CN110641054B - Forming method for pressing inorganic particles into softened resin membrane layer by layer, anti-puncturing composite resin sheet and application - Google Patents
Forming method for pressing inorganic particles into softened resin membrane layer by layer, anti-puncturing composite resin sheet and application Download PDFInfo
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- CN110641054B CN110641054B CN201910922244.8A CN201910922244A CN110641054B CN 110641054 B CN110641054 B CN 110641054B CN 201910922244 A CN201910922244 A CN 201910922244A CN 110641054 B CN110641054 B CN 110641054B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
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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 a forming method for pressing inorganic particles into a softened resin membrane layer by layer and an anti-puncturing composite resin sheet. The forming method comprises uniformly laying inorganic particles with high temperature on a softened resin film sheet, immediately hot rolling into the film sheet to separate the resin film sheet into inorganic particles, immersing the inorganic particles into a dense layer and a pure resin layer, covering another resin film sheet thereon, hot rolling and bonding with a lower layer, and laying high-heat inorganic particles; the rolling process is repeated to form the composite resin sheet with a multiple circulation structure. The composite resin sheet is formed by stacking inorganic particles at high density and laminating a flexible resin layer and self-adhering the inorganic particles and the flexible resin layer. The resin sheet is a multi-layer composite structure of a composite layer with rigid upper part and flexible lower part, can passivate the puncture tip, then has friction energy consumption, and strengthens, separates and prevents puncture layer by layer, so that the puncture-preventing effect is stronger, the quality is lighter, the flexibility is better, and the resin sheet can be used as a protective dressing material for individuals of explosion prevention, fire protection, explosion, earthquake search and rescue and national defense and military.
Description
Technical Field
The invention relates to an individual stab-resistant and cut-resistant dress-wearing material, belongs to the field of functional technical textiles, and particularly relates to a flexible, light and high-efficiency stab-resistant, cut-resistant and cut-resistant dress-wearing resin composite sheet 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 materials mainly rely on hard metal to destroy the cutting edge and separate the sharp-edged tool, or use hard non-metal materials to block and damage the cutting tool, or use hard metal materials to prevent the sharp-edged tool from being damagedThe high polymer is used for extruding and friction dissipation of 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. Under the current process technology and raw material properties, the stab-resistant effect can only be achieved by means of thickened laminate materials and increased mass of the substances and by means of material hardness selection, 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 base cloth such as the existing aramid woven fabric to form a stab-resistant layer so as to achieve the 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, and the weight is basicallyThe inorganic coating stab-resistant cloth or the 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 flexible material for preventing from cutting and piercing (patent publication No. CN108058469A) further coats the surface of fabric, membrane material, rubber material or leather with adhesive, then pastes organic macromolecule such as epoxy resin or inorganic particle such as diamond and silicon carbide to obtain composite material, then obtains flexible material for preventing from cutting and piercing through hot pressing, 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 existing hard or soft stab-resistant materials still generally have the defects of uniform structure, heavy weight, rigidity and low efficacy of single damping.
Disclosure of Invention
The invention aims to solve the problems that: in the study of stab resistance, the unique composition of the singulation of the single resin sheets, the singulation of the structure, and the singulation of the number of layers in the technical layer is the only significant limitation of the conventional academic thinking paradigm. That is, the composition singularization results in reliance on hard, thick, heavy materials on stab resistant cutting mechanisms and is limited to either barrier mechanisms or friction grip mechanisms; the singularization of the structure results in a stab-resistant mechanism that relies only on the mixing of inorganic particles (hard) with high polymer resins (soft), but does not know the more effective function of layer lamination; the simplification of the number of layers fixes the thought to the conventional forming method of thicker layered adhesive sheets without the concept or intent of the unconventional, difficult, and sought-after fabrication of multiple composite light and thin resin sheets with micron-scale layer thickness, certainly not leading to the multi-layer stepped crash barrier passivation stab-resistant mechanism of the present invention and the stab-resistant composite resin sheets with higher efficiency without changing quality and thickness. By the principle and the action mechanism, the problems of heavy weight, poor flexibility and general puncture-proof efficacy of the puncture-proof material in the market can be solved at one stroke. Based on the design and preparation method of the layer composite structure of the multilayer composite pair of layers, the invention provides the forming method for pressing the inorganic particles into the softened resin membrane layer by layer, which has excellent stab resistance, light weight and thin thickness, and the composite resin sheet.
In order to solve the technical problem, the invention provides a forming method for pressing inorganic particles into a softened resin film layer by layer, which is characterized by comprising the following steps of:
step a, putting a resin membrane into a polytetrafluoroethylene template groove box with the temperature 1-15 ℃ higher than the softening point temperature of the resin membrane, and heating and softening the resin membrane, wherein the shape of the resin membrane is consistent with that of the polytetrafluoroethylene template groove box;
b, uniformly laying inorganic particles with the preheating temperature higher than the softening point of the resin diaphragm by 10-20 ℃ on the resin diaphragm, and immediately hot rolling the inorganic particles to immerse the inorganic particles into the resin diaphragm; then cooling to the softening point of the resin without soaking, and stopping sinking to form a dense layer with the upper inorganic particles immersed and compact surface and a composite layer of the inorganic particles and the resin of the lower pure resin layer; because the temperature of the inorganic particles is far higher than the melting point temperature of the resin, instantaneous melting infiltration sinking and bonding can be generated; the temperature of the 1 st inorganic particle is obviously higher than the softening point of the resin membrane, and the purpose is to enable the inorganic particles to generate strong wetting and sinking tendency, so that the inorganic particles and the resin can form good bonding, and the inorganic particles can sink in the resin liquid to form gradient distribution;
c, heating the exposed inorganic particles for 0.5-2.0 min by using the hot air with the temperature higher than the preheating temperature by 10-20 ℃ in the step b, covering a layer of resin film, and then hot rolling and bonding; the temperature of the inorganic particles at the 2 nd time is obviously higher than the softening point of the resin membrane, and the aim is that the high-temperature inorganic particles can melt the thermoplastic resin at the periphery of the inorganic particles to generate strong infiltration and rotation, so that the stacking internal stress is eliminated, and the inorganic particles on the surface are more flat under the action of a rolling surface, so that the collision block probability is increased;
and d, repeating the cycle of the step b and the step c until the required lamination composite number is reached, so as to form the composite resin sheet with the multiple circulation structure and the upper surface sealed, namely the stab-resistant composite resin sheet.
Preferably, in the step a, the resin film includes, but is not limited to, one of Polyester (PET), Polycarbonate (PC), polypropylene (PP), Polyethylene (PE), or polyamide resin (PA).
Preferably, in the step b, the inorganic particle and resin composite layer has a significant layered structure or a non-significant layered structure, and is significantly layered when the natural stacking volume or the thickness of the uniform layer of the inorganic particles is not more than 2/3 of the volume or the thickness of the resin film sheet; 2/3 which is greater than the volume or thickness of the resin film sheet, is not significantly delaminated; the significantly layered composite resin sheet is of a flexible structure; the composite resin sheet is not significantly delaminated and has a rigid structure.
Preferably, in the step b, the inorganic particles have an average particle size of 3 to 300 μm, i.e., a mesh number of 150 to 15000 meshes. The inorganic particles comprise one or more of artificial diamond, silicon carbide, boron carbide and boron nitride, and the average particle size of the particles is in the range of most of micrometer scale (namely 1-100 mu m) and less than 1/3 part of submillimeter scale (namely 100 mu m-1 mm); the inorganic particles preferably take the form of cubic, polyhedral or hexagonal crystals. Wherein the small inorganic particles act as materials for reverse cleavage mechanism; the large particles, especially the multi-planar ones, act as a mechanism of impact barrier and passivation.
Preferably, in the step b, the inorganic particles include, but are not limited to, one or more of synthetic diamond particles, silicon carbide particles, boron carbide particles or boron nitride particles; the inorganic particles are in the form of a cubic, polyhedral or hexagonal crystal. Wherein the small inorganic particles act as materials for reverse cleavage mechanism; the large particles, especially the multi-planar ones, act as a mechanism of impact barrier and passivation.
Preferably, in the step d, the thickness of each composite pair of layers of the composite resin sheet is 20 μm to 0.6mm, the number of the composite pair layers is 2 to 10, and the total thickness of the composite resin sheet is not more than 2.5 mm.
Preferably, in the step d, the inorganic particles have a distinct layered structure when the total filling mass fraction in the composite resin sheet is 15 to 60 wt% and less than 40 wt%.
The invention also provides the stab-resistant composite resin sheet prepared by the method.
The invention also provides the application of the anti-puncturing composite resin sheet prepared by the method in basic materials for individual protection dressing of terrorism, riot control, fire control, explosion prevention, earthquake search and rescue and national defense and military, and is characterized in that the anti-puncturing composite resin sheet is used as a rigid anti-puncturing material and is adhered to a flexible fabric material to form a rigid and flexible protective layer.
The invention relates to a forming method for pressing inorganic particles into a softened resin membrane layer by layer and an anti-puncturing composite resin sheet. Uniformly laying inorganic particles with higher temperature on a softened resin film sheet, immediately hot rolling the resin film sheet into the film sheet to divide the resin film sheet into a dense layer and a resin layer which are immersed with the inorganic particles and have compact surfaces, covering another resin film sheet on the film sheet, and laying high-heat inorganic particles after hot rolling and bonding with a lower layer; the above process is repeated to form the composite resin sheet in a multiple-cycle structure. The composite resin sheet is formed by stacking inorganic particles at high density and laminating and bonding the inorganic particles and a flexible resin layer. Because the composite resin sheet is a multi-layer composite structure of a composite layer with rigid upper part and flexible lower part, the puncture tip can be passivated firstly, then the friction energy consumption is increased, and the barrier puncture prevention is enhanced layer by layer, so that the material has stronger puncture prevention effect, lighter weight, better flexibility and simple and convenient forming process.
The invention has the beneficial effects that:
(1) solid-liquid conversion manipulation is relatively easy: because the resins are all thermoplastic resins, the melting temperature is lower, and the composite pair is easy to process and mold; the resin has low density and good toughness, and a single pure resin layer has large effect of delaying the impact speed of the cutter;
(2) the effectiveness of the reverse cutting can be determined according to the size and shape of the single crystal: because the size of the polygonal closed angle of the inorganic particles is smaller or far smaller than the cutting edge or the tip of a common cutter in the micron scale, and simultaneously, the hardness of the inorganic particles is far harder than that of a metal cutter and comprises high-hardness metal, the inorganic particles can cut into the cutting edge of the cutter to form reverse cutting; and for thicker inorganic particles, if the particles with the cubic shape with larger planes are adopted, a compact barrier layer can be formed on the surface layer, so that the collision passivation of the tip end of the cutter is directly caused, and the damping effect of the penetration of the cutter is further increased.
(3) Advantages of thermoplastic polymers in shaping: due to the adoption of a thermoplastic mode, the quality and the thickness of the resin sheet are lighter and thinner, the flexibility of the sheet is better, the strength is stronger, particularly, the thickness of a composite layer in forming is easy to control, and the composite layer is regulated and controlled in a micrometer scale; meanwhile, the inorganic particles can be filled more compactly, uniformly and flatly on the surface layer, and layering, stacking and forming can be carried out to obtain efficient reverse cutting and rapid blocking and deceleration of the high-density layer to the cutter;
(4) the adhesive and the hardening of the inorganic particles are enhanced, and the temperature can be directly controlled to adjust the fluidity of the thermoplastic resin, so the preparation period is shorter, the preparation process is simple, and the industrialization can be directly realized.
Drawings
FIG. 1 is a process flow diagram of a method for forming a composite resin sheet in which inorganic particles are pressed into a softened resin film layer by layer according to the present invention; wherein 1 a-inorganic particles; 2 a-a thermoplastic resin film; 1-a dense layer of inorganic particles; 2-a layer of pure resin;
FIG. 2 is a schematic cross-sectional view of a composite resin sheet product of the present invention, which is obtained by mixing inorganic particles with resin powder and hot rolling and casting; wherein 1 a-inorganic particles; 2 a-a thermoplastic resin film; 1-a dense layer of inorganic particles; 2-a layer of pure resin; 3-inorganic particles and resin composite 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.
The raw materials and equipment in examples 1-4 were subsidized by the national stress development program (2016YFC 0802802).
As shown in fig. 1-2, the present invention provides a method for forming a film of softened resin by pressing inorganic particles layer by layer, which comprises the following steps:
step a, putting a resin membrane into a polytetrafluoroethylene template groove box with the temperature 1-15 ℃ higher than the softening point temperature of the resin membrane, and heating and softening the resin membrane, wherein the shape of the resin membrane is consistent with that of the polytetrafluoroethylene template groove box; the resin membrane is one of polyester, polycarbonate, polypropylene, polyethylene or polyamide resin;
b, uniformly laying inorganic particles with the preheating temperature higher than the softening point of the resin diaphragm by 10-20 ℃ on the resin diaphragm, and immediately hot rolling the inorganic particles to immerse the inorganic particles into the resin diaphragm; then cooling to the softening point of the resin without soaking, and stopping sinking to form a dense layer with the upper inorganic particles immersed and compact surface and a composite layer of the inorganic particles and the resin of the lower pure resin layer; because the temperature of the inorganic particles is far higher than the melting point temperature of the resin, instantaneous melting infiltration sinking and bonding can be generated; the temperature of the 1 st inorganic particle is obviously higher than the softening point of the resin membrane, and the purpose is to enable the inorganic particles to generate strong wetting and sinking tendency, so that the inorganic particles and the resin can form good bonding, and the inorganic particles can sink in the resin liquid to form gradient distribution;
the average particle size of the inorganic particles is 3-300 mu m, the inorganic particles are one or a mixture of more of artificial diamond, silicon carbide, boron carbide and boron nitride, and the average particle size range of the particles is the majority of micrometer scale (namely 1-100 mu m) and the part below 1/3 of submillimeter scale (namely 100 mu m-1 mm); the inorganic particles preferably take the form of cubic, polyhedral or hexagonal crystals. Wherein the small inorganic particles act as materials for reverse cleavage mechanism; large particles, especially multi-planar ones, act as a mechanism of action for collision barrier and passivation;
the inorganic particle and resin composite layer is of a significant layered structure or a non-significant layered structure, and when the volume or the thickness of the uniformly-stacked inorganic particle is not more than 2/3 of the volume or the thickness of the resin diaphragm, the inorganic particle and resin composite layer is significantly layered; 2/3 which is greater than the volume or thickness of the resin film sheet, is not significantly delaminated; the significantly layered composite resin sheet is of a flexible structure; the composite resin sheet without obviously layering is a rigid structure
C, heating the mixture by hot air with the temperature 10-20 ℃ higher than the preheating temperature in the step b, covering the exposed inorganic particles for 0.5-2.0 min, covering a layer of resin film, and then hot rolling and bonding; the temperature of the inorganic particles at the 2 nd time is obviously higher than the softening point of the resin membrane, and the aim is that the high-temperature inorganic particles can melt the thermoplastic resin at the periphery of the inorganic particles to generate strong infiltration and rotation, so that the stacking internal stress is eliminated, and the inorganic particles on the surface are more flat under the action of a rolling surface, so that the collision block probability is increased;
d, repeating the circulation of the steps b and c until the required lamination composite number is reached, so as to form the composite resin sheet with a multi-circulation structure and sealed upper surface, namely the stab-resistant composite resin sheet; the thickness of each composite pair of layers of the composite resin sheet is 20 mu m-0.6 mm, the number of the composite pair layers is 2-10, and the total thickness of the composite resin sheet is not more than 2.5 mm; the total filling mass fraction of the inorganic particles in the composite resin sheet is 15-60 wt%.
The total surface density and the thickness of the prepared anti-puncturing resin sheet are listed in detailed table 1, the protection requirement is met according to the standard detection of GA68-2008 & lt & gt police anti-puncturing clothes & gt of Ministry of public Security of China, and the total surface density required by the existing non-metal anti-puncturing material to reach the standard is higher than 3.33kg/m in multiple2The 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
Pressing 100 μm boron carbide particles into thermoplastic polypropylene resin film layer by layer to mix and pile, wherein the whole square meter gram weight of 5 layers of resin sheets with pile filling mass fraction of 55.7% is 2.94kg/m2See table for details.
The penetration probability of the multilayer composite fabric formed by attaching the composite resin sheet to the multilayer fabric is zero. If the conversion is 3.33kg/m at present2The fabric of (2) has a stab resistance energy of 27.9J, corresponding to the current conventional square meter grammage (3.33 kg/m)2) In other words, the weight can be reduced by about 13.7%, the resin sheet is a multi-layer composite structure of an upper rigid composite layer and a lower flexible composite layer, the stabbing tips can be passivated firstly and then have friction energy consumption, and the stabbing prevention is enhanced layer by layer, so that the stabbing prevention effect is stronger, the weight is lighter and the flexibility is better.
Example 2
Pressing 50 μm silicon carbide particles into thermoplastic polyethylene resin film layer by layer to mix and pile, wherein the whole square meter gram weight of 3 layers of resin sheet with the obtained pile filling mass fraction of 37.7% is 2.95kg/m2See table for details.
The penetration probability of the multilayer composite fabric formed by attaching the composite resin sheet to the multilayer fabric is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 31.9J, which is equivalent to the current conventional square meter gram weight (3.33 kg/m)2) In other words, the weight can be reduced by about 11.4%, the resin sheet is a multi-layer composite structure of an upper rigid composite layer and a lower flexible composite layer, the stabbing tips can be passivated firstly and then have friction energy consumption, and the stabbing prevention is enhanced layer by layer, so that the stabbing prevention effect is stronger, the weight is lighter, and the flexibility is better.
Example 3
Pressing 30 μm artificial diamond particles into thermoplastic polyimide resin membrane layer by layer, and mixing and stacking to obtain 8 layers of resin sheets with stacking filling mass fraction of 24.1% and having a whole square meter gram weight of 2.86kg/m2See table for details.
The penetration probability of the multilayer composite fabric formed by attaching the composite resin sheet to the multilayer fabric is zero. If the conversion is 3.33kg/m at present2The resin sheet of (1) has a puncture resistance of 30.3J, which corresponds to the conventional square meter grammage (3.33 kg/m)2) By weight reduction of about 14.1%, the resin sheet is rigid at the upper part and flexible at the lower partThe multilayer composite structure of the laminated layers can passivate the puncture tip, then has friction energy consumption, and strengthens the barrier puncture prevention layer by layer, so that the puncture prevention effect is stronger, the weight is lighter, and the flexibility is better.
Example 4
Pressing 3 μm cubic boron nitride particles into thermoplastic polyamide resin film layer by layer to mix and pile, wherein the overall square meter gram weight of 10 layers of resin sheets with 18.6% pile filling mass fraction is 2.84kg/m2See table for details.
The penetration probability of the multilayer composite fabric formed by attaching the composite resin sheet to the multilayer fabric is zero. If the conversion is 3.33kg/m at present2The resin sheet of (1) has a puncture resistance energy of 29.2J, which corresponds to the conventional square meter grammage (3.33 kg/m)2) In other words, the weight can be reduced by about 14.7 percent, the resin sheet is a multi-layer composite structure of an upper rigid composite layer and a lower flexible composite layer, the stabbing tips can be passivated firstly and then have friction energy consumption, and the stabbing prevention is enhanced layer by layer, so that the stabbing prevention effect is stronger, the weight is lighter and the flexibility is better.
TABLE 1 technological formulation and conditions and implementation results of the puncture-proof composite resin sheet
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 GsRatio of
δ＝(GS-G0)/GS*100％ (1)
Wherein the puncture probability p is the percentage of the number n of punctures in 10 tests
p＝n/10*100％ (2)
The penetration energy is the energy E for minimum penetration of the stab-resistant composite fabric0。
Claims (9)
1. A forming method for pressing inorganic particles into a softened resin membrane layer by layer is characterized by comprising the following steps:
step a, putting a resin membrane into a polytetrafluoroethylene template groove box with the temperature 1-15 ℃ higher than the softening point temperature of the resin membrane, and heating and softening the resin membrane, wherein the shape of the resin membrane is consistent with that of the polytetrafluoroethylene template groove box;
b, uniformly laying inorganic particles with the preheating temperature higher than the softening point of the resin diaphragm by 10-20 ℃ on the resin diaphragm, and immediately hot rolling the inorganic particles to immerse the inorganic particles into the resin diaphragm; then cooling to the softening point of the resin without soaking, and stopping sinking to form a dense layer with the upper inorganic particles immersed and compact surface and a composite layer of the inorganic particles and the resin of the lower pure resin layer;
c, heating the exposed inorganic particles for 0.5-2.0 min by using the hot air with the temperature higher than the preheating temperature by 10-20 ℃ in the step b, covering a layer of resin film, and then hot rolling and bonding;
and d, repeating the cycle of the step b and the step c until the required lamination composite number is reached, so as to form the composite resin sheet with a multi-cycle structure and sealed upper surface, namely the composite resin sheet formed by pressing the inorganic particles into the softened resin film layer by layer.
2. The method of claim 1, wherein in step a, the resin film is one of polyester resin, polycarbonate resin, polypropylene resin, polyethylene resin and polyamide resin.
3. The method of claim 1, wherein in step b, the inorganic particles and resin composite pair layer has a significant layering structure or a non-significant layering structure, and when the natural stacking volume or the uniform layer thickness of the inorganic particles is not more than 2/3 of the volume or the thickness of the resin film sheet, the inorganic particles are significantly layered; 2/3 which is greater than the volume or thickness of the resin film sheet, is not significantly delaminated; the significantly layered composite resin sheet is of a flexible structure; the composite resin sheet is not significantly delaminated and has a rigid structure.
4. The method according to claim 1, wherein in step b, the inorganic particles have an average particle diameter of 3 to 300 μm.
5. The method for forming a soft resin membrane by pressing inorganic particles layer by layer according to claim 1, wherein in the step b, the inorganic particles are one or more of artificial diamond particles, silicon carbide particles, boron carbide particles or boron nitride particles; the inorganic particles are in the form of a cubic, polyhedral or hexagonal crystal.
6. The method of claim 1, wherein in step d, the composite resin sheet has a thickness of 20 μm to 0.6mm per composite pair, the number of composite pairs is 2 to 10, and the total thickness of the composite resin sheet is not more than 2.5 mm.
7. The method according to claim 1, wherein the inorganic particles are filled into the composite resin sheet in a total amount of 15 to 60 wt% in the step d.
8. A stab-resistant composite resin sheet produced by the method of any one of claims 1 to 7.
9. The use of the stab-resistant composite resin sheet prepared by any one of claims 1 to 7 as a base material for individual protection clothing for preventing terrorism, riot, fire, explosion, earthquake, search and rescue, and national defense and military, wherein the stab-resistant composite resin sheet is used as a rigid stab-resistant material and is adhered to a flexible fabric material to form a rigid and flexible protection layer.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201081612Y (en) * | 2006-12-25 | 2008-07-02 | 张振民 | Light weight flexible reinforced bullet-proof and short-guard chip |
| CN102493202A (en) * | 2011-12-01 | 2012-06-13 | 山东三达科技发展公司 | Composite puncture-proof sheet and bulletproof puncture-proof composite material |
| CN102519310A (en) * | 2011-12-16 | 2012-06-27 | 宁波荣溢化纤科技有限公司 | Composite bulletproof plate made of ultra-high molecular weight polyethylene/silicon carbide |
| CN205272786U (en) * | 2015-11-12 | 2016-06-01 | 河北安泰富源安全设备制造有限公司 | Sheet is prevented stinging by nonmetal |
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| US20120295057A1 (en) * | 2011-05-16 | 2012-11-22 | Multi Axial, Llc | Multi-layer material comprising impregnated and axially-oriented fiber fabrics; ballistic resistance, stab resistance and anti-trauma; manufacturing method and protection garment produced thereby. |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201081612Y (en) * | 2006-12-25 | 2008-07-02 | 张振民 | Light weight flexible reinforced bullet-proof and short-guard chip |
| CN102493202A (en) * | 2011-12-01 | 2012-06-13 | 山东三达科技发展公司 | Composite puncture-proof sheet and bulletproof puncture-proof composite material |
| CN102519310A (en) * | 2011-12-16 | 2012-06-27 | 宁波荣溢化纤科技有限公司 | Composite bulletproof plate made of ultra-high molecular weight polyethylene/silicon carbide |
| CN205272786U (en) * | 2015-11-12 | 2016-06-01 | 河北安泰富源安全设备制造有限公司 | Sheet is prevented stinging by nonmetal |
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