CN110500918B - Micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet and preparation method and application thereof - Google Patents
Micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet and preparation method and application thereof Download PDFInfo
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- CN110500918B CN110500918B CN201910922561.XA CN201910922561A CN110500918B CN 110500918 B CN110500918 B CN 110500918B CN 201910922561 A CN201910922561 A CN 201910922561A CN 110500918 B CN110500918 B CN 110500918B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
- F41H5/0478—Fibre- or fabric-reinforced layers in combination with plastics layers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
Abstract
The invention relates to a micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet and preparation and application thereof. The resin sheet is formed by a mixed layer of inorganic powder with the particle size of 1-100 mu m and coating resin and pure resin layers which are distributed at intervals. The thickness of each pair of composite layers is 20 mu m-0.5 mm; the number of the composite pairs is 2-10; the thickness of the resin sheet is not more than 2 mm. The resin sheet is prepared by coating thermosetting resin layer by layer, spreading inorganic particles, hot rolling and immersing, surface heating and delayed curing; coating, spreading, hot rolling and curing are carried out in a recycling mode until the number of the required composite pairs is up; finally, heating, tempering and pressing for shaping to prepare the stab-resistant resin sheet. The resin sheet has a multi-layer step structure, the high-density inorganic powder is tightly stacked on the upper part, and the resin layer is arranged on the lower part, so that the effects of step purification and roughening, energy consumption buffering and holding and positioning can be generated for the tip of the cutter. The resin sheet is light and flexible, and can be used as a protective dressing material for individuals with violence prevention, fire control, explosion, earthquake search and rescue, 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
Preventing terrorism, riot, fire-fighting in peace period,In rescue and escape such as sudden accident, and in war or armed sports, specialized protection 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 use of "hard-to-hard" polymers is also deficient in tool barriers; 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 (patent publication No. CN101125040A) thereof adopt carborundum, silicon carbide and the like as reinforcing particles and polyurethane, epoxy resin and the like as bonding agentsCoating points with the interval of 2-20 mm and the arrangement thickness of 0.1-1 mm on the cloth are made into a composite stab-resistant fabric, and the fabric is very soft and 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 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, the inorganic particle layer is easy to disintegrate and break due to the thin fabricThe effect, and the squeezing effect of the inorganic particle pairs after the knife is penetrated are basically lost, 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: overcomes the limitations of the traditional academic thinking paradigm of the single-piece resin sheet composition simplification, the structure simplification and the layer number simplification in the prior art. The micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet with excellent stab-resistant performance, light weight and thin thickness and the corresponding preparation method are provided.
In order to solve the technical problem, the invention provides a micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet, which is characterized by comprising a plurality of composite layer pairs formed by compounding a high-density stacking rigid layer and a simple thermosetting resin flexible layer, wherein the uppermost layer of the composite layer pairs is coated with a surface coating for preventing inorganic powder from dissociating, and the total thickness of the stab-resistant resin sheet is not more than 2.0 mm;
the high-density stacking rigid layer is positioned on the upper layer of the composite pair layer, is used for high-efficiency blocking and collision passivation and directly faces the penetrating direction of the cutter; the simple thermosetting resin flexible layer is positioned at the lower layer of the composite pair of layers and is used for keeping the flexibility of the composite pair of layers and efficiently rubbing to hold and position the cutter;
the thickness of the composite pair of layers is 20 mu m-0.5 mm, and the number of layers is 2-10; the high-density stacking rigid layer is formed by uniformly mixing 1-100 mu m micrometer inorganic powder and thermosetting resin; the average particle size of the inorganic powder is 1/8-1/2 of the thickness of the high-density stacking rigid layer, the average particle size is 1-100 mu m, and the mesh number is 50-5000 meshes; the filling total mass fraction of the inorganic powder in the anti-puncturing resin sheet is 15-45%; the thickness of the surface coating is 1 to 100 μm.
Preferably, the inorganic powder comprises a mixture of one or more of synthetic diamond, silicon carbide, boron carbide or boron nitride.
Preferably, the inorganic powder takes a crystal form of polyhedron, cube or hexahedron.
Preferably, the thermosetting resin is one of epoxy resin, phenolic resin or polyetherimide resin.
Preferably, the thickness of the high-density stacking rigid layer in the composite pair layer is the same as or different from that of the flexible layer.
The invention also provides a preparation method of the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet, which is characterized by comprising the following steps of:
step 1: uniformly coating thermosetting resin in the template slot box, and carrying out heating treatment; and simultaneously heating the inorganic powder to 3-5 ℃ above the heat treatment temperature of the thermosetting resin;
step 2: uniformly spreading the heated inorganic powder in the step 1 on the heated thermosetting resin liquid, and soaking for 2-10 min; then pressurizing by a pressurizing plate, slowly pressing the powder floating on the thermosetting resin liquid into the thermosetting resin liquid, and taking the pressurizing plate as a standard that the pressurizing plate does not touch the liquid surface; forming a dense high-density stacking rigid layer and a flexible layer in the composite pair of layers, and keeping for 1-5 min; and stopping infiltration;
and step 3: keeping the position of the pressurizing plate unchanged for 10-105 min, and crosslinking and curing the composite pair of layers to form a composite pair of layers;
and 4, step 4: repeating the processes of the steps 1-3 until the required composite pair number n is obtained; then, applying a thermosetting resin to the uppermost surface to form a surface coating;
and 5: and carrying out cross-linking curing and tempering setting treatment on the surface coating to prepare the stab-resistant resin sheet.
Preferably, the heating-out temperature in the step 1 is a temperature at which the thermosetting resin is significantly cross-linked.
Preferably, the template slot box in the step 1 is a hexagonal, square or round flat template slot box made of polytetrafluoroethylene.
The invention also provides application of the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet in basic materials for individual protection dressing of terrorism, riot, fire fighting, explosion prevention, earthquake search and rescue and national defense and military. The protective layer is used as a rigid puncture-proof material and is adhered to a flexible fabric material to form a rigid-flexible protective layer.
The invention relates to a multilayer composite of a composite layer formed by compounding a high-density stacking rigid layer A formed by blending thermosetting resin and inorganic particles and a simple thermosetting resin flexible layer B, wherein the uppermost layer of the multilayer composite layer is a flaky body formed by covering and sealing a surface coating C layer for preventing inorganic powder from dissociating; the composite resin sheet is formed by combining and die-casting a plurality of groups of sheet bodies; the composite resin sheet can produce step purification and roughening to the tip of the cutter through the separating action of the rigid body and the flexible body, and has high efficiency and no prick.
The invention has the beneficial effects that:
(1) under the condition that the thickness and the filling density of the composite resin sheet are basically unchanged (the quality is almost unchanged), according to the size of inorganic particles, the number of protective barrier layers is increased, multi-step-by-step barriers are formed, the weight can be equivalently reduced, the stab-resistant effect is unchanged, and the composite resin sheet is an innovative processing technology for efficient stab-resistant structural design and accurate multilayer forming.
(2) Because the resin is thermosetting resin and is blended with the inorganic particles, the composite layer is easy to process and form; and the high-density inorganic powder is closely stacked on the mixed layer, and the elastic pure resin layer is arranged below the mixed layer to form a composite layer.
(3) Because the inorganic particles are mostly polygonal, the size of a sharp corner is smaller than or far smaller than the cutting edge or the tip end of a common cutter, and meanwhile, the hardness of the inorganic particles is far harder than that of a metal cutter, including high-hardness metal which is generally 6-20 times that of hard metal, the inorganic particles can cut into the cutting edge of the cutter to form reverse cutting and passivate the cutting edge.
(4) Due to the adoption of a thermosetting mode, the quality and the thickness of the resin sheet are lighter and thinner, the flexibility of the sheet is better, particularly, the thickness of the composite pair layer is easy to control, and the control is realized on a micrometer scale.
(5) The reinforcing of the bonding effect of the inorganic particles can adjust the fluidity of the thermosetting resin through curing time delay, so the preparation period is shorter, the preparation process is simple, and the mass production can be directly realized.
Drawings
FIG. 1 is a schematic cross-sectional view of a micrometer-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet of the present invention; wherein A is a high-density stacking layer formed by uniformly mixing inorganic particles and thermoplastic resin; b-a layer of pure resin; c-surface powder free prevention coating; 1-inorganic particles; 2-a thermosetting resin;
FIG. 2 is a middle schematic view of a multi-layer stacking process of the composite pair of the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheets of the present invention; wherein 1-inorganic particles; 2-a thermosetting resin; 3-a pressurizing device.
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).
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 the ministry of public Security of China, and the total surface density required by the existing nonmetal puncture-proof material reaching 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.
As shown in fig. 1-2, the method for preparing the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet of the invention specifically comprises the following steps:
(1) uniformly coating the thermosetting resin in a template groove box, and then heating under the condition of the set treatment temperature or the combination of time and temperature to ensure that the delay time of the whole process of wetting, pressurized resin liquid immersion and crosslinking curing of the inorganic powder is within 2 hours; and simultaneously heating the inorganic powder to 3-5 ℃ above the set treatment temperature;
(2) pressurizing by a pressurizing plate, and slowly pressing the powder floating on the thermosetting resin liquid into the thermosetting resin liquid until the pressurizing plate does not touch the liquid surface; forming a dense high-density stacking rigid layer A and a flexible layer B in the composite pair of layers, and keeping for 1-5 min; and stopping infiltration;
(3) keeping the position of the pressurizing plate unchanged for 10-105 min, and crosslinking and curing the composite pair of layers to form a composite pair of layers;
(4) repeating the processes (1) to (3) until the required composite pair number n is obtained; then, the same thermosetting resin as described above is applied to the uppermost surface to form a surface coating layer C;
(5) and carrying out cross-linking curing and tempering setting treatment on the formed surface coating C to prepare the stab-resistant resin sheet.
Example 1
The embodiment provides a silicon carbide particle layer-by-layer composite ladder anti-stab resin sheet which comprises 3 composite layer pairs formed by compositing a high-density stacking rigid layer A and a flexible layer B, wherein the uppermost layer of the composite layer pairs is coated with a surface coating C for preventing silicon carbide particles from dissociating;
the high-density stacking rigid layer A is positioned at the upper layer of the composite opposite layer, the flexible layer B is positioned at the lower layer of the composite opposite layer,
the number of the composite pair layers is 3; the high-density stacking rigid layer A is formed by uniformly mixing 100-micron silicon carbide particles and epoxy resin; the flexible layer B and the surface coating C are both made of epoxy resin; the total filling mass fraction of the inorganic powder in the anti-puncturing resin sheet is 45.0 percent, and the thickness ratio of the high-density stacking rigid layer A to the flexible layer B in the composite pair layer is 1.5.
The composite fabric is formed by paving silicon carbide particle layer-by-layer composite ladder-shaped anti-stab resin sheets on the multi-layer fabric, and the gram weight of the whole square meter of the composite fabric is 2.97kg/m2The specific process parameters are listed in the table. The puncture probability of the composite fabric is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 28.3J, and is relatively to the current conventional square meter gram weight (3.33 kg/m)2) By the method, the weight can be reduced by about 10.8%, and the stepped collision barrier passivation stab-resistant and cutting-resistant mechanism can achieve a good stab-resistant and cutting-resistant effect.
Example 2
The embodiment provides a boron carbide particle layer-by-layer composite stepped stab-resistant resin sheet which comprises 5 composite layer pairs formed by compounding a high-density piled rigid layer A and a flexible layer B, wherein the uppermost layer of the composite layer pairs is coated with a surface coating C for preventing boron carbide particles from dissociating;
the high-density stacking rigid layer A is positioned at the upper layer of the composite opposite layer, the flexible layer B is positioned at the lower layer of the composite opposite layer,
the number of the composite pair layers is 5; the high-density stacking rigid layer A is formed by uniformly mixing 50-micron boron carbide particles with phenolic resin; the flexible layer B and the surface coating C are both made of phenolic resin; the total filling mass fraction of the inorganic powder in the anti-puncturing resin sheet is 30.4 percent; the thickness ratio of the high-density stacking rigid layer A to the flexible layer B in the composite pair layer is 1.25.
The composite fabric is formed by paving boron carbide particles on the multilayer fabric and compounding stepped stab-resistant resin sheets layer by layer, and the gram weight of the whole square meter of the composite fabric is 2.88kg/m2The specific process parameters are listed in the table. The puncture probability of the composite fabric is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 29.9J, and is relatively to the current conventional square meter gram weight (3.33 kg/m)2) By the method, the weight can be reduced by about 13.5%, and the stepped collision barrier passivation stab-resistant and cutting-resistant mechanism can achieve a good stab-resistant and cutting-resistant effect.
Example 3
The embodiment provides a layer-by-layer composite stepped anti-stab resin sheet of artificial diamond particles, which comprises 10 composite layers formed by compositing a high-density piled rigid layer A and a flexible layer B, wherein the uppermost layer of each composite layer is coated with a surface coating C for preventing the artificial diamond particles from dissociating;
the high-density stacking rigid layer A is positioned at the upper layer of the composite opposite layer, the flexible layer B is positioned at the lower layer of the composite opposite layer,
the number of the composite pair layers is 10; the high-density stacking rigid layer A is formed by uniformly mixing artificial diamond particles with the particle size of 100 mu m and polyetherimide resin; the flexible layer B and the surface coating C are both made of polyetherimide resin; the total filling mass fraction of the inorganic powder in the anti-puncturing resin sheet is 20.5 percent; the thickness ratio of the high-density stacking rigid layer A to the flexible layer B in the composite pair layer is 1.
The composite fabric is formed by paving artificial diamond particles on the multi-layer fabric and compounding stepped stab-resistant resin sheets layer by layer, and the gram weight of the whole square meter of the composite fabric is 2.81kg/m2The specific process parameters are listed in the table. The puncture probability of the composite fabric is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 33.7J, and is relatively to the current conventional square meter gram weight (3.33 kg/m)2) By the aid of the stepped collision baffle passivation stab-resistant mechanism, the stab-resistant performance of the fabric can be obviously improved, and the fabric can be lightened and softened, and the weight can be reduced by about 15.6%.
Example 4
The embodiment provides a cubic boron nitride particle layer-by-layer composite step stab-resistant resin sheet which comprises 8 composite layer pairs formed by compounding a high-density stacking rigid layer A and a flexible layer B, wherein the uppermost layer of the composite layer pairs is coated with a surface coating C for preventing cubic boron nitride particles from dissociating;
the high-density stacking rigid layer A is positioned at the upper layer of the composite opposite layer, the flexible layer B is positioned at the lower layer of the composite opposite layer,
the number of the composite pair layers is 8; the high-density stacking rigid layer A is formed by uniformly mixing 30-micron cubic boron nitride particles and phenolic resin; the flexible layer B and the surface coating C are both made of phenolic resin; the total filling mass fraction of the inorganic powder in the anti-puncturing resin sheet is 15.1 percent; the thickness ratio of the high-density stacking rigid layer A to the flexible layer B in the composite pair layer is 0.75.
The composite fabric is formed by paving cubic boron nitride particles on a multi-layer fabric and compounding stepped stab-resistant resin sheets layer by layer, and the gram weight of the whole square meter of the composite fabric is 2.78kg/m2The specific process parameters are listed in the table. The puncture probability of the composite fabric is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 30.1J, and is relatively to the current conventional square meter gram weight (3.33 kg/m)2) By the method, the weight can be reduced by about 16.5%, and the stepped collision baffle passivation stab-resistant mechanism obviously improves the stab-resistant performance of the fabric and can achieve light weight and soft softening.
Table 1 process recipe and conditions and implementation results of 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 (6)
1. A method for preparing a micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet is characterized by comprising the following steps of:
step 1: uniformly coating thermosetting resin in the template slot box, and carrying out heating treatment; and simultaneously heating the inorganic powder to 3-5 ℃ above the heat treatment temperature of the thermosetting resin;
step 2: uniformly spreading the heated inorganic powder in the step 1 on the heated thermosetting resin liquid, and soaking for 2-10 min; then pressurizing by a pressurizing plate, and slowly pressing the inorganic powder floating on the thermosetting resin liquid into the thermosetting resin liquid until the pressurizing plate does not touch the liquid surface; forming a high-density stacking rigid layer (A) and a flexible layer (B) in the composite pair of layers, and keeping for 1-5 min; and stopping infiltration;
and step 3: keeping the position of the pressurizing plate unchanged for 10-105 min, and crosslinking and curing the composite pair of layers to form a composite pair of layers;
and 4, step 4: repeating the processes of the steps 1-3 until the required composite pair number n is obtained; then, applying a thermosetting resin to the uppermost layer to form a surface coating layer (C);
and 5: carrying out cross-linking curing and tempering setting treatment on the surface coating (C) to prepare the stab-resistant resin sheet;
the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet comprises a plurality of composite layer pairs formed by compounding a high-density stacking rigid layer (A) and a flexible layer (B), wherein the uppermost layer of the composite layer pairs is coated with a surface coating (C) for preventing inorganic powder from dissociating, and the total thickness of the stab-resistant resin sheet is not more than 2.0 mm;
the high-density stacking rigid layer (A) is positioned at the upper layer of the composite dyad layer, and the flexible layer (B) is positioned at the lower layer of the composite dyad layer; the thickness of the composite pair of layers is 20 mu m-0.5 mm, and the number of layers is 2-10; the high-density stacking rigid layer (A) is formed by uniformly mixing inorganic powder and thermosetting resin with the size of 1-100 mu m micrometers; the flexible layer (B) and the surface coating (C) are both made of thermosetting resin; the average particle size of the inorganic powder is 1/8-1/2 of the thickness of the high-density stacking rigid layer (A), the average particle size is 1-100 mu m, and the mesh number is 50-5000 meshes; the total filling mass fraction of the inorganic powder in the anti-puncturing resin sheet is 15-45%; the thickness of the surface coating (C) is 1 to 100 μm.
2. The method for preparing the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet according to claim 1, wherein the inorganic powder comprises a mixture of one or more of synthetic diamond, silicon carbide, boron carbide, or boron nitride.
3. The method for preparing the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet according to claim 1, wherein the thermosetting resin is one of epoxy resin, phenolic resin or polyetherimide resin.
4. The method for preparing the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet according to claim 1, wherein the heating treatment temperature in the step 1 is a temperature at which thermosetting resin is significantly cross-linked.
5. The method for preparing the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet according to claim 1, wherein the template slot box in the step 1 is a hexagonal, square or circular flat template slot box made of polytetrafluoroethylene.
6. The use of the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet prepared by the method for preparing the micron-scale inorganic powder layer-by-layer composite stepped stab-resistant resin sheet according to any one of claims 1 to 3 as a base material for individual protection and dressing in terrorism and riot prevention, fire fighting, explosion prevention, earthquake search and rescue, and national defense and military.
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| CN1288513A (en) * | 1998-01-22 | 2001-03-21 | 阿克佐诺贝尔公司 | Stab and bullet proof protective clothing |
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| CN110103556A (en) * | 2019-05-10 | 2019-08-09 | 山东三达科技发展有限公司 | A kind of flexible ballistic-resistant stab-resistant material and preparation method thereof |
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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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| CN1288513A (en) * | 1998-01-22 | 2001-03-21 | 阿克佐诺贝尔公司 | Stab and bullet proof protective clothing |
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