CN103906870B

CN103906870B - Low BFS composite and preparation method thereof

Info

Publication number: CN103906870B
Application number: CN201280054009.XA
Authority: CN
Inventors: H.G.阿迪夫; J.A.杨; R.克莱因; T.Y-T.谭
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2011-09-06
Filing date: 2012-08-31
Publication date: 2016-11-30
Anticipated expiration: 2032-08-31

Abstract

Manufacture the method for forming the soft composite with hard armor.More specifically, have the ballistic performance of improvement, including the manufacture method of the ballistic fiber composite of low backing cup depth.The method utilizes Fiber strength to improve applied material on the fiber surface fixing, it is thus achieved that low layer is from being inclined to and corresponding benefit.

Description

Low BFS composite and preparation method thereof

To Cross-Reference to Related Applications

This application claims co-pending U.S. Provisional Application sequence number No. 61/531,255 of JIUYUE in 2011 submission on the 6th Rights and interests, the full text is incorporated herein by reference for the disclosure of which.

Background of invention.

Invention field

The present invention relates to the manufacture method for forming the soft composite with hard armor.More specifically, this Invention relates to the ballistic properties with improvement, including the ballistic fiber of low backing cup depth (backface signature) The manufacture method of composite.

Description of Related Art

The ballistic-resistant article being made up of the composite comprising high strength synthetic fibre is known.Permitted eurypalynous high intensity Fiber is known, and all types of fiber has specific characteristic and the character of oneself.Thus, a definitional spy of fiber Levying is fiber and surface coating, such as cold coating bonding or the ability of adhesion.Such as, superhigh molecular weight polyethylene fibers is the most lazy Property, and aramid fibre has the high energy surface containing polar functional group.Correspondingly, resin is generally fine to aromatic polyamides Dimension table reveals the affinity that comparison inertia UHMW PE fiber is strong.But, the most commonly known conatus of synthetic fibers amasss in electrostatic Therefore coalescence usually requires that and applies the composite that fiber surface finishing agent is beneficial to be further processed into can use.Fibre trimmer For reducing electrostatic accumulation, in the case of non-twist or non-entangled fiber, help to maintain fiber cohesion.Finishing agent also lubricates Fiber surface, protects the fibers from damage of facilities and protection equipment from fiber destruction.Teach that for various industry Permitted eurypalynous fiber surface finishing agent.See for example United States Patent (USP) 5,275,625,5,443,896,5,478,648,5, 520,705,5,674,615,6,365,065,6,426,142,6,712,988,6,770,231,6,908,579 and 7,021, 349, they teach the spin finish composition for being spun into fiber.

But, typical fiber surface finishing agent is not the most desirable.It is whole that one major reason is because fiber surface Reason agent can disturb polymeric adhesive material at fiber surface, including the interfacial adhesion on aramid fibre surface or bonding. Polymeric adhesive material be bonded in by force ballistic fabric, especially non-woven composite, such as Honeywell The system of the non-woven SPECTRA SHIELD composite that International Inc. of Morristown, NJ produce It is important in making.Polymeric adhesive material bonding deficiency on the fiber surface may reduce fibre-fibre bonds intensity and Fiber-bond agent bonding strength also thus makes the fiber of combination disconnected from each other and/or makes binding agent leafing from fiber surface.? Attempt also identifying similar adhesion problem when being applied on woven fabric by protectiveness polymeric compositions.This deleteriously affects this type of The ballistic properties (ballistic performance) of composite also causes catastrophic product failure.

The ballistic performance of composite armor can characterize in a different manner.One common attribute is V₅₀Speed, it is Experiment draws, the impact velocity of statistical computation, expects that projectile 50% completely penetrates through plate armour and at this in this time at such speeds In time, 50% is stopped completely by plate armour.For the composite that surface density (i.e. the weight of composite plate is divided by surface area) is equal, V₅₀ The highest, the penetration-resistant of this composite is the best.But, even if bulletproof armour be enough to prevent projectile from penetrating, but projectile is in plate armour On impact will also result in the blunt wound of significant non-penetrative (" wound ").Correspondingly, another important measuring of ballistic performance is dress First backing cup depth.Backing cup depth (" BFS ") is also referred to as backing deformation (backface in the art Deformation) or trauma signature, the flak jackets deforming depth caused by bullet impact is weighed.When bullet is answered When condensation material plate armour is blocked, the blunt wound being likely to result in likely when bullet penetrates plate armour and enters health be to cause individuality Life.This especially occurs in helmet plate armour field, and the instantaneous protrusion wherein caused by the bullet blocked still passes through wearer's cranium The plane of bone also causes the brain injury making people weak or fatal.

The V of composite₅₀The intensity of the known component fibre with this composite of ballistic performance is directly related.Fibre strength Character, as known in the raising of toughness and/or stretch modulus and V₅₀The raising of speed is associated.But, not yet it is similarly recognized that Improve with fiber strength properties and correspondingly improve backing cup depth and reduce.Therefore, manufacture is needed to have in the art excellent Different V₅₀The method of the ballistic composite of ballistic performance and low backing cup depth.The present invention provides for this demand and solves Scheme.

It has been surprisingly found that at the component fibre of the backing cup depth caused by ballistic impact Yu ballistic composite Mutually leafing and/or with there is directly related property between the tendency of fiber surface coating leafing.By improving fiber surface with fine Bonding between dimension table coating materials, reduces Fiber-Fiber and separates and/or fiber-coating leafing effect, thus improves on fiber Friction and improve being engaged of projectile and fiber.Correspondingly, improve composite structure character and become to reduce composite backing The mode of shape dissipates ballistic impact energy.

The present invention is by or becoming woven fabric by fiber weaving before fiber combinations is become fibrous nonwoven layer or fabric From fiber, at least partly remove fiber surface finishing agent before, thus make with after-applied material, such as polymeric adhesive material Directly bond with fiber surface so that this material is main and fiber surface directly contacts rather than main on this finishing agent top, Solve these needs in this area.At least partly removing of fiber surface finishing agent can process such as etc. with kinds of surface Gas ions processes or sided corona treatment combines the ability being adsorbed onto, be adhered to or being adhered to fiber surface to further enhance material. Finishing agent remove and optional surface process alleviate due to ballistic impact ballistic composite component fibre leafing each other and/or From the trend of fiber surface coating leafing, hence improve the backing cup depth performance of composite.

Summary of the invention

The invention provides method, the method includes:

A) the many polymer fibers with the surface at least partly covered by fiber surface finishing agent are provided；

B) at least some of described fiber surface finishing agent is removed from fiber surface；

C) optionally under conditions of effectively strengthening with after-applied adsorbate adsorptivity on the fiber surface, fibre is processed Dimension table face；

D) optionally adsorbate is applied at least part of fiber at least some of on；Then

E) optionally woven or non woven fibre composite is manufactured by plurality of fibers.

Present invention also offers the product manufactured by method, the method includes:

Present invention also offers and form the fibrous composite comprising the fiber with the coating being directly bonded to its surface Method, the method includes providing the many polymer fibers with at least partly surface without fiber surface finishing agent, and/or Many are provided to have the polymer fiber at least partly covering the surface with fiber surface finishing agent；At least one is removed from fiber surface The fiber surface finishing agent of any existence of part；Optional treatment fiber surface is to strengthen with after-applied material fiber surface Bonding and/or adhesion；Apply material at least some of described fiber, thus described material is directly bonded and/or viscous Fiber surface；Optionally manufactured many by described fiber before, during and/or after by described material applying to described fiber Individual woven fibrous layers and/non woven fibre synusia；Optionally consolidate the plurality of woven fibrous layers and/or non woven fibre synusia with Manufacture fibrous composite.

Detailed Description Of The Invention

By modified and/or process fiber surface with the friction improved between adjacent fiber and/or improve fiber surface and Bonding between fiber surface coating (such as, resin or the coating of polymeric adhesive material), it is thus achieved that present when ballistic impact Low Fiber-Fiber separates and/or the fibrous composite of low fiber-coating leafing.This fiber surface coating can extensively change, but Except fiber surface finishing agent, such as outside spin finish (it is typically used as processing aid).Improve fiber surface and fiber table Bonding between finishing coat also improves the bonding adjoining between fibrous layer, thus alleviates the leafing adjoining between fibrous layer.? Find that the Fiber-Fiber increased engages and/or fiber-coating leafing of reduction obtains the desirable of composite backing cup depth Reduce.According to above-mentioned definition, adjoin fibrous layer and can include adjoining one-way tape and/or adjoining woven fabric.Adjoin one-way tape generally with Conventional cross stacking 0/90 orientation arranges to maximize anti-ammunition penetrance (such as, by standardization V₅₀Test determines), to the greatest extent Manage this orientation not to be compulsory orientation and necessarily optimize for minimizing the backing deformation of composite.Retouch in further detail below That states use polymeric adhesive material consolidation adjoins one-way tape.Different from supatex fabric, woven fabric need not polymeric binder Material is to interconnect component fibre to form single fiber layer.However, it may generally be desirable to binding agent or polymeric adhesive material will be will be many Individual woven fibrous layers consolidates or is merged into multi-layer fiber composite.

Backing cup depth weighs soft or hard armor due to ballistic impact in back lining materials or to user body The degree of depth of internal deformation.More specifically, BFS, be also referred to as in the art " backing deformation ", " trauma signature " or " blunt force injury (blunt force trauma) " weighs the projectile when plate armour stop projectile penetrates and leaves many Shaochongs below plate armour Hit, show the blunt wound that the health below plate armour can suffer from.Term " backing cup depth ", " backing deformation ", " trauma Signature " or " blunt force injury " there is the identical meaning in the art and use can be exchanged in this article.NIJ Standard 0101.04, Type IIIA outlines the standard method of the BFS measuring soft armor, and it determines by non-penetrating The composite physical deformation that property ballistic impact causes transfers to the deformable being contained in open surface (open face) box class fixture Method in clay back lining materials, is wherein affixed directly to the front of clay backing by tested plate armour.Use NIJ as usual at present Criterion evaluation is for the soft armor composite of military use.

For the purpose of the present invention, the goods of the anti-ammunition penetrance with excellence describe the anti-deformable bullet showing excellence (such as bullet) and anti-crushing (such as shrapnel) penetrates character." fibrous layer " used herein can comprise unidirectionally oriented fiber Single-layer sheet, multiple synusia, multiple consolidation synusia of unidirectionally oriented fiber, woven fabric, multiple of not consolidating of unidirectionally oriented fiber The woven fabric of consolidation or by many fibroplastic other fabric constructions any, including felt, pad and other structure, as random in comprised Those of orientation fiber." layer " describes general plane and arranges.Each fibrous layer has outer end face and outer bottom.Unidirectionally oriented fiber " single-layer sheet " comprises the layout of the non-overlapped fiber with the arrangement of unidirectional substantially parallel array.Such fiber is arranged in ability Territory is also referred to as " single tape (unitape) ", " one-way tape ", " UD " or " UDT "." array " used herein describes fiber or yarn The ordered arrangement of line, this is that woven fabric is exclusive, and " parallel array " describes the most arranged in parallel of fiber or yarn.Just " orientation Fiber " used by term " be orientated " and refer to and the fiber contrary fiber alignment of stretching.Term " fabric " " describe can include one or The structure of multiple fiber synusia, these synusia pass through or without molding or consolidation.Such as, woven fabric or felt can comprise single fibre Dimension synusia.The supatex fabric formed by unidirectional fibre generally comprises multiple fiber synusia that are the most superimposed and that consolidate.Institute herein " monolayer " structure any overall fibre structure of referring to be made up of one or more independent synusia or independent stratum, it is with poly- Close adhesive material to be merged into together, be i.e. consolidated into single overall structure by low pressure lamination or by high-pressure moudling." consolidate " Refer to that polymeric adhesive material is combined into single integral layer together with each fiber synusia.Can by being dried, cool down, heat, pressure Or combinations thereof realizes consolidation.Heat and/or pressure are not likely to be necessary, because fiber or tissue layer can only be adhesive in one Rise, as in the case of wet laminate process.Term " composite " refers to the group of fiber and at least one polymeric adhesive material Close." complex composite material " used herein refers to multiple fibrolaminar consolidated combination." non-woven " as herein described fabric bag Include all fabric constructions not formed by weaving.Such as, supatex fabric can comprise multiple one-way tape, they at least partially by Polymeric adhesive material is coated with, and stacking/overlapping is also consolidated into monolayer integral member and comprising and is preferably combined by polymeric binder The felt being non-parallel, randomly oriented fiber of thing coating or pad.

For the purpose of the present invention, " fiber " is the slender bodies that length is much larger than the lateral dimension of width and thickness.For this The cross section of bright fiber can vary, and their cross section can be circular, flat or oblong.Therefore term is " fine Dimension " include that there is rule or the irregular monofilament of cross section, band, bar etc., but this fiber preferably has substantially round cross section.This Term " yarn " used by literary composition refers to the Dan Shu being made up of many fibers.Ultimate fibre can be formed by only one threads or by many Long filament is formed.The fiber formed by only one threads is herein referred to as " monofilament " fiber (" monofilament " Fiber), plurality of threads the fiber formed is herein referred to as " multifilament " fiber.

Bottom line is pre-existing in by least partly removing from fiber before fiber process is become fabric Fiber surface finishing agent realizes Fiber-Fiber during ballistic impact and separates and/or the attenuating of fiber-coating leafing, is wherein formed and knits Thing includes making fiber interconnect to be consequently formed woven layer, non-woven fabric layer or non woven fibre synusia.Non-woven being formed Fiber surface finishing agent is removed the most not for people institute before tissue layer or non woven fibre synusia or before woven fabric is weaved Know because fiber surface finishing agent generally described above be considered as necessary processing aid.Such as, in the system of supatex fabric In making, it usually needs fiber surface finishing agent, to reduce electrostatic accumulation, prevents fibre matting, lubricant fiber is with can be at loom Slide on parts and improve in the course of processing, including the fiber cohesion during fiber drawing steps.Fiber-Fiber separates And/or the attenuating of fiber-coating leafing produces and has bigger interlayer lap shear strength, bigger for high speed non-penetrating projectile Flexural strength performance and the composite of the most excellent backing cup depth performance.

Although typically requiring fiber surface finishing agent in conventional fiber process, but they are generally helpless to finally knit Physical property matter.On the contrary, by covering fiber surface, the finishing agent interference ability that contacts with each other of fiber surface also disturbs fiber surface straight Connect and adsorb with after-applied adsorbate, as applied to the liquid or solid resin on fiber or the energy of polymeric adhesive material Power, so that adsorbate is positioned on finishing agent rather than is located immediately on fiber surface.This is debatable.In former case, Finishing agent serves as the lubricant on fiber surface and thus reduces the friction between adjacent fiber.In latter case, finishing agent Hinder and directly and be bound firmly on fiber surface with after-applied material, may totally block adhesion of coatings to fiber and In ammunition impact process, there is risk of delamination.For reinforcing fiber-fibre frictoin and permission resin or polymeric adhesive material Be directly bonded on fiber surface, thus improve fiber-adhesion of coatings intensity, it is necessary to from constitute fibrous composite some or At least partly remove on the whole or a part of fiber surface of all components fiber, the most substantially completely remove the fiber table of existence Face finishing agent.

At least partly removing of fiber surface finishing agent is preferably opened in time completing in all fibres drawing/stretching step Begin.Washing fiber or otherwise remove the step of fibre trimmer and remove enough fibre trimmer to expose at least one Beneath portions fiber surface, although should expect that different removing conditions removes different amounts of finishing agent.Such as, the group of detergent Become mechanical attributes (the such as power of water contact fiber of (such as water), washing technology；The agitation etc. of washing bath) etc factor meeting The amount of the finishing agent that impact removes.For this paper purpose, for realizing the minimum of the bottom line removing of fibre trimmer Degree processing generally exposes the fiber surface area of at least 10%.Preferably remove fiber surface finishing agent so that fiber is mainly without fibre Dimension surface finishing agent.The fiber of " mainly not containing " used herein fiber surface finishing agent is to have removed at least the 50 of its finishing agent Weight %, more preferably removes the fiber of at least about 75 weight % of its finishing agent.This fiber is more preferably substantially free of fiber surface Finishing agent.The fiber " being substantially free of " fibre trimmer is at least about 90 weight % having removed its finishing agent, the most removes Remove the fiber of at least about 95 weight % of its finishing agent, thus expose the quilt before of at least about 90% or at least about 95% The fiber surface area that fiber surface finishing agent covers.Most preferably, any residual finishing agent is to account for fibre weight+finishing agent weight Amount less than or equal to about 0.5 weight %, preferably less than or equal to approximately 0.4 weight %, more preferably less than or equal to about 0.3 Weight %, more preferably less than or equal to about 0.2 weight %, most preferably accounts for being less than or equal to of fibre weight+finishing agent weight The amount of about 0.1 weight % exists.

According to the surface tension of fibre trimmer compositions, finishing agent may show inclining from distribution on the fiber surface To, even if removing the finishing agent of significant quantity.Therefore, the main fiber without fiber surface finishing agent may still some surface Amass and covered by the very thin coating of fibre trimmer.But, this residual fibers finishing agent is usually used as the residual speckle of finishing agent And non-continuous coating exists.Correspondingly, the fiber having the main surface without fiber surface finishing agent preferably has at least portion Dividing the surface come out and do not covered by fibre trimmer, the fiber surface area of the most preferably smaller than 50% is by fiber surface Finishing agent covers.The fibrous composite of the present invention comprising the main fiber surface without fibre trimmer is viscous with polymerization subsequently Mixture material is coated with.If the removing of fibre trimmer causes the fiber surface area less than 50% to be covered by fiber surface finishing agent, Polymeric adhesive material thus directly will contact with the fiber surface area more than 50%.

Most preferably, from fiber, substantially completely remove fiber surface finishing agent and substantially completely expose fiber surface. In this respect, substantially completely removing fiber surface finishing agent is to remove at least about 95%, more preferably at least about 97.5%, optimum The fiber surface finishing agent of at least about 99.0% is removed in blanking, and thus fiber surface at least about 95% exposes, the most greatly About 97.5% exposes, and the most about 99.0% exposes.It is desirable that remove the fiber surface finishing agent of 100%, thus expose Go out the fiber surface area of 100%.Removing after fiber surface finishing agent, further preferably by polymeric adhesive material, resin or other Adsorbate removes the finishing agent granule of any removing from fiber before being applied on the fiber surface of exposure.

Owing to the fiber process of the bottom line removing for realizing fibre trimmer generally exposes at least about 10% Fiber surface area, not yet similar washing or process expose few with the suitable composite removing at least some of fibre trimmer Fiber surface area in 10% has 0% surface and exposes or substantially do not have fiber surface to expose.

As it has been described above, the removing reinforcing fiber-fibre frictoin of fiber surface finishing agent and fiber with after-applied painting Bonding strength between material.Improve Fiber-Fiber friction and raising fiber-adhesion of coatings intensity has been observed that raising projectile is with fine The occlusion of dimension, thus improves the ability being stopped projectile by described fibroplastic fibrous composite, reduces and is made by ballistic impact The backing cup depth become, and improve other performance of this composite, such as composite flexural property and component fibre Interlaminar shear strength between Ceng.Improve fiber-adhesion of coatings intensity also reduce fiber is fully bonded together required The amount of binding agent.This reduction of amount of binder allows to comprise more substantial fiber in fabric, and this may produce has improvement The lighter bullet resistant material of intensity.This anti prick function improved further also resulting in gained Fabric composites and composite The multiple impact of anti-reflective of raising.

Can be used in the background of the present invention for removing any conventionally known method of fiber surface finishing agent, including Mechanically and chemically technological means.Necessary method generally depends on the composition of finishing agent.Such as, in the side of being preferable to carry out of the present invention In case, with the finishing agent coated fiber only just can washed off with water.Generally, fibre trimmer comprise one or more lubricants, one Kind or multiple nonionic emulsifier (surfactant), one or more antistatic additive, one or more moistenings and coalescent and The combination of one or more Antimicrobe compounds.Finishing agent formula preferred herein can only wash with water.Can also be with Chemical reagent is used together machinery means to improve the efficiency of chemical removal.For example, it is possible to by control water apply process power, Direction, speed etc. improve the efficiency using deionized water to remove finishing agent.

Most preferably, wash with water with fibrous web and/or rinse fiber, deionized water is preferably used, after washing Optionally drying fiber, does not use other chemicals any.In this finishing agent other embodiments water-fast, Ke Yiyong Such as abrasive cleaner, chemical cleaner or enzyme cleaning agent remove or wash finishing agent off.Such as, the U.S. being incorporated herein by this reference is special Profit 5,573,850 and 5,601,775 teach make yarn through containing nonionic surfactant (Hostapur CX, commercially available From Clariant Corporation of Charlotte, N.C.), tertiary sodium phosphate and the bath of sodium hydroxide, then rinse fibre Dimension.Other available chemical agent not exclusively includes alcohol, such as methanol, ethanol and 2-propanol；Aliphatic series and aromatic hydrocarbon, such as hexamethylene and Toluene；Chlorinated solvent, such as dichloromethane and chloroform.Washing fiber also removes other surface contaminant any, to realize fibre More close contact between dimension and resin or other coating.

It is not intended to be restricted with the optimal way of water cleaning fiber, arranges as long as fiber surface can be removed from fiber substantially Agent.In a preferred method, by including making fleece through pressurization water spout to wash (or flushing) and/or physics on fiber The method removing finishing agent realizes the removing of finishing agent.Optionally make fiber before described pressurization water spout by fiber in advance Soak in a water bath, and/or make fiber soak after described pressurization water spout, and also optionally in any described optional leaching By making fiber be rinsed through additional pressurization water spout after bubble step.Washing/immersion/flushed fiber preferably exists It is dried after wash/soak/having rinsed.Equipment and mode for washing fiber are not intended to be restricted, and simply it must be able to wash Wash single multifilament fiber/multifilament yarn and non-woven, i.e. will their weavings or before being formed as fibrous nonwoven layer or synusia.

Before formation of fabrics, remove fiber surface finishing agent be particularly intended in this article produce by consolidating multiple comprising The supatex fabric that the fiber synusia of many unidirectional array fibers is formed.For forming non-woven unidirectional array fiber synusia In typical method, guide from bobbin cradle delivery of fibers bundle and via deflector roll and one or more spreader bar (spreader bars) In collimation comb (collimating comb), then use polymeric adhesive material coated fiber.Or, fiber can run into Before spreader bar coating or they can two groups of spreader bars (one group coating section before, one group coating section after) between be coated with Cloth.Typical fibre bundle (such as yarn) has about 30 to about 2000 mono filaments, and each fiber generally includes, but do not limits In, about 120 to about 240 mono filaments.Spreader bar and collimation comb disperse and spread out bunched fiber, make them in a coplanar fashion Recombinate side by side.Preferably fiber sprawl so that ultimate fibre or even mono filament in ultimate fibre face arranged next to each other, to be formed The substantially unidirectional parallel array of fiber, minimal amount of fiber overlaps each other.Fibre is removed before or during step this sprawling Dimension surface finishing agent can strengthen due to the Physical interaction of cleaning agent (such as water) that interacts with fibers/filaments and add Speed this parallel array of fiber lay down generated.After fiber is sprawled and collimated, the fiber of this parallel array is thick generally according to fiber Degree is containing about 3 to 12 fibre end/inches (1.2 to 4.7 ends/centimetre).Correspondingly, the removing of fiber surface finishing agent realizes The dual benefits with after-applied material/adsorbate bonding strength on the fiber surface is sprawled and improved to reinforcing fiber.

Although the removing of fiber surface finishing agent itself realizes above-mentioned benefit, but by after at least part of finishing agent removes Carry out bonding enhancement process on the fiber surface and can realize bigger result.In particular, it was found that the fall of backing cup depth Low and Fiber-Fiber friction and fiber-adhesion of coatings intensity raising is directly proportional.By bonding enhancement process before formation of fabrics Method processes or modified fibre surface has been observed that and realizes the bigger improvement that composite backing cup depth reduces, particularly when viscous Close enhancement process with washing fiber with when at least partly removing fibre trimmer combines.By adsorbate, such as polymeric adhesive (such as it is conventionally used to manufacture supatex fabric or in Woven fabric and at least portion when agent material or resin are applied on fiber surface Divide and remove the after-applied polymeric adhesive material of fiber surface finishing agent or resin), this is the most obvious.Adsorbate is (the most poly- Compound/resin) the strongest with the bonding of fiber surface, the reduction of backing cup depth is the biggest.Correspondingly, in the present invention most preferably In embodiment, after at least partly removing of fiber surface finishing agent, but before fabric forming, it is therefore highly desirable that effectively Strengthen and carry out with under conditions of the adsorptivity/bonding on the fiber surface of after-applied adsorbate (such as polymer/resin) The process of fiber surface.The removing of fibre trimmer can make these additional process directly act on fiber surface rather than act on fibre Tie up surface finishing agent or act on surface contaminant.This is the most desirable, because surface finishing agent tends to interfere with process fiber surface Trial, serve as barrier or pollutant.The removing of finishing agent the most also improves the quality of Fiber strength subsequently with equal Even property.Finishing agent removing and these benefits processed further are accumulative, and the improvement of backing cup depth performance is with arrangement The agent removing raising of percentage ratio and the raising for the treatment of effeciency and improve.

To this end, available process or modification include effectively strengthening with the absorption on the fiber surface of after-applied adsorbate Property any process or modification, wherein adsorbate can be any solid, liquid or gas, including polymeric adhesive material and Resin, and wherein absorption includes that this material is adhered on fiber surface in any form.Various ways is had to can be used for realizing this Point, including making the process of rough surface, adds polarity, oxidized fibre surface or fiber surface part, improves fiber to surface Surface can, drop low-fiber contact angle, improve the wettability of fiber, change the crosslink density of fiber surface, to fiber table The phase interaction between chemical functional group, ablated surface or improvement body fiber (bulk fiber) and fiber surface coating is added in face In order to improve coating anchoring any alternate manner on the fiber surface.The phase of this modification it is readily seen in the improvement of BFS Interaction.

Suitably Fiber strength or surface modification includes method as known in the art, as sided corona treatment fiber, etc. Gas ions process fiber, plasma coated fiber, be directly fluorinated with element fluorine fiber surface, chemical treatment as chemistry UV connect Branch, or rough surfaceization process, as chromium etches.Removing fiber surface finishing agent after but strengthened before fabric forming and inhaled Addendum absorption or any material is adhered to expose and ability on the fiber surface that processed be not yet developed for extensive The process of purposes is the most suitable.These illustrative methods each can be used for according to fiber (by they effects on the fiber surface) Chemical modification, improve or reduce body fiber and with the interaction between after-applied coating.These methods can be used Any combination and these subprocess can be arranged in different order, although according to various factors, such as fiber type or natural fibre Dimension table surface properties, some order are better than other order.The various process steps of the present invention can be used as controlling fiber so that this is multiple Condensation material is at performance such as interlayer lap shear strength, flexural strength (such as yield stress), dynamic modulus, backing cup depth Deng required in the range of means.Cut less than intended interlayer overlap joint if lap shear measurements determination particular composite has Shearing stress (such as less than 170 lbf), or less than intended yield stress (such as, less than 7.50 ksi (~ 51.71 MPa)) This show to carry out further fiber wash and/or further surface process (such as sided corona treatment, Cement Composite Treated by Plasma etc.) with Improve described performance further to fall within a desired range.

Most preferably process is sided corona treatment and the Cement Composite Treated by Plasma of fiber surface of fiber surface.Sided corona treatment is to make Fiber, through corona discharge station, thus makes fleece be inclined to through the method for a series of high-voltage discharges, described high-voltage discharge In acting on the surface of fleece in every way, including spot corrosion, it is roughened and passes through partial oxidation fiber surface and introduce polarity Functional group.Sided corona treatment usual oxidized fibre surface and/or to fiber surface add polarity.Sided corona treatment is also by fiber table Face burns pitting or hole plays a role.When fiber is oxidable, degree of oxidation depends on the power of sided corona treatment, voltage and frequency The factor of rate etc.The time of staying in corona discharge field is also a factor, and this can be designed by corona treatment or logical Cross the wire velocity control of the method.Suitably sided corona treatment unit can such as available from Enercon Industries Corp., Menomonee Falls, Wis., available from Sherman Treaters Ltd, Thame, Oxon., UK or available from Softal Corona & Plasma GmbH & Co of Hamburg, Germany。

In a preferred embodiment, fiber is imposed about 2 Watts/ft²/ MIN to about 100 Watts/ft²/ MIN, more preferably from about 20 Watts/ft²/ MIN to about 50 Watts/ft²The sided corona treatment of/MIN.About 1 Watts/ ft²/ MIN to about 5 Watts/ft²The more low-energy sided corona treatment of/MIN also can be used, less effective.Except executing to fiber surface Adding outside electric charge, sided corona treatment can make this rough surface by spot corrosion (pitting) fiber surface.

In Cement Composite Treated by Plasma, usually the fiber of fibrous web is through over-filling inertia or non-inert gas, such as oxygen Gas, argon, helium, ammonia or the most suitable inertia or non-inert gas, including the ionization gas in the room of the combination of above-mentioned gas Atmosphere, thus makes fiber contact with electric discharge.At fiber surface, charged particle (ion) impact surfaces causes momentum transfer and electronics to be handed over Change.Additionally, the collision between surface with free radical causes similar chemical rearrangement.Excited atom and the dividing to lower state that relax The ultraviolet bombardment fiber surface that son is launched also causes the chemical change of fibrous substrate.

Owing to these interact, Cement Composite Treated by Plasma can change the chemical constitution of fiber and the shape of fiber surface Looks.Such as, being similar to sided corona treatment, Cement Composite Treated by Plasma can also add polarity and/or oxidized fibre surface to fiber surface Part.Cement Composite Treated by Plasma can also be used for improving the surface energy of fiber, reduces contact angle, changes the crosslink density of fiber surface, Improve fusing point and the anchoring quality of coating subsequently, it is possible to add chemical functional group and possible ablation fiber table to fiber surface Face.These effects are similarly dependent on fibre chemistry, also depend on the type of plasma used.

It is important that required surface is processed by the selection of gas, because using different plasma gass differently change table The chemical constitution in face.This is determined by those skilled in the art.It is known that it is, for example possible to use ammonia plasma treatment is by amine official's energy Group introduces fiber surface, it is possible to use oxygen plasma to introduce carboxyl and hydroxyl.Correspondingly, atmosphere reactive can comprise argon One or many other gas of gas, helium, oxygen, nitrogen, ammonia and/or the known Cement Composite Treated by Plasma be applicable to fabric Kind.This reactant gas can comprise one or more in these gases of atom, ion, molecule or radical form.Such as, In the preferred continuation method of the present invention, make fiber array through preferably comprising ar atmo, oxygen molecule, argon ion, oxonium ion, oxygen The controlled reaction atmosphere of free radical and other trace species.In a preferred embodiment, this atmosphere reactive comprises Concentration is of about 90% to about 95% argon and the argon of about 5% to about 10% oxygen and oxygen, and the argon/oxygen concentration of 90/10 or 95/5 is Preferably.In another preferred embodiment of the present, this reactant gas comprises concentration and is of about 90% to about 95% helium and about 5% To helium and the oxygen of about 10% oxygen, the helium/oxygen concentration of 90/10 or 95/5 is preferred.Another available atmosphere reactive is zero gas Bromhidrosis atmosphere (zero gas atmosphere), i.e. comprises the Interior Space of about 79% nitrogen, about 20% oxygen and other gas on a small quantity Gas, it can also be used for sided corona treatment to a certain extent.

Cement Composite Treated by Plasma can in a vacuum chamber or be carried out in keeping room in atmospheric conditions.Cement Composite Treated by Plasma Difference with sided corona treatment essentially consists in, and Cement Composite Treated by Plasma is carried out in controlled reactant gas atmosphere, and at corona In reason, atmosphere reactive is air.Atmosphere in plasma processor is easily controlled and keeps, thus with than sided corona treatment more Controlled and flexibly mode realize surface polarity.Electric discharge is by RF energy, its gaseous dissociation is become electronics, ion, Free radical and metastable product.The electronics produced in plasma and free radical collision fiber surface, to destroy on fiber surface Covalent bond also produces free radical.In batch process, after predetermined reaction time or temperature, Cutting process gas and RF energy also remove Remove residual gas and other by-product.In this article in preferred continuity method, make fiber array through comprising selected reactive gas The controlled reaction atmosphere of the atom of body, molecule, ion and/or free radical and other trace species.It is continuously generated and supplements Atmosphere reactive, after some time it is possible to reach stable state form, and do not cut off or quencher until stop coating machine.

Cement Composite Treated by Plasma can use any available commercially available plasma processor, as available from Softal Corona & Plasma GmbH & Co of Hamburg, Germany；4^th State, Inc of Belmont California；Plasmatreat US LP of Elgin Illinois；Enercon Surface Treating Systems of Milwaukee, the plasma processor of Wisconsin is carried out.Preferably plasma processing method is about Atmospheric pressure, i.e. 1 atm(760 mm Hg (760 torr)) under carry out with the room temperature of about room temperature (70-72).Deng from Temperature in seed cell is likely to be due to processing procedure and changes, but temperature generally dependently cools down in processing procedure or heats, And it is considered not affect fiber treatment, because they are quickly through plasma processor.Plasma electrode and fleece it Between temperature be typically about 100 DEG C.Plasma processing method is preferably at about 0.5 kW to about 3.5 kW, more preferably from about Carry out under the RF power of 1.0 kW to about 3.05 kW, be most preferably with set in the atmospheric plasma processes machine of 2.0 kW Carry out Cement Composite Treated by Plasma.This power is distributed on the width (or length of electrode) in Cement Composite Treated by Plasma district, this power Also with the rate distribution that is inversely proportional to through the linear velocity of the atmosphere reactive of plasma processor with fleece at substrate or fibre In the length of dimension net.This energy (watt/square foot per minute or W/SQFT/MIN) of per unit area time per unit or Flux of energy is the mode that can be used for comparison process level.The virtual value of flux of energy preferably about 0.5 is to about 200 Watts/SQFT/MIN, more preferably from about 1 to about 100 Watts/SQFT/MIN, the most about 1 to about 80 Watts/SQFT/MIN, most preferably from about 2 to about 40 Watts/SQFT/MIN.Total gas flow rate is of about 16 liters/min, But this is not intended to constitute strict restriction.The plasma treatment time (or time of staying) of fiber is of about 2 seconds, although this is with used The size of plasma processor is relevant and is not intended to constitute strict restriction.More appropriate tolerance is with in time through being applied to The Cement Composite Treated by Plasma amount of the RF energy meter on per unit area fiber.

Plasma coating refers to the surface of activated fiber net and makes the fleece of activation through containing vinyl monomer, second Thiazolinyl oligomer or the atmosphere of some other reactive species.Plasma coating can add very specificity to fiber surface Chemical functional group and different polymerization property can be added to fiber surface.In direct fluorination treatment, by with element fluorine Directly fluorination fiber and modified fibre surface.For example, it is possible to by making fiber surface and 10% F at 25 DEG C₂/ 90% He's is mixed Compound contact is fluorinated fiber surface with deposition of elements fluorine on said surface.Element fluorine present on fiber surface serve as with The functional group of after-applied adhesion of coatings.Referring also to such as United States Patent (USP) 3,988,491 and 4,020,223, it is quoted through this It is expressly incorporated herein, which teach and use the mixture of element fluorine, elemental oxygen and carrier gas to be directly fluorinated fiber.UV grafting is also this area Method known in.In the optional UV Graft Method on ballistic fiber surface, fiber (or fabric) is immersed in monomer, photosensitizer and With with at least part of coated fiber/fabric face of monomer and photosensitizer in the solution of solvent.The fiber of coating is then such as this area Such ultraviolet radiation known in irradiates.Those skilled in the art change and easily determine monomer type, photosensitive on demand Agent type and the specific selection of type of solvent.Such as, such as entitled " Studies on surface modification of UHMWPE fibers via UV initiated grafting " article, Jieliang Wang et al., the Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi’an, Shaanxi 710072, PR China. Applied Surface Science, volume 253, Issue on November 15th, 2,2006, the 668-673 page (the disclosure of which is with the most compatible Degree on be incorporated herein by this reference) in discussed, via acrylamide graft monomer, acrylamide group can be grafted to On UHMWPE polymer chain.

It addition, the fiber of the present invention can process by these optional treatment methods a kind of or more than one.Such as, fiber can With by chromium etching roughening and Cement Composite Treated by Plasma, or sided corona treatment and plasma coating, or Cement Composite Treated by Plasma and etc. Gas ions is coated with.It addition, the composite of the present invention and fabric can comprise some fibers processed and some untreated fibres Dimension.Such as, composite herein can by the fiber of the fiber of some sided corona treatment He some Cement Composite Treated by Plasma, or one Fiber and some unfluorinated fibers of a little fluorinations are made.

These process after each leisure at least partly removes fiber surface finishing agent but are applying any binding agent/substrate tree Carry out before fat or other surface adsorbate/coating.Most preferably just with polymeric adhesive material or resin-coated arrangement Fleece pre-treatment expose fiber surface because fiber manufacture process is caused lowest interference and makes fiber the most in short-term by it Between keep state that is modified and that be not protected.It is preferably to unwind from fiber spool (the fiber package of winding) at fiber and incite somebody to action Fiber alignment removes fiber surface finishing agent immediately and processes the fiber surface exposed after becoming fleece, immediately followed by with polymerization Thing/cold coating is coated or impregnated with fiber.This also makes that the holding of fiber shortest time processed and uncoated state, it should examine Consider storage life or the rate of decay of the surface modification of fiber.But, this is mainly due to causing minimum to whole manufacture process Interference and preferable, be not lap shear strength or the BFS performance realizing this composite improvement necessary to.

Fibrous composite according to method described herein manufacture has been observed that the backing cup depth showing excellence Performance.When component fibre is polyethylene fibre (natural other fiber that is better than of its bulletproof ability, but have and relatively low be coated with polymer The native affinity of material) time, this is the most obvious.Use before manufacturing the polyvinyl fabric formed by it, locates as above Any combined treatment polyethylene fibre surface of reason achieves and is relatively better than other fiber type any and (includes that aromatic polyamides is fine Dimension) structural property, anti-ammunition penetrance and the combination of backing cup depth resistance.

In this respect, the fibrous composite of the present invention by with about 427 m/s to about 445 m/s(1430 foot/ Second (fps) ± 30 fps) 124 grains (grain) the 9 mm FMJ RN ballistic impact of speed injection time have less than about The preferred backing cup depth that the composite with 2.0 psf surface densities is recorded of 8 mm.This is not to say that the present invention's All fibres composite or goods all have the surface density of 2.0 psf, are not all fibres composite of the present invention Or goods all have the BFS of 8 mm to the described FMJ RN projectile under described speed.This only determines the method according to the invention The composite made is characterised by, when being manufactured into 2.0 psf plate, this 2.0 psf plate is to described under described speed FMJ RN projectile has the BFS less than about 8 mm.Should also be understood that the deformation of term BFS, backing, trauma Signature and blunt force injury are not to measure the recessed degree of depth of composite caused by ballistic impact, but measure by ballistic impact The recessed degree of depth in back lining materials or in user health caused.This in particular concerns hard plate armour, particularly helmet dress The research of first, because generally testing helmet BFS, wherein by by the helmet by being placed on metal head model by the prototype helmet The helmet is fixed on head model by the suspension separating inch (1.27 centimetres) with head model.The district of this head model Block is by clay filled, and measures the recessed degree of depth in these clay regions as BFS, does not the most include this inch pitch The degree of depth.This is in order to the actual BFS stood when laboratory BFS test being used at the scene with soldier is associated, wherein due to head The internal bedding and padding of helmet or suspension/setting tool (retention harness.), the typical helmet comprises typical and head 1/2 inch of offset distance.On the other hand, the BFS of soft armor is placed directly within surface of clay away from ground continuously conventionally by by this plate armour On test, this with its actual field use in position consistency.Correspondingly, BFS depth measurements and examination used Proved recipe method is correlated with, when relatively BFS depth measurements, it is necessary to confirm that test method used is that sample is placed directly within the back of the body by requirement On lining material or the most spaced apart with back lining materials.In this respect, the BFS of the fibrous composite of the present invention tests 2.0 Measure in the case of there is 1/2 inch of space between psf sample and clay back lining materials.In the preferred embodiments of the invention In, the fibrous composite of the present invention under the conditions of the projectile launch of NIJ Standard 0101.04 by with about 427 m/s Have during to 124 grain 9 mm FMJ ballistic impact of the speed injection of about 445 m/s and be less than the preferred of about 7 mm Backing cup depth, more preferably less than about 6 mm, more preferably less than about 5 mm, more preferably less than about 4 mm, more preferably Less than about 3 mm, more preferably less than about 2 mm, most preferably penetrated with the speed of about 427 m/s to about 445 m/s Tool during 124 grain 9 mm FMJ RN projectile (not including base, comprise about 90% bronze medal and the bullet of the 10% zinc) impact gone out There is the backing cup depth less than about 1 mm.For 124 lattice penetrated with the speed of about 427 m/s to about 445 m/s It is common in this area for making 9 mm FMJ RN projectile test b FS.

Realizing each self-contained multiple fibrous layers that adjoin of described fibrous composite of these BFS values, each fibrous layer comprises tool Have the fiber on the surface at least partly covered by polymeric material, wherein said fiber mainly without fiber surface finishing agent so that institute State polymeric material mainly directly to contact with fiber surface, and there are and have at least about 170 lbf, more preferably at least about 185 lbf, more preferably at least about 200 lbf, more preferably at least about 225 lbf, more preferably at least about 250 lbf, more The preferably at least about interlayer lap shear between 275 lbf and the fibrous layer at room temperature of most preferably from about 300 lbfs Intensity.Realize the described fibrous composite of these BFS values and this type of interlayer lap shear strength character further preferably show to Few about 1750 feet per seconds (fps) (533.40 m/s), more preferably at least about 1800 fps(548.64 m/s), more excellent Choosing at least about 1850 fps(563.88 m/s), the most about 1900 fps(579.12 m/s) broken to 17 grains The V of sheet imitating shell (FSP)₅₀.All above-mentioned V₅₀Value is both for having about 1.0 lbs/ft²(psf) (4.88 kg/m² (ksm) armour plate of composite surface density).All above-mentioned BFS values are both for having 2.0 lbs/ft²(psf) (7.96 kg/m²(ksm) armour plate of composite surface density).As BFS, this is not to say that all fibres of the present invention is combined Material or goods all have certain surface density, and all fibres composite or the goods that are not the present invention all have the biggest The V to 17 grain FSP of about 1750 feet per seconds₅₀.This only determines that the feature of composite that the method according to the invention makes exists In, when being manufactured into 1.0 psf plate, this 1.0 psf plate has the V to 17 grain FSP of at least about 1750 feet per seconds₅₀。

The fibrous layer formed herein and composite are preferably by preventing that high intensity high stretch modulus polymer fiber is formed Elastic composite material.This fiber most preferably comprises and can be used for forming bullet resistant material and the high intensity high tensile modulus fibers of goods.This " high intensity high tensile modulus fibers " used by literary composition is the preferred toughness, at least about with at least about 7 g denier or bigger The preferred tensile modulus of 150 g denier or bigger, the fiber preferably causing disconnected energy of at least about 8 J/g or bigger, each via ASTM D2256 measures.Term used herein " denier " refers to equal to every 9000 meters of fibers or the line of the quality (in gram) of yarn Property density unit.Term used herein " toughness " refers to represent with power (gram)/unit linear density (denier) of unstressed sample Tensile stress." initial modulus " of fiber is the material character representing its anti-deformation behavior.Term " stretch modulus " refer to gram- The ratio of the toughness change that power/denier (g/d) represents and the strain variation represented with the mark (in/in) of original fiber length.

The polymer forming fiber is preferably adapted to manufacture the high intensity high stretch modulus fibre of ballistic composite/fabric Dimension.The specially suitable high intensity high tensile modulus fibers material being particularly useful for the formation ballistic composite and goods includes gathering Olefin(e) fibre, including high density and Low Density Polyethylene.Particularly preferably extended chain polyolefine fiber, such as highly oriented high score Sub-weight polyethylene fiber, particularly superhigh molecular weight polyethylene fibers and polypropylene fibre, particularly ultrahigh molecular weight polypropylene Fiber.Aramid fibre is also suitable, particularly to aramid fibre, Fypro, poly terephthalic acid second two Alcohol ester fiber, polyethylene naphthalate fiber, extended chain vinal, extended chain polyacrylonitrile fibre, polyphenyl azoles Fiber, such as polybenzoxazole (PBO) and polybenzothiozole (PBT) fiber, Liquid crystal copolyester fibers and other rigid rodlike fiber, Such as M5 fiber.These fiber types are individually in this area conventionally known.The copolymer of above-mentioned material, block polymer and Blend is also applied for manufacturing polymer fiber.

The most preferred fiber type of ballistic fabric includes polyethylene, particularly extended chain polyethylene fibre, aromatics polyamides Amine fiber, polybenzazole fiber, Liquid crystal copolyester fibers, polypropylene fibre, the most highly oriented extended chain polypropylene fibre, poly- Alcohol fibers, polyacrylonitrile fibre and other rigid rodlike fiber, particularly M5 fiber.Most preferably fiber is the most fragrant Polyamide fiber.

In the case of polyethylene, preferred fiber be molecular weight be at least 500,000, preferably at least 1,000,000, more preferably The extended chain polyethylene of 2 million to 5 million.Such extended chain polyethylene (ECPE) fiber can be as being incorporated herein by this reference United States Patent (USP) 4,137,394 or 4, grow in solution spinning described in 356,138, or can be as being also incorporated by through this By solvent spinning to form gel structure described in United States Patent (USP) 4,551,296 and 5,006,390 herein.For the present invention's Particularly preferred fiber type is the polyethylene sold with trade mark SPECTRA by Honeywell International Inc Fiber.SPECTRA fiber is as known in the art and is described in such as United States Patent (USP) 4,623,547 and 4,748,064. In addition to polyethylene, additionally available polyolefine fiber type is polypropylene (fiber or band), as being purchased from Milliken & The TEGRIS fiber of Company of Spartanburg, South Carolina.

Aromatic polyamides (aromatic polyamide) or the most particularly preferred to aramid fibre.These are commercially available And be described in such as United States Patent (USP) 3,671,542.Such as, DuPont with trade mark KEVLAR commodity production can poly-(right Phenylene terepthalamide).DuPont with poly-(mpd-i) fiber of trade mark NOMEX commodity production and Teijin is with the fiber of trade mark TWARON commodity production；Kolon Industries, Inc. of Korea is with trade mark The aramid fibre of HERACRON commodity production；Kamensk Volokno JSC of RussiaBusiness Produce to aramid fibre SVM and RUSAR and JSC Chim Volokno of Russia commodity production Aramid fibre be can also be used for implementing the present invention by ARMOS.

The polybenzazole fiber being applicable to implement the present invention is commercially available and be disclosed in such as United States Patent (USP) 5,286,833,5, 296,185,5,356,584,5,534,205 and 6, in 040,050, each it is incorporated herein by this reference.It is applicable to implement this Bright Liquid crystal copolyester fibers is commercially available and is disclosed in such as United States Patent (USP) 3,975,487；4,118,372 and 4, in 161,470, Each it is incorporated herein by this reference.Suitably polypropylene fibre includes the United States Patent (USP) 4,413 as being incorporated herein by this reference, Highly oriented extended chain polypropylene (ECPP) fiber described in 110.Such as in the United States Patent (USP) 4 being incorporated herein by this reference, Suitable polyvinyl alcohol (PV-OH) fiber is described in 440,711 and 4,599,267.Such as it is being incorporated herein by this reference United States Patent (USP) 4,535,027 discloses suitable polyacrylonitrile (PAN) fiber.These fiber types are individually conventionally known And it is widely commercially available.

M5 fiber is by pyridobisimidazole-2, and 6-diyl (2,5-dihydroxy-to phenylene) is formed, by Magellan Systems International of Richmond, Virginia manufacture and be described in such as United States Patent (USP) 5,674,969, 5,939,553,5,945,537 and 6, in 040,478, each it is incorporated herein by this reference.The combination of all above-mentioned materials is also closed Suitable, all these the most commercially available.For example, it is possible to by aramid fibre, UHMWPE fiber (such as SPECTRA fiber), The combination of one or more in carbon fiber etc. and glass fibre and the lower material of other performance forms fibrous layer.But, BFS and V₅₀Value can become with fiber type.

This fiber can have an any suitable denier, such as, 50 to about 3000 denier, more preferably from about 200 to 3000 denier, The most about 650 to about 2000 denier, most preferably from about 800 to about 1500 denier.By considering shellproof effect and cost Determine this selection.Manufacture and the weaving cost of more fine fibre are higher, but can produce the shellproof effect of bigger per unit weight.

As it has been described above, high intensity high tensile modulus fibers be have the preferred toughness of about 7 g denier or bigger, about 150 The preferred tensile modulus of g denier or bigger and the fiber preferably causing disconnected energy of about 8 J/g or bigger, each via ASTM D2256 measures.In a preferred embodiment of the invention, the toughness of fiber should be of about 15 g denier or bigger, preferably approximately 20 g denier or bigger, more preferably from about 25 g denier, the most about 30 g denier or bigger, the most about 37 g denier Or bigger, the most about 40 g denier or bigger, the most about 45 g denier or bigger, the most about 50 grams/ Denier or bigger, the most about 55 g denier or bigger, most preferably from about 60 g denier or bigger.Preferably fiber also has greatly About 300 g denier or bigger, more preferably from about 400 g denier or bigger, more preferably from about 500 g denier or bigger, more preferably from about 1,000 g denier or bigger, most preferably from about 1, the preferred tensile modulus of 500 g denier or bigger.Preferably fiber also has greatly About 15 J/g or bigger, more preferably from about 25 J/g or bigger, the preferably cause of more preferably from about 30 J/g or bigger breaks energy, Preferably there is the cause of about 40 J/g or bigger break energy.These comprehensive high strength properties can use known method to obtain.Beautiful State's patent 4,413,110,4,440,711,4,535,027,4,457,985,4,623,547,4,650,710 and 4,748,064 Substantially discuss the formation of preferred high intensity extended chain polyethylene fibre.This type of method, including solution growth or gelatinous fibre Method is as known in the art.Form other preferred fiber type each, including being also ability to the method for aramid fibre In territory conventionally known, and these fibers are commercially available.The fibrous composite of the present invention further preferably comprise have about 1.7 grams/ The fiber of the fiber areal densities of cubic centimetre or lower.

Remove after at least some of fiber surface finishing agent from fiber surface on demand and in office be selected in effectively strengthen with After processing fiber surface under conditions of after-applied adsorbate adsorptivity on the fiber surface, subsequently optionally by adsorbate Be applied at least some fiber at least some of on.Term used herein " adsorbs " (or " adsorptivity ") and is broadly intended to bag Include (solid, liquid, gas or the plasma) physical absorption of any material and chemisorbed on the fiber surface, wherein " physics Absorption " it is defined herein as being material physical adhesion on the fiber surface, " chemisorbed " is defined herein as It is material chemical bond on the fiber surface, wherein on fiber (i.e. adsorbent) surface exposed, chemical reaction occurs.Herein Term used " adsorbs " any possibility being intended to include Material Physics or chemistry being pasted, adhere or be adhered on substrate surface Means, include but not limited to, improve fiber fiber moistening/bonding in the polymer matrix means.This clearly includes appointing What solid, liquid or gas material are adhered or are coated with on the fiber surface, including any monomer, oligomer, polymer or resin And include that any organic material or inorganic material are applied on fiber surface.In this respect, the definition of " adsorbate " is also not intended to It is construed as limiting and clearly includes can be used as all polymer of polymeric adhesive material, resin or polymer matrix material.But, For the purpose of the present invention, the kind of available adsorbate clearly gets rid of the material not having bond property, arranges including fiber surface Agent material, such as spin finish agent material, they are not the adhesive materials with bond property, on the contrary according to the present invention specially from Fiber surface removes.

Term " adsorbate " the most clearly comprises inorganic material, silicon oxide, titanium oxide, aluminium oxide, tantalum oxide, hafnium oxide, Zirconium oxide, titanium aluminate, titanium silicate, hafnium, hafnium silicate, zirconium aluminate, Zirconium orthosilicate., boron nitride or a combination thereof, as jointly held U.S. Patent Application Publication no. 2008/0119098 disclosed in, its content is incorporated by reference into the application.

Although the applying of adsorbate is preferred, it is only optional.The most most preferably use polymeric adhesive Agent material is coated or impregnated with being formed the fiber of the woven or non-woven material of the present invention.This polymeric adhesive material adsorbate, Such as resin, partially or substantially each fiber of coated fiber layer, preferably each each fiber fibrolaminar of basic coating.This polymerization is glued Mixture material is the most often referred to as " polymeric matrices " material, and these terms are used interchangeably herein.These Term is conventionally known in this area and describes the adhesion characteristic intrinsic by it or standing known heat and/or pressure strip The material after part, fiber being bonded together.This " polymeric matrices " or " polymeric binder " material can also provide it for fabric The character that it is desirable, such as wearability and the toleration to hostile environment situation, even if therefore its bond property is inessential (as to machine For fabric), it may also be desirable to this adhesive material coated fiber.

Suitably polymeric adhesive material includes low modulus elastomer material and high-modulus rigid material.Lead to herein Term stretch modulus used by Pian refers to pass through ASTM 2256 for fiber and pass through ASTM for polymeric adhesive material The elastic modelling quantity that D638 records.Low or high-modulus adhesive can comprise multiple polymerization and non-cohesive material.Preferably polymeric adhesive Agent comprises low modulus elastomer material.For the purpose of the present invention, low modulus elastomer material has about 6,000 psi(41.4 Or the lower stretch modulus recorded according to ASTM D638 test program MPa).Low modulus polymers preferably has about 4,000 Psi(27.6 MPa) or lower, more preferably from about 2400 psi(16.5 MPa) or lower, more preferably 1200 psi(8.23 MPa) or lower, most preferably from about 500 psi(3.45 MPa) or lower elastomeric stretch modulus.The vitrification of elastomer turns Temperature (Tg) preferably less than about 0 DEG C, more preferably less than about-40 DEG C, most preferably below about-50 DEG C.This elastomer is also Have at least about 50%, the preferred breaking extension of more preferably at least about 100%, most preferably there is the cause of at least about 300% and break Elongation.

The diversified material with low modulus and preparation can be used as polymeric binder.Representative example includes polybutadiene Alkene, polyisoprene, natural rubber, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, polysulfide are polymerized Thing, polyurethane elastomer, chlorosulfonated polyethylene, polychloroprene, plastized polyvinyl chloride, butadiene acrylonitrile elastomer, poly-(isobutyl Alkene-copolymerization-isoprene), polyacrylate, polyester, polyethers, fluoroelastomer, elastomer silicone, ethylene copolymer, poly- Amide (can be used for some fiber type), acronitrile-butadiene-styrene, Merlon and combinations thereof, and less than fiber Other low modulus polymers of fusing point curable and copolymer.The blend of different elastomeric materials or elastomeric material and Kind or multiple thermoplastic blend it is also preferred that.

The block copolymer of conjugated diene and vi-ny l aromatic monomers is particularly useful.Butadiene and isoprene are preferred Conjugated diene elastomers.Styrene, vinyltoluene and t-butyl styrene are preferred conjugated aromatic monomers.Comprise poly-isoamyl The hydrogenatable generation of block copolymer of diene has the thermoplastic elastomer (TPE) of saturated hydrocarbons elastomer chain segments.This polymer can be A- The simple triblock copolymer of B-A type, (AB)_nThe segmented copolymer of (n=2-10) type or R-(BA)_x(x=3-150) class The radiated structure copolymer of type；Wherein A is from the block of polyvinyl aromatic monomer and B from conjugated diene elastomers Block.These polymer many are also described in circular by Kraton Polymers of Houston, TX commodity production " Kraton Thermoplastic Rubber ", in SC-68-81.Sell with trade mark PRINLIN and be purchased from Henkel Technologies(is positioned at D ü sseldorf, Germany) styrene-isoprene-phenylethene (SIS) block copolymer Resin dispersion also can use.It is raw that particularly preferred low modulus polymeric binder polymer comprises Kraton Polymers business The styrene block copolymer sold with trade mark KRATON produced.Particularly preferred polymeric adhesive material comprises with trade mark Polystyrene-polyisoprene-polystyrene-block copolymer that KRATON sells.

Although low modulus polymeric matrices adhesive material can be used for most forming soft armor, such as bullet-proof vest, but can be used for Forming hard armor goods, the high-modulus rigid material such as the helmet is particularly preferred at this.Preferably high-modulus rigid material is usual There is the initial tensile modulus higher than 6,000 psi.The preferred high-modulus rigid polymer adhesive material available at this includes Polyurethane (ether and ester group), epoxy resin, polyacrylate, phenols/polyvinyl butyral resin (PVB) polymer, vinyl acetate are poly- Compound, styrene-butadiene block copolymer, and the mixture of polymer, such as vinyl acetate and diallyl phthalate, Or phenolic aldehyde and polyvinyl butyral resin.Particularly preferred rigid polymer adhesive material for the present invention is thermosetting polymerization Thing, is preferably soluble in carbon-to-carbon saturated solvent, has recorded at least about such as butanone and when solidification by ASTM D638 1x10⁶Psi(6895 MPa) high stretch modulus.Particularly preferred rigid polymer adhesive material is United States Patent (USP) 6,642, Those described in 159, the disclosure of which is incorporated herein by this reference.This polymeric binder, either low-modulus material is still High modulus material, may also include filler, such as white carbon black or silicon dioxide, can use oil increment, or can be as known in the art Such sulfur, peroxide, metal-oxide or Radiation-curing system sulfuration.

It is most particularly preferable that polar resin or polar polymer, is particularly of about 2 in stretch modulus, 000 psi (13.79 MPa) is to about 8,000 psi(55.16 MPa) flexibility and rigid material in the range of polyurethane.The most poly- Urethane as most preferably but be not necessary to co-solvent aqueous pu dispersions use.This includes aqueous anionic polyurethane Dispersion, waterborne cation polyurethane dispersion and aqueous non-ionic polyurethane dispersion.Particularly preferably aqueous anion Dispersions of polyurethanes；Aqueous aliphatic polyurethane dispersion, most preferably aqueous anionic aliphatic polyurethane dispersion, all These are preferably highly the dispersion of co-solvent.This includes aqueous anionic polyester based polyurethane dispersion；Aqueous aliphatic polyester Based polyurethane dispersion；With aqueous anionic aliphatic polyester based polyurethane dispersion, all these preferably highly co-solvent Dispersion.This also includes aqueous anion polyether polyurethane dispersion；Aqueous aliphatic polyether based polyurethane dispersion；And aqueous Anionic aliphatic polyether based polyurethane dispersion, the dispersion of all these preferably highly co-solvent.It is similar to preferably All corresponding variant (the polyester base of waterborne cation and aqueous nonionic dispersion；Aliphatic polyester base；Polyether-based；Aliphatic series is poly- Ether etc.).Most preferably there is the aliphatic urethane dispersion of the modulus under 100% elongation of about 700 psi or bigger Body, particularly preferred scope is 700 psi to about 3000 psi.More preferably there are about 1000 psi or bigger, then The aliphatic polyurethane dispersion of the modulus under 100% elongation of more preferably from about 1100 psi or bigger.Most preferably have 1000 psi or bigger, the aliphatic polyether base Anionic Polyurethane Dispersion of the modulus of preferably 1100 psi or bigger.

The rigidity of the goods formed by the composite of the present invention, impact and ballistic properties are by the polymeric adhesive of coated fiber The stretch modulus impact of agent polymer.Such as, United States Patent (USP) 4,623,574 disclose by stretch modulus less than about 6,000 Psi(41,300 kPa) the answering of polymer architecture of fibre reinforced composites and use more high-modulus of elastomeric matrices structure Condensation material is compared and all has more excellent ballistic properties with compared with the identical fibre structure of polymeric adhesive material.But, Low stretch modulus polymeric adhesive material polymer also produces the composite of relatively low rigidity.Additionally, in some purposes, particularly In those purposes that composite must play a role with shellproof and structural models, need the excellent combination of bullet-proof and rigidity. Correspondingly, the most suitable type of polymeric binder polymer used is with the class of the goods to be formed by the composite of the present invention Type and become.In order to realize the compromise of both character, suitable polymeric binder can be combined low modulus and high modulus material To form single polymeric binder.

This polymeric adhesive material can simultaneously or sequentially be applied to be arranged as fleece (such as parallel array or felt) To form coating net on many fibers, it is applied on woven fabric form the woven fabric of coating, or arranges as another, thus use Adhesive-dipping fibrous layer.Term used herein " impregnates " and " embedding " and " coating " or be otherwise applied as coating together Justice, during wherein adhesive material is diffused into fibrous layer rather than be simply located in fiber layer surface.This polymeric material can also be executed Be added to not be on the most a series of fibers of a part for fleece, then these fiber weavings are become woven fabric or then according to Method preparation supatex fabric previously described herein.Forming woven and non woven fibre synusia, layer and fabric technology is As known in the art.

Although it is not required that, the fiber constituting woven fiber mat is coated with at least partially by polymeric binder, then carries out with right The similar consolidation step that fibrous nonwoven layer is carried out.This consolidation step can be carried out so that multiple woven fiber mat is harmonious mutually And, or make binding agent merge with the fiber of described woven fabric further.Such as, multiple woven fiber mat not necessarily must consolidate, And other means can be passed through, as engaged by traditional binders or by stitching.

Generally, polymeric binder coating is effectively to merge, and i.e. consolidates necessary to multiple non woven fibre synusia.Can be by Polymeric adhesive material is applied on the whole surface area of each fiber or is applied only to the part surface of fiber and amasss.Most preferably will The coating of polymeric adhesive material is applied to constitute on the most whole fibrolaminar each filamentary surface area of the present invention.If Fibrous layer comprises threads, preferably constitutes each fiber of one-ply yarn with polymeric adhesive material coating.

Any suitable applying method can be used for applying this polymeric adhesive material and term " is coated with " and is not intended to limit it It is applied to the method on long filament/fiber.Use any suitable method that those skilled in the art easily determine by polymeric adhesive Agent material is applied directly on fiber surface, and binding agent is the most as described herein to be diffused in fibrous layer.Such as, this polymerization Adhesive material can by by the solution spraying of this polymeric material, extrude or be rolled onto on fiber surface with solution, breast Shape liquid or dispersion apply, and a portion solution comprises required polymer, and a part of solution comprise can dissolve or Disperse the solvent of this polymer, be then dried.Or, it is possible to use conventionally known technology, as by slot die, or pass through Other technology as known in the art, such as direct intaglio plate, Meyer rod and air knife system, is expressed into fibre by polymeric adhesive material In dimension.Other method is with liquid, sticky solid or the granule of suspension or fluid bed form by the straight polymer of adhesive material It is applied on fiber.Or, can as the solution that can not adversely affect at a temperature of applying in the suitable solvent of fibre property, Emulsion or dispersion apply coating.For example, it is possible to fiber conveying is coated with basic through the solution of polymeric adhesive material Fiber, is then dried.

In another coating technique, fiber can be immersed in containing the polymeric binder being dissolved or dispersed in suitable solvent In the solution bath of material, then by evaporation or the vaporizing and drying of solvent.This method is preferably at least part of with this polymeric material It is coated with each ultimate fibre, is preferably substantially coated with or encapsulates each ultimate fibre with polymeric adhesive material and cover the most whole length Silk/fiber surface area.Impregnating process can be repeated as desired for for several times to be applied on fiber by the desired amount of polymeric material.

Other technology being applied on fiber by coating can be used, including being coated with gel fiber precursor in due course, as By making gelatinous fibre solution through suitable coating polymer under conditions of obtaining required coating.Or, can be by fibre Dimension is expressed in the fluid bed of suitable polymer powder.

Although preferably must exist with after-applied adsorbate in enhancing after at least partly removing fiber surface finishing agent Polymeric binder coated fiber is used on the surface of the adsorptivity on fiber surface after processing, but can fiber alignment is become one or Before or after multiple layers of sheet/layer, or used polymeric binder coated fiber before or after fiber is made into woven fabric.Permissible Techniques well known in the art are used to use any fabric tissue, such as plain weave, the crowfoot (crowfoot) tissue, side Flat tissue, satin weave, twill-weave etc. form woven fabric.Plain weave is most commonly, and wherein fiber is with orthogonal 0 °/90 ° Orientation is woven in together.Before or after weaving, the ultimate fibre of each woven fabric materials can be with or without polymeric binder material Material coating.Before with polymeric binder coated fiber, generally carry out the weaving of fabric, the most thus with this machine of adhesive-dipping Fabric.But, the present invention is not intended to be limited by the stage being applied on fiber by polymeric binder, is not the most used for applying polymerization The means of binding agent limit.

The manufacture method of supatex fabric is as known in the art.In preferred embodiment in this article, by many Fiber alignment becomes at least one array, is typically arranged to comprise the fiber of the plurality of fibers with substantially parallel unilateral array arrangement Net.As it has been described above, in the typical method for forming non-woven unidirectional array fiber synusia, from bobbin cradle delivery of fibers bundle also It is directed in collimation comb via deflector roll and one or more spreader bar, then uses polymeric adhesive material coated fiber.Typically Fibre bundle has about 30 to about 2000 ultimate fibres.Spreader bar and collimation comb dispersion and spread out bunched fiber, make they with Coplanar manner is recombinated side by side.Preferably fiber sprawl so that mono filament or ultimate fibre in ultimate fibre face arranged next to each other, with Form the substantially unidirectional parallel array of fiber, and do not have fiber to overlap each other.Now, this sprawl step before or during Removing fiber surface finishing agent can strengthen sprawls into this parallel array with accelerating fibers.

With after adhesive material coated fiber, become to comprise the fibrous nonwoven layer of multiple overlap by the fibre forming of coating The fibrous nonwoven layer of sheet (they are consolidated into monolayer integral member).In the preferred nonwoven fabric structure of the present invention, formed The overlapping one-way tape of multiple stackings, wherein relative to the longitudinal fiber direction of each single-layer sheet, each single-layer sheet (one-way tape) parallel Fiber and the parallel fiber quadrature arrangement of each adjacent monolayer sheet.The stacked body of overlapping non woven fibre synusia is under heat and pressure Consolidation or the coating by each fiber synusia of stickup consolidate, and to form monolayer integral member, it is the most single in the art Layer consolidated network, wherein " consolidated network " describes consolidation (fusion) combination of fiber synusia and polymeric matrices/binding agent.The present invention Goods also can comprise woven fabric and the hydridization consolidated combination of supatex fabric and by unidirectional fibre synusia formed non-woven Fabric and the combination of non-woven mat fabric.

Most commonly, fibrous nonwoven layer or fabric include 1 to about 6 synusia, but can need bag depending on various uses Include the most about 10 to about 20 synusia.The bigger number of lamina means bigger bullet-proof, but also implies that bigger weight.Phase Ying Di, constitute the fiber number of lamina of the fibrous layer composite of the present invention and/or Fabric composites or goods with this fabric or The final use of goods and become.Such as, in the bullet-proof vest of military use, in order to formed needed for realization 1.0 pounds/flat The goods composite of super superficial or more areal density (4.9 Kilograms Per Square Meter), it may be necessary to the most about 100 synusia (or Layer) to about 50 single-layer sheet (or layer), wherein these layer of sheet/layer can be the machine formed by high strength fibre as herein described Knit, knitting, felt or supatex fabric (there is parallel-oriented fiber or other arrangement).In another embodiment, it is used for holding The bullet-proof vest of method purposes can have synusia/number of plies based on NIJ threat level.Such as, to NIJ Threat Level IIIA For vest, may there be 40 synusia altogether.For relatively low NIJ Threat Level, it is possible to use less layer sheet/layer. With other known to compared with ballistic structure, the present invention can be incorporated to greater amount of fiber synusia to realize required level of ballistic protection, And do not improve fabric weight.

As conventionally known in this area, when each fiber synusia is cross layered so that the fiber alignment side of a synusia Excellent bullet-proof is realized relative to the fiber direction of another synusia in time rotating at a certain angle.Fiber synusia is most preferably With 0 and 90 jiao of orthogonal crossover stacking, but adjacent lamina can be relative to the longitudinal fiber direction of another synusia with about 0 He Substantially any angle arrangement between about 90.Such as, five layers of non-woven structure can have with 0/45/90/45/0 or The synusia of other angular orientation.Such rotated unidirectional alignments is described in such as United States Patent (USP) 4,457,985；4,748,064；4, 916,000；4,403,012；4,623,574；With 4,737,402, all these all not with in the degree conflicted herein through this It is incorporated herein by reference.

Consolidation fibre synusia is known to form the method for fibrous layer and composite, as by United States Patent (USP) 6, and 642, Method described in 159.Can by being dried, cool down, heat, pressure or combinations thereof realize consolidation.Heat and/or pressure may It is dispensable, because fiber or tissue layer can be the most glued together, as in the case of wet laminate process.Generally, pass through Being enough to make these synusia to be merged under the heat of integral fabric and pressure condition, each mutual superposition of fiber synusia is consolidated. Consolidation can be at about 50 DEG C to about 175 DEG C, at a temperature of preferably approximately 105 DEG C to about 175 DEG C and at about 5 psig (0.034 MPa) is to about 2500 psig(17 MPa) pressure under carry out about 0.01 second to about 24 hours, the most greatly The about .02 second was to about 2 hours.When heating, polymeric binder coating can be made tacky or flow and incomplete fusion.But, Generally, if enabling polymeric adhesive material (if it melts) to melt, need relatively small pressure initiation composite, And if only adhesive material is heated to stick point, it usually needs bigger pressure.As conventionally known in this area, can To consolidate in calender group (calender set), flatbed laminator, press or autoclave.Most commonly, binding agent is used Polymer by multiple orthogonal fiber nets " gluing " together and through flatbed laminator with improve bonding uniformity and intensity.This Outward, consolidation and polymer applying/adhesion step can comprise two single steps or single consolidation/layering step.

Or, consolidation can be realized by moulding under heat and pressure in suitable device for molding.Generally, about 50 Psi(344.7 kPa) to about 5,000 psi(34,470 kPa), more preferably from about 100 psi(689.5 kPa) to about 3,000 psi(20,680 kPa), most preferably from about 150 psi(1,034 kPa) to about 1,500 psi(10,340 kPa) Pressure under mould.Or can be at about 5,000 psi(34,470 kPa) to about 15,000 psi(103,410 KPa), more preferably from about 750 psi(5,171 kPa) to about 5,000 psi, more preferably from about 1,000 psi to about 5, Mould under the higher pressure of 000 psi.Molding process can spend about 4 seconds to about 45 minutes.Preferably molding temperature It is of about 200 (~ 93 DEG C) to about 350 (~ 177 DEG C), at a temperature of more preferably at about 200 to about 300, Preferably at a temperature of about 200 to about 280.The fibrous layer of the molding present invention and the pressure of Fabric composites are usual The rigidity of gained mechanograph or flexibility are had and directly affects.Molding generally produces harder material at elevated pressures, until Certain limit.In addition to molding pressure, the amount of fiber synusia, thickness and composition and polymeric binder coating type also directly affect The rigidity of the goods formed by this composite.

Although each molding as herein described is similar with concretion technology, but each method is different.Especially, molding is batch process, Consolidation is substantially continuous method.Additionally, molding be usually directed to use mould, as mould or formed flat board time be matching die (match-die mold), and not necessarily produce planar products.Generally in flatbed laminator, calendering mip rolls group Close in (calendar nip set) or as wet layer and carry out consolidating to manufacture soft (flexible) flak jackets fabric.Molding is generally used Hard armoring in manufacturing, such as rigid plate.In either method, suitable temperature, pressure and time generally depend on polymeric adhesive The type of agent coating, polymeric binder content, method therefor and fiber type.

In order to manufacture the textile article with sufficient ballistic properties, the gross weight of binding agent/aabase paint preferably comprises fiber About 2 weight % of+coating weight to about 50 weight %, more preferably from about 5% to about 30%, more preferably from about 7% to about 20%, most preferably from about 11% to about 16 weight %, 16% is wherein most preferred for supatex fabric.Relatively low adhesive/ Matrix content is suitable for woven fabric, wherein more than 0 but leads to less than the polymeric binder content of 10 weight % of fiber+coating weight The most most preferably.This is not intended to be construed as limiting.Such as, the woven aramid fabrics of phenols/PVB dipping sometimes with about 20% to The more high resin content of about 30% manufactures, although about 12% content is generally preferable.

After fibrolaminar weaving or consolidation, by conventional method, optional thermoplastic polymer layer can be adhered to fibre On one or two outer surface of dimension composite.The polymer being applicable to this thermoplastic polymer layer not exclusively includes thermoplastic Property polymer, its not exclusively selected from polyolefin, polyamide, polyester (particularly polyethylene terephthalate (PET) and PET copolymer), polyurethane, polyvinyl, ethylene-vinyl alcohol copolymer, ethylene octane copolymer, acrylonitrile copolymer, Acrylate copolymer, polyvinyl, Merlon, polystyrene, fluoropolymer etc. and their copolymer and mixed Compound, including ethylene vinyl acetate (EVA) and ethylene acrylic.Natural and synthetic rubber polymer also can be used.Wherein, polyene Hydrocarbon and aramid layer are preferred.Preferably polyolefin is polyethylene.The limiting examples of available polyethylene is low-density Polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), linear density polyethylene (LMDPE), linear very low density polyethylene (VLDPE), linear ultra low density polyethylene (ULDPE), high density polyethylene (HDPE) And their copolymer and mixture (HDPE).It is purchased from Spunfab, Ltd, of Cuyahoga Falls, Ohio's SPUNFAB polyamide web (registered trade mark of Keuchel Associates, Inc.) and be purchased from Protechnic THERMOPLAST and HELIOPLAST net, network and the film of S.A. of Cernay, France also can be used.This thermoplasticity Polymeric layer can use known technology, as hot laminating is adhered on composite material surface.Generally, by making these layers being enough to It is merged into mutual for each layer superimposed layout under the heat of integral membrane and pressure condition to carry out lamination.By mutual for each layer superimposed layout, The most generally make this combination through the roll gap of a pair heating lamination roller by techniques well known in the art.Lamination heating can be About 95 DEG C to about 175 DEG C, at a temperature of preferably approximately 105 DEG C to about 175 DEG C, at about 5 psig(0.034 MPa) To about 100 psig(0.69 MPa) pressure under carry out about 5 seconds to about 36 hours, preferably approximately 30 seconds to about 24 Hour.

Each fabric/composite/fibrolaminar thickness is fibrolaminar be incorporated in fabric corresponding to filamentary thickness Quantity.Preferably woven fabric have about 25 microns to about 600 microns/layer, more preferably from about 50 microns are micro-to about 385 Rice, the most preferably from about 75 microns preferred thickness to about 255 microns/layer.Preferably supatex fabric, the most non-woven monolayer Consolidated network has about 12 microns to about 600 microns, more preferably from about 50 microns to about 385 microns, most preferably from about The preferred thickness of 75 microns to about 255 microns, wherein single-layer, consolidated network generally include two consolidation synusia (i.e. two unidirectional Band).Any thermoplastic polymer layer is the thinnest, has about 1 micron to about 250 microns, and more preferably from about 5 microns extremely About 25 microns, the preferred layer thickness of most preferably from about 5 microns to about 9 microns.Discontinuous network, as SPUNFAB is non-woven Network optimization choosing has the basic weight of 6 grams/m (gsm).Although these thickness are preferred, it is to be understood that, can be manufactured it Its thickness is to meet specific needs, but still falls within the scope of the present invention.

Fabric/the composite of the present invention has about 20 grams/m of (0.004 pound/square English before consolidation/molding Chi (psf)) to about 1000 gsm(0.2 psf) preferred surface density.Fabric/the composite of the present invention is in consolidation/molding Before preferred surface density be of about 30 gsm(0.006 psf) to about 500 gsm(0.1 psf).The fabric of the present invention/ The composite most preferred surface density before consolidation/molding is of about 50 gsm(0.01 psf) to about 250 gsm(0.05 Psf).The goods comprising the multiple fibrolaminar present invention stacking mutually and consolidating have about 1000 gsm(~ 0.2 psf) extremely About 40,000 gsm(8.2 psf), more preferably from about 2000 gsm(~ 0.41 psf) to about 30,000 gsm(6.1 Psf), more preferably from about 3000 gsm(~ 0.61 psf) to about 20,000 gsm(4.1 psf), most preferably from about 3750 Gsm(0.77 psf) to about 15,000 gsm(3.1 psf) preferred composite materials surface density.It is molded into the composite wood of the helmet The typical range of material products is of about 7,500 gsm(1.54 psf) to about 12,500 gsm(2.56 psf).

The fabric of the present invention can be used for multiple use to use known technology to form multiple different ballistic-resistant article, including soft Property soft armor goods and rigid, hard armor articles.Such as, it is adaptable to the technology forming ballistic-resistant article is described in such as beautiful State's patent 4,623,574,4,650,710,4,748,064,5,552,208,5,587,230,6,642,159,6,841,492 and 6,846,758, all these it be not incorporated herein by this reference with in the degree conflicted herein.This composite is the most available In forming hard armor and the molding formed during manufacturing hard armor goods or unformed assembly intermediate." hard Matter " plate armour refers to have sufficient mechanical strength and the most flat collapses to keep structural rigidity when standing significant quantity stress and be able to support oneself Goods, such as the helmet, the plate of military vehicle or protective shield.Such hard product is preferred, but is not necessary to use high stretch modulus Adhesive material is formed.

This structure can be cut into many discrete sheets and stack to form goods, before maybe can they being molded into Body, it is subsequently used for forming of goods.Such technology is as known in the art.A most preferred embodiment party in the present invention In case, it is provided that multiple fibrous layers, multiple fiber synusia of each self-contained consolidation, wherein consolidating the consolidation step of multiple fiber synusia Before Zhou, among or afterwards thermoplastic polymer is adhered on each at least one outer surface fibrolaminar, pass through the most subsequently Another consolidation step of the assembly (sub-assembly) that multiple fibrous layers are consolidated into armor articles or armor articles merges many Individual fibrous layer.

The ballistic properties of the fibrous composite of the present invention can be measured, including anti-bullet according to techniques well known in the art Medicine penetrance and backing cup depth.

The following example is used for illustrating the present invention:.

Embodiment

Assessment fibre trimmer removing and optionally other Fiber strength interlayer lap shear to various composites Intensity, flexural property (such as yield stress) and the impact of backing cup depth performance, specify in table 2 below A and 2B to produce Result.It is carried out as follows fibre processing technologies:

Fibre trimmer removes

Many multifilament fibers unwind from multiple fiber spool (one reel of every multifilament fiber), are then passed through fixing Collimation comb is with fleece fibrous tissue being uniformly spaced.Then fleece was led the preimpregnation containing deionized water soaked Bathing, the substantially time of staying is of about 18 seconds.After leaving pre-soaking water-bath, rushed by 30 water spouts of a row (a bank of) Wash fiber.The hydraulic pressure of each water spout is of about 42 psi, and water flow velocity is each nozzle about 0.5 gallon per minute.Leave nozzle Water is formed as the stream of relative flat, and the angle of incidence of the stream that water contact angle on fiber penetrates relative to adjacent nozzle is 0 or 30 º.Recording water temperature is 28.9 DEG C.It is of about 4 m/min to about through pre-soaking water-bath with through the linear velocity of row's water spout 20 m/min.Water in soaking bath and transport to the water of nozzle by first passing around single deionization system deionization.Washed Fiber is subsequently dried and is sent to be processed further.

The representativeness being only used for illustrating the amount how some washing variable affects the finishing agent removed from fiber summarized by table 1 Embodiment.Each sample is made up of 4 ends (ends) on a sample reel of the bunchy together.Each sample traveling at least 400 English Chi, amounts to 60 grams of fibers of each sample.% residual on fiber represents to be stayed on fiber after the condition washing of regulation according in table The gravimetric analysis measurement result of amount of finishing agent.This gravimetric analysis measurement result exists based in unwashed control fiber The comparison of amount of finishing agent.

Table 1

Sample	Bleed type	Nozzle exit pressure (psi)	Linear velocity (Ft/ min)	Nozzle output (gpm)	% residual on fiber
						I	A1	42	15	0.20	2.3
II	B1	30	15	0.29	2.4
						III	C1	30	15	0.41	3.1
IV	C2	15	15	0.30	3.1
						V	A2	42	15	0.20	4.0
VI	B2	30	15	0.29	4.1
						VII	A3	56	50	0.23	5.0
VIII	C3	15	15	0.30	5.1
						IX	A4	56	30	0.23	5.5
X	C4	30	15	0.41	5.9
						XI	C5	34	30	0.44	5.9
XII	C6	34	60	0.44	6.2

Sided corona treatment

The web that the 18-inch of washed fiber is wide is wide continuously across having 30 inches with the speed of about 15 ft/min The corona treatment of electrode, this corona treatment is set as 2kW power.This causes power to be distributed in fiber area, with watt Special densimeter 2000W/ (2.5Ft x 15-FPM) or 53 Watts/ft²/ min is applied on fiber.Fiber is in corona field The time of staying is of about 2 seconds.Process at normal atmospheric pressure.

Cement Composite Treated by Plasma

The wide web of the 29-inch of washed fiber with the speed of about 12 ft/min continuously across atmosphere plasma (model: Enercon Plasma3 Station Model APT12DF-150/2, from Enercon for datatron Industries Corp., has 29 inches of wide electrodes), this plasma processor is set as 2kW power.This causes power It is distributed in fiber area, 2000W/ in terms of watt density (29 in. x 12-FPM) or 67 Watts/ft²/ min is applied to On fiber.The fiber time of staying in plasma processor is of about 2 seconds.Process at normal atmospheric pressure.

Interlayer lap shear is measured

In all embodiments of the invention illustrated below, carry out lap shear survey at the enterprising row of fibrous nonwoven layer Examination, measures between the 2-synusia or 4-synusia fibrous nonwoven layer of two lamination 1 " interlayer lap shear at lap splice Intensity.Each 2-synusia fibrous nonwoven layer comprises the first fiber synusia with 0 orientation and the second fiber synusia with 90 orientations. Each 4-synusia fibrous nonwoven layer comprises 0/90/0/90 structures, and it is equal to 2-multi-layer sheet structure, but has 4 synusia.Will The fiber of tested composite is embedded in various polymeric binder (polymeric matrices) material.Each composite comprises identical poly-second Alkene fiber type, each comfortable fiber comprises different anion resin adoption ester-based polyurethane coating.Relatively various process are with aobvious Showing the effect of fiber treatment, wherein fiber treatment is unique variable.By the temperature and about at about 270 (132 DEG C) Under the pressure of 500psi, 2-synusia or 4-synusia fibrous layer are laminated together about 10 minutes formation lap splices.According to ASTM The condition of D5868, carries out the lap shear test in each sample under the room temperature (unless otherwise noted) about 70.Use logical Test with Instron 5585 test machine.

The measurement of flexural property

Except as otherwise noted, according to the specification of the three-point bend test method of ASTM standard D790 about 72 standard Test under ambient room temperature.According to this method, by beam shape or rod sample on the supporter at the opposite end of this beam/rod all Even placement, has the open span of distance to a declared goal between described supporter.Such as use and load nose with assigned rate by negative Lotus is loaded into the center of sample, causes sample to bend.Load applies the time specified.According to ASTM D790 method, apply load Until sample reaches flexure or until the specimen broke of 5%.

In the embodiment of the present invention shown in below, fibrous nonwoven layer carries out flexural property test, according to ASTM D790 program A, with the strain rate (crosshead speed set is 0.128 in/min) of 0.01 in/in/min, for having About 6 " length of (15.24 cm), about 0.5 " (12.7 mm) ± about 0.02 " width of (0.508 mm), about 0.31 " (7.874 mm) ± about 0.02 " (0.508 mm), the degree of depth (1.5psf surface density), about 4.8 " (12.192 The sample of span cm) measures yield point displacement, yield strain, Yield Load, yield stress and yield point energy.By greatly At a temperature of about 270 (132 DEG C) and under the pressure of about 500 psi, 40 2-synusia fibrous layers are molded together 10 Minute formed composite.For the object of the invention, apply a load to few until there is at least portion of at least some of composite Be layered from.Use the general purpose I nstron 5585 stretching-machine type test with three-point mount.

V ₅₀ Measure

According to conventionally known standardized technique, in particular according to Department of Defense Test Method The condition of Standard MIL-STD-662F obtains V₅₀Data.

Backing cup depth is measured

The standard method of the BFS measuring soft armor is described by NIJ Standard 0101.04, type-iii A, Wherein armoring sample contacts placement with the surface of deformable clay back lining materials.This NIJ method is generally used for obtaining actual BFS's Rationally budgetary estimate and prediction, it can be in the ammunition thing directly relied on or the plate armour of the closely health of user uses at the scene It is expected during part.But, for and non-immediate dependence or the closely health of user or the plate armour of head, by making dress The spaced surface of first and deformable clay back lining materials comes and obtains more preferably budgetary estimate or the prediction of actual BFS.Therefore, in table 2A really Fixed backing cup depth data are measured not according to the method for NIJ Standard 0101.04, Type IIIA.On the contrary, profit With with NIJ Standard 0101.04, the newly-designed method that the method for Type IIIA is similar, is not by composite system Product are placed directly on flat ball clay, but make by inserting the distance piece of customization processing between composite product and ball clay This composite and ball clay separate inch (12.7 millimeters).The distance piece of customization processing comprises and has border and by described limit The element of the inner chamber that boundary delimit, wherein exposes clay through this inner chamber, and its spacers directly contacts with the front of clay Arrange.Projectile is at target location directive this composite product corresponding with the inner chamber of this distance piece.Projectile with distance piece The position impact composite product that inner chamber is corresponding, and every time ballistic impact cause in clay measurable recessed.In table 2A All BFS measurements simply mean to according to this method recessed degree of depth in clay and the degree of depth that do not considers distance piece, i.e. table BFS in 2A measures the actual range not including between composite and clay.

Leafing is measured

Leafing in table 2A refers to measuring of the actual rear portion deforming depth by test plate (panel), rather than back lining materials recessed deeply Degree.This measurement result of leafing is less than BFS measurement result+1/2 " (12.7 mm) air gap degree of depth, because at ballistic impact After, the fabric portions retraction at shock zone.Leafing is measured and is carried out after described retraction, and carries out with air-gap method as herein described BFS surveying record fabric rear portion deformation integrated degree.Generally by cutting the cross section of plate and measuring not being subject to from plate The plane at the damage back side measures the deformation after described retraction to the deepest outside degree of depth of deformed area.

For each embodiment, measure and there are the surface density of 2.0 pounds per square foots (psf) and 53 grams/m (gsm) The 12 of fiber areal densities (single parallel fiber synusia, the i.e. surface density of an one-way tape) " x 12 " BFS of square sample. For each embodiment, for the 9 mm 124 grain FMJ penetrated with the speed of about 1430 feet per second (fps) ± 30 fps BFS measured by RN projectile

Table 2A

Table 2A show compare by do not wash with untreated fibroplastic fabric with by the fiber standing multiple process The BFS recorded during the fabric formed and the difference of leafing.Each product I-VI comprises identical fiber type but comprises on fiber Different resins (that is, polymeric adhesive material).Next two columns in table 2A specifies BFS+" (12.7 mm) gap subtracts Leafing is gone to determine fabric amount of recovery and show the complete expection for measuring hard armor BFS in actual field uses The more high accuracy of the air gap separation BFS measurement method of degree.

Table 2B

Table 2B shows the anti-ammunition penetrance (V as differentiated by fiber treatment₅₀), interlayer lap shear and flexural strength The difference of character.

Although having been particularly shown and described the present invention with reference to preferred embodiment, but those of ordinary skill in the art being easy Recognize, various changes and modifications can be made without departing from the spirit and scope of the present invention.Claims purport Contain disclosed embodiment, those alternatives having been discussed above and their all equivalents being interpreted.

Claims

1. the method forming fibrous composite, the method includes:

B) removing a part of described fiber surface finishing agent from fiber surface, wherein residual fibers surface finishing agent is retained in fibre On dimension table face, wherein the few fibers surface of every polymer fiber keeps being covered by fiber surface finishing agent and every polymerization fibre The few fibers surface of dimension is exposed and is not covered by fiber surface finishing agent, and the fiber surface area of at least a part of which 50% is by cruelly Reveal and do not covered by fiber surface finishing agent；

C) optionally process under conditions of effectively strengthening with after-applied adsorbate adsorptivity on the fiber surface and to expose Fiber surface；

D) optionally adsorbate is applied at least some fiber surface at least some of on, some of them adsorbate is executed It is added on the fiber surface of exposure and some adsorbates are applied on the fiber surface finishing agent of reservation, thus produce painting The fiber of cloth；Then

E) optionally woven or non woven fibre composite is manufactured by the fiber of many coatings.

2. the process of claim 1 wherein that removing a part of described fiber surface finishing agent from described fiber surface exposes The fiber surface that 50.0%-99.0% had previously been covered by fiber surface finishing agent.

3. the method for claim 2, wherein exposes 75%-97.5% fiber surface area thus not by residual fibers surface dressing Agent covers.

4. the process of claim 1 wherein at least partly removes described by washing described fiber with water from described fiber surface Fiber surface finishing agent.

5. the process of claim 1 wherein and implement described Fiber strength, including Cement Composite Treated by Plasma.

6. the process of claim 1 wherein and implement described Fiber strength, including sided corona treatment.

7. the process of claim 1 wherein and carry out step c)-e).

8. the process of claim 1 wherein and carry out step c), do not carry out step d), and by weaving combination plurality of fibers with shape Become woven fabric composite to carry out step e), and wherein after step e), adsorbate is applied to described woven fabric is combined The fiber surface of material.

9. the method for claim 1, farther includes to be formed as the described woven of step e) or non woven fibre composite Goods.

10. fibre composite products, described product is by including prepared by following method:

B) a part of described fiber surface finishing agent is removed from fiber surface；

C) optionally under conditions of effectively strengthening with after-applied adsorbate adsorptivity on the fiber surface, described fibre is processed Dimension table face；

E) optionally woven or non woven fibre composite is manufactured by plurality of fibers；

Wherein residual fibers surface finishing agent retains on the fiber surface, and wherein the few fibers surface of every polymer fiber keeps Covered by fiber surface finishing agent and the few fibers surface of every polymer fiber is exposed and is not arranged by fiber surface Agent covers, and the fiber surface area of at least a part of which 50% is exposed and is not covered by fiber surface finishing agent.

The product of 11. claim 10, wherein carries out step c)-e).

The product of 12. claim 10, wherein carries out step c), does not carry out step d), and by weaving combination plurality of fibers with Form woven fabric composite and carry out step e), and wherein after step e), adsorbate is applied to woven fabric composite wood The fiber surface of material.

The product of 13. claim 10, wherein said adsorbate comprises resin or polymeric adhesive material, and wherein in step Expose 50%-99.0% fiber surface area after b) thus do not covered by residual fibers surface finishing agent.

14. methods forming the fibrous composite comprising the fiber with the coating being directly bonded to fiber surface, the method Including providing the many polymer fibers with the surface at least partly not containing fiber surface finishing agent, and/or many are provided to have The polymer fiber on the surface at least partly covered by fiber surface finishing agent；At least some of any existence is removed from fiber surface Fiber surface finishing agent；Wherein residual fibers surface finishing agent retains on the fiber surface, the wherein portion of every polymer fiber Divide fiber surface holding to be covered by fiber surface finishing agent and the few fibers surface of every polymer fiber is exposed and does not has Being covered by fiber surface finishing agent, the fiber surface area of at least a part of which 50% is exposed and is not covered by fiber surface finishing agent, Wherein residual fibers surface finishing agent exists as the finishing agent speckle on fiber surface；Optional treatment expose fiber surface with Strengthen with after-applied material the bonding of described fiber surface and/or adhesion；Apply material at least the one of described fiber In part, thus described material directly bonded and/or be adhered on described fiber surface；Optionally manufactured multiple by described fiber Woven fiber mat and/or non woven fibre synusia, wherein described material is applied to before described fiber, among and/or it The described fibrous layer of rear manufacture and/or synusia；And optionally consolidate the plurality of woven fiber mat and/or non woven fibre synusia with Manufacture fibrous composite.

15. fibrous composites manufactured by the method for claim 14.