CN110500918A - Anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder and preparation method thereof and purposes - Google Patents
Anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder and preparation method thereof and purposes Download PDFInfo
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- CN110500918A CN110500918A CN201910922561.XA CN201910922561A CN110500918A CN 110500918 A CN110500918 A CN 110500918A CN 201910922561 A CN201910922561 A CN 201910922561A CN 110500918 A CN110500918 A CN 110500918A
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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
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- Life Sciences & Earth Sciences (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The present invention relates to the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder and its preparation and purposes.Mixed layer and pure resin layer of the resin sheet by partial size for 1~100 μm of inorganic powder and coating resin are spaced apart and constitute.Each pair of composite layer with a thickness of 20 μm~0.5mm；Compound is 2~10 layers to the number of plies；Resin sheet thickness is not more than 2mm.The resin sheet is by successively coating thermosetting resin, spreading inorganic particle, hot rolling immersion, surface heating and delay curing；Coating, spreading, hot rolling and solidification are recycled, until required compound to the number of plies；Finally heated tempering, pressurization setting, and it is prepared into anti-stab resin sheet.The multistage grid structure of resin sheet, and the close stack layers of highly dense inorganic powder are upper, resin layer can generate the purifying of ladder with roughening and buffering energy-consumption to tool tip and hold the effect of positioning under.Resin sheet lightweight, flexible, can be used for the individual of anti-riot, fire-fighting, explosion, earthquake search and rescue and defense military protects package material.
Description
Technical field
The present invention relates to individual it is anti-stab cut, shellproof package material, function of dominant Technical Textiles field is especially flexible, light
Matter, high effect are anti-stab, cut, cut dressing resin compounded sheet material and its technology of preparing.
Background technique
Peacetime it is anti-probably, anti-riot, fire-fighting, the rescue such as mutation accident in escape and war or militant campaigns,
Need the protective gear of specialization.The basic demand of these equipments is: safeguard function and light soft, the inaction obstacle of high effect
Requirement；And the latter becomes increasingly important, and becomes increasingly light soft.China to the control of gun in comparison extremely
Strictly, it although there is also the control of cutter, is easier to obtain and carry.Therefore in the anti-dressing probably made in sudden and violent, especially have
Clothes that are anti-stab, the functions such as cutting, cut are to ensure rescue personnel's personal safety and the accessible basic equipment of action.Due to anti-stab
It is anti-stab, cut, cut three effect in be to be most difficult to reach, and require highest safeguard function, old friends are primarily upon anti-stab.It is existing
Stab-resistant material, rely primarily on the metal failure blade and barrier sharp weapon of hard, or stopped and damaged with hard non-metallic material
Cutter, or squeezed with hard high-polymer, Friction dissipation impact energy.Obviously, the metal material " firmly to hard " is in weight
Existing defects；And the high polymer of " firmly to hard " also Shortcomings in cutter barrier；Although inorganic hard material is in hardness
With advantage, but it is brittle easy to crack.How both of the above to be combined, is the field that people are seldom related at present.And done
Research have focused largely on fabric coating and resin sheet bonded with fabric it is technical.In current technology and raw material property
Under, anti-stab effect can only be realized by way of the quality of the laminated material and increasing substance thickened and selection material hardness
Fruit, this belongs to the rudimentary, initial stage.The attainable best effects of institute are to wear under 24 joules of impact forces without obvious at present for it
The minimum 6.67kg/m of fabric weight per square meter of (national standard) thoroughly2, i.e. 0.3 square metre of vest is 2kg.If allowing to penetrate maximum
Exposed length 7mm (European standard) is most gently 3.33kg/m2, i.e. 0.3 square metre of vest is 1kg.
Many researchs are had been carried out to the above-mentioned anti-stab material that cuts at present, are mainly concentrated on following several.
The first kind is to form antipricking layer using thermosetting resin or thermoplastic material to reach anti-stab effect.Such as a kind of non-gold
Belong to the method that bulletproof stab-resistant clothes (patent publication No.: CN201577566U) uses thermoplastic resin coating, and accurate using fiber
Permutation technology makes Aramid No-Woven Cloth into 0 °/90 ° arrangements to reach anti-stab bulletproof effect；A kind of shellproof, stabproof vest (patent disclosure
Number: protective sheet is solidified using resin-impregnated aramid fabric laminating hot pressing in CN203657618U), has very strong toughness
And elasticity；A kind of modified second of aramid fiber reinforced resin base thorn-proof composite material (patent publication No.: CN102632665B) utilization
Ene based resins dipping kevlar fabric forms sheet material and overlaps to be formed, and between sheet material independently of one another, is subtracted in terms of hardness and quality
It is few；A kind of flexible puncture-proof material that shellproof and anti-stab composite material (patent publication No.: CN107580550A) provides mainly wraps
It includes three regions and constitutes composite anti-stabbing material, wherein the secondth area comprising fabric and elastomer resin or thermoplastic resin is as master
Want antipricking layer；The nonmetallic stab-resistant chip of high-performance (patent publication No.: CN105696357A) is by epoxy resin and acetone according to certain
Molding and dry solidification are carried out coated in aramid fiber woven fabric two sides than mixing according to certain mass with polyamide again after ratio mixing
It is made, so that anti-stab performance becomes more stable, the relatively strong stab-resistant material of anti-stab performance；Thorn-proof composite material and its preparation
Method (patent publication No.: CN101936684A) forms reinforcement, the resin base being compounded in reinforcement using high-performance fiber
System starts independent a part for using resin as composite anti-stabbing material at single layer composite；Multi-layer nonwoven is fabric
Bulletproof anti-puncturing be mostly used composite material and preparation method (patent publication No.: US2013/0219600A1) impregnated using resin or
Stab-resistant material is made by multi-angle laying in the non-woven cloth of filler, and the lock knot of non-woven cloth reaches anti-stab performance；With stretching
The anti-stab watch box (patent publication No.: CN107478095A) of contracting function provides a kind of by base fabric and enhancing composite thermoplastic resin
The anti-stab structure sheaf of piece composition, mutually overlap joint is constituted array into a ladder, and there is this antipricking layer contractile function it can be improved
Protective performance pliability and gas permeability are more preferable；Bulletproof anti-puncturing structure and protective garment (patent publication No.: CN206832131U) provide
A kind of stab-proof/bulletproof material include fibrous layer, fibrous layer and resin matrix composite layer, cloth in 90 ° between fibrous layer and fibrous layer
It sets, the construction weight is relatively light and does not interfere with the comfort level and flexibility of wearer；A kind of Z-shaped resin forming flexible puncture-proof
Fabric and preparation method thereof (patent publication No.: CN105544228B) obtains Z-shaped tree by 3D printing technique or injection molding technology
Rouge solidfied material is simultaneously solidificated on ready-made clothes fabric by hot-melt adhesive powder, is made after then carrying out drying, have it is light-weight it is comfortable,
The features such as flexible；A kind of composite thermoplastic bulletproof anti-puncturing sheet material (patent publication No.: CN207180483U) will enhance thermoplasticity material
For material hot-melting and injection-molding on ballistic fiber aggregate, being equipped with through-hole on ballistic fiber aggregate, reinforced partly thermoplastic material is warm
Infiltration, which enters into the through-hole, forms reverse side reinforcement, is integrally formed formula structure, and such scheme significantly enhances anti-stab effect,
But it is poor to process relatively difficult and durability.It is impregnated above by resin or the stab-resistant material that coats is to reaching standard
The anti-stab requirement of " the police stab-resistance body armor of GA68-2008 ", need bigger quality, the thicker number of plies and material flexibility be deteriorated and
Lead to heavy wearing and not flexible, reason is to only exist slightly hard resin film, anti-stab low efficiency.If direct metal cladding,
First is that thickness can not be done, not only increases weight, is also easily rupturable；Two are machined to sheet material, and anti-stab main function is still resin, the hardness of resin
It is limited, only increase sheet thickness i.e. increase material and can not loss of weight.
Second class is high polymer of the coating containing inorganic particle in the base fabrics such as existing aramid fiber woven fabric, forms antipricking layer
To reach anti-stab effect.A kind of stab-resistant material, for this coated carrier, and (patent is public for the clothes made of the material
The number of opening: EP0972169B1) by polyurethane as adhesive by diameter be 0.1~3mm inorganic particle abrasive grain be adhered to fabric
Surface is to reach anti-stab effect, and anti-stab particle (patent publication No.: US2004/0048536A1) in high-performance fiber by knitting
A certain amount of solid rigid particulate matter of object surface adhesion, coating layer thickness can be passivated cutter Penetration Depth in 0.1~2mm；It is anti-
Pierce composite material (patent publication No.: US2007/0105471A1) in by by coating inorganic particles in kevlar fabric surface to change
The anti-stab performance of kind material；Composite anti-stabbing lining and preparation method thereof (patent publication No.: CN101125040A) using diamond dust,
Silicon carbide etc. is spaced 2~20mm as binder as enhancing particle, polyurethane, epoxy resin etc. in base fabric, thickness of arranging
Composite anti-stabbing lining is made for the coating point of 0.1~1mm, quality is very soft to be suitable for processing all kinds of Anti-prick clothes；Flexibility is anti-
Pierce material, the thermoplasticity grain that the molding bonded method (patent publication No.: CN103791778B) of stab-proof body produces Shooting Technique
Son or composite reinforcing material it is particle-filled with a thickness of 3~30mm, die hole depth in 0.3~2mm, distance at a distance of 1~20mm, mould
Hole gap is in the mold of 0.2~2mm, then uniform coated with adhesive or hot melt adhesive powder curing are bonded in base fabric, system
Obtain flexible puncture-proof material；A kind of a kind of inorganic powder coating thronproof cloth/bulletproof composite stab-resistant material (patent publication No.:
CN206430639U/CN206648524U) inorganic powder coatings such as silicon carbide are formed on aramid fiber woven fabric using PU glue etc.
A kind of inorganic dust coating thronproof cloth, single layer surface density is up to 150~500g/m2, for the number of plies no more than 10 layers, weight is essentially existing
There is the floor level in stab-resistant material, and using this inorganic coating thronproof cloth or ultra-thin anti-stab steel disc as antipricking layer, high-performance is fine
Woven cloth is tieed up as burster course, bulletproof anti-puncturing composite material is made.A kind of preparation method of anti-stab anti-cutting flexible material (patent public affairs
The number of opening: CN108058469A) further in fabric, membrane material, rubber material or leather surface coating adhesive, then glue
The inorganic particles such as organic polymers or diamond, silicon carbide such as patch epoxy resin obtain composite material, then obtain by hot pressing
It is anti-stab to cut flexible material, the features such as invented technology is simple at low cost, light-weight；A kind of flexibility is anti-to cut anti-stab watch box (patent public affairs
The number of opening: CN207180485U) it the anti-stab sheet material of enhancing thermoplasticity being arranged in base fabric is divided into several with flexible gap opens
Any shape is combined into particle pattern, and is made with protrusion, and particle and protrusion can be improved preferably anti-in this scheme
Thorn effect, but easily wear-out failure.It is above-mentioned by inorganic particulate coatings or pure resin piece be pasted onto the anti-stab of scrim surfaces
Material, although improving flexibility, anti-stab effect of cutting does not increase, can even be declined.Moreover, the former can use
Cheng Zhong makes surface particle fall off because constantly rubbing, and causes the anti-stab decline for cutting performance, and brings very big security risk；Together
When, because fabric is too thin, inorganic particles easily disintegrate and broken hole and fail and cutter be pierced into after inorganic particle pair squeezing action
Basic to lose, friction cuttings effect almost disappears.
Third class stab-resistant material is to pass through package, entrainment, superposition using traditional woven fabric, looped fabric or non-woven cloth
Hard or flexible shear thickening body or increase reinforced structure make it have anti-stab performance.As (patent is public for a kind of hard stab-resistance body armor
The number of opening: CN207084185U) announce a kind of hard protection clothes, wherein internal layer is by high impact polystyrene plate, high impact poly third
Alkene plate and foam layer collocation, detachable sheet metal, outer layer add copper, aluminum strip to prevent as the buffer layer of reinforcing rib as main
Pierce layer；Buffering protrusion is introduced in a kind of flexible puncture-proof fabric and preparation method thereof (patent publication No.: CN107650458A) to repeat
It is connected after the wavy and meticulous laying of the anti-acacia of carbon fibre reinforcement, cutting, bound edge, sparse quilting are to get flexible puncture-proof
Fabric；A kind of flexible puncture-proof knitted fabric fabric and its preparation process (patent publication No.: CN107587247A) disclose a kind of spy
Stab-resistant material made from different knitting, is made of the coil of six rows including flotation line and lopping tissue, and repetitive cycling system
Obtain anti-stabbing lining；A kind of preparation method (patent publication No.: CN107815870A) introducing shearing of softness permanent seal cooling stab-resistant material
Thickening body is sufficiently mixed compound with fabric, improves the durability and flexibility of stab-resistant material；A kind of flexible puncture-proof material and its
A kind of stab-resistant material that preparation method (patent publication No.: CN107385676A) is announced is by comfort liner 1, core antipricking layer and comfortable
Layer；2, consolidation forms thorn-proof composite material after spun lacing after being laminated in sequence.The stab-resistant material of above-mentioned several types is dashed forward
Deficiency is that processing technology is excessively complicated, and cost of labor is larger out, is not easy to produce in batches, and reinforcement material be fiber when, it
Flexibility make moderate progress, but anti-stab function it is limited and be easy to destroy and weight increase；It is flexible when reinforcement material is metal grill
Sharply decline, and anti-stab efficiency and grid coarse net and its grid have passs in vain, is a kind of quality, hardness and the flexible knot in inverse ratio
Structure.
4th class stab-resistant material is using stab-resistant material made from hard or soft material.A kind of flexible puncture-proof fabric is (special
Sharp publication number: CN107212485A) use resin sheet, fiber-reinforced resin piece or metal alloy film as protection module, and lead to
Blind-mate is crossed, thus reach anti-stab effect, the very big flexibility for improving stab-resistant material, but it is anti-mainly by sheet metal
Thorn, therefore weight is laid particular stress on.Stab-resistant material such as is made according to various bionics principles, a kind of scale and shell based on hollow micro- eggshell is spliced
Stab-resistance body armor (patent publication No.: CN108095222A) uses for reference the arrangement mode of animal scale and shell hierarchical overlay, according to upper lower leaf
Alignment placement arranges all substrate levels anti-stab as made from plastic material, and has on stab-proof body multiple hollow half ellipse
Global shell can mitigate stab-resistant material weight in being staggered side by side, but anti-stab effect is influenced by overlapping unevenness；Scale and shell formula
Anti-puncturing chip and anti-stab equipment (patent publication No.: CN105403106A) made of it are based on bionics principle reference crocodile
Scale and shell designs anti-puncturing chip structure, is fan-shaped cylindrical component comprising " pyramid " and section, it is sharp to disperse well cutter etc.
The puncture of device, dissection but easily causes and gathers puncture；Nanotube, which gathers materials, to be applied and prepares in carbon nanotube anti-ballistic materials
Method (patent publication No.: WO2017128944 (A1)) absorbs a large amount of impact energy using the hollow structure of carbon nanotube,
Carbon nano-tube macroscopic is orderly, microcosmic disordered state, makes every effort to the anti-stab explosion-proof effect being optimal, but scale is too small, material stiffness
Deficiency, anti prick function can increase small and increased costs；It is a kind of based on carbon fiber board splicing block stab-resistance body armor (patent publication No.:
CN106858769A) the stab-resistant chip being process using multiple carbon fiber boards and CNC, and sheet metal is accompanied, it is sutured through machine
It seals and stab-resistant material is made, anti-stab function admirable but too heavy too hard is suitable for mosaic or discontinuous sheet body.Above scheme is made
Stab-resistant material main deficiency and the excessive problem of quality, and along with preparation process complexity, this and early stage manual manufacture
The problem of armour, is identical.
To sum up, existing some hard or soft stab-resistant material, still generally existing structure are uniform, heavy, firm and single
The defect of low effect of one damping.
Summary of the invention
Problem to be solved by this invention is: overcoming composition unification, the structure list of monolithic resin sheet in the prior art
The limitation for only forming important traditional academic thought normal form of one change, number of plies unification.There is provided it is a kind of not only anti-stab have excellent performance but also
The thin anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder of light weight, thickness and its corresponding preparation method.
In order to solve the above-mentioned technical problems, the present invention provides a kind of layer-by-layer composite step of micro-meter scale inorganic powder is anti-stab
Resin sheet, which is characterized in that rigid layer is piled up by high density including multilayer and is combined with simple thermosetting resin flexible layer
It is compound to layer, and the compound top layer to layer is coated with the surface covering that anti-inorganic powder dissociates, anti-stab resin sheet overall thickness
No more than 2.0mm；
The high density piles up rigid layer and is located at the compound upper layer to layer, for efficient barrier and collision passivation, directly
In face of the direction that cutter is pierced into；The simple thermosetting resin flexible layer is located at the compound lower layer to layer, for keeping multiple
It closes and aligned cutting tool is held to layer flexibility and efficient friction；
It is described it is compound to layer with a thickness of 20 μm~0.5mm, the number of plies is 2~10 layers；The high density piles up rigidity
Layer is made of the uniform mixing of the inorganic powder and thermosetting resin of 1~100 μm of micro-meter scale；The inorganic powder is averaged grain
The size of diameter is that high density piles up the 1/8~1/2 of rigid layer thickness, and for average grain diameter at 1~100 μm, mesh number is 50~5000
Mesh；Filling total mass fraction of the inorganic powder in the anti-stab resin sheet is 15~45%；Surface covering with a thickness of 1~
100μm。
Preferably, the inorganic powder includes one of diamond, silicon carbide, boron carbide or boron nitride or more
The mixing of kind.
Preferably, the inorganic powder takes the crystalline form of polyhedral body, cube or hexahedron.
Preferably, the thermosetting resin is one of epoxy resin, phenolic resin or polyetherimide resin.
Preferably, the compound thickness for piling up rigid layer and flexible layer to layer middle-high density is identical or different.
The present invention also provides the preparation method of the anti-stab resin sheet of the above-mentioned layer-by-layer composite step of micro-meter scale inorganic powder,
It is characterized in that, comprising the following steps:
Step 1: thermosetting resin being uniformly coated in template slot box, is heated；And it heats simultaneously inorganic
3~5 DEG C on powder to thermosetting resin heat treatment temperature；
Step 2: the uniform shakedown of heating inorganic powder in step 1 being dispersed on the thermosetting resin liquid after heating, infiltration 2
~10min；Then it is pressurizeed with pressure plate, the powder floated on thermosetting resin liquid is slowly pressed into thermosetting resin liquid, with
Pressure plate is non-sticky to be touched subject to liquid level；It forms the compound close high density in layer and piles up rigid layer and flexible layer, keep 1~
5min；And terminate infiltration；
Step 3: keeping pressurization Board position constant, 10~105min makes compound to layer crosslinking curing, and it is compound right to form one
Layer；
Step 4: step 1~3 processes are repeated, until compound to number of plies n needed for obtaining；Then, thermosetting resin is coated
Surface covering is formed to upper space；
Step 5: crosslinking curing and tempering setting processing being done to surface covering, anti-stab resin sheet is made.
Preferably, it is the temperature that thermosetting resin generates obvious Cross-linked that heating, which comes out temperature, in the step 1.
Preferably, the template slot box in the step 1 is hexagon, square or circular flat made of polytetrafluoroethylene (PTFE)
Flat-die board slot box.
The present invention also provides the anti-stab resin sheet of the above-mentioned layer-by-layer composite step of micro-meter scale inorganic powder it is anti-probably it is anti-riot, disappear
Application in the individual protection dressing basic material of anti-, blast protection, earthquake search and rescue and defense military.It is anti-stab as rigidity
Material is worn, pastes on flexible fabric material, forms the protective layer of hard and soft merger.
The present invention is that thermosetting resin is blended to the high density constituted to pile up rigid layer A and simple thermosetting with inorganic particle
The compound MULTILAYER COMPOSITE to layer that property resin flexible layer B is combined, and MULTILAYER COMPOSITE has anti-inorganic powder to the top layer of layer
Plates made of free C layers of covering closing of surface covering；Compound resin piece made of die casting is combined by multiple groups plates；
The compound resin piece by the barrier action of rigid body and flexible body, tool tip can be generated ladder purifying and roughening and
Buffering energy-consumption and the efficient stab-resistant chip for holding positioning.
The beneficial effects of the present invention are:
(1) under conditions of the thickness of compound resin piece and packed density are basically unchanged (quality is almost unchanged), according to
The scale of inorganic particle, both increase protection the barrier number of plies, formed multi-ladder lattice step by step gear, and can equivalent mitigation weight, and
Keep anti-stab effect constant, is the innovation processing technology of efficiently anti-stab structure design and accurate multilevel shaping.
(2) it since resin is all made of thermosetting resin, is blended with inorganic particle, it is easily processed into type compound to layer；And it is high
The close close heap mixed layer of inorganic powder is upper, and elastic pure resin layer is in the compound to layer of lower formation.
(3) since the inorganic particle is mostly polygonal, wedge angle size be less than or much smaller than general cutter cutting edge
Or tip, meanwhile, the hardness of inorganic particle is considerably harder than metal knife, including high rigidity metal, usually 6~20 times of hard metal,
Therefore inorganic particle can cut cutting edge roundness, form reverse cut, and be passivated cutting edge.
(4) due to taking thermosetting property mode, resin tablet quality and thickness are more frivolous, sheet material flexibility is more preferable, especially
The easily controllable compound thickness to layer, and regulate and control in micro-meter scale.
(5) to the enhancing of the cementation of inorganic particle, can by solidifying the mobility of delay adjustment thermosetting resin,
Therefore manufacturing cycle is shorter, and preparation process is simple, it can direct volume production.
Detailed description of the invention
Fig. 1 is the schematic cross-section of the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder of the invention；Wherein
The high density heap course that the uniform mixing of A- inorganic particle and thermoplastic resin is constituted；B- pure resin layer；The anti-powder trip in the surface C-
From coating；1- inorganic particle；2- thermosetting resin；
Fig. 2 is compound pair of multiple-layer stacked of the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder of the invention
Schematic diagram among technique；Wherein 1- inorganic particle；2- thermosetting resin；3- pressurizing device.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Raw material and equipment in embodiment 1-4 are the money that state key researches and develops planning item (2016YFC0802802)
It helps.
It is listed in the detailed table of total areal density, thickness of obtained anti-stab resin sheet, according to the Ministry of Public Security, China GA 68-
2008 " police stab-resistance body armor " standard detections, reach requirement of shelter, and current existing nonmetallic stab-resistant material, which reaches the standard, to be wanted
The total areal density asked is higher than 3.33kg/m at double2, therefore experiment allows the penetration length no more than 6mm, and pierces through probability and be denoted as
0.The fabric weight-loss ratio δ for recording its effectively anti-stab gross energy as a result, and being not punctured.
As shown in Figs. 1-2, the preparation method of the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder of the invention,
Specific preparation process is as follows:
(1) thermosetting resin is uniformly coated in template slot box, then its setting treatment temperature or
When-under conditions of both temperature combines, enable that inorganic powder completes infiltration, resin liquid is immersed in pressurization and crosslinking curing overall process is prolonged
The slow time within 2 hours, is heated；And heat simultaneously the inorganic powder to the setting treatment temperature it
Upper 3~5 DEG C；
(2) it will then be pressurizeed with pressure plate, the powder floated on thermosetting resin liquid is slowly pressed into thermosetting resin liquid
In, pressure plate of being subject to is non-sticky to touch liquid level；It forms the compound close high density in layer and piles up rigid layer A and flexible layer B, keep 1
~5min；And terminate infiltration；
(3) keep pressurization Board position constant, 10~105min makes compound to layer crosslinking curing, and it is compound to layer to form one；
(4) above-mentioned (1)~(3) process is repeated, until compound to number of plies n needed for obtaining；Then, by above-mentioned identical thermosetting
Property resin is coated to upper space and to form surface covering C；
(5) crosslinking curing and tempering setting processing are done to formation surface covering C, anti-stab resin sheet is made.
Embodiment 1
Present embodiments provide a kind of anti-stab resin sheet of layer-by-layer composite step of silicon-carbide particle, including 3 layers by high density heap
Block rigid layer A and flexible layer B is combined compound to layer, and the compound top layer to layer is free coated with anti-silicon-carbide particle
Surface covering C；
High density piles up rigid layer A and is located at the compound upper layer to layer, and flexible layer B is located at the compound lower layer to layer,
The compound number of plies to layer is 3 layers；The high density piles up rigid layer A by 100 μm of silicon-carbide particle
Composition is uniformly mixed with epoxy resin；The flexible layer B and surface covering C is made of epoxy resin；Inorganic powder is described
Anti-stab resin sheet in filling total mass fraction 45.0%, it is compound that rigid layer A's and flexible layer B is piled up to layer middle-high density
Thickness ratio is 1.5.
Compound fabric made of the anti-stab resin sheet of the layer-by-layer composite step of paving silicon-carbide particle, entirety in multilayer fabric
Gram Mass is 2.97kg/m2, specific process parameter is detailed in table listed.The puncture probability of the compound fabric is zero.If folding
It is counted as current 3.33kg/m2Fabric, it is 28.3J that resistance to thorn, which cuts energy, relative to current conventional Gram Mass (3.33kg/
m2) for, it can be with loss of weight about 10.8%, it is seen that this stepped collision barrier, which is passivated anti-stab mechanism and can achieve, preferably prevents
Thorn cuts effect.
Embodiment 2
Present embodiments provide a kind of anti-stab resin sheet of layer-by-layer composite step of boron carbide particles, including 5 layers by high density heap
Block rigid layer A and flexible layer B is combined compound to layer, and the compound top layer to layer is free coated with anti-boron carbide particles
Surface covering C；
High density piles up rigid layer A and is located at the compound upper layer to layer, and flexible layer B is located at the compound lower layer to layer,
The compound number of plies to layer is 5 layers；The high density pile up rigid layer A by 50 μm boron carbide particles with
Phenolic resin uniformly mixes composition；The flexible layer B and surface covering C is made of phenolic resin；Inorganic powder is described
Filling total mass fraction in anti-stab resin sheet is 30.4%；The compound thickness that rigid layer A Yu flexible layer B are piled up to layer middle-high density
Degree is than being 1.25.
Compound fabric made of the anti-stab resin sheet of the layer-by-layer composite step of paving boron carbide particles, entirety in multilayer fabric
Gram Mass is 2.88kg/m2, specific process parameter is detailed in table listed.The puncture probability of the compound fabric is zero.If folding
It is counted as current 3.33kg/m2Fabric, it is 29.9J that resistance to thorn, which cuts energy, relative to current conventional Gram Mass (3.33kg/
m2) for, it can be with loss of weight about 13.5%, it is seen that the anti-stab mechanism of this stepped collision barrier passivation can achieve good anti-
Thorn cuts effect.
Embodiment 3
Present embodiments provide a kind of anti-stab resin sheet of layer-by-layer composite step of synthetic diamond particles, including 10 layers by highly dense
It is compound to layer that degree piles up rigid layer A and flexible layer B is combined, and the compound top layer to layer is coated with anti-diamond
The free surface covering C of particle；
High density piles up rigid layer A and is located at the compound upper layer to layer, and flexible layer B is located at the compound lower layer to layer,
The compound number of plies to layer is 10 layers；The high density piles up rigid layer A by 100 μm of diamond
Particle uniformly mixes composition with polyetherimide resin；The flexible layer B and surface covering C are by polyetherimide resin structure
At；Filling total mass fraction of the inorganic powder in the anti-stab resin sheet is 20.5%；It is compound that layer middle-high density is piled up
The thickness ratio of rigid layer A and flexible layer B is 1.
The compound fabric made of the anti-stab resin sheet of the layer-by-layer composite step of paving synthetic diamond particles in multilayer fabric,
Whole Gram Mass is 2.81kg/m2, specific process parameter is detailed in table listed.The puncture probability of the compound fabric is zero.
If being converted to current 3.33kg/m2Fabric, it is 33.7J that resistance to thorn, which cuts energy, relative to current conventional Gram Mass
(3.33kg/m2) for, it can be with loss of weight about 15.6%, it is seen that this stepped collision barrier is passivated anti-stab mechanism and makes fabric
Anti-stab performance be obviously improved, and can accomplish lighting and softness.
Embodiment 4
Present embodiments provide a kind of anti-stab resin sheet of layer-by-layer composite step of cubic boron nitride particle, including 8 layers by highly dense
It is compound to layer that degree piles up rigid layer A and flexible layer B is combined, and the compound top layer to layer is coated with anti-cubic boron nitride
The free surface covering C of particle；
High density piles up rigid layer A and is located at the compound upper layer to layer, and flexible layer B is located at the compound lower layer to layer,
The compound number of plies to layer is 8 layers；The high density piles up rigid layer A by 30 μm of cubic boron nitride
Grain uniformly mixes composition with phenolic resin；The flexible layer B and surface covering C are made of phenolic resin rouge；Inorganic powder exists
Filling total mass fraction in the anti-stab resin sheet is 15.1%；It is compound that rigid layer A and flexibility are piled up to layer middle-high density
The thickness ratio of layer B is 0.75.
The compound fabric made of the anti-stab resin sheet of the layer-by-layer composite step of paving cubic boron nitride particle in multilayer fabric,
Whole Gram Mass is 2.78kg/m2, specific process parameter is detailed in table listed.The puncture probability of the compound fabric is zero.
If being converted to current 3.33kg/m2Fabric, it is 30.1J that resistance to thorn, which cuts energy, relative to current conventional Gram Mass
(3.33kg/m2) for, it can be with loss of weight about 16.5%, it is seen that this stepped collision barrier is passivated anti-stab mechanism and makes fabric
Anti-stab performance be obviously improved, and can accomplish lighting and softness.
The process recipe and condition and result of implementation of 1 compound resin piece of table
Note: wherein the weight-loss ratio δ is existing level Gram Mass GsWith actual measurement fabric Gram Mass G0Difference
With existing level Gram Mass GsRatio
δ=(GS-G0)/GS* 100% (1)
Wherein the puncture Probability p is the percentage of the frequency n of the puncture in 10 tests
P=n/10*100% (2)
The puncture energy refers to the ENERGY E that anti-stab compound fabric minimum pierces through0。
Claims (7)
1. a kind of anti-stab resin sheet of layer-by-layer composite step of micro-meter scale inorganic powder, which is characterized in that including multilayer by high density
It piles up rigid layer (A) and that flexible layer (B) is combined is compound to layer, and the compound top layer to layer is coated with anti-inorganic powder
Free surface covering (C), anti-stab resin sheet overall thickness are not more than 2.0mm；
The high density piles up rigid layer (A) and is located at the compound upper layer to layer, and flexible layer (B) is located at the compound lower layer to layer；
It is described it is compound to layer with a thickness of 20 μm~0.5mm, the number of plies is 2~10 layers；The high density piles up rigid layer (A) by 1
The uniform mixing of the inorganic powder and thermosetting resin of~100 μm of micro-meter scales is constituted；The flexible layer (B) and surface covering
(C) it is made of thermosetting resin；The size of the inorganic powder average grain diameter is that high density piles up rigid layer (A) thickness
1/8~1/2, for average grain diameter at 1~100 μm, mesh number is 50~5000 mesh；Filling of the inorganic powder in anti-stab resin sheet is total
Mass fraction is 15~45%；Surface covering (C) is with a thickness of 1~100 μm.
2. the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder as described in claim 1, which is characterized in that described
Inorganic powder include one of diamond, silicon carbide, boron carbide or boron nitride or a variety of mixing.
3. the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder as described in claim 1, which is characterized in that described
Thermosetting resin be one of epoxy resin, phenolic resin or polyetherimide resin.
4. the preparation side of the anti-stab resin sheet of the described in any item layer-by-layer composite steps of micro-meter scale inorganic powder of claims 1 to 3
Method, which comprises the following steps:
Step 1: thermosetting resin being uniformly coated in template slot box, is heated；And inorganic powder is heated simultaneously
3~5 DEG C on to thermosetting resin heat treatment temperature；
Step 2: the uniform shakedown of heating inorganic powder in step 1 is dispersed on the thermosetting resin liquid after heating, infiltration 2~
10min；Then it is pressurizeed with pressure plate, the powder floated on thermosetting resin liquid is slowly pressed into thermosetting resin liquid, to add
Pressing plate is non-sticky to be touched subject to liquid level；It forms the compound close high density in layer and piles up rigid layer (A) and flexible layer (B), keep 1~
5min；And terminate infiltration；
Step 3: keep pressurization Board position constant, 10~105min, make it is compound to layer crosslinking curing, formed one layer it is compound to layer；
Step 4: step 1~3 processes are repeated, until compound to number of plies n needed for obtaining；Then, thermosetting resin is coated to most
Upper layer and form surface covering (C)；
Step 5: crosslinking curing and tempering setting processing being done to surface covering (C), anti-stab resin sheet is made.
5. the preparation method of the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder as claimed in claim 4, special
Sign is that it is the temperature that thermosetting resin generates obvious Cross-linked that heating, which comes out temperature, in the step 1.
6. the preparation method of the anti-stab resin sheet of the layer-by-layer composite step of micro-meter scale inorganic powder as claimed in claim 4, special
Sign is that the template slot box in the step 1 is hexagon, square or circular flat die board slot made of polytetrafluoroethylene (PTFE)
Box.
7. the claims 1 to 3 anti-stab resin sheet of described in any item layer-by-layer composite steps of micro-meter scale inorganic powder is anti-probably anti-
Cruelly, the application in the individual protection dressing basic material of fire-fighting, blast protection, earthquake search and rescue and defense military.
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| CN114234721A (en) * | 2021-12-29 | 2022-03-25 | 咸宁海威复合材料制品有限公司 | Fireproof, heat-insulating and flame-retardant ultrahigh molecular weight polyethylene bulletproof plate and manufacturing method thereof |
| CN115928455A (en) * | 2023-02-15 | 2023-04-07 | 河北安泰富源安全设备制造有限公司 | Anti-puncture layer construction process and anti-puncture clothes |
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