CN108351190A - Impact resistance composite material - Google Patents

Abstract

The present invention relates to a kind of pre-formed sheet materials for the ballistic performance for having and improving, it is that at least the network of fibers of 1.5GPa, the plastic material include multiphase (methyl) acrylic acid based polymer dispersion it includes the tensile strength impregnated at least 10% plastic material.The polymeric dispersions have the first phase and the second phase, for first phase at least 40 DEG C of lowest glass transition temperature and weight average molecular weight less than 80000g/mol, second phase has 30 DEG C or lower maximum glass transition temperature and the weight average molecular weight more than 100000g/mol.

Description

Impact resistance composite material

The present invention relates to a kind of pre-formed sheet materials, are extremely it includes the tensile strength impregnated at least 10% plastic material The network of fibers of few 1.5GPa.The invention further relates to the assembly of at least two pre-formed sheet materials and include the assembly Flexible ballistic resistant product.

US4623574 describes a kind of improved ballistic composite articles, and it includes the networks of fibers or reality as fabric Parallel unidirectional array fiber and basis material in matter, stretch modulus of the soft-type basis material at 23 DEG C are less than 41.3MPa, and glass transformation temperature is less than 0 DEG C, preferably shorter than -40 DEG C.Disclosed matrix system includesThree is embedding Section polystyrene-polyisoprene-polystyrene copolymer.

WO2004039565A describes a kind of method of manufacture ballistic-resistant article, wherein forms the lamination of multiple single layers, often One single layer includes the reinforcing fiber of one-way orientation and the plastic matrix material of at most 30 weight %, and the reinforcing fiber is height Polyethylene (UHMWPE) fiber of drawing, and the machine direction in each single layer is relative to the machine direction rotation in adjacent monolayer Turn.The plastic matrix material has 100% modulus of 5-500MPa.It has been displayed：Rigidity plastics matrix base claimed Body system under 80 DEG C of higher temperature there is high projectile to prevent performance, and at room temperature, softer matrix system performance is more It is good.

EP0987363A1 describes purposes of the adhesive based on polymer powder in manufacturing ballistic fabric, described poly- Object powder is closed based on crosslinkable unsaturated ethylene and its Tg is higher than 40 DEG C.Multiphase (methyl) is not pointed out in EP0987363A1 The presence of acrylic acid based polymer dispersion.In the embodiment 1 of the publication, with including 98wt% Styrene And Chloroalkyl Acrylates fourths Ester copolymer (it contains 5% acrylic acid, and Tg is 60 DEG C) and 12 layers of aramid fiber of electrostatic powder spraying of 5wt% epoxy crosslinking agents are knitted Object then cures 2 minutes at 170 DEG C, then stacks each layer, and 1 minute is then pressed under conditions of 180 DEG C, 1bar to be formed The plate of 6mm thickness.In contrast experiment 3, the Styrene And Butyl-acrylate copolymer containing 5% acrylic acid and 5wt% epoxies are handed over The water-borne dispersions of connection agent are coated on 30 grams of amount in the same manner as in Example 1 in aramid layers, then stack 12 layers and 180 DEG C, press under conditions of 1bar 1 minute to form the plate that thickness is similarly 6mm thickness.From when 10 meters of distance shootings, embodiment 1 is shown Plate prevent all bullets, and test 3 plate and completely penetrated through by all bullets.Plate is analyzed with scanning electron microscope Show that the aramid fiber in embodiment 1 is irregularly covered, and the fiber in embodiment 3 is completely covered by adhesive material.

Although it is in fact known that composite article show rational ballistic performance, there is still a need for the bullet of enhancing prevent energy Power.

An object of the invention is to provide flexible composite, and increasing is shown relative to the composite material being currently known Strong bullet prevents ability.

By including the plastic matrix material of multiphase (methyl) acrylic acid based polymer dispersion, the target is realized.Institute Stating polymeric dispersions has the first phase (oligomer phase) and the second phase (polymer phase), and first phase is at least 40 DEG C Lowest glass transition temperature and weight average molecular weight less than 80000g/mol, second phase have 30 DEG C or lower highest Glass transition temperature and weight average molecular weight more than 100000g/mol.

Including the acrylic matrix system of oligomer and polymer is well known in the present art, be mainly used as dispersion with Film, paint vehicle, adhesive and coating are provided.When oligomer is more more hydrophilic than polymer, oligomer and polymer tend to form two Phase system, there are huge differences can lead to nucleocapsid structure for the hydrophilic nmature of two-phase, (the The as described in such as Lee and Ishikawa Formation of Inverted Core-Shell Latexes, J.Poly.Sci., volume 21, the 147-154 pages (1983))。

In addition, disclosing the two-phase system suitable for the present invention in WO95/29963, the document is by quoting entirety simultaneously Enter herein.In such applications, the lower-molecular-weight component for being referred to as oligomer or oligomer phase is prepared first, then there are low The second high molecular weight component for being referred to as polymer or polymer phase is prepared under conditions of polymers.Can also by oligomer with polymerize Object is blended, and wherein blending sequence is not critical and can arbitrarily select.

The oligomer is typically sour functional oligomers, and it includes enough bands sour (acid bearing) copolymerization is single Body, such as acrylic acid, methacrylic acid, itaconic acid or β-carboxyethyl acrylate, so that the oligomer generated is complete or partial It is dissolved in water.Based on the precursor comprising acidic group, the amount of acrylic acid oligomer can be 0.1-20 weight %, preferably 0.5-15 weights Measure %, more preferable 1.0-12 weight %；In addition, being based on-OH functional monomers, the amount of acrylic acid oligomer can be 0-30 weights Measure %, preferably 0-20 weight %, more preferable 0-15 weight %, most preferably 0-10 weight %.The weight average molecular weight of oligomer is usual For 500-80000g/mol, preferably 2000-60000, more preferable 5000-50000, most preferably 10000-40000g/mol.Propylene The Tg of acid based oligomerization object is at least 25 DEG C, preferably at least 35 DEG C, more preferably at least 45 DEG C, even more desirably at least 55 DEG C.In general, The Tg of oligomer is more typically in the range of 25-120 DEG C in the range of 30-90 DEG C.

Polymer (typically hydrophobic polymer) includes the uncrosslinked monomer of non-acid function, especially methyl methacrylate Ester, ethyl methacrylate, n-BMA or Tert-butyl Methacrylate.The Weight-average molecular of acrylic polymer Amount is generally at least 4000g/mol, more frequently at least 80000g/mol.The upper limit is typically not greater than 3000000g/mol.It is typical Ground, the range of weight average molecular weight is between 40000g/mol and 3000000g/mol, preferably in 80000g/mol and 2000000g/ Between mol, more preferably between 100000g/mol and 1000000g/mol.The vitrifying of acrylic thermoplastic polymer turns Temperature is less than 30 DEG C, preferably shorter than 15 DEG C, more preferably less than 0 DEG C.In general, ranges of the Tg of polymer at -60 DEG C to 30 DEG C It is interior, it is more typically in the range of -30 DEG C to 10 DEG C.

The glass transition temperature of oligomer lower than the glass transition temperature of polymer at least 30 DEG C, preferably 40 DEG C, more It is preferred that 50 DEG C.

The preparation of two-phase system mentioned above based on acrylic resin is for example described in WO 95/29944A1, more It is preferred that being described in WO95/29963.Two-phase system can be crosslinked.This method is known to technical staff.

In the case where oligomer dispersion and polymeric dispersions are blended, using Tg and Weight-average molecular same as described above Measure range.Oligomer dispersion：The weight ratio of polymeric dispersions is 10:90 to 70:Between 30 (wt/wt), preferably 20:80 To 60:Between 50, most preferably 25:75 to 50:Between 50.

Ability is prevented to be represented as V armoring bullet₅₀, or relative to its weight/thickness, it is represented as energy absorption Eabs.The pre-formed sheet material of the present invention has improved Eabs.The advantages of high Eabs, is：Fragment with given speed is penetrated Bullet can be prevented with the lower layered article of quilt cover quality entity.Face quality representation：Quality/m of product²Surface, also referred to as face Density.Low face quality is extremely important for improving wearing comfort, and the wearing comfort and good protection of raising are that exploitation is anti- Play the main target when new material in clothes.For example, in the case of vehicle or helicopter plate armour, quality reduction is also advantageous that 's.

Including the other advantage of the product of a variety of pre-formed sheet materials according to the present invention is improved printability and anti-stab Property.Anti prick function is believed to keep out (such as utilizing knife) thorn in the art.The product that ballisticimpact and thorn can be kept out is logical It is commonly referred to as blended threat purposes.Meanwhile higher rigidity (stiffness) can lead to the final of rigidity (rigidity) raising Product.This is (special for for example armoring (improved " rigidity (ear-to-ear stiffness) between ear "), pressing insert Not when with ceramic combination) and structural vehicle part for be important.In being applied for soft body and wear When comfort needs additional improvement, pre-formed sheet material of the invention can (multiple) warpage, corrugation or be otherwise subjected to repeatedly Bending is to improve its flexibility.

Network of fibers, which can be fabric, (has such as plain weave, basket weave, satin weave and claw type (crow Feet) the woven of tissue), but it can also be woven network or forms fabric with any one of various routine techniques Network.For example, network of fibers can also be " non-woven ", including felt.

In above-mentioned network of fibers, the amount based on the thermoplastic material of acrylic compounds in pre-formed sheet material is at most 70 weight %, preferably up to 60 weight %, more preferably up to 50 weight %.The network of fibers of pre-formed sheet material includes at least 10%, the preferably at least thermoplastic material based on acrylic compounds of 20 weight %.Typically, the thermoplasticity material based on acrylic compounds Expect that the amount in pre-formed sheet material is 10-60 weight %, preferably 20-50 weight %, more preferable 30-40 weight %.

Network of fibers can include the stacking of two or more layers fabric.In the stacking of two or more tissue layers, It is the minimum angles between two machine directions in the adjacent layer stacked that can have angle beta, wherein β between two adjacent layers. Angle beta is typically between 0 degree and 45 degree.Preferably, the angle beta between two adjacent layers is 0 degree.

Alternatively, network of fibers includes one or more single layers of substantial parallel unidirectional array fiber.

In the context of this application, single layer refer to one layer be embedded in it is substantial in plastics (or plasticity) basis material Parallel reinforcing fiber.Term " basis material " refers to holding the fibers in together and preferably completely or at least partially wrapping Seal the material of fiber.In 95/00318 A1 of such as EP 191306 and WO, this single layer is disclosed (also by art technology Personnel are known as prepreg) and the method that obtains this single layer.Single layer can be obtained by following methods：Such as by from fiber line If axis pass through broach withdrawing dry fibers or yarn, by it is coplanar with it is parallel in a manner of plurality of fibers is taken in one plane To, and before, during or after orientation in a known manner, impregnate the fiber with plastic matrix material.In this side In method, the polymer-coated fiber used in advance different from the plastic matrix material can be used, for example to locate Fiber is protected during reason, or to obtain the adhesion strength on better fiber to the plastics of single layer.Preferably, using without The fiber of coating.Fiber can be handled before being coated with plastic matrix material or being contacted fiber.It is this processing include etc. Gas ions processing or sided corona treatment.

In the pre-formed sheet material with two or more layers, the fiber arranged direction in stacking in two continuous single layers Typically difference angle α.Although can selected angle α in a wide range, angle [alpha] is preferably between 45-135 degree, more preferably Between 65-115 degree, most preferably between 80 and 100 degrees.In preferred scope below, particularly preferred angle [alpha] is about 90 Degree.The pre-formed sheet material generated according to the preferred embodiment is represented as cross-level (cross ply) in the art.

In cross-level, network of fibers occupies the different proportion of sheet material total volume.It is preferable, however, that network of fibers accounts for again At least about 50 volume % of condensation material, more preferably from about 70 volume %, most preferably at least about 75 volume %, matrix optionally occupy surplus Remaining volume.

Term fiber includes not only monofilament, but also includes polyfilament yarn or flat strip.Term " the fibre of one-way orientation Dimension " refers to the fiber of substantial parallel orientation in one plane.The width of flat strip is preferably between 2mm and 100mm, more It is preferred that between 5mm and 60mm, most preferably between 10mm and 40mm.The thickness of flat strip preferably 10 μm and 200 μm it Between, more preferably between 25 μm and 100 μm.Flat strip can be made of a kind of solid memder of material, but can also include The fiber of one-way orientation and optional basis material.

The pre-formed sheet material of the present invention includes network of fibers, and the fiber can include polyolefin, superhigh molecular weight polyethylene Alkene fiber, polypropylene fiber of superhigh molecular weight, aramid fiber, ultra-high molecular weight polyethylene alcohol fiber, from liquid crystal polymer Or mixtures thereof fiber,.The homopolymer and copolymer of suitable polyolefin especially ethylene and propylene can also contain a small amount of One or more of other polymers, especially other alkene -1- polymer.Preferably, network of fibers includes supra polymer Weight polyethylene fiber.

The intensity of the fiber used in the network of the present invention is at least 1.5GPa, preferably at least 2.5GPa.It is highly preferred that this The intensity of the fiber used in the network of invention is at least 3.5GPa, this causes with the rigidity and/or back side mark enhanced Final products and high projectile prevent the even preferably combination of performance.Even further preferably, the fibre used in the network of the present invention The intensity of dimension is at least 4GPa to obtain the product with better blended threat performance, and most preferably, and intensity is at least 4.5GPa。

If selecting linear polyethylene (PE) as polyolefin, good result can be obtained.Linear polyethylene is at this It is understood to mean every 100 C atoms in text having less than 1 side chain and preferably every 300 C atoms are having less than 1 side The polyethylene of chain；Side chain or branch usually contain at most 10 C atoms.Linear polyethylene can further contain at most 5mol% The other alkene of one or more that can be copolymerized with it, such as propylene, butylene, amylene, 4- methylpentenes, octene.Preferably, Linear polyethylene has the inherent viscosity (IV, based on molten in decahydronaphthalenes at 135 DEG C of high molecular weight and at least 4dl/g Liquid measures)；The more preferably at least inherent viscosity of 8dl/g.This polyethylene is also referred to as ultra-high molecular weight polyethylene (UHPE).

It is preferably used in being prepared by gel spinning technique described in such as GB 2042414A or WO 01/73173 High-performance polyethylene (HPPE) fiber being made of polyethylene filament.Gel spinning technique substantially comprises the steps of：System The solution of the standby linear polyethylene with high inherent viscosity, is spun into long filament by the solution at a temperature above the dissolving temperature, The long filament is cooled to less than gelation temperature, to be gelled, and institute is stretched before, during or after removing solvent State long filament.This stretching causes intensity to be at least drawn fibers of 1.5GPa.If these polyethylene fibres by height drawing, Their intensity is at least 3.0GPa.

Band described above can also be manufactured by gel spinning technique, but can also be obtained by solid state process, In solid state process, by polymer powder compacting and drawing is to obtain the band with expectation strength.

Pre-formed sheet material optionally further includes seperation film, the seperation film in the pre-formed sheet material at least one It is on a outer surface and in connection.This seperation film ensure the present invention pre-formed sheet material assembly or in ballistic-resistant article one A or multiple pre-formed sheet materials (optionally with other sheet combinations) maintain separately from each other.This embodiment has following excellent Point：The flexibility or snugness of fit of ballistic-resistant article or assembly are higher.If using viscous matrix material, this seperation film It is particularly preferred.Used seperation film can be for example including polyolefin film, including with trade markAvailable line Property low density polyethylene (LDPE), polypropylene screen, polyester film.The thickness of this film is usually 1-50 microns, preferably 2-25 microns.More preferably 2-10 microns, most preferably 3-6 microns.

Preferably, seperation film is biaxial stretch-formed polyolefin film.The example is biaxial stretch-formed high density polyethylene (HDPE) and twin shaft Stretched polypropylene films.

It is fabric, woven network or in the case of " non-woven " in network of fibers, with the thermoplasticity based on acrylic resin Material impregnates the network and is realized typically with aqueous based dispersions.It is preforming after water evaporating completely or part are evaporated Sheet material can pass through the pressure apparatus of heating, including pressure roll.

The fiber that unidirectional array is impregnated with plastic matrix material can for example be accomplished by the following way：By one layer or more Multilayer plastic film is coated to the top, bottom or both sides of fiber plane, them is then made to pass through the pressure of heating together with fiber Roller.It is preferable, however, that after fiber is orientated in parallel in a plane, a certain amount of modeling containing single layer is coated to it Expect the liquid substance of basis material.The advantages of doing so is can be rapider and preferably to impregnate fiber.The liquid substance can To be solution, dispersion or the melt of such as plastics.If manufacturing single layer using the solution of plastic matrix material or dispersion, Then this method further includes evaporation solvent or dispersant, is preferably then compressed at elevated temperatures.Such temperature and pressure holds It is easily determined by routine experiment, and typically at 70 DEG C between the fusion temperature of fiber, preferably between 75-135 DEG C, and Between 1-100bar, between preferably 5-80bar, between more preferable 10-60bar.

Particularly preferred embodiment is related to the purposes of the water-borne dispersions of thermoplastic matrix materials according to the present invention, In coating to after HPPE fibers, water at least partly, preferably at least 90 weight %, more preferably at least 99 weight % be evaporated, Wherein these fibers have at least intensity of 3.5GPa.

The invention further relates to the assemblies of at least two pre-formed sheet materials according to the present invention.These sheet materials substantially not that This connection.With the increase of pre-formed sheet material quantity, level of ballistic protection is improved, but the weight of assembly increases, and flexibility It reduces.In order to obtain highest flexibility, the adjacent sheet in assembly is not preferably connected to each other.However, in order to realize certain Horizontal continuity, such as can be in the assembly of such as corner through and through suture preform sheet material.Alternatively, can be by preform The assembly of sheet material is put into covering or big envelope.According to ballistic threats and desired level of protection, those skilled in the art The optimum value of sheet material quantity can be found by some experiments.

Another embodiment includes ballistic-resistant article comprising at least one assembly defined above.

The invention further relates to the ballistic-resistant articles for including multiple pre-formed sheet materials according to the present invention.Preferably, ballistic-resistant article Including network of fibers, the network of fibers includes the fabric containing fiber, and the fiber is the polyethylene fibre of height drawing.This Kind embodiment has at least 115J/kg/m to the 9mm*19Natoball DM11 A1B2 bullets that German MEN is manufactured²'s Eabs。

Another preferred embodiment is related to soft ballistic-resistant article, described preforming it includes multiple pre-formed sheet materials Sheet material contains the height drawing polyethylene fibre that intensity is at least unidirectional array of 3.5GPa；It is multiphase (methyl) propylene with form The acrylic resin of acid-based polymer dispersion, contains the first phase and the second phase, first phase have at least 40 DEG C most Lower glass transition temperatures and weight average molecular weight less than 80000g/mol, second phase have 30 DEG C or lower highest glass Glass transition temperature and weight average molecular weight more than 100000g/mol, the 9mm* that the product manufactures German MEN 19Natoball DM11 A1B2 bullets have at least 180J/kg/m²Eabs, and the product also have at most 100mm Deflect down.Preferably, this soft ballistic-resistant article has at least 190J/kg/m²Eabs and also have at most 90mm Deflect down.It is highly preferred that this soft ballistic-resistant article has at least 200J/kg/m²Eabs and also have at most 80mm's deflects down.

The invention further relates to the ballistic-resistant articles for including multiple pre-formed sheet materials, and wherein network of fibers includes fabric, the system Product also include at least two networks of unidirectional array fiber and optional matrix.Preferably, in fabric or unidirectional array fiber It is at least polyethylene fibre of 3.5GPa to obtain good blended threat performance that fiber at least one, which is intensity, and more Preferably, at least 4.0GPa.Ballistic-resistant article can be in the form of repressed product (so-called hard ballistics), or is in flexibility The form of product (so-called soft ballistics).

The basis material used in unidirectional array network of fibers can be that glass transition temperature according to the present invention is extremely Few 25 DEG C of acrylic thermoplastic material.Alternatively, the present invention pre-formed sheet material can with include unidirectional array fiber and base The sheet combination of body.This matrix can include another material different from acrylic based resin.For unidirectional array fiber The suitable alternative basis material of network includes thermoplastic material and thermosets.Preferably, thermoplastic is as base Body material application is particularly suitable to can be used as those of the dispersion application in water matrix.The reality of suitable polymer material Example include：Acrylate, polyurethane, improved polyalkene, including SEBS and SIS polymer, as known in ballistic-resistant article field Those and ethylene vinyl acetate.Preferably, basis material contains polyurethane.It is highly preferred that polyurethane is poly(ether-urethane)；Its Based on polyetherdiol, because this provides good performance within the scope of broad temperature.In a special embodiment, gather Urethane or poly(ether-urethane) are based on aliphatic vulcabond, because this further improves properties of product, including its colour stability. 100% modulus of these plastic matrix materials for unidirectional array fiber is at least 3MPa.Preferably, 100% modulus is extremely Few 5MPa.100% modulus is usually less than 500MPa.

In another preferred embodiment, the suitable alternative basis material for unidirectional array fiber is from water Property dispersion applicationPolymer includes the styrene-isoprene-that 100% modulus is 1.4MPa Styrene (SIS) triblock copolymer compositions.

Detect program

The 9mm*19Natoball DM11 A1B2 bullets manufactured using German MEN, utilize the inspection according to Stanag 2920 Ranging sequence measures ballistic performance V50 and Eabs at 21 DEG C, in this application, is surveyed on the sample that surface density is 5.4km/m2 Amount.It, will be shellproof using flexible-belt (strap) after adjusting shellproof sample adaptation under 21 DEG C and 65% relative humidity at least 18 hours Sample is fixed on the supporter filled with Roma back lining materials, and above support is adapted to by preconditioning at 35 DEG C.By bullet In V₅₀When kinetic energy (0.5*m_Bullet*V₅₀ ²) divided by armoring total areal density to obtain so-called Eabs values.Eabs reflects plate armour Prevention ability relative to its weight/thickness.Eabs values are higher, and ballistic performance is better.

The modulus of basis material is measured according to ISO 527.It is 100mm (drift between clip) and width in length To measure 100% modulus on the film item of 24mm.100% modulus is the secant modulus measured between 0% and 100% strain.

Tensile strength (or intensity) is limited and is measured on polyfilament yarn according to regulation in ASTM D885M, is used The nominal gauge length of the fiber of 500mm, the crosshead speed of 50%/min, measures at 25 DEG C.In the stress-strain measured On the basis of curve, as 0.3 and 1% gradient between strain measure modulus.In order to calculate modulus and intensity, by what is measured Tensile stress divided by fiber number, fiber number by weigh 10 meters fiber measure；It is assumed that density is 0.97g/cm³, calculate in terms of GPa Value.

In embodiment the glass transition temperature of oligomer use by differential scanning calorimetry DSC test it is determining by DEG C in terms of Value, the peak value of differentiation curve is as Tg.

The polymer average molecular weight of acrylic thermoplastic's material is to pass through gel infiltration according to DIN 55672 at 40 DEG C Chromatography determination, wherein using tetrahydrofuran as solvent, styrene/divinylbenzene uses poly- as packaging material Styrene Mp 160-10000000 (standard items of Polymer Standards service (PSS) DIN certifications) are corrected.

The inherent viscosity (IV) of UHMWPE measures at 135 DEG C in decahydronaphthalenes according to ASTM D1601, dissolves Time is 16 hours, uses dosage to be the DBPC of 2g/l solution viscous as antioxidant, and by what is measured under various concentration It is outside one's consideration the viscosity for pushing away to obtain under zero-dose.

Now will by following embodiment and experiment the present invention is furture elucidated, however, the present invention is not limited thereto.

Comparative experiment A

It is 3.5GPa's by intensityUHMWPE fibers generate the non-woven products of form of single sheet.For this purpose, drawing It leadsFiber passes through broach so that its is arranged in parallel, then with the water-borne dispersions of the basis material wetting fibre Dimension.After drying, obtained single layer contains the UHMWPE fibers and 16wt% of 33 grams of parallel (unidirectional) arrangementsThermoplastic Property elastomer (the polystyrene-polyisoprene-polystyrene block copolymer that Tg is about -40 DEG C) be used as basis material.Thermoplastic elastomer (TPE) is a kind of well known matrix for being used for armor application, provides best bullet and prevents ability. Generate pre-formed sheet material in the following manner：4 single layers are stacked, wherein the machine direction in adjacent monolayer is with 90 degree of angle It is orientated, thickness is then stacked on the outside of lamination and is 7.6 microns (it is about 7g/m to be equivalent to surface density²)Then linear low density polyethylene film reinforces lamination at a temperature of the pressure of about 2MPa and about 130 DEG C.

Flat ballistic-resistant article is made of the loose disconnected assembly of several pre-formed sheet materials, and the assembly exists Corner through and through suture.The trajectory of three kinds of different assemblies is detected using type of bullet 9mm*19Natoball DM11 A1B2 Energy；Table 1 gives V₅₀With the result of Eabs.The pre-formed sheet material of acquisition is cut into the bar of 38cm long and 10cm wide, is passed through One bar is placed on flat surface and stretches out 16cm from platform to detect their rigidity.Measure bar without branch Deflecting down for the outermost portion of section is supportted, wherein higher deflect down the lower rigidity of instruction.

Embodiment I

By intensity it is 3.5GPa's in a manner of identical with Comparative experiment AUHMWPE fibers generate single layer. In this case, using from DSM Neoresins'As basis material.After drying, obtained single layer contains There are the UHMWPE fibers and 16wt% of 33 grams of parallel (unidirectional) arrangements(multiphase (methyl) acrylate core shell is total Copolymer dispersion, there are two-phase, a kind of Tg of phase is less than 30 DEG C, and the Tg of another phase is higher than 40 DEG C) it is used as basis material.With with The identical mode of Comparative experiment A is by stacking 4 single layers and outsideLinear low density polyethylene film comes Generate pre-formed sheet material.

Flat ballistic-resistant article is made of the loose disconnected assembly of several pre-formed sheet materials, and the assembly exists Corner through and through suture.The testing result of ballistic-resistant article is as shown in table 1.

Pre-formed sheet material deflects down as 64mm, less than deflecting down for Comparative experiment A, thereby indicate that sheet material is higher Rigidity.

Table 1：

Table 1 is shown：Although sheet material according to the present invention has higher rigidity, good projectile prevention property can be reached Energy.This is with broad idea on the contrary, broad idea, that is, best projectile prevents performance using soft (not being hard) base What body system and sheet material were realized.

Claims (15)

1. it is at least fibre of 1.5GPa it includes the tensile strength impregnated at least 10% plastic material a kind of pre-formed sheet material Tie up network, it is characterised in that：The plastic material includes multiphase (methyl) acrylic acid based polymer dispersion, the polymer point Granular media has the first phase and the second phase, and first phase is at least 40 DEG C of lowest glass transition temperature and is less than The weight average molecular weight of 80000g/mol, second phase have 30 DEG C or lower maximum glass transition temperature and are more than The weight average molecular weight of 100000g/mol.

2. pre-formed sheet material according to claim 1, wherein the glass transition temperature of oligomer is than the polymer Glass transition temperature is at least 30 DEG C low.

3. the pre-formed sheet material according to claim 1 or claim 2, wherein multiphase polymer dispersion form core-shell structure copolymer Structure.

4. according to the pre-formed sheet material described in claim 1-3, wherein the network of fibers includes fabric.

5. according to the pre-formed sheet material described in claim 1-3, wherein the network of fibers includes unidirectional array fiber.

6. according to the pre-formed sheet material described in claim 1-5, wherein the fiber is UHMWPE fibers.

7. according to the pre-formed sheet material described in claim 1-6, wherein the pre-formed sheet material is on its at least one outer surface Including seperation film.

8. pre-formed sheet material according to claim 7, wherein the seperation film is biaxial stretch-formed polyolefin film.

9. the assembly of at least two pre-formed sheet materials according to any one of the preceding claims, the sheet material are substantial It is not connected to each other.

10. a kind of ballistic-resistant article, it includes at least one assemblies according to claim 9.

11. a kind of ballistic-resistant article, it includes multiple pre-formed sheet materials according to claim 2, for 9mm*19 Natoball DM11 A1B2 bullets, which have, is more than 115J/kg/m²Eabs.

12. ballistic-resistant article according to claim 11 further includes optional matrix and unidirectional array fiber extremely Few two kinds of networks.

13. ballistic-resistant article according to claim 12, wherein the matrix for the unidirectional array fiber includes modified poly- Alkene, SIS or SEBS.

14. ballistic-resistant article according to claim 12, wherein the matrix for the unidirectional array fiber is to form first The acrylic thermoplastic polymer of phase also includes the oligomer in the second phase, wherein the glass transition temperature of the polymer Degree is at least 25 DEG C.

15. use of the plastic material comprising multiphase (methyl) acrylic acid based polymer dispersion in manufacturing ballistic composite On the way, there is the polymeric dispersions the first phase and the second phase, first phase to have at least 40 DEG C of minimum glass transition Temperature and weight average molecular weight less than 80000g/mol, second phase have 30 DEG C or lower maximum glass transition temperature With the weight average molecular weight more than 100000g/mol.