than 3.33kg/m in multiples2The test allows a penetration length of not more than 6mm and the penetration probability is noted as 0. Thus, the total energy for its effective stab resistance and the fabric weight loss δ without being punctured were recorded.
Example 1
The invention provides a boron carbide particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet, which is a composite sheet body formed by pressing boron carbide particles with high heat and average particle size of 200 mu m into molten polyamide resin liquid to form a three-layer structure, and then cooling and solidifying; the three-layered structure, the top layer is the highest stacking density and inorganic particle is mostly the structural layer that makes progress in the plane, the intermediate level is the even stacking structure layer of high density, the inlayer is the pure resin layer. The filling mass fraction of the boron carbide particles in the puncture-resistant thermoplastic resin sheet was 45.1 wt%.
The composite fabric is formed by paving closely-arranged collision barrier type anti-piercing thermoplastic resin sheets with boron carbide particles on the surface layer of the multilayer fabric, and the gram weight of the whole square meter of the composite fabric is 2.71kg/m2The specific process parameters are detailed in table 1. The multilayer composite fabric has a puncture probability of zero. If the conversion is 3.33kg/m at present2The fabric has the front surface stab-resistant energy of 27.9J and the back surface stab-resistant energy of 22.9J, and the difference rate of the stab-resistant energy is about 17.9 percent, compared with the current conventional square meter grammage (3.33 kg/m)2) In other words, weight can be reducedAbout 18.6 percent, the difference rate of the piercing-cutting energy of the front side and the back side is relatively large, which is related to the grain diameter and the arrangement mode of inorganic particles, and the path from high density to low density can quickly passivate the tip end of the knife, thereby increasing the piercing resistance, and simultaneously the weight-reducing effect of the composite fabric is obvious, thereby improving the anti-piercing performance and realizing the lightening and softening.
Example 2
The invention provides a silicon carbide particle surface layer close-packed collision barrier type anti-puncture thermoplastic resin sheet, which is a composite sheet body formed by pressing silicon carbide particles with high heat average particle size of 50 mu m into molten polyester resin liquid to form a two-layer structure and then cooling and solidifying the two-layer structure; the surface layers of the two layered structures are structural layers with the highest stacking density and most of inorganic particles face upwards, and the inner layer is a high-density uniform stacking structural layer. The filling mass fraction of the silicon carbide particles in the puncture-resistant thermoplastic resin sheet was 50.2 wt%.
The composite fabric is formed by paving closely-arranged collision barrier type anti-puncturing thermoplastic resin sheets with silicon carbide particles on a multi-layer fabric, and the gram weight of the whole square meter of the composite fabric is 3.04kg/m2The specific process parameters are detailed in table 1. The multilayer composite fabric has a puncture probability of zero. If the conversion is 3.33kg/m at present2The fabric has the front surface stab-resistant energy of 27.1J and the back surface stab-resistant energy of 24.2J, and the difference rate of the stab-resistant energy is about 10.7 percent, compared with the current conventional square meter grammage (3.33 kg/m)2) In other words, about 8.7% of weight can be reduced, the difference rate of the piercing-cutting energy of the front side and the back side is small, which is related to the average particle size and the arrangement mode of the inorganic particles, when the particle size is too small, the advantage of the path from high density to low density is not obvious, but the energy of reverse cutting is increased, the tip end of the knife is passivated, the piercing resistance is increased, meanwhile, the weight reduction effect of the composite fabric is not obvious, but the piercing resistance can be improved.
Example 3
The invention provides a cubic boron nitride particle surface layer close-packed collision barrier type anti-piercing thermoplastic resin sheet, which is a composite sheet body formed by pressing cubic boron nitride particles with high heat and average particle size of 300 mu m into molten polypropylene resin liquid to form a three-layer structure, and then cooling and solidifying; the three-layered structure, the top layer is the highest stacking density and inorganic particle is mostly the structural layer that makes progress in the plane, the intermediate level is the even stacking structure layer of high density, the inlayer is the pure resin layer. The filling mass fraction of the cubic boron nitride particles in the puncture-resistant thermoplastic resin sheet was 45.6 wt%.
The composite fabric is formed by paving cubic boron nitride particle surface layer close-packed collision barrier type anti-puncturing thermoplastic resin sheets on a multi-layer fabric, and the gram weight of the whole square meter of the composite fabric is 2.83kg/m2The specific process parameters are detailed in table 1. The multilayer composite fabric has a puncture probability of zero. If the conversion is 3.33kg/m at present2The fabric has the front surface stab-resistant energy of 28.4J and the back surface stab-resistant energy of 21.1J, and the difference rate of the stab-resistant energy is about 25.7 percent, compared with the current conventional square meter grammage (3.33 kg/m)2) In other words, the weight can be reduced by about 15.0%, the difference rate of the piercing energy of the front side and the back side is relatively large, which is related to the arrangement mode of the composite sheet and the particle size of the inorganic particles, and the paths from high density to low density and the large particles are added, so that the tip end of the knife can be rapidly passivated to increase the piercing resistance, and meanwhile, the weight reduction effect of the composite fabric is obvious, so that the piercing resistance is improved, and the weight is lightened and the composite fabric is softened.
Example 4
The invention provides a closely-arranged collision barrier type anti-piercing thermoplastic resin sheet for the surface layer of artificial diamond particles, which is a composite sheet body formed by pressing the artificial diamond particles with high heat and average particle size of 100 mu m into molten thermoplastic resin liquid to form a two-layer structure and then cooling and solidifying the two-layer structure; the surface layer of the two layered structures is a structural layer with the highest stacking density and most of inorganic particles are upward in a plane, and the inner layer is a high-density uniform stacking structural layer; the packing mass fraction of the artificial diamond particles in the puncture-proof thermoplastic resin sheet was 54.4 wt%.
The composite fabric is formed by paving closely-arranged collision barrier type anti-piercing thermoplastic resin sheets on the surface layers of the artificial diamond particles on the multi-layer fabric, and the overall square meter gram weight of the composite fabric is 2.69kg/m2The concrete process parameters are detailed inListed in table 1. The multilayer composite fabric has a puncture probability of zero. If the conversion is 3.33kg/m at present2The fabric has the front surface stab-resistant energy of 25.4J and the back surface stab-resistant energy of 22.9J, and the difference rate of the stab-resistant energy is about 6.7 percent, compared with the current conventional square meter grammage (3.33 kg/m)2) In other words, the weight can be reduced by about 19.2%, the difference rate of the piercing energy of the front and back surfaces is large, which is related to the average particle size and the arrangement mode of the inorganic particles, when the particle size is relatively small, and when the particles are subjected to forward or reverse cutting, the smaller particle size is pushed open when being subjected to the piercing action of a tool nose, so that the piercing prevention effect is poor. However, the combination of the two substances can lead the weight reduction effect of the material to be very obvious, improve the stab resistance to a certain extent and lead the material to be lightened and softened.
TABLE 1 Process recipe and conditions and results for the production of crash barrier thermoplastic resin sheets
Note: wherein the weight loss delta is the gram weight G of the existing horizontal square metersThe measured square meter gram weight G of the fabric0Difference of (2) from the existing horizontal square meter grammage GsThe ratio of (A) to (B):
δ＝(GS-G0)/GS*100％
the difference rate v of the piercing energies is a positive piercing energy EzPiercing energy E with the reverse sidefDifference of (D) and front piercing energy EzThe ratio of (A) to (B):
v＝(Ez-Ef)/Ez*100％
wherein the puncture probability p is the percentage of the number of punctures n in 10 trials:
p＝n/10*100％
the penetrating energy refers to the energy of the minimum penetration of the stab-resistant composite fabric.
Claims (8)
1. A closely-arranged collision barrier type anti-piercing thermoplastic resin sheet with inorganic particle surface layers is characterized in that inorganic particles with high heat and average particle size of 10-1000 mu m are pressed into molten thermoplastic resin liquid to form a two-layer structure or three-layer structure, and then the composite sheet body is formed after cooling and solidification; the surface layer of the two layered structures is a structural layer with the highest stacking density and most of inorganic particles are upward in a plane, and the inner layer is a high-density uniform stacking structural layer; in the three-layered structure, the surface layer is the highest stacking density, most of the inorganic particles are planar upward structural layers, the middle layer is a high-density uniform stacking structural layer, and the inner layer is a pure resin layer; the surface layer is a structural layer with the highest stacking density and most of inorganic particles facing upwards, so that a high-probability collision and blocking mechanism is formed, and the penetrating tips are quickly passivated to reduce the speed and consume energy; the inner layer or the middle layer is a high-density uniformly-distributed structural layer which plays roles of reversely cutting and passivating the sharp object and supporting inorganic particles on the surface layer.
2. The stab-resistant thermoplastic resin sheet of claim 1, wherein the inorganic particles have an average particle size of 30 to 300 μm; the filling mass fraction of the inorganic particles in the puncture-proof thermoplastic resin sheet is 40-55 wt%.
3. The anti-puncture thermoplastic resin sheet according to claim 1, wherein the inorganic particles are one or more of silicon carbide particles, boron nitride particles, and synthetic diamond particles.
4. The inorganic particle surface layer close-packed collision barrier type anti-cutting thermoplastic resin sheet according to claim 1, wherein the thermoplastic resin is one of polyester resin, polycarbonate resin, polypropylene resin, polyethylene resin, or polyamide resin.
5. The inorganic particle surface layer closely-spaced collision barrier type anti-stab cutting thermoplastic resin sheet according to claim 1, wherein the thickness of the inorganic particle surface layer closely-spaced collision barrier type anti-stab cutting thermoplastic resin sheet is 0.2 to 2 mm.
6. The method for producing the inorganic particle surface layer close-packed collision barrier type anti-cutting thermoplastic resin sheet according to any one of claims 1 to 5, comprising the steps of:
(1) placing the thermoplastic resin powder or the film in a polytetrafluoroethylene template slot box, and softening and melting the thermoplastic resin powder or the film at high temperature; simultaneously heating the inorganic particles to 5-10 ℃ above the high temperature; the high temperature is 5-20 ℃ higher than the melting temperature of the used thermoplastic resin;
(2) uniformly spreading hotter inorganic particles on the surface of the heat-softened molten thermoplastic resin in (1) until the required mass fraction is reached; or stopping the spreading of the inorganic particles until the volume occupied by the inorganic particles is less than or equal to the volume of the molten resin; the hotter inorganic particles are inorganic particles with the temperature 3-8 ℃ higher than the high temperature in the step (1);
(3) slowly pressing and immersing the exposed inorganic particles into the softened and melted thermoplastic resin under the action of constant pressure;
(4) keeping the constant pressure and standing for 5-30 min, vacuumizing to remove bubbles, and gradually cooling and solidifying to obtain the inorganic particle surface layer close-packed collision barrier type anti-stab cutting thermoplastic resin sheet.
7. The method for producing the anti-cutting thermoplastic resin sheet with closely-spaced collision barriers on the surface layers of inorganic particles according to claim 6, wherein the template slot case in (1) is a hexagonal, square or circular flat template slot case made of polytetrafluoroethylene.
8. Use of the inorganic particle surface layer close-packed collision barrier type anti-puncture thermoplastic resin sheet according to any one of claims 1 to 5 in individual protective clothing materials for riot, fire, explosion, earthquake search and rescue and national defense and military.
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