CN110591290B - Inorganic particle filled reverse cutting type anti-piercing thermosetting resin sheet and preparation method and application thereof - Google Patents
Inorganic particle filled reverse cutting type anti-piercing thermosetting resin sheet and preparation method and application thereof Download PDFInfo
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- CN110591290B CN110591290B CN201910922706.6A CN201910922706A CN110591290B CN 110591290 B CN110591290 B CN 110591290B CN 201910922706 A CN201910922706 A CN 201910922706A CN 110591290 B CN110591290 B CN 110591290B
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- thermosetting resin
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/58—Cuttability
- B32B2307/581—Resistant to cut
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2571/00—Protective equipment
- B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of 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 C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
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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
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- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- General Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to an inorganic particle filled reverse cutting type anti-piercing thermosetting resin sheet and a preparation method and application thereof. The resin sheet is a sheet-like body formed by uniformly mixing and curing micron-scale inorganic particles with a thermosetting resin in a template slot box at a high packing density. The preparation method comprises the steps of continuously and uniformly dispersing inorganic particles on the surface of liquid thermosetting resin doped with a crosslinking curing agent at normal temperature, and stopping applying the inorganic particles when the inorganic particles naturally settle under the action of gravity until the piled particles are exposed out of the liquid surface of the resin; and then moving the template groove box into an oven to be heated and solidified into the composite resin sheet. The resin sheet has high hardness, thin thickness, softness and light weight, and more importantly, the inorganic particles can reversely cut sharp devices penetrated so as to achieve rapid passivation and deceleration and achieve high-efficiency anti-piercing. Can be used as an individual protection dressing material for preventing terrorism and riot, fire fighting, explosion prevention, earthquake search and rescue and national defense and military.
Description
Technical Field
The invention relates to an individual stab-resistant and cut-resistant dressing material, belongs to the field of functional technical textiles, and particularly relates to a flexible, light and high-efficiency resin composite sheet for stab-resistant, cut-resistant and cut-resistant dressing and a preparation technology thereof.
Background
Anti-terrorism, anti-riot and fire-fighting in peace periodAnd in rescue and escape such as sudden change accidents, and in war or armed forces, specialized protective equipment is needed. The basic requirements of these installations are: high efficacy protective function and light weight, softness and no mobility disorder; the latter are becoming increasingly important and becoming increasingly light and soft. The control of firearms in China is relatively strict, and although the control of cutters also exists, the firearms are easy to acquire and carry about. Therefore, dressing in terrorism and riot control, in particular to a garment with the functions of puncture prevention, cutting, chopping and the like is basic equipment for ensuring the personal safety and the barrier-free action of rescue personnel. The stab-resistance is the most difficult of three functions of stab-resistance, cutting and chopping, and the highest protection function is required, so people mainly pay attention to the stab-resistance. The existing stab-resistant material mainly depends on hard metal to destroy a blade and a sharp blocking device, or uses hard non-metal materials to block and damage a cutter, or uses hard high polymer to extrude and rub to dissipate impact energy. Obviously, a metallic material "hard on hard" has a deficiency in weight; the 'soft to hard' high polymer also has the defects on the cutter baffle; inorganic hard materials, although advantageous in terms of hardness, are brittle and easily broken. How to combine the two is a field which is rarely related to people at present. Much of the research has focused on fabric coatings and resin sheet-to-fabric bonding techniques. 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.
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; flexible stab-resistant material, method for bonding and molding stab-resistant body (patent publication)Number: CN103791778B) filling thermoplastic particles or composite reinforced material particles produced by an injection molding process into a mold with the thickness of 3-30 mm, the depth of a mold hole of 0.3-2 mm, the distance of 1-20 mm and the gap of the mold hole of 0.2-2 mm, and then uniformly coating a binder or hot melt adhesive powder to be cured and adhered on the base fabric to prepare the flexible stab-resistant material; 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, because the fabric is too thin, the inorganic particle layer is easy to disintegrate and break holes to lose effectiveness, and the extrusion effect of the inorganic particles is basically lost after the cutter is penetrated, and the friction cutting effect is almost disappeared.
The third kind of stab-resistant material is made of traditional woven fabric, knitted fabric or non-woven fabric, and has stab-resistant performance by wrapping, clamping, superposing a hard or flexible shear thickening body or adding a reinforced structure. For example, a hard protective garment disclosed in a hard stab-resistant garment (patent publication No. CN207084185U), in which the inner layer is composed of a high impact polystyrene plate, a high impact polypropylene plate and a foam plastic layer, the inner layer is a detachable metal sheet, and the outer layer is provided with a buffer layer with copper and aluminum strips as reinforcing ribs as a main stab-resistant layer; a flexible stab-resistant fabric and a preparation method thereof (patent publication No. CN107650458A) are characterized in that buffering bulges are introduced to be repeatedly connected and form a wave shape, carbon fiber reinforced material stab-resistant blocks are elaborately layered, and then the fabric is cut, wrapped and sparsely quilted to obtain the flexible stab-resistant fabric; a flexible stab-resistant knitted fabric and a preparation process thereof (patent publication No. CN107587247A) disclose a stab-resistant material prepared by a special knitting process, which comprises floating threads and loop-forming tissues formed by six courses of stitches, and the stab-resistant fabric is prepared by repeated circulation; a preparation method of a soft and durable stab-resistant material (patent publication No. CN107815870A) introduces a shear thickening body to be fully mixed and compounded with a fabric, thereby improving the durability and the flexibility of the stab-resistant material; a flexible stab-resistant material and a preparation method thereof (patent publication No. CN107385676A) disclose a stab-resistant material which comprises a comfort layer 1, a core stab-resistant layer and a comfort layer; 2. the materials are sequentially laminated and then are solidified after being spun-laced to form the stab-resistant composite material. The outstanding disadvantages of the above types of stab-resistant materials are that the processing technology is too complex, the labor cost is high, the mass production is not easy, and when the reinforced material is fiber, the flexibility is improved to some extent, but the stab-resistant function is limited and easy to damage and the weight is increased; when the reinforced material is a metal grid, the flexibility is sharply reduced, the stab-resistant efficiency is related to the grid coarse mesh and the grid space thereof, and the reinforced material is a structure with the quality, the hardness and the flexibility in inverse proportion.
The fourth type of stab-resistant material is a stab-resistant material made of hard or soft materials. A flexible stab-resistant fabric (patent publication No. CN107212485A) uses resin sheets, fiber reinforced resin sheets or metal alloy sheets as protective modules, and achieves stab-resistant effect by gapless fit, greatly improves the flexibility of stab-resistant materials, but is mainly stab-resistant by metal sheets, so the weight is heavier. For example, the anti-stab material is prepared according to various bionics principles, the scale shell splicing type anti-stab clothes (patent publication No. CN108095222A) based on the hollow micro-eggshell is formed by horizontally arranging all anti-stab base plates prepared from plastic materials according to the arrangement layout of upper and lower layers by using the arrangement mode of overlapping the scale shells of animals, and a plurality of hollow semi-ellipsoid shells are arranged on the anti-stab body in a parallel and staggered way, so that the weight of the anti-stab material can be reduced, but the anti-stab effect is influenced by uneven overlapping; the scale-type stab-resistant chip and stab-resistant equipment (patent publication No. CN105403106A) made of the scale-type stab-resistant chip are designed by referring to the scale of crocodile based on the principle of bionics, comprise pyramid and columnar members with sector sections, can well disperse the puncture of sharp instruments such as cutters and the like, and are easy to cause gathering and puncture under the cutting action; the application and preparation method of the nanotube aggregate in the carbon nanotube impact-resistant material (patent publication number: WO2017128944(A1)) utilizes the hollow structure of the carbon nanotube to absorb a large amount of impact energy, the carbon nanotube is in macroscopically ordered and microscopically disordered states, and the optimal puncture-proof and explosion-proof effects are strived to be achieved, but the scale is too small, the rigidity of the material is insufficient, the puncture-proof performance is slightly increased, and the cost is increased; a stab-resistant garment (patent publication No. CN106858769A) based on carbon fiber plate splice blocks is made up of multiple carbon fiber plates, and a stab-resistant sheet made of CNC (computerized numerical control) plate with metal sheet through sewing and sealing. The main deficiency of the stab-resistant material prepared by the scheme is the problem of overlarge quality, and the preparation process is complicated, which is the same as the problem of the early artificial armature manufacturing.
In conclusion, the defects of heavy weight, rigidity and low efficacy of single damping still commonly exist in the existing hard or soft stab-resistant materials.
Disclosure of Invention
The invention aims to solve the problems that: in the existing stab-resistant research, the stab-resistant efficacy and mechanism are simplified (basically, a blocking mechanism or a friction holding mechanism) to realize the reverse cutting mechanism of the superhard microparticles, namely, the single crystal multi-edge form and the particle size of the microparticles are selected to complete high-probability collision and scraping effects so as to realize efficient blocking of reverse cutting passivation. Aiming at the problems of heavy weight, poor flexibility and the like of the stab-resistant material in the market, the invention provides the inorganic particle filled reverse cutting type stab-resistant thermosetting resin sheet which has excellent stab-resistant performance, light weight and thin thickness and a preparation method thereof.
In order to solve the technical problems, the invention provides an inorganic particle filled reverse cutting type anti-cutting thermosetting resin sheet, which is characterized in that inorganic particles with the average particle size of micron scale and thermosetting resin liquid are randomly and uniformly mixed in a high-density stacking manner and are formed into a sheet-shaped body after the thermosetting resin liquid is heated, crosslinked and cured, wherein the reverse cutting means that the R/R is more than or equal to 10 even though the tool steel tool tip used by standard measurement is smaller than the R value (R < < R) of the radius of the edge angle of the inorganic particles. Thus, the edges and corners of the inorganic particles act to penetrate the tool tip in a reverse direction, cutting, scraping, etc., thereby dulling and roughening the tool tip. Thus, the frictional resistance of the cutter to penetrate into the resin body can be greatly or exponentially increased, and the penetration of the resin body can be effectively prevented.
Preferably, the average particle size of the inorganic particles is 1-100 μm, i.e. the mesh number is 50-5000 meshes; the filling mass fraction of the inorganic particles in the inorganic particle filled reverse cutting type anti-puncturing resin sheet is 45-55 wt%.
Preferably, the inorganic particles include, but are not limited to, one or more of silicon carbide particles, boron nitride particles, or synthetic diamond particles.
Preferably, the thermosetting resin includes but is not limited to one of phenolic resin, epoxy resin, unsaturated resin, thermosetting polyurethane, thermosetting polyimide, etc. and is used together with its counterpart crosslinking curing agent.
Preferably, the thickness of the inorganic particle filled reverse cutting type anti-puncturing resin sheet is 0.5-2.5 mm.
The preparation method of the inorganic particle filled reverse cutting type anti-cutting thermosetting resin sheet is characterized by comprising the following steps:
step 1: pouring the thermosetting resin liquid doped with the crosslinking curing agent into a template groove box to form a resin liquid layer;
step 2: at normal temperature, continuously and uniformly shaking and scattering the inorganic particles on the liquid surface of the thermosetting resin in the step 1, naturally settling under the action of self gravity, and stopping adding the inorganic particles until the inorganic particles are piled to be exposed out of the liquid surface, or uniformly scattering the inorganic particles according to a set inorganic particle filling mass fraction value;
and step 3: and (3) moving the template groove box loaded with the mixed solution of the inorganic particles and the thermosetting resin in the step (2) into an oven, heating to a temperature 10-25 ℃ higher than the melting temperature of the thermosetting resin at a heating rate of 1-3 ℃/min, and accelerating crosslinking to solidify into the reverse cutting type anti-stab-cutting thermosetting resin sheet filled with the inorganic particles.
Preferably, the template slot box in step 1 is a hexagonal, square, rectangular or circular flat template slot box made of polytetrafluoroethylene.
The application of the inorganic particle filled reverse cutting type anti-piercing thermosetting resin sheet in basic materials for individual protection dressing of terrorism, riot control, fire control, explosion prevention, earthquake search and rescue and national defense and military is characterized in that the inorganic particle filled reverse cutting type anti-piercing thermosetting resin sheet is used as a rigid anti-piercing material and is adhered to a flexible fabric material to form a rigid-flexible protective layer.
The invention has the beneficial effects that:
(1) the density of the resin and the inorganic particles is far lower than that of metal, particularly hard metal, but the hardness of the inorganic particles is generally much higher than that of the hard metal and is 6-20 times higher than that of the hard metal. The quality of the resin sheet with the same puncture-proof effect can be reduced by times, and light puncture-proof, cutting, chopping and composite materials thereof are prepared;
(2) because the inorganic particles can be filled to 45% -55%, and the inorganic particles are mostly polygonal, the size of a sharp corner is micron scale and is smaller than or far smaller than the cutting edge or the tip of a common cutter, and simultaneously, the hardness of the inorganic particles is far harder than that of a metal cutter, including high-hardness metal, the inorganic particles can cut into the cutting edge of the cutter to form reverse cutting and passivate the tip and the cutting edge.
(3) Because of adopting the thermosetting resin, the inorganic particles can be fully soaked and adhered in the resin liquid to form a more flexible composite resin sheet; because the crosslinking curing speed is very low when the inorganic particles are not heated, the inorganic particles can be naturally settled and piled, so that the filling density is higher and more uniform, and the blocking deceleration of efficient reverse cutting of the high-density layer to the cutter and the acceleration of the layer by layer and the like can be obtained;
(4) the preparation process is simple, the curing agent amount, the temperature and the time can be used, and the fluidity and the curing point of the thermosetting resin can be directly adjusted, so that the preparation period can be adjusted and shortened, and the industrialization degree is high.
Drawings
FIG. 1 is a schematic cross-sectional view of an inorganic particle-filled reverse-cut puncture resistant thermosetting resin sheet of the present invention; 1-inorganic particles; 2-a thermosetting resin.
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 invention discloses a preparation method of an inorganic particle filled reverse cutting type anti-puncturing thermosetting resin sheet, which comprises the following specific steps:
step 1: pouring the thermosetting resin liquid doped with the crosslinking curing agent into a template groove box made of polytetrafluoroethylene to form a resin liquid layer; the shape of the template slot box is a hexagonal, square, rectangular or round flat template slot box; the template slot box is a hexagonal, square, rectangular or round flat template slot box made of polytetrafluoroethylene;
step 2: at normal temperature, continuously and uniformly shaking and scattering the inorganic particles on the liquid surface of the thermosetting resin in the step 1, naturally settling under the action of self gravity, and stopping adding the inorganic particles until the inorganic particles are piled to be exposed out of the liquid surface, or uniformly scattering the inorganic particles according to a set inorganic particle filling mass fraction value;
and step 3: and (3) moving the template groove box loaded with the mixed solution of the inorganic particles and the thermosetting resin in the step (2) into an oven, heating to a temperature 10-25 ℃ higher than the melting temperature of the thermosetting resin at a heating rate of 1-3 ℃/min, and accelerating crosslinking to solidify into the reverse cutting type anti-stab-cutting thermosetting resin sheet filled with the inorganic particles.
The total surface density and the thickness of the prepared anti-puncturing resin sheet are listed in detailed table 1, the anti-puncturing resin sheet meets the protection requirement according to the standard detection of GA68-2008 'police anti-puncturing clothes', and the total surface density required by the existing non-metal anti-puncturing material to reach the standard is higher than 3.33kg/m2The test allows a penetration length of not more than 6mm and the penetration probability is noted as 0. Thus, the total energy for its effective stab resistance and the fabric weight loss δ without being punctured were recorded.
Example 1
The boron carbide particles with the particle size of 300 mu m and the epoxy resin are settled, mixed and randomly piled, and the obtained piled filling mass fraction is 54.8%; the resultant composite fabric obtained by laying a thermosetting resin sheet on a multi-layer fabric had an overall square-meter basis weight of 3.29kg/m2The specific process parameters are listed in the table. The multilayer composite fabric has a puncture probability of zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 25.1J, and the gram weight of the fabric is 3.33kg/m relative to the conventional square meter at present2) In other words, the weight can be reduced by about 1.2%, and it is seen that the improvement of the stab resistance is not so great, and although it is soft, the weight reduction effect is very small because the coating is easily broken.
Example 2
The method comprises the following steps of (1) settling, mixing and randomly piling 100-micron silicon carbide particles and thermosetting polyurethane resin, wherein the obtained piled filling mass fraction is 47.3%; the resulting composite fabric, having a thermosetting resin sheet applied to a multi-layer fabric, has an overall square meterThe gram weight is 2.93kg/m2See table for details. Its puncture probability is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 29.3J, and is relatively to the current conventional square meter gram weight (3.33 kg/m)2) In other words, the weight can be reduced by about 12.0%, so that the stab resistance of the fabric is obviously improved, and the fabric can be lightened and softened.
Example 3
The artificial diamond particles with the particle size of 75 microns and thermosetting polyimide resin are settled, mixed and randomly piled, and the obtained piled filling mass fraction is 50.6%; the resultant composite fabric obtained by laying a thermosetting resin sheet on a multi-layer fabric had an overall square meter grammage of 2.80kg/m2See table for details. Its puncture probability 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 15.9%, so that the weight reduction effect is obvious, the stab resistance is improved, and the effects of lightening and softening can be achieved.
Example 4
The cubic boron nitride particles with the particle size of 10 mu m and phenolic resin are settled, mixed and randomly piled, and the obtained piled filling mass fraction is 52.8%; the resultant composite fabric obtained by laying a thermosetting resin sheet on a multi-layer fabric had an overall square-meter basis weight of 2.86kg/m2See table for details. Its puncture probability is zero. If the conversion is 3.33kg/m at present2The fabric has the stab resistance energy of 27.9J, and is relatively to the current conventional square meter gram weight (3.33 kg/m)2) In other words, the weight can be reduced by about 14.1%, so that the weight reduction effect is improved, the stab-resistant energy is improved, and the effects of weight reduction and softening can be achieved.
TABLE 1 Process recipe and conditions for thermosetting resin sheet and implementation results
Note: wherein the weight loss delta is the gram weight G of the existing horizontal square metersAnd actually measureGrammage of fabric G0Difference 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 (7)
1. The inorganic particle filled reverse cutting type anti-piercing thermosetting resin sheet is characterized in that inorganic particles with the average particle size of micron are randomly and uniformly mixed with thermosetting resin liquid in a high-density stacking manner and form a sheet body after the thermosetting resin liquid is heated, crosslinked and cured, wherein the reverse cutting means that the edge radius value R of the inorganic particles is far smaller than the radius value R of the tip of a piercing cutter, and R/R is more than or equal to 10; the average particle size of the inorganic particles is 1-100 μm; the filling mass fraction of the inorganic particles in the inorganic particle filled reverse cutting type anti-puncturing resin sheet is 45-55 wt%.
2. The inorganic particle-filled reverse-cutting puncture-resistant thermosetting resin sheet according to claim 1, wherein the inorganic particles are one or a mixture of silicon carbide particles, boron nitride particles, or synthetic diamond particles.
3. The inorganic particle-filled reverse-cutting type puncture-resistant thermosetting resin sheet according to claim 1, wherein the thermosetting resin is one of a phenol resin, an epoxy resin, an unsaturated resin, a thermosetting polyurethane, and a thermosetting polyimide.
4. The inorganic particle-filled reverse cutting type stab-resistant thermosetting resin sheet as claimed in claim 1, wherein the thickness of the inorganic particle-filled reverse cutting type stab-resistant thermosetting resin sheet is 0.5 to 2.5 mm.
5. The method for producing the inorganic particle-filled reverse cutting type stab-resistant thermosetting resin sheet as claimed in any one of claims 1 to 4, comprising the steps of:
step 1: pouring the thermosetting resin liquid doped with the crosslinking curing agent into a template groove box to form a resin liquid layer;
step 2: at normal temperature, continuously and uniformly shaking and scattering the inorganic particles on the liquid surface of the thermosetting resin in the step 1, naturally settling under the action of self gravity, and stopping adding the inorganic particles until the inorganic particles are piled to be exposed out of the liquid surface, or uniformly scattering the inorganic particles according to a set inorganic particle filling mass fraction value;
and step 3: and (3) moving the template groove box loaded with the mixed solution of the inorganic particles and the thermosetting resin in the step (2) into an oven, heating to a temperature 10-25 ℃ higher than the melting temperature of the thermosetting resin at a heating rate of 1-3 ℃/min, and accelerating crosslinking to solidify into the reverse cutting type anti-stab-cutting thermosetting resin sheet filled with the inorganic particles.
6. The method for producing an inorganic particle-filled reverse cutting type stab-resistant thermosetting resin sheet according to claim 5, wherein the template well case in the step 1 is a hexagonal, square, rectangular or circular flat template well case made of polytetrafluoroethylene.
7. The use of the inorganic particle-filled reverse cutting type stab-resistant thermosetting resin sheet according to any one of claims 1 to 4 as a base material for personal protective clothing against terrorism, riot, fire, explosion, earthquake, search and rescue, and national defense and military, wherein the base material is used as a rigid stab-resistant material and is adhered to a flexible fabric material to form a rigid and flexible protective layer.
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