TW201710574A - Ballistic resistant composite material - Google Patents

Abstract

The present disclosure relates to a ballistic resistant composite 20 including a bimodal binder, the composite formable in a manner in which it is exposed to low pressure for a short duration of time and at a controlled temperature. More particularly, the bimodal binder of composite 20 allows the composite to be formed with a flat-bed laminator, for example, which may be less expensive than other processing methods, such as a steel belt press.

Description

Bulletproof composite Cross-reference to related applications

The present application claims the benefit of the U.S. Provisional Application Serial No. 62/138,548, the entire disclosure of which is hereby incorporated by reference in its entirety in .

This invention relates to a composite formed from a bimodal binder. In particular, the present invention relates to a ballistic resistant composite formed from a plurality of fibers and a dual mode cement and a method of forming the ballistic resistant composite.

The ballistic resistant article may contain high strength fibers that may be formed into a variety of articles such as vests, helmets, vehicle panels, additional clothing items, and additional items for military or police applications that resist penetration of bullets, shrapnel, and cartridges. item. Exemplary high strength fibers are polyethylene fibers, aramid fibers, graphite fibers, nylon fibers, glass fibers, and the like. For many applications, such as ballistic apparel articles, such fibers can be used in woven or woven fabrics. For other applications, the fibers can be encapsulated or embedded in a polymeric matrix material to form a woven or nonwoven composite.

Hard or rigid body armor provides good ball resistance, but can be bulky and hard. Thus, body armored garments, such as bulletproof vests, are preferably formed from a flexible or soft armor material. However, although such flexible or soft armor materials have good ballistic quality, such materials can exhibit low abrasion resistance that affects the durability of the armor. In addition, hard bulletproof objects And the soft ballistic resistant material is necessary to degrade the material's anti-elasticity. For example, due to the nature of military applications, ballistic resistant articles can be exposed to a variety of environmental conditions (such as seawater, gasoline, gun lubricants, and petroleum) that can degrade materials. As such, the ballistic resistant article should be formed to resist this degradation when exposed to environmental conditions or materials.

Referring to Figure 1, a method for producing a soft bulletproof body armor utilizes a belt press, such as a steel belt press 2. By way of illustration, a steel belt press 2 is an equal pressure steel belt press or a double belt press comprising a first belt 10, a second belt 12, and a first plurality of rollers 4 supporting the first belt 10. The second plurality of rollers 6 and the temperature unit 8 supporting the second belt 12. As shown in FIG. 1, the first plurality of rollers 4 are rotated in a clockwise direction and positioned above the second plurality of rollers 6. Conversely, the second plurality of rollers 6 rotate in a counterclockwise direction in conjunction with the clockwise rotation of the first plurality of rollers 4 to advance the composite 14 through the steel belt press 2.

The composite 14 can be composed of high performance fibers and a binder. The binder can be formed at least in part from a polymeric material and can be applied to the fibers by conventional coating processes (eg, casting, dispersion).

When the composite 14 enters the steel belt press 2, the first belt 10 and the second belt 12 are configured to be continuous up to about 70 bar or 1,000 psi as the composite 14 advances through the steel belt press 2. Pressure is applied to the composite 14. Further, the composite 14 passes through the temperature unit 8 including the heating portion 8a and the cooling portion 8b. As such, the composite 14 receives continuous high pressure from the first belt 10 and the second belt 12 while being both heated and cooled, which results in a high degree of compression and a reduction in air voids in the composite 14. It is believed that the compression from the strip press 2 removes voids and other gaps within the composite 14, thereby providing a smooth surface that resists corrosion and degradation conditions.

One disadvantage of using the steel belt press 2 to create the ballistic resistant composite 14 is that the cost associated with producing the composite 14 can be high due to the high cost of the steel belt press 2. However, other less expensive processing techniques configured to apply pressure, heat, and cooling to the composite 14 may not be configured to apply a similar level of pressure and/or continuous pressure. In addition, body armor and other ballistic resistant materials produced by such relatively inexpensive processing techniques should be configured to Environmental conditions (eg, fuel, brine, humidity, etc.) that are believed to degrade material properties without compromising the ballistic properties of such composites. Therefore, there is a need for a low cost method of producing soft ballistic resistant articles that can withstand a variety of environmental conditions.

The present invention provides a ballistic resistant composite comprising a plurality of fibers and a bimodal binder applied to the plurality of fibers.

In one form of the invention, the invention provides a ballistic resistant composite comprising a plurality of fibers and a bimodal binder applied to the plurality of fibers. The binder contains a crystalline component having a melting temperature and an amorphous component having a softening temperature. The crystalline component and the amorphous component have at least one of the following properties with respect to each other: (1) the melting temperature of the crystalline component is less than the softening temperature of the amorphous component; (2) above the The viscosity of the crystalline component at a temperature at which the crystalline component is at a melting temperature is less than the viscosity of the amorphous component; and (3) the surface of the crystalline component at a temperature above the melting temperature of the crystalline component It can be smaller than the surface energy of the amorphous component.

In certain embodiments, the crystalline component is selected from the group consisting of wax materials: palm wax, stearylamine wax, polyethylene wax, paraffin wax, polyolefin wax, and microcrystalline wax, and the non-crystalline The crystalline component is selected from the group consisting of polymeric materials consisting of acrylic acid, polyurethane, nitrile rubber, acrylonitrile butadiene copolymer, and fluorocarbon. Additionally, the plurality of fibers may be comprised of polyethylene.

In certain embodiments, the plurality of fibers define at least a first fiber laminate and a second fiber laminate oriented 90 degrees from the first fiber laminate.

In certain embodiments, the amorphous component constitutes from 60 wt.% to 95 wt.% of the bimodal binder, and the crystalline component constitutes from 5 wt.% to 40 wt.% of the bimodal binder.

In certain embodiments, the melting temperature of the crystalline component is between about 50 ° C and 140 ° C.

In another form of the invention, the invention provides a method of forming a ballistic resistant composite, comprising: providing a first plurality of fibers oriented in a unidirectional direction; providing a unidirectional orientation a second plurality of fibers; and a binder having an amorphous component and a crystalline component. The method further includes: coating the first plurality of fibers with the binder; coating the second plurality of fibers with the binder; positioning the first plurality of fibers at an angle of 90 degrees to the second plurality of fibers a fiber; heating the first and second plurality of fibers to a temperature within a melting temperature range of the crystalline component; and when the first and second plurality of fibers are at a temperature within a melting point of the crystalline component, Applying a pressure of less than 1 bar to the first and second plurality of fibers; and cooling the first and second plurality of fibers.

In certain embodiments, the pressure step is performed using a flat bed laminator.

In certain embodiments, the applying step comprises: applying a first pressure of less than 0.5 psi to the composite during the heating step; and when the composite is at the temperature within the melting point of the crystalline component Apply a second pressure of 10 psi to 300 psi.

In certain embodiments, the composite can be heated and/or cooled for as little as 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, 3.0 seconds, or up to 1 minute, 2 minutes, 3 Minutes, 4 minutes, or 5 minutes or any range defined by any of the foregoing values.

There is also provided a method of forming a ballistic resistant composite, comprising: providing a first fiber laminate comprising a plurality of unidirectionally oriented first fibers, wherein the first fibers are coated with an amorphous component and a crystalline component a first bimodal binder; providing a second fiber stack comprising a plurality of unidirectionally oriented second fibers, wherein the second fibers are coated with a second pair comprising an amorphous component and a crystalline component a modal binder; positioning the first fiber laminate and the second fiber laminate in a stacked configuration, heating the first fiber laminate and the second fiber laminate to a melting temperature range of the crystalline component a temperature; when the first fiber laminate and the second fiber laminate are at a temperature within the melting temperature range of the crystalline component, a pressure of less than 1 bar is applied to the laminate, whereby the first fiber The laminate and the second fiber laminate are attached to each other and thereby form a ballistic resistant composite; and the first fiber laminate and the second fiber laminate are cooled.

2‧‧‧Steel belt press

4‧‧‧First multiple rolls

6‧‧‧Second multiple rolls

8‧‧‧Temperature unit

8a‧‧‧heating section

8b‧‧‧cooling section

10‧‧‧First Belt

12‧‧‧Second belt

14‧‧‧Complex

20‧‧‧Bulletproof composites/composites

20a‧‧‧Fiber/fibrous material/exemplary fiber material

20b‧‧‧Bimodal polymeric matrix/bonding material/dual mode binder material/exemplary binder material/bonding agent

30‧‧ ‧ flat bed laminating machine

32‧‧‧First belt/upper belt/illustrative first belt/belt

33‧‧‧roll

34‧‧‧Second belt/lower belt/belt

35‧‧‧roll

36‧‧‧ pathway

38‧‧‧heating section/heating zone

40‧‧‧Cooling section/cooling zone

42‧‧‧Clamping roller/pressure roller/roller

44‧‧‧ Coating device

44a‧‧‧First coating device/coating device

44b‧‧‧Second coating device/coating device

46‧‧‧roll

50‧‧‧tangential

The above-mentioned features and advantages and other features and advantages of the present invention, as well as the manner in which the features and advantages are obtained, will become more apparent and BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic cross-sectional view of an isobaric steel belt press and a composite material formed therein; Figure 2 is a schematic view of a flat bed laminator; and Figure 3 is a plurality of coating devices Schematic of an extended flat bed laminator.

The present invention is directed to a ballistic resistant composite 20 comprising a bimodal binder which can be formed in such a manner that the composite is exposed to low pressure for a short duration of time and at a controlled temperature. More specifically, the bimodal binder of composite 20 allows for the formation of the composite using, for example, a flat bed laminator that is inexpensive compared to other processing methods, such as steel belt presses.

Composite 20 comprises a plurality of fibers 20a (Fig. 3) embedded in a bimodal polymeric matrix or binder material 20b. The dual mode cement material 20b comprises a first mode of amorphous components and a second mode of crystalline components, as further detailed herein. More specifically, the amorphous component constitutes most of the components of the binder material 20b and may be chemically and/or physically incompatible with the crystalline component. For example, as further detailed herein, at least the softening temperature (or another choice, glass transition temperature) and material structure of the amorphous component is different from the softening temperature of the crystalline component (or another selection, glass). Transition temperature) and material structure.

A. Fiber material

The ballistic resistant composite 20 comprises a fibrous material 20a embedded with a bimodal cement material 20b. The fibrous material 20a is formed from a plurality of fibers, each of the plurality of fibers having an elongated body having a length that is much greater than the transverse dimension of the width and thickness. The cross-section of the fibers of the fibrous material 20a can be round, flat or oblong. Therefore, surgery The term "fiber" includes filaments, ribbons, strips, and the like having a regular or irregular cross section. Each of the fibers 20a may also have a regular or irregular multi-lobed profile that protrudes from the linear or longitudinal axis of the fibers.

Exemplary fibrous material 20a comprises a nonwoven, cross-laminated unidirectional fabric. More specifically, the fibrous material 20a comprises a plurality of unidirectional fiber laminates oriented in a cross-laminate configuration in which the first laminate of fibrous material 20a is adjacent to the second laminate of fibers Oriented 90 degrees. The fibers within each laminate are adjacent to each other and parallel to each other, and thus, the fibers are oriented in a unidirectional configuration. In one embodiment, each fiber may be about 0.063 inches or 1.588 mm in diameter.

The fibrous material 20a may be composed of polyethylene fiber, aramid fiber, graphite fiber, nylon fiber, glass fiber, and the like. For example, in one embodiment, the fibrous material 20a is comprised of ultra high molecular weight polyethylene (such as Honeywell 1150-denier SPECTRA ^® Merge 95121 UHMWPE fiber and/or Honeywell 1300-denier SPECTRA ^® Merge 95159 UHMWPE fiber). Each of the fibrous materials 20a can have a fiber layup of from about 15 g/m ² to about 250 g/m ² (typically from about 20 g/m ² to about 100 g/m ² and often from about 25 g/m ² to about A fiber areal density of 70 g/m ² and most preferably about 35 g/m ² ). Fiber areal density refers to the weight of only fibers per unit area (ie, without the binder). Additional details of fiber material 20a are disclosed in U.S. Patent No. 7,994,075, issued on Aug. 9, 2011, and U.S. Pat. It is expressly incorporated herein.

B. Bimodal binder material

The bimodal binder material 20b is applied to the fibrous material 20a to form the ballistic resistant composite 20. The exemplary binder material 20b is a bimodal binder composed of an amorphous component having an amorphous phase which is permeable to amplification and a crystalline component having a crystal phase which is identifiable by amplification, such as It is known to those skilled in the art.

Amorphous component

The amorphous component of the binder material 20b is characterized as amorphous because it does not have the long-range order of the properties of the crystalline material. The lack of long-range order allows the amorphous component to be flexible, which allows for flexibility in the composite 20 and can be necessary to form soft body armor that is configured to bend and move when worn. The exemplary amorphous component of the binder material 20b defines most of the components of the binder material 20b. For example, the amorphous component can constitute at least 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 99% or at least the total weight of the binder material 20b. Any range defined by any of the foregoing values.

The amorphous component may be composed of a liquid or a powdered resin such as a polyurethane resin, an acrylic resin, a nitrile rubber resin, an acrylonitrile butadiene copolymer resin, a fluorocarbon resin, a polybutadiene resin, and a polyisoprene. An olefin resin, an ethylene-propylene resin, a polysulfide resin, a polyacrylate resin, a polyester resin, and/or a polyether resin. For example, the amorphous component of the binder material 20b can be an aqueous dispersion of an acrylonitrile butadiene copolymer supplied at 40% solids (such as TYLAC ^® 873, available from Charlotte (Charlotte) , available from Mallard Creek Polymers of NC000000) and/or aqueous dispersions of fluorocarbon resins (such as NUVA ^® 2040, available from Clariant GMBH, Germany).

The exemplary amorphous component of the binder material 20b has a greater viscosity, surface energy, and/or softening temperature than the crystalline component when at a temperature within the melting temperature of the crystalline component. More particularly, in one embodiment, the crystalline component and the amorphous component are selected such that the melting temperature of the crystalline component is less than the softening temperature of the amorphous component, and/or when melting above the crystalline component At the temperature of the temperature, the viscosity of the crystalline component is less than the viscosity of the amorphous component. Further, the amorphous component and the crystalline component may be selected such that the surface energy of the crystalline component is less than the surface energy of the amorphous component at a temperature higher than the melting temperature of the crystalline component. For example, in one embodiment, the softening temperature of the amorphous component of the binder material 20b is less than the degradation temperature of the fibrous material 20a but substantially greater than the melting temperature of the crystalline component such that when the crystalline component melts and begins to flow At the time, the amorphous component does not significantly melt or undergo physical changes and may even exhibit flow resistance. More specifically, the amorphous material may not have a different melting point but will begin to soften in the softening temperature range and will continue to soften as the temperature increases. Conversely, crystalline materials have a true melting temperature and the hard solids change drastically into a fluid over a much shorter temperature range. In this manner, the amorphous component is incompatible with the crystalline component because the amorphous component does not physically modify or chemically react with the crystalline component during physical conversion of the crystalline component. In one example, Honeywell 1150-denier SPECTRA ^® Merge 95121 UHMWPE fiber and/or Honeywell 1300-denier SPECTRA ^® Merge 95159 UHMWPE fiber can have a degradation temperature of about 140 ° C, and the crystalline component can have a melting temperature of up to 140 ° C. , as further detailed herein. Therefore, the softening temperature of the amorphous component can be as low as 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 ° C, 150 ° C, 160 ° C, 170 ° C, 180 ° C, 190 ° C or up to 200 ° C, 210 °C, 220 ° C, 230 ° C, 240 ° C, 250 ° C, 260 ° C or more or may be within any of the ranges defined by any of the foregoing values.

Alternatively, in one embodiment, the softening temperature of the amorphous component can be less than the melting temperature of the crystalline component. However, since the viscosity and/or surface energy of the amorphous component is greater than the viscosity and/or surface energy of the crystalline component when at a temperature within the melting temperature of the crystalline component, the amorphous component will remain solid or elevated. Viscosity, and therefore, the crystalline component will flow around the amorphous component such that the amorphous component does not mix with the crystalline component. Additional details of the amorphous component of the binder material 20b are disclosed in U.S. Patent No. 7,994,075, issued on Aug. 9, 2011, and U.S. Patent No. 8,017,530, issued on Sep. 13, 2011. The complete disclosure is expressly incorporated herein by reference.

2. Crystallized components

The crystalline component of the binder material 20b is added to the amorphous component or doped to the amorphous component. The crystalline component of the binder material 20b is characterized as being crystalline because it contains a highly ordered molecular structure defined by the crystal lattice. The crystal lattice of the crystalline component can be discerned by amplification, as is known to those skilled in the art. Unlike the amorphous component, the crystalline component may have less flexibility but is included in the binder material 20b because it allows for a treated strip having reduced pressure The compression and densification of the composite 20 under the article thereby increasing the ballistic resistance of the composite 20. Moreover, as discussed further below, during processing of the composite of the present invention, the crystalline material undergoes a phase change (such as melting) that allows the flow of the crystalline material relative to the amorphous material and subsequent resolidification to provide desired properties (such as smoothness and density). Enhancement to provide resistance to corrosive environments.

The crystalline component of the binder material 20b is a minority component of the binder material 20b. For example, the crystalline component may constitute 45%, 40%, 35%, 30%, 25%, 20%, 15%, 10%, 5%, 1% or more of the total weight of the binder material 20b. Any of the ranges defined by the foregoing values.

The crystalline component can be composed of any crystalline polymer that is incompatible with the amorphous component. More specifically, the crystalline component can be incompatible with the amorphous component such that the two components do not mix or act as a single material. For example, the crystalline component of the present invention can be a wax material such as palm wax, polyethylene wax, polyolefin wax, paraffin wax, stearin wax, and/or microcrystalline wax. Wax is generally defined as a material that is solid at room temperature but melts or softens above about 40 ° C without decomposition. Waxes are generally organic and water-insoluble at room temperature, but they may be water-wettable and may form pastes and gels in certain solvents, such as non-polar organic solvents. The wax may have a molecular weight ranging from about 400 g/mol to about 25,000 g/mol and may have a melting point ranging from about 40 °C to about 150 °C. Waxes generally do not form separate films like higher order polymers and are typically aliphatic hydrocarbons containing more carbon atoms than oils and oils.

The viscosity of the wax can generally range from low to high depending on the molecular weight and crystallinity of the wax. The viscosity of a wax above its melting point is generally low. As used herein, "low viscosity wax" describes a wax having a melt viscosity of less than or equal to about 500 centipoise (cps) at 140 °C. Preferably, the low viscosity wax has a viscosity of less than about 250 cps at 140 ° C. Most preferably, the low viscosity wax has a viscosity of less than about 100 cps at 140 °C. However, certain linear polyethylene waxes (molecular weights of from about 2,000 g/mol to about 10,000 g/mol) and polypropylene waxes may have a medium to high viscosity (i.e., up to 10,000 cps) after melting. Viscosity value is used here Techniques are well known in the art for measurement and can be measured, for example, using a capillary rheometer, a rotating rheometer or a moving body rheometer. A preferred measuring tool is a Brookfield rotational viscometer.

Suitable waxes include both natural and synthetic waxes and include, not exclusively, animal waxes (such as beeswax, Chinese wax, shellac wax, cetyl wax and wool wax (lanolin)); vegetable waxes (such as laurel) Wax, candelilla wax, palm wax, ramie wax, reed wax, Japan wax, jojoba oil wax, small crown coconut wax, rice bran wax and soybean wax); mineral wax (such as pure ceresin ( Ceresin wax), montan wax, ozocerite wax and peat wax; petroleum wax (such as paraffin wax and microcrystalline wax); and synthetic wax containing polyolefin wax, polyethylene, polypropylene wax, Fischer-Tropsch wax (Fischer-Tropsch wax), stearylamine wax (containing ethylenebisstearylamine wax), polymeric alpha-olefin wax, substituted guanamine wax (eg esterified or saponified substituted guanamine wax) and others Chemically modified wax. In addition, suitable waxes are set forth in U.S. Patent No. 4,544,694, the entire disclosure of which is expressly incorporated by reference. Preferred waxes for such suitable waxes include paraffin waxes, microcrystalline waxes, Fischer-Tropsch waxes, branched and linear polyethylene waxes, polypropylene waxes, large particle size polyethylene waxes, palm waxes, and ethylenebisstearylamines (EBS). Wax and combinations thereof.

For example, exemplary crystalline material 20b of the binder material can be based: carnauba wax of an aqueous 35% solids supply of the dispersion (such as a wax HYDROCER ^TM EC-35, which is available from the New Jersey Newark An aqueous dispersion of a large particle size polyethylene wax (such as LL405 available from Michelman, Inc. of Cincinnati, Ohio) supplied as a 40% solids; supplied as a solid at 35% An aqueous dispersion of high density polyethylene wax (such as LL411 from Michelman); an aqueous dispersion of paraffin supplied at 32% solids (such as 454 from Michelman); water based on microcrystalline wax supplied at 40% solids A dispersion (such as HL-480 from Michelman); and/or an aqueous dispersion of Fischer Tropsch polyethylene wax (such as ME98040 from Michelman) supplied at 40% solids.

The exemplary crystalline component of the binder material 20b can have a low melt viscosity and a melting temperature of: 50 ° C, 55 ° C, 60 ° C, 65 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C, 95 ° C, 100 ° C, 105 ° C, 110 ° C, 115 ° C, 120 ° C, 125 ° C, 130 ° C, 135 ° C, 140 ° C or any range defined by any of the foregoing values. More specifically, the palm wax may have a melting point of about 75 ° C to 85 ° C and a low melt viscosity. Similarly, the microcrystalline wax may have a melting temperature of about 60 ° C to 90 ° C and a low melt viscosity. Further, the Fischer-Tropsch wax may have a melting temperature of 95 ° C to 100 ° C and a low melt viscosity. Further, the paraffin wax may have a melting temperature of 50 ° C to 70 ° C and a low melt viscosity. Further, the polyethylene wax may have a melting temperature of from 90 ° C to 140 ° C and may have a low viscosity, a medium viscosity or a high viscosity depending on the structure of the polyethylene wax. As such, the crystalline component has a sharp melting temperature range that can only span about 5 ° C to 50 ° C allowing the crystalline component to melt and rapidly cool.

As detailed herein, the melting point and melt viscosity of the crystalline component can be different from the softening temperature and viscosity of the amorphous component. In this way, when the crystalline component is exposed to a temperature within its melting point, the crystalline component rapidly melts and begins to flow around the solid amorphous component at the melting point of the crystalline component. It does not melt significantly at temperatures within the range. The molten crystalline component can then fill any voids within the blended binder material 20b and can also fill any voids within the composite 20. In addition, when the crystalline component is exposed to a temperature less than its melting point range, the crystalline component is rapidly cooled to form a solid phase again. However, since the crystalline component flows around the solid amorphous component while being at its melting temperature, the crystalline component is embedded with an amorphous component and mixed with the amorphous component upon cooling.

For example, if the amorphous synthetic rubber defines the amorphous component of the binder 20b and the crystalline polyurethane resin defines the crystalline component of the binder 20b, the cast film of the binder material 20b maintains a relatively large mass of amorphous synthesis. A discrete region of the crystalline polyurethane resin in the rubber. When heat is applied to the composite 20, for example, in a flat bed laminator, the amorphous region of the synthetic rubber remains solid, but the discrete crystalline regions of the polyurethane resin melt and flow into the fibrous material 20a. In the gap, this reduces the capillary force and reduces the composite 20 The fluid resistance of the composite 20 is improved by the total effective surface area. In this way, the composite 20 maintains flexibility due to the amorphous synthetic rubber, but has improved ballistic resistance due to the crystalline polyurethane resin.

Alternatively, in one embodiment, the softening temperature of the amorphous component can be less than the melting temperature of the crystalline component. However, since the viscosity and/or surface energy of the amorphous component is greater than the viscosity and/or surface energy of the crystalline component when at a temperature greater than the melting temperature of the crystalline component, the amorphous component will remain solid or elevated. The viscous, and thus crystalline, component will flow around the amorphous component and the amorphous component will not mix with the crystalline component. More particularly, in one embodiment, the crystalline component and the amorphous component are selected such that the melting temperature of the crystalline component is less than the softening temperature of the amorphous component and/or when the melting temperature is higher than the crystalline component The viscosity of the crystalline component at the temperature is less than the viscosity of the amorphous component. Further, the amorphous component and the crystalline component may be selected such that the surface energy of the crystalline component is lower than the surface energy of the amorphous component at a temperature higher than the melting temperature of the crystalline component. Additional details of the crystalline component of the binder material 20b are disclosed in U.S. Patent No. 7,994,075, issued on Aug. 9, 2011, and U.S. Patent No. 8,017,530, issued on Sep. 13, 2011. The disclosure is expressly incorporated herein by reference.

C. Bulletproof composite

In order to form the bimodal binder material 20b, the crystalline component and the amorphous component are mixed together by various processes.

1. Preparation of bimodal binder

In one embodiment, the crystalline component can be mixed with the amorphous component by forming a wet blended emulsion and/or a wet blending solution. More specifically, the wet blended emulsion and/or wet blend solution comprises a solvent in which both the amorphous component and the crystalline component are soluble. This wet blending solution and/or wet blended emulsion can then be cast into a dried film in which the crystalline and amorphous components are maintained in discrete regions of the dried film.

It is also possible to roughly disperse the crystalline component in a solid form to the aqueous component of the amorphous component. The binder material 20b is mixed in the emulsion or roughly dispersed in a solvent-based solution of the amorphous component (Fig. 3).

2. Apply a bimodal binder to the fiber

Once mixed, the binder material 20b is applied to the fibrous material 20a to form the composite 20. The binder material 20b is applied to the fibrous material 20a by various processes such as by means of a spray gun, fiber pultrusion, fiber impregnation, hot melt extrusion, gravure coating, and/or other roller coating methods. For example, a fiber impregnation method can be used to apply the binder material 20b to the fiber material 20a. An excess aqueous emulsion or dispersion of the binder material 20b is applied to the fibrous material 20a using a fiber impregnation method. A series of fixing strips and pressure rolls then extrude excess binder material 20b to form composite 20. The composite 20 can then be temporarily cast onto a polyoxynized coated release paper and conveyed by the polyoxynitrene coated release paper, and when the water is dried, the composite 20 is wound onto the drum to For further processing.

Additionally, a combination of these foregoing methods can be used to apply the binder material 20b to the fibrous material 20a. For example, a single aqueous emulsion of an amorphous component can be applied to the fibrous material 20a by a fiber impregnation process. Next, the crystalline component can be applied to the surface of the composite 20 in a dry form by means of an electrostatic sprayer. The dried crystalline component can be applied to the fibrous material 20a before or after the water from the aqueous emulsion of the amorphous component is dried.

Further, in an embodiment, the amorphous component may be applied to the fibrous material 20a as a solvent cast film using the aforementioned fiber impregnation method. The crystalline component is then applied to the surface of the solvent cast film of the amorphous component in a dry form.

Regardless of the method selected to apply the binder material 20b to the fibrous material 20a, the fibrous material 20a may be washed with deionized water and dried before the binder material 20b is applied to the fibrous material 20a. The fibrous material 20a can then be plasma treated with an energy flux of from 50 watts/ft ² /min to 80 watts/ft ² /min, preferably 67 watts/ft ² /min. The binder material 20b is then applied to the fibrous material 20a through one or more of the foregoing processes for adhering individual fibers of the fibrous material 20a together and for adhering the various laminates of the fibrous material 20a to each other. More specifically, the fibrous material 20a is coated with a binder material 20b at a resin content of 5% to 30% and preferably at a resin content of 17%. Once the binder material 20b is applied to the fibrous material 20a, the fibrous material 20a can be rolled onto the spool and stored in rolls until further processing occurs.

3. Flat bed laminating machine

Referring to Figure 2, after applying the binder material 20b to the fibrous material 20a, the binder material 20b is applied to at least another layer of the fibrous material 20a to define a second laminate of fibers. The various layers of the fiber stack are then positioned in a stacked configuration and each stack is oriented at 90 degrees with the adjacent stack. Any number of laminates can be included in the composite 20 to accommodate the various applications of the composite 20.

The composite 20 can then be formed using a flat bed laminator 30 comprising a first belt or upper belt 32 rotatable about a plurality of rollers 33 and a second belt or lower belt 34 rotatable about a plurality of rollers 35. . The first strip 32 and the second strip 34 may be coated with a non-stick coating (for example, a fluoropolymer-based material such as TEFLON ^® , which is available from EI DuPont De Nemours and Company, Wilmington, Delaware. Purchased)). The first strip 32 and the second strip 34 are spaced apart from one another by passages 36 for the composite 20 to pass through. As shown in FIG. 2, the illustrative first belt 32 rotates in a counterclockwise direction and the second belt 34 rotates in a clockwise direction, which advances the composite 20 through the flat bed laminator 30. In one embodiment, the first belt 32 and the second belt 34 are rotated at a speed of from 1 meter per second to 15 meters per second and preferably at a speed of 3 meters per second. By way of illustration, the first strap 32 and the second strap 34 have approximately the same length such that the composite 20 is in contact with both the first strap 32 and the second strap 34 for approximately the same length of time.

The flat bed laminator 30 of FIG. 2 further includes a heating portion or heating zone 38, a cooling portion or cooling zone 40, and a plurality of nip rollers or pressure rollers 42 positioned intermediate the heating portion 38 and the cooling portion 40. As the composite 20 advances within the flat bed laminator 30, the composite 20 is heated in the heated portion 38. For example, the heating portion 38 can be configured for use at temperatures as low as 50 ° C, 60 ° C, 70 ° C, 80 ° C, or up to 90 ° C, 100 ° C, 110 ° C, 120 ° C, 130 ° C, 140 °C, 150 ° C or operated at any temperature within any of the ranges defined above. The temperature of the heating portion 38 is within the melting temperature range of the crystalline component, so that the crystalline component of the binder 20b is melted in the heating portion 38. In one embodiment, the composite 20 can be heated up to 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, 3.0 seconds, or up to 1 minute, 2 minutes, 3 minutes, 4 minutes. Or 5 minutes or any range defined by any of the foregoing values. The heating time and temperature are based on the nature of the crystalline component and its specific melting temperature range.

As the composite 20 exits the heating portion 38, pressure is applied to the composite 20 as it passes through the pressure roller 42 as the crystalline component is melted. The pressure roller can be constructed from a variety of materials such as metal (eg, steel), polymers (eg, elastomeric rubber), and/or ceramics. Additionally, one of the pressure rollers 42 may have a fixed position and the other of the pressure rollers 42 may be movable when a force is applied thereto such that when a force is applied to one of the pressure rollers 42, A force is also applied to the composite 20. More specifically, the pressure roller 42 can apply a pressure of less than 1 bar to the composite 20. For example, pressure roller 42 can be 10 psi, 30 psi, 50 psi, 70 psi, 90 psi, 110 psi, 130 psi, 150 psi, 170 psi, 190 psi, 210 psi, 230 psi, 250 psi, 270 psi, 290 psi, 310 psi, or as defined by any of the foregoing values. Clamping pressure in any range is applied to the composite 20. In one embodiment, the pressure roller can apply a pressure of 14 psi to the composite 20. The maximum pressure applied to the composite 20 occurs at a tangent 50 to the pressure roller 42 that is parallel to the first belt 32 and the second belt 34. However, due to the circular cross-section of the pressure roller 42, a small amount of pressure is applied to the composite 20 when the surface of the pressure roller 42 adjacent the tangential line 50 is in contact with the composite 20. For example, as one portion of the composite 20 moves through the flat bed laminator 30, an increased amount of pressure gradient is applied to the composite 20 because the composite 20 is initially positioned between the pressure rolls 42. When the composite 20 is moved toward the tangent 50 of the pressure roller 42, a greater pressure is applied to the composite 20, wherein the maximum pressure is applied to the composite 20 when the composite 20 is directly between the tangent 50 of the pressure roller 42. Additionally, as the composite 20 moves past the tangent 50, a reduced amount of pressure gradient is applied to the composite 20 until the composite 20 is no longer positioned between the pressure rolls 42.

The different designs of the flat bed laminator 30 can apply different pressures to the composite 20. For example, if the pressure roller 42 has an outer surface made of steel, the contact footprint of the pressure roller 42 on the composite 20 is relatively small and the average point pressure applied to the composite 20 is large. However, if the pressure roller 42 has an outer surface composed of elastic rubber, the contact occupation area of the pressure roller 42 on the composite 20 is relatively large and the average point pressure applied to the composite 20 is small.

The pressure from the pressure roller 42 is applied to the composite 20 for about 0.02 seconds to about 5 seconds. More specifically, pressure can be applied to the composite 20 for as little as about 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, or as much as 3.0 seconds, 3.5 seconds, 4.0 seconds, 4.5 seconds, 5.0. Seconds or duration in any range defined by any of the foregoing values. In one embodiment, pressure can be applied to the composite 20 for a duration of from 0.01 seconds to 0.05 seconds. In addition, since the pressure roller 42 has a circular cross section, the aforementioned time indicates the total duration of the pressure experienced by the laminate 20. For example, using an order of magnitude calculation, if the length of the occupied area between the pressure rolls 42 is 1 cm and the line speed of the flat bed laminator 30 is 5 m/min, the composite 20 undergoes the retention of the pressure applied by the pressure roll 42. The time is 0.12 seconds. However, since 0.12 seconds indicates the total amount of time that the composite 20 is subjected to the pressure from the pressure roller 42, there is a gradient of the rising pressure for the first half of 0.06 seconds and a gradient of the decreasing pressure for the latter half of 0.06 seconds. Thus, in the embodiment of FIG. 2, the pressure applied by the pressure roller 42 to the composite 20 is discontinuous because the composite 20 does not apply pressure to the composite 20 as it passes through the heating portion 38 and the cooling portion 40. . Alternatively, the flat bed laminator 30 can be configured to apply pressure to the composite 20 while the composite 20 is still within the heated portion 38 and the crystalline components have melted. However, when the composite 20 passes through the cooling section 40, no pressure will be applied to the composite 20 in order to minimize the stress applied to the composite 20 during cooling. As such, the flat bed laminator 30 is not configured to apply continuous pressure to the composite 20.

After pressure is applied to the composite 20 using the rollers 42, the composite 20 moves through the cooling portion 40 and then exits the flat bed laminator 30. In one embodiment, the cooling portion 40 is It is configured for a temperature less than the melting temperature of the crystalline component of the binder material 20b. For example, the cooling portion 40 can be configured to be used at 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C depending on the particular crystalline component contained within the binder material 20b. 35 ° C, 40 ° C, 45 ° C, 50 ° C, 60 ° C, 70 ° C, 80 ° C, 90 ° C or at any temperature within any range defined by the foregoing values. Since the length of the cooling portion 40 is about the same as the length of the heating portion 38, the composite 20 can be cooled up to about the same amount of time as it is heated. More specifically, the composite 20 can be cooled down to 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, 3.0 seconds, or up to 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 Minutes or any range defined by any of the foregoing values. As the composite 20 passes through the cooling portion 40, the composite 20 is required to remain flat and not curved to minimize the stress applied to the composite 20 during cooling. Alternatively, since heat transfer occurs rapidly in the crystalline component, if the composite 20 may radiate sufficient heat to its surroundings to lower its temperature below the melting temperature of the crystalline component to allow the crystalline component to solidify. The cooling portion 40 can be eliminated from the flat bed laminator 30.

Additionally, as detailed herein, it may be desirable to minimize or eliminate the stress to the composite 20 when cooled below the melting temperature of the crystalline component of the binder material 20b. Since no pressure is applied to the composite 20 when cooled, stress is not introduced into the crystal structure of the crystalline component. Furthermore, since heat transfer occurs rapidly within the crystalline component, a discrete portion of the crystalline component that flows around the amorphous component and flows into any voids within the fibrous material 20a while the crystalline component is molten is maintained without being chemically It is mixed with or physically mixed with an amorphous component. As such, the amorphous component and the crystalline component remain discrete and incompatible with each other within the binder material 20b.

Additionally, the first belt 32 and the second belt 34 can apply a lower pressure than the pressure applied by the roller 42 to the composite 20. Since the pressure applied by the first belt 32 and the second belt 34 is low, no additional stress is introduced into the composite 20 as the composite 20 passes through the cooling portion 40. Alternatively, when the composite 20 passes through the cooling portion 40, the belts 32, 34 may not What pressure is applied to the composite 20. In one example, when the composite 20 passes through the heating portion 38 and the cooling portion 40, the first belt 32 and the second belt 34 can be as low as 0.01 psi, 0.05 psi, 0.10 psi, 0.15 psi, 0.20 psi, or 0.25 psi. Or up to 1.0 psi, 2.0 psi, 3.0 psi, 4.0 psi, 5.0 psi, 6.0 psi, 7.0 psi, 8.0 psi, 9.0 psi or 10.0 psi or any pressure within any range defined by the foregoing values applied to the composite Object 20. In one embodiment, the pressure applied by the first belt 32 and the second belt 34 is less than 0.5 psi. More specifically, the pressure applied by the first belt 32 and the second belt 34 is applied for a duration that is inversely proportional to the belt speed of the flat bed laminator 30. In one embodiment, the residence time of the pressure applied to the composite 20 by the first belt 32 and the second belt 34 is as little as 1 second, 3 seconds, 5 seconds, 7 seconds, 9 seconds, or 11 seconds or more. Up to 1 minute, 2 minutes, 3 minutes, 4 minutes, or 5 minutes or within any range defined by any of the foregoing values. As such, the composite 20 can undergo two distinct pressures - a first low pressure applied by the first belt 32 and the second belt 34 as it passes through the heating portion 38 and/or the cooling portion 40 and a second applied by the pressure roller 42 Higher pressure.

Referring to Figure 3, composite 20 can also be formed using an alternate embodiment of a flat bed laminator 30 shown as a flat bed laminator 30'. The flat bed laminator 30' includes a first belt 32 that is rotatable about the roller 33 in a counterclockwise direction and a second belt 34' that is rotatable about a plurality of rollers 35' in a clockwise direction. In one embodiment, the first belt 32 and the second belt 34' are rotated at a speed of from 1 m/sec to 15 m/sec and preferably at a speed of 3 m/sec. By way of illustration, the length of the second strap 34' is greater than the length of the first strap 32 such that the composite 20 is in contact with the second strap 34' for a longer period of time than contact with the first strap 32.

Still referring to Fig. 3, the flat bed laminator 30' further includes a heating portion 38, a cooling portion 40, and a pressure roller 42 positioned therebetween. Based on the position of the pressure roller 42, the composite 20 is not under pressure as it moves through the heating portion 38 and the cooling portion 40, but does receive 10 psi, 30 psi, 50 psi, 70 psi, 90 psi, 110 psi when passing between the rollers 42. 130psi, 150psi, 170psi, 190psi, 210psi, 230psi, 250psi, 270psi, 290psi, 310psi or in any range defined by any of the foregoing values Holding pressure.

The flat bed laminator 30' of Figure 3 also includes at least one coating device 44. By way of illustration, the flat bed laminator 30' includes a first coating device 44a and a second coating device 44b, which may be a hot melt applicator or a dry coating applicator. More specifically, the coating devices 44a, 44b are positioned upstream of the heating portion 38 and the cooling portion 40, and the first coating device 44a is configured to apply the binder material 20b contained therein to the second belt 34' The second coating device 44b is configured to apply the binder material 20b contained therein to the top of the fibrous material 20a before the fibrous material 20a enters the passageway 36.

As shown in Figure 3, the fibrous material 20a moves along the plurality of rollers 46 toward the first belt 32 and the second belt 34'. The first coating device 44a applies a predetermined amount of the binder material 20b to the second belt 34'. Thus, when the fibrous material 20a contacts the second belt 34', the binder material 20b on the second belt 34' is applied to the lower surface of the fibrous material 20a. Additionally, the binder material 20b from the second coating device 44b is applied to the top surface of the fibrous material 20a before the fibrous material 20a contacts the first belt 32. In this manner, the binder material 20b is applied to both the top and bottom surfaces of the fibrous material 20a to define the composite 20 before the composite 20 enters the passage 36, the heating portion 38, the cooling portion 40, and the pressure roller 42.

When the composite 20 enters the heating portion 38, the crystalline component of the binder material 20b melts and flows into the fibrous material 20a to integrate with the fibrous material 20a. Pressure is applied to the composite 20 by the pressure roller 42. More specifically, and as detailed herein with respect to the flat bed laminator 30, the pressure roller 42 can apply pressure as little as about 0.01 seconds, 0.50 seconds, 1.0 seconds, 1.5 seconds, 2.0 seconds, 2.5 seconds, or as much as 3.0. Seconds, 3.5 seconds, 4.0 seconds, 4.5 seconds, 5.0 seconds or a duration in any range defined by any of the foregoing values. After applying pressure to the composite 20 using the rollers 42, the composite 20 moves through the cooling portion 40 and exits the flat bed laminator 30'. As such, the pressure applied by the pressure roller 42 to the composite 20 is discontinuous because the composite 20 does not apply pressure to the composite 20 as it passes through the heating portion 38 and the cooling portion 40.

Since the crystalline component of the binder material 20b has a lower melting viscosity than the amorphous component and The surface energy can have a lower melting temperature than the amorphous component, so when the pressure roller 42 applies pressure to the composite 20, there may be greater wetting, larger displacement, and greater compression in the crystalline component. . Thus, the presence of voids, cavitation, gaps or other internal openings in the amorphous component is reduced during formation of the composite 20 in the flat bed laminator 30, 30'. In this manner, the composite 20 comprises a generally void-free, smooth surface that reduces capillary forces and the total effective surface area of the composite 20, thereby not penetrating due to environmental conditions such as seawater, gasoline, petroleum, solvents, and lubricants. The composite 20 increases the ballistic resistance of the composite 20. In addition, in addition to reducing the voids at the surface of the composite 20, internal voids, pockets, and channels within the composite 20 are removed by compression of the composite 20 or internal voids, pockets, and channels within the composite 20 are removed. Gas, thereby reducing the tendency to wicking fluid or other permeate. The composite 20 formed in accordance with the foregoing disclosure can be used in ballistic resistant articles and against environmental conditions that can degrade the composite 20.

Instance Example A: Saline test of bimodal binder material

Various samples of the composite are formed from varying amounts of crystalline components within the binder material. These samples of the composite are then exposed to the brine for an extended period of time to determine if the presence of the crystalline component affects the corrosion resistance of the composite.

Formation of complex

To form these samples, various concentrations of the binder material were formed according to Table 1 to define Comparative Example 1, Example 1 of Composite 20, and Example 2 of Composite 20.

The binder material was applied to a fibrous material composed of Honeywell 1150-denier SPECTRA ^® Merge 95121 UHMWPE fibers. More specifically, the binder material is applied to the first unidirectional web and the coated web is dried using a fiber dip coater. The dried web is wound onto a drum. A second roll of the second unidirectional web is also coated with a fiber dip coater, dried and wound onto a drum. The first coated web on the first roll is cut into square pieces. A second roll of wound fibers is mounted at or near the entrance of the flat bed laminator 30, 30' and the second web is spread and fed through the flat bed laminator 30, 30'. The temperature of the heating portion 38 of the flat bed laminator 30, 30' is set to a temperature lower than the melting temperature of the crystalline component. When the second coated web begins to travel into the flat bed laminator 30, 30', the square of the first coated web is placed before the second web enters the flat bed laminator 30, 30' On top of the second coated web. The fiber direction of each square piece of the first web is positioned at an orientation of 90 degrees to the fiber direction of the second web. Additionally, each square piece of the first web is positioned to abut the previously adjacent square piece of the second web to define a continuous, coated, double laminate fiber material. This continuous, double laminate fiber material enters the flat bed laminator 30, 30' and the pressure applied by the roll 42 adheres the square piece of the first web to the second web. However, the pressure from the roll 42 and the heat of the heated portion 38 do not melt the crystalline component of the cement material (if any crystalline component is present in the binder material). The double laminate web formed from the continuous web of the cut web of the first web and the second web is then wound onto the drum after passing through the flat bed laminators 30, 30' and adhering together. The temperature of the heated portion 38 of the flat bed laminator 30, 30' is then increased to a temperature within the melting point range of the crystalline component (if any crystalline component is present) in the binder material. The roll of double laminate fiber material is then spread out and the double laminate fiber material is passed through a flat bed laminator 30, 30'. Since the temperature of the heating portion 38 is within the melting range of the crystalline component and the binder material, compression or densification is applied to the dual laminate fiber material as it passes through the roll 42. After the double laminate fiber material passes through the flat bed laminator 30, 30', the double laminate fiber material is cut into square pieces and a ballistic sample is produced by stacking 52 layers of the double laminate fiber material. The total areal density of each sample or the total weight of the area of multiple layers per fabric is 0.89 lbs/ft ² .

Testing of complexes

Comparative Example 1, Example 1, and Example 2 were each immersed in brine (sea salt in tap water) at a concentration of 3.5% for 24 hours. Comparative Example 1, Example 1 and Example 2 were suspended by dripping with water for 15 minutes. Next, Comparative Example 1, Example 1, and Example 2 were each placed on a clay block or platform, as further disclosed in Level III of NIJ STD 0101.06, and 357 Magnum SJHP Remington at 1430 +/- 30 ft/sec. The shots were fired at Comparative Example 1, Example 1, and Example 2.

Each of the two samples of Comparative Example 1, Example 1, and Example 2 was each fired three times with a 357 Magnum SJHP Remington bullet to determine the depth of penetration into each of the bullets in each sample. As shown in Table 2, Shot 2 and Shot 3 of each sample of Comparative Example 1 completely penetrated the composite as indicated by "Complete" in Table 2. However, none of the samples of Example 1 or Example 2 were completely penetrated. More specifically, the bullet penetrated minimally into the sample of Example 1 containing the fluorocarbon amorphous component and the palm wax crystalline component.

Example B: Bimodal binder material having varying concentrations of amorphous and crystalline components

Forming a variety of composites with varying amounts of crystalline components in the binder material this. These samples of the composite were then fired with a 9 mm bullet to determine if the presence of the crystalline component affected the ballistic resistance of the composite.

Formation of complex

To form these samples, various concentrations of the binder material were formed according to Table 3 to define Comparative Example 1, Example 1 of Composite 20, Example 2 of Composite 20, and Example 3 of Composite 20. The coating and composite treatment conditions used to form these samples were the same as those of Example 1 above for coating and composite processing.

Testing of complexes

Samples of Comparative Example 1 and Examples 1 through 3 were each placed on a clay block or platform, as further disclosed in Level III of NIJ STD 0101.06, and a 9 mm shot was fired at a rate of change as shown in Table 4 for a comparative example. 1 and each of the samples of Examples 1 to 3. More specifically, Table 4 provides that 50% of the bullets were stopped in Comparative Example 1 and Examples 1 to 3 and 50% of the bullets completely penetrated the theoretical speed V50 of Comparative Example 1 and Examples 1 to 3. For example, to determine the V50 speed, a plurality of shots are fired at each of Comparative Example 1 and Example 1 through Example 3 at varying speeds to determine the speed range at which the bullet completely penetrates the sample and the partial penetration of the sample by the bullet. Speed range. These shot groups for each sample were subjected to statistical analysis to determine the V50 speed for each of Comparative Example 1 and Examples 1 through 3 tested.

As shown in Table 4, Comparative Example 1 which is not a bimodal binder has the lowest V50 speed compared to Example 1, Example 2, and Example 3. As such, the samples of Examples 1 through 3 can withstand bullets fired at higher speeds in the event that the bullet does not completely penetrate the sample. Further, Example 1 containing 15% of the crystalline component and Example 3 containing 40% of the crystalline component each had a similar V50 speed.

Example C: Bimodal binder material with varying crystalline components

Various samples of the composite are formed from varying amounts of crystalline components within the binder material. These samples of the composite were then fired with a 9 mm bullet to determine if the presence of the crystalline component affected the ballistic resistance of the composite.

Formation of complex

To form these samples, various concentrations of the binder material were formed according to Table 3 to define Comparative Example 1, Example 1 of Composite 20, Example 2 of Composite 20, Example 3 of Composite 20, Example 4 of Composite 20, Example 5 of Composite 20 and Example 6 of Composite 20. The coating and composite treatment conditions used to form these samples were the same as those of Example 1 above for coating and composite processing.

Testing of complexes

Each of Comparative Examples 1 and 1 to 6 was placed on a clay block or platform, as further disclosed in Level III of NIJ STD 0101.06, and a 9 mm shot was fired at the rate of change shown in Table 6. Each of Example 1 and Example 1 to Example 6 was compared. More specifically, Table 6 provides that 50% of the bullets were stopped in Comparative Example 1 and Examples 1 to 6 and 50% of the bullets completely penetrated the theoretical speed V50 of Comparative Example 1 and Examples 1 to 6. For example, to determine the V50 speed, a plurality of shots are fired at each of Comparative Example 1 and Example 1 through Example 6 at varying speeds to determine the speed range at which the bullet completely penetrates the sample and the partial penetration of the sample by the bullet. Speed range. These shot groups for each sample were subjected to statistical analysis to determine the V50 speed for each of Comparative Example 1 and Examples 1 through 6 tested.

Table 6: 9mm FMJ V50 test results

As shown in Table 5, Comparative Example 1 which is not a bimodal binder has the lowest V50 speed as compared with Examples 1 to 6. As such, the samples of Examples 1 through 6 can withstand bullets fired at higher speeds in the event that the bullet does not completely penetrate the sample. In addition, Example 3 containing microcrystalline wax has a maximum V50.

Although the present invention has been particularly shown and described with reference to the preferred embodiments of the present invention, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The scope of the patent application is intended to cover the disclosed embodiments, the alternatives discussed above, and all equivalents thereof.

2‧‧‧Steel belt press

4‧‧‧First multiple rolls

6‧‧‧Second multiple rolls

8‧‧‧Temperature unit

8a‧‧‧heating section

8b‧‧‧cooling section

10‧‧‧First Belt

12‧‧‧Second belt

14‧‧‧Complex

Claims (10)

A ballistic resistant composite comprising: a plurality of fibers; and a bimodal binder applied to the plurality of fibers, the binder comprising a crystalline component having a melting temperature and an amorphous component having a softening temperature, the crystal The component and the amorphous component have at least one of the following properties with respect to each other: (1) the melting temperature of the crystalline component is less than the softening temperature of the amorphous component; and (2) is higher than the crystalline group At a temperature at which the melting temperature is divided, the viscosity of the crystalline component is less than the viscosity of the amorphous component; and (3) at a temperature above the melting temperature of the crystalline component, the surface energy of the crystalline component is less than The surface energy of the amorphous component. The ballistic resistant composite of claim 1, wherein the crystalline component is selected from the group consisting of wax materials: palm wax, stearylamine wax, polyethylene wax, paraffin wax, polyolefin wax, and microcrystalline wax. . The ballistic resistant composite of claim 1, wherein the amorphous component is composed of at least one selected from the group consisting of acrylic materials, polyurethanes, nitrile rubbers, acrylonitriles Alkene copolymers and fluorocarbons. The ballistic resistant composite of claim 1, wherein the amorphous component constitutes from 60 wt.% to 95 wt.% of the bimodal binder, and the crystalline component constitutes from 5 wt.% to 40 wt% of the bimodal binder. .%. The ballistic resistant composite of claim 1, wherein the melting temperature of the crystalline component is from 50 ° C to 140 ° C. A method of forming a ballistic resistant composite, comprising: providing a first fiber stack comprising a plurality of unidirectionally oriented first fibers, The first fibers are coated with a first bimodal binder comprising an amorphous component and a crystalline component; a second fiber laminate comprising a plurality of unidirectionally oriented second fibers, wherein the first The second fiber is coated with a second bimodal binder comprising an amorphous component and a crystalline component; the first fiber laminate and the second fiber laminate are positioned in a stacked configuration, the first fiber laminate and The second fiber laminate is heated to a temperature within a melting temperature range of the crystalline component; when the first fiber laminate and the second fiber laminate are at a temperature within the melting temperature range of the crystalline component, Applying a pressure of less than 1 bar to the laminates, whereby the first fiber laminate and the second fiber laminate are attached to each other and thereby forming a ballistic resistant composite; and the first fiber laminate and the second fiber laminate The layer is cooled. The method of claim 6, wherein the step of applying pressure to the first fiber laminate and the second fiber laminate is performed using a flat bed laminator. The method of claim 6, wherein the step of applying pressure to the first fiber laminate and the second fiber laminate comprises: applying a first pressure of less than 0.5 psi to the stacked stack during the heating step And applying a second pressure from 10 psi to 300 psi to the stacked stacks when the stack is at the temperature within the melting point of the crystalline component. The method of claim 6, wherein the amorphous component comprises an acrylic polymer, a polyurethane, a nitrile rubber, an acrylonitrile butadiene copolymer, a fluorocarbon polymer, or a combination thereof, and wherein the crystalline component These include palm wax, stearylamine wax, polyethylene wax, paraffin wax, polyolefin wax, microcrystalline wax, or a combination thereof. A method of forming a ballistic resistant composite, comprising: providing a first plurality of fibers oriented in a unidirectional direction; Providing a second plurality of fibers oriented in a unidirectional manner; providing a binder having an amorphous component and a crystalline component; coating the first plurality of fibers with the binder; coating the second plurality of the plurality of fibers with the binder a fiber; positioning the first plurality of fibers at an angle of 90 degrees to the second plurality of fibers; heating the first and second plurality of fibers to a temperature within a melting temperature range of the crystalline component; Applying a pressure of less than 1 bar to the first and second plurality of fibers when the first and second plurality of fibers are at a temperature within the melting point of the crystalline component; and causing the first and second plurality Fiber cooling.