WO2007067405A1

WO2007067405A1 - Flame retardant shield

Info

Publication number: WO2007067405A1
Application number: PCT/US2006/045790
Authority: WO
Inventors: Ashok Bhatnargar; Lori L. Wagner; Brian Arvidson
Original assignee: Honeywell International Inc.
Priority date: 2005-12-06
Filing date: 2006-11-30
Publication date: 2007-06-14
Also published as: JP2009518618A; CN101336360A; EP1957931A1; IL191969A0

Abstract

Flame resistant, ballistic resistant composite fabrics are provided. More particularly, structures are formed from a material having excellent flame and ballistic resistance. The fabrics and structures incorporate a non-halogen containing charring flame retardant that is preferably intumescent, whereby the material being charred forms a char foam, providing an insulating barrier when exposed to heat. While adding flame retardance, the fabrics and structures retain the excellent optimum ballistic resistant properties of the original material.

Description

FLAME RETARDANT SHIELD BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

This invention relates to flame resistant, ballistic resistant composite fabrics. More particularly, the invention pertains to structures formed from a material having excellent flame and ballistic resistance properties.

DESCRIPTION OF THE RELATED ART

Ballistic resistant articles containing high strength fibers that have excellent properties against deformable projectiles are known. Articles such as bulletproof vests, helmets, vehicle panels and structural members of military equipment are typically made from fabrics comprising high strength fibers. High strength fibers conventionally used include polyethylene fibers, para-aramid fibers such as poly(phenylenediamine terephthalamide), graphite fibers, nylon fibers, glass fibers and the like. For many applications, such as vests or parts of vests, the fibers may be used in a woven or knitted fabric. For many of the other applications, the fibers are encapsulated or embedded in a matrix material to form either rigid or flexible fabrics.

Various ballistic resistant constructions are known that are useful for the formation of articles such as helmets, panels and vests. For example, U.S. patents 4,403,012, 4,457,985, 4,613,535, 4,623,574, 4,650,710, 4,737,402, 4,748,064, 5,552,208, 5,587,230, 6,642,159, 6,841,492, 6,846,758, all of which are incorporated herein by reference, describe ballistic resistant composites which include high strength fibers made from materials such as extended chain ultrahigh molecular weight polyethylene. These composites display varying degrees of resistance to penetration by high speed impact from projectiles such as bullets, shells, shrapnel and the like.

For example, U.S. patents 4,623,574 and 4,748,064 disclose simple composite structures comprising high strength fibers embedded in an elastomeric matrix. U.S. patent 4,650,710 discloses a flexible article of manufacture comprising a plurality of flexible layers comprised of high strength, extended chain polyolefin (ECP) fibers. The fibers of the network are coated with a low modulus elastomeric material. U.S. patents 5,552,208 and 5,587,230 disclose an article and method for making an article comprising at least one network of high strength fibers and a matrix composition that includes a vinyl ester and diallyl phthalate. U.S. patent 6,642,159 discloses an impact resistant rigid composite having a plurality of fibrous layers which comprise a network of filaments disposed in a matrix, with elastomeric layers there between. The composite is bonded to a hard plate to increase protection against armor piercing projectiles.

One problem associated with current ballistic resistant fabrics and articles is their limited flame retardance. Flame retardance in ballistic resistant materials is highly desirable to maximize the protection provided by ballistic resistant articles. In general, a preferred route available for improving the flame retardance of polymeric materials is the incorporation of flame retardant additives in the polymer. Flame retardants act by interfering with the combustion process of polymers or other materials. Different classes of additives are available, each of which generally provide flame retardance through different modes of activity. For example, one class known as condensed-phase active flame retardants facilitate charring by reducing or limiting the amount of fuel available to a fire. Another class of flame retardants, known as volatile-phase active flame retardants, inhibit the combustion process by reducing heat released during combustion. Particular types of additives non-exclusively include charring types of additives that facilitate the charring of a material; heat-sink additives, such as aluminum trihydrate and magnesium hydroxide, that absorb and dissipate heat into the surrounding atmosphere; toxicant suppressants, which when added to a combustible material significantly reduce or prevent one or more toxic gases from being generated during thermal decomposition; and combinations of additives that take advantage of synergistic effects, i.e. multiple additives with differing but cooperative modes of activity in optimized combinations. Thus, different flame retardants may be effective at different stages in the combustion process compared to other flame retardants, and different flame retardants may also have certain advantages or disadvantage compared to other additives for certain applications based on the manner in which they perform.

For example, U.S. patent 5,480,706 provides a flame resistant, ballistic resistant article that incorporates a halogenated flame retardant, such as a halogenated paraffin, to add flame resistance. However, halogenated flame retardants are undesirable due to environmental and safety concerns. For example, halogenated flame retardants generate highly toxic gases, such as chlorine and bromine, during burning. Further, very strong acids are formed when these substances are mixed with water. These byproducts can be extremely harmful to the user of the ballistic resistant article, in addition to presenting an environmental hazard. Other additive types may have a significant effect on the physical properties of the original polymer. In some applications, relatively large amounts of flame retardant are required, and there can be large changes in the balance of properties dependent on whether the flame retardant behaves as a plasticizer or a filler. For example, large quantities of a filler material such as clay or sand may be useful for increasing flame retardance, but would not be useful for ballistic resistant articles because such materials substantially increase the weight of the ballistic articles, restricting their usefulness.

Accordingly, it would be highly desirable and advantageous in the art of ballistic resistant articles to provide a ballistic resistant material having excellent flame retardance without compromising the ballistic resistance properties, which is also less hazardous to both the user and the environment. The presently claimed invention provides a solution to this need. The presently claimed invention provides a flame resistant, ballistic resistant fabric comprising high strength fibers united in a matrix composition, the matrix composition comprising a charring flame retardant. The matrix composition generally comprises a binder material (matrix polymer), and the charring flame retardant may be on or blended with this binder material. Charring is a process of incomplete combustion that removes hydrogen and oxygen from the material being burned, such that char is composed primarily of carbon. The advantages of char formation include reduced mass of volatiles, wherein part of the carbon and hydrogen stays in the condensed phase, reducing the mass of volatile combustible degradation fragments evolved;

increased thermal capacity, wherein the formation of a char-polymer mixture increases the thermal capacity of the material relative to the uncharred material; and obstruction of combustible gases, whereby a charred surface may act as a physical barrier, obstructing the flow of combustible gases generated from the degradation of the underlying uncharred material, and hindering the access of oxygen to the surface of the polymer. Furthermore, char formation also provides thermal insulation, whereby as the polymer degrades, a char layer is formed over the remaining uncharred polymer, and the low thermal conductivity of this layer enables it to act as thermal insulation, absorbing some of the heat input and therefore reducing the heat flux reaching the uncharred polymer. The charring flame retardant is preferably non-halogen emitting, and is preferably an intumescent type flame retardant, whereby the material being charred expands in volume when exposed, forming a foam, and providing an insulating barrier when exposed to heat. For example, a non-halogenated, intumescent char consisting of numerous small bubbles has better insulation characteristics than a hard, brittle, dense char typically formed by halogenated flame retardants. It has also been found that the intumescent, charring behavior of the incorporated flame retardant additive has a negligible effect on the ballistic resistant properties of the fabric of the invention, retaining the optimum ballistic resistant properties of the original material.

SUMMARY OF THE INVENTION

The invention provides a flame resistant, ballistic resistant fabric comprising: a) a plurality of fibers arranged in an array, said fibers being united and forming a fabric, said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; and

b) a matrix composition comprising a charring flame retardant on the fibers.

The invention also provides a flame resistant, ballistic resistant fabric comprising at least one consolidated network of fibers, said consolidated network of fibers comprising a plurality of cross-plied fiber layers, each fiber layer comprising a plurality of fibers arranged in a substantially parallel array; said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; said fibers having a matrix composition thereon, which matrix composition comprises a charring flame retardant; the plurality of cross-plied fiber layers being consolidated with said matrix composition to form said consolidated network of fibers.

The invention further provides a flame resistant, ballistic resistant article which comprises a flame resistant, ballistic resistant fabric, which flame resistant, ballistic resistant fabric comprises:

a) a plurality of fibers arranged in an array, said fibers being united and forming a fabric, said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; and

b) a matrix composition comprising a charring flame retardant on the fibers.

The invention still further provides a method of producing a flame resistant, ballistic resistant fabric comprising:

a) forming at least two fiber layers, each fiber layer being formed by arranging a plurality of fibers into a substantially parallel, unidirectional array; said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; said fibers being coated with a matrix composition comprising a charring flame retardant;

b) arranging said fiber layers wherein the unidirectional array of fibers of each layer are cross-plied relative to each adjacent layer; and

c) bonding said cross-plied layers under conditions sufficient to form a single- layer, consolidated network, and thereby forming a fabric.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention presents flame resistant fabric composites having superior ballistic penetration resistance. For the purposes of the invention, fabrics having superior ballistic penetration resistance describe those which exhibit excellent properties against deformable projectiles. The flame resistant fabrics of the invention preferably comprise a single-layer, consolidated network of fibers in an elastomeric or rigid polymer composition, referred to in the art as a matrix composition, wherein the matrix composition comprises at least one charring flame retardant. The network of fibers comprises a plurality of fiber layers stacked together, each fiber layer comprising a plurality of fibers coated with said matrix composition and arranged in a substantially parallel array, and said fiber layers being consolidated to form said single-layer, consolidated network. The consolidated network may also comprise a plurality of yarns that are coated with such a matrix composition, formed into a plurality of layers and consolidated into a fabric.

For the puiposes of the present invention, a "fiber" is an elongate body the length dimension of which is much greater than the transverse dimensions of width and thickness. The cross-sections of fibers for use in this invention may vary widely. They may be circular, flat or oblong in cross-section. Accordingly, the term fiber includes filaments, ribbons, strips and the like having regular or irregular cross- section. They may also be of irregular or regular multi-lobal cross-section having one or more regular or irregular lobes projecting from the linear or longitudinal axis of the fibers. It is preferred that the fibers are single lobed and have a substantially circular cross-section.

As used herein, a "yarn" is a strand of interlocked fibers. An "array" describes an orderly arrangement of fibers or yarns, and a "parallel array" describes an orderly parallel arrangement of fibers or yarns. A fiber "layer" describes a planar arrangement of woven or non- woven fibers or yarns. A fiber "network" denotes a plurality of interconnected fiber or yarn layers. A fiber network can have various configurations. For example, the fibers or yarn may be formed as a felt or another woven, non- woven or knitted, or formed into a network by any other conventional technique. According to a particularly preferred consolidated network configuration, a plurality of fiber layers are combined whereby each fiber layer comprises fibers unidirectionally aligned in an array so that they are substantially parallel to each other along a common fiber direction. A "consolidated network" describes a consolidated combination of fiber layers with a matrix composition. As used herein, a "single layer" structure refers to structure composed of one or more individual fiber layers that have been consolidated into a single unitary structure. In general, a "fabric" may relate to either a woven or non- woven material.

As used herein, a "high-strength, high tensile modulus fiber" is one which has a preferred tenacity of at least about 7 g/denier or more, a preferred tensile modulus of at least about 150 g/denier or more, both as measured by ASTM D2256 and preferably an energy-to-break of at least about 8 J/g or more. As used herein, the term "denier" refers to the unit of linear density, equal to the mass in grams per 9000 meters of fiber or yarn. As used herein, the term "tenacity" refers to the tensile stress expressed as force (grams) per unit linear density (denier) of an unstressed specimen. The "initial modulus" of a fiber is the property of a material representative of its resistance to deformation. The term "tensile modulus" refers to the ratio of the change in tenacity, expressed in grams-force per denier (g/d) to the change in strain, expressed as a fraction of the original fiber length (in/in).

Particularly suitable high-strength, high tensile modulus fiber materials include extended chain polyolefm fibers, such as highly oriented, high molecular weight polyethylene fibers, particularly ultra-high molecular weight polyethylene fibers, and ultra-high molecular weight polypropylene fibers. Also suitable are extended chain polyvinyl alcohol fibers, extended chain polyacrylonitrile fibers, para- aramid fibers, polybenzazole fibers, such as polybenzoxazole (PBO) and polybenzothiazole (PBT) fibers and liquid crystal copolyester fibers. Each of these fiber types is conventionally known in the art.

In the case of polyethylene, preferred fibers are extended chain polyethylenes having molecular weights of at least 500,000, preferably at least one million and more preferably between two million and five million. Such extended chain polyethylene (ECPE) fibers may be grown in solution spinning processes such as described in U.S. patent 4,137,394 or 4,356,138, which are incorporated herein by reference, or may be spun from a solution to form a gel structure, such as described in U.S. patent 4,551,296 and 5,006,390, which are also incorporated herein by reference.

The most preferred polyethylene fibers for use in the invention are polyethylene fibers sold under the trademark Spectra® from Honeywell International Inc. Spectra® fibers are well known in the art and are described, for example, in commonly owned U.S. patents 4,623,547 and 4,748,064 to Harpell, et al.

Ounce for ounce, Spectra® high performance fiber is ten times stronger than steel, while also light enough to float on water. The fibers also possess other key properties, including resistance to impact, moisture, abrasion chemicals and puncture.

Suitable polypropylene fibers include highly oriented extended chain

polypropylene (ECPP) fibers as described in U.S. patent 4,413,110, which is incorporated herein by reference. Suitable polyvinyl alcohol (PV-OH) fibers are described, for example, in U.S. patents 4,440,711 and 4,599,267 which are incorporated herein by reference. Suitable polyacrylonitrile (PAN) fibers are disclosed, for example, in U.S. patent 4,535,027, which is incorporated herein by reference. Each of these fiber types is conventionally known and are widely commercially available.

Suitable aramid (aromatic polyamide) or para-aramid fibers are commercially available and are described, for example, in U.S. patent 3,671,542. For example, useful poly(p-phenylene terephyhalamide) filaments are produced commercially by Dupont corporation under the trade name of KEVLAR®. Also useful in the practice of this invention are poly(m-phenylene isophthalamide) fibers produced commercially by Dupont under the trade name NOMEX®. Suitable

polybenzazole fibers for the practice of this invention are commercially available and are disclosed for example in U.S. patents 5,286,833, 5,296,185, 5,356,584, 5,534,205 and 6,040,050, each of which are incorporated herein by reference. Preferred polybenzazole fibers are ZYLON® brand fibers from Toyobo Co. Suitable liquid crystal copolyester fibers for the practice of this invention are commercially available and are disclosed, for example, in U.S. patents 3,975,487; 4,118,372 and 4,161,470, each of which is incorporated herein by reference.

The other suitable fiber types for use in the present invention include glass fibers, fibers formed from carbon, fibers formed from basalt or other minerals, M5® fibers and combinations of all the above materials, all of which are commercially available. M5® fibers are manufactured by Magellan Systems International of Richmond, Virginia and are described, for example, in U.S. patents 5,674,969, 5,939,553, 5,945,537, and 6,040,478, each of which is incorporated herein by reference. Specifically preferred fibers include M5® fibers, polyethylene

Spectra® fibers, poly(p-phenylene terephthalamide) and poly(p-phenylene-2,6- benzobisoxazole) fibers. Most preferably, the fibers comprise high strength, high modulus polyethylene Spectra® fibers. The most preferred fibers for the purposes of the invention are high-strength, high tensile modulus extended chain polyethylene fibers. As stated above, a high- strength, high tensile modulus fiber is one which has a preferred tenacity of about 7 g/denier or more, a preferred tensile modulus of about 150 g/denier or more and a preferred energy-to-break of about 8 J/g or more, each as measured by ASTM D2256. In the preferred embodiment of the invention, the tenacity of the fibers should be about 15 g/denier or more, preferably about 20 g/denier or more, more preferably about 25 g/denier or more and most preferably about 30 g/denier or more. The fibers of the invention also have a preferred tensile modulus of about 300 g/denier or more, more preferably about 400 g/denier or more, more preferably about 500 g/denier or more, more preferably about 1,000 g/denier or more and most preferably about 1,500 g/denier or more. The fibers of the invention also have a preferred energy-to-break of about 15 J/g or more, more preferably about 25 J/g or more, more preferably about 30 J/g or more and most preferably have an energy-to-break of about 40 J/g or more. These combined high strength properties are obtainable by employing well known solution grown or gel fiber processes. U.S. patents 4,413,110, 4,440,711, 4,535,027, 4,457,985, 4,623,547 4,650,710 and 4,748,064 generally discuss the preferred high strength, extended chain polyethylene fibers employed in the present invention.

The fibers of the invention are coated on, impregnated with, embedded in, or otherwise applied with a matrix composition by applying the matrix composition to the fibers and then consolidating the matrix composition-fibers combination. By "consolidating" is meant that the matrix material and each individual fiber layer are combined into a single unitary layer. Consolidation can occur via drying, cooling, heating, pressure or a combination thereof. The fabric composites of the invention may be prepared using a variety of matrix materials, including both low modulus, elastomeric matrix materials and high modulus, rigid matrix materials. The term "matrix" as used herein is well known in the art, and is used to represent a binder material, such as a polymeric binder material, that binds the fibers together after consolidation. The term "composite" refers to consolidated combinations of fibers with the matrix material. Suitable matrix materials non-exclusively include low modulus, elastomeric materials having an initial tensile modulus less than about 6,000 psi (41.3 MPa), and high modulus, rigid materials having an initial tensile modulus at least about 300,000 psi (2068 MPa), each as measured at 37⁰C by ASTM D638. As used herein throughout, the term tensile modulus means the modulus of elasticity as measured by ASTM 2256 for a fiber and by ASTM D638 for a matrix material.

An elastomeric matrix composition may comprise a variety of polymeric and non- polymeric materials. The preferred elastomeric matrix composition comprises a low modulus elastomeric material. For the purposes of this invention, a low modulus elastomeric material has a tensile modulus, measured at about 6,000 psi (41.4 MPa) or less according to ASTM D638 testing procedures. Preferably, the tensile modulus of the elastomer is about 4,000 psi (27.6 MPa) or less, more preferably about 2400 psi ( 16.5 MPa) or less, more preferably 1200 psi (8.23 MPa) or less, and most preferably is about 500 psi (3.45 MPa) or less. The glass transition temperature (Tg) of the elastomer is preferably less than about 0⁰C, more preferably the less than about -40°C, and most preferably less than about - 50⁰C. The elastomer also has an preferred elongation to break of at least about 50%, more preferably at least about 100% and most preferably has an elongation to break of at least about 300%. A wide variety of elastomeric materials and formulations having a low modulus may be utilized as the matrix. Representative examples of suitable elastomers have their structures, properties, formulations together with crosslinking procedures summarized in the Encyclopedia of Polymer Science, Volume 5 in the section Elastomers- Synthetic (John Wiley & Sons Inc., 1964). Preferred low modulus, elastomeric matrix materials include polyethylene, cross-linked polyethylene, cholorosulfmated polyethylene, ethylene copolymers,

polypropylene, propylene copolymers, polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, polychloroprene, plasticized polyvinylchloride using one or more plasticizers that are well known in the art (such as dioctyl phthalate), butadiene aciylonitrile elastomers, poly (isobutylene- co-isoprene), polyacrylates, polyesters, unsaturated polyesters, polyethers, fluoroelastomers, silicone elastomers, thermoplastic elastomers, phenolics, polybutyrals, epoxy polymers, styrenic block copolymers, such as styrene- isoprene-styrene or styrene-butadiene-styrene types, and other low modulus polymers and copolymers curable below the melting point of the fiber. Also preferred are blends of different elastomeric materials, or blends of elastomeric materials with one or more thermoplastics.

Particularly useful are block copolymers of conjugated dienes and vinyl aromatic monomers. Butadiene and isoprene are preferred conjugated diene elastomers. Styrene, vinyl toluene and t-butyl styrene are preferred conjugated aromatic monomers. Block copolymers incorporating polyisoprene may be hydrogenated to produce thermoplastic elastomers having saturated hydrocarbon elastomer segments. The polymers may be simple tri-block copolymers of the type A-B-A, multi-block copolymers of the type (AB)_n (n= 2-10) or radial configuration copolymers of the type R-(BA)_x (x=3-150); wherein A is a block from a polyvinyl aromatic monomer and B is a block from a conjugated diene elastomer. Many of these polymers are produced commercially by Kraton Polymers of Houston, TX and described in the bulletin "Kraton Thermoplastic Rubber", SC-68-81. The most preferred matrix polymer comprises styrenic block copolymers sold under the trademark Kraton® commercially produced by Kraton Polymers.

Preferred high modulus, rigid matrix materials useful herein include materials such as a vinyl ester polymer or a styrene-butadiene block copolymer, and also mixtures of polymers such as vinyl ester and diallyl phthlate or phenol formaldahyde and polyvinyl butyral. A particularly preferred rigid matrix material for use in this invention is a thermosetting polymer, preferably soluble in carbon- carbon saturated solvents such as methyl ethyl ketone, and possessing a high tensile modulus when cured of at least about 1x10⁶ psi (6895 MPa) as measured by ASTM D638. Particularly preferred rigid matrix materials are those described in U.S. patent 6,642, 159, which is incorporated herein by reference.

The rigidity, impact and ballistic properties of the articles formed from the fabric composites of the invention are effected by the tensile modulus of the matrix polymer. For example, U.S. patent 4,623,574 discloses that fiber reinforced composites constructed with elastomeric matrices having tensile moduli less than about 6000 psi (41,300 kPa) have superior ballistic properties compared both to composites constructed with higher modulus polymers, and also compared to the same fiber structure without a matrix. However, low tensile modulus matrix polymers also yield lower rigidity composites. Further, in certain applications, particularly those where a composite must function in both anti-ballistic and structural modes, there is needed a superior combination of ballistic resistance and rigidity. Accordingly, the most appropriate type of matrix polymer to be used will vary depending on the type of article to be formed from the fabrics of the invention. In order to achieve a compromise in both properties, a suitable matrix composition may combine both low modulus and high modulus materials to form a single matrix composition. In the preferred embodiment of the invention, the proportion of fiber preferably comprises from about 70 to about 95% by weight of the composite, more preferably from about 79 to about 91% by weight of the composite, and most preferably from about 83 to about 89% by weight of the composite. The remaining portion of the composite is a combination of matrix and a flame retardant. The matrix composition may also include fillers such as carbon black or silica, may be extended with oils, or may be vulcanized by sulfur, peroxide, metal oxide or radiation cure systems as is well known in the art. The matrix composition may further include anti-oxidant agents, such as those sold under the Irganox® trademark, commercially available from Ciba Specialty Chemicals Corporation of Switzerland, particularly Irganox® 1010 ((tetrakis-(methylene- (3,5-di-terbutyl-4-hydrocmnamate)methane)); and surfactants that keep the flame retardant from settling in the matrix composition, such as those sold under the Cirrasol® trademark, commercially available from Uniqema of the Netherlands, particularly Cirrasol® G1096 (polyoxyethylene sorbitol ester).

In accordance with the invention, the matrix composition comprises at least one charring flame retardant. During combustion, the charring flame retardant combines with the fiber and matrix materials to form a char. As used herein, the term "charring flame retardant" refers to a flame retarding compound, composition or blend that generates a char or facilitates the charring of a material, wherein charring is a process of incomplete combustion that removes hydrogen and oxygen from the material being burned, such that a substance composed primarily of carbon remains. Preferred charring flame retardants include non- halogen emitting intumescent materials. As used herein, the term "intumescent" refers to materials that expand in volume when exposed to heat or flames exceeding a specified temperature. Suitable non-halogenated charring flame retardants non-exclusively include metal hydroxides such as alumina trihydrate and magnesium hydroxide (or hydrated magnesium), hydrated carbonate, calcium carbonate, boron containing flame retardants including zinc borate, aromatic boronic acids such as 1 ,4-benzenediboronic acid and phenylboronic acid, pentaerythritol, novolacs, non-halogen emitting iron additives such as ferric oxide and polyphenylene oxide and phosphorus, phosphorus containing compounds such as diphenyl phosphate and triphenyl phosphate, and combinations of the above. Of these, phosphorus, and phosphorus containing additives are the most preferred.

Within the class of charring flame retardants, different types of materials or blends may function in different ways. For example, phosphorus based retardants act primarily in the condensed phase by promoting charring, generally through the formation of phosphoric acid (when heated), and a decreased release of flammable volatiles. The formation of phosphoric acid occurs when the phosphorus compound is heated, which acid combines with carbon in polymers to cause a char. Alternately, metal hydroxides such as magnesium hydroxide or aluminum trihydroxide, decompose in the heat of a flame and release water of hydration. Such substances also act as smoke suppressants. These flame retardants may also be used as secondary additives to flame retarded polymer systems in which other flame retardants are present (e.g. phosphorus based compounds).

In the preferred embodiment of the invention, the charring type of flame retardant preferably comprises a blend of materials. For example, the charring flame retardant of the invention preferably comprises a blend which includes additives such as one or more synergists that increase the effectiveness of the char formation, spumifϊc agents that will blow the char up into the form of a foam, or charring catalysts that increases the rate of charring. Suitable synergists include melamine polyphosphate, ammonium polyphosphate and nitrogen gas emitting materials; suitable spumific agents (blowing agents) include amines/amides, melamine, dicyandiamide, urea and many other blowing agents which mainly emit nitrogen when heated; suitable catalysts include materials that emit boric, phosphoric or sulfuric acid during the burning process which combines with the polymers of the composite during the burning process to form the char such as phosphorous compounds, such as ammonium phosphate and phosphate esters, aromatic boronic acids and boron compounds as discussed above. For example, the spumifϊc agent melamine releases nitrogen gas, increasing the loft of a char and combining with, for example, phosphorous, to char the material. The nitrogen gas released by the melamine is also inert and slows the burning process.

Accordingly, suitable charring flame retardants preferably comprise a blend of the above materials.

Particularly preferred charring flame retardants include materials available under the Intumax® (previously known as Maxichar™), Exolit® and Budit® trademarks, particularly intumescent blends including melamine pyrophosphate and bis(melamine pyrophosphoric) acid available under the trademark Intumax®, sold by Broadview Technologies of Newark, NJ; intumescent blends including ammonium polyphosphate, available under the trademark Budit® 3077 BG, sold by Chemische Fabrik Budenheim Kg Limited Partnership of Germany; and intumescent blends including ammonium polyphosphate available under the trademark Exolit® AP 752, sold by Clariant International Ltd. of Switzerland. The charring flame retardant is preferably blended with the binder of the matrix composition using techniques which are well known in the art. For example, mixing the flame retardant into a solvent in a large vessel with a propeller type mixer with the help of a surfactant to keep the flame retardant in solution, then dissolving the matrix binder polymer to make the blend. In the preferred embodiment of the invention, the charring flame retardant comprises from about 1% to about 20% by weight of the total matrix composition, more preferably from about 3% to about 10%, and most preferably from about 5% to about 7% of the total matrix composition. Alternately, the charring flame retardant may be applied onto a layer of the matrix polymer using techniques well known in the art, thereby forming, for example, a two layer matrix composition. In the event that the charring flame retardant material is not blended with the matrix polymer, and the retardant is in powder form prior to application on the matrix polymer, the flame retardant may optionally be combined with a separate binding agent such as an epoxy, acrylic material, or other polymeric or non-polymeric material as is well known in the art. In the preferred embodiment of the invention, the matrix composition comprises a blend of the charring flame retardant and the matrix polymer binder, such as blend of a phosphorus or phosphorus containing charring flame retardant with a Kraton® polymer.

In general, the flame resistant, ballistic resistant fabrics of the invention are formed by arranging the high strength fibers into one or more fiber layers. Each layer may comprise an array of individual fibers or yarns. The matrix

composition is preferably applied to the high strength fibers either before or after the layers are formed, then followed by consolidating the matrix material-fibers combination together to form a multilayer complex. The matrix may be applied to the fiber in a variety of ways, such as by spraying or roll coating a solution of the matrix composition onto fiber surfaces, followed by drying. One method is to apply a neat polymer of the coating material to fibers either as a liquid, a sticky solid or particles in suspension or as a fluidized bed. Alternatively, the coating may be applied as a solution or emulsion in a suitable solvent which does not adversely affect the properties of the fiber at the temperature of application. For example, the fiber or yarn can be transported through a solution of the matrix composition to substantially coat the fiber or yarn and then dried to form a coated fiber or yarn. The resulting coated fiber or yarn can then be arranged into the desired network configuration. In another coating technique, a layer of fibers is first arranged, followed by dipping the layer into a bath of a solution containing the matrix material, and then dried through evaporation of the solvent. The dipping procedure may be repeated several times as required to place a desired amount of matrix material coating on the fibers.

While any liquid capable of dissolving or dispersing a polymer may be used, preferred groups of solvents include water, paraffin oils and aromatic solvents or hydrocarbon solvents, with illustrative specific solvents including paraffin oil, xylene, toluene, octane, cyclohexane, methyl ethyl ketone (MEK) and acetone. The techniques used to dissolve or disperse the coating polymers in the solvents will be those conventionally used for the coating of similar materials on a variety of substrates.

Other techniques for applying the coating to the fibers may be used, including coating of the high modulus precursor (gel fiber) before the fibers are subjected to a high temperature stretching operation, either before or after removal of the solvent from the fiber (if using the gel-spinning fiber forming technique). The fiber may then be stretched at elevated temperatures to produce the coated fibers. The gel fiber may be passed through a solution of the appropriate coating polymer under conditions to attain the desired coating. Crystallization of the high molecular weight polymer in the gel fiber may or may not have taken place before the fiber passes into the solution. Alternatively, the fiber may be extruded into a fluidized bed of an appropriate polymeric powder. Furthermore, if a stretching operation or other manipulative process, e.g. solvent exchanging, drying or the like, is conducted, the coating may be applied to a precursor material of the final fiber. In the most preferred embodiment of the invention, the fibers of the invention are first coated with the matrix composition, followed by arranging a plurality of fibers into either a woven or non- woven fiber layer. Such techniques are well known in the art.

The application of the matrix material preferably coats at least one surface of the fibers or yarns with the chosen matrix composition, preferably substantially coating or encapsulating each of the individual fibers. Following the application of the matrix material, the individual fibers in layer may or may not be bonded to each other prior to consolidation, which consolidation unites multiple fiber or yarn layers by pressing together and fusing as such coated fibers. The fabric composites of the invention preferably comprise a plurality of woven or non- woven fiber layers that are consolidated into a single layer, consolidated fiber network. In the preferred embodiment of the invention, the layers comprise non- woven fibers, each individual fiber layer of said consolidated fiber network preferably comprising fibers aligned in parallel to one another along a common fiber direction. Successive layers of such unidirectionally aligned fibers can be rotated with respect to the previous layer. Preferably, individual fiber layers of the composite are preferably cross-plied such that the fiber direction of the unidirectional fibers of each individual layer are rotated with respect to the fiber direction of the unidirectional fibers of adjacent layers. An example is a five layer article with the second, third, fourth and fifth layers rotated +45°, -45°, 90° and 0° with respect to the first layer, but not necessarily in that order. For the purposes of this invention, adjacent layers may be aligned at virtually any angle between about 0° and about 90° with respect to the longitudinal fiber direction of another layer. A preferred example includes two layers with a 0°/90° orientation. Such rotated unidirectional alignments are described, for example, in U.S. patents 4,457,985; 4,748,064; 4,916,000; 4,403,012; 4,623,573; and 4,737,402. The fiber networks can be constructed via a variety of well known methods, such as by the methods described in U.S. patent 6,642,159. It should be understood that the single-layer consolidated networks of the invention may generally include any number of cross-plied layers, such as about 20 to about 40 or more layers as may be desired for various applications.

In a preferred embodiment of the invention, the fibers of the invention are first coated with an elastomeric matrix composition using one of the above techniques, followed by arranging a plurality of fibers into a non- woven fiber layer.

Preferably, individual fibers are positioned next to and in contact with each other \ and are arranged into sheet-like arrays of fibers in which the fibers are aligned substantially parallel to one another along a common fiber direction. In a particularly effective technique for arranging the fibers into such a configuration, the fibers are pulled through a bath containing a solution of the elastomeric material, and are then helically wound into a single sheet-like layer around and along the length of a suitable form, such as a cylinder. The solvent from the solution is then evaporated leaving a pre-preg sheet of parallel arranged fibers that can be removed from the cylindrical form and cut to a desired size. Alternatively, a plurality of fibers can be simultaneously pulled through the bath of elastomer solution and laid down in closely positioned, substantially parallel relation to one another on a suitable surface. Evaporation of the solvent leaves a pre-preg sheet comprised of elastomer coated fibers which are substantially parallel and aligned along a common fiber direction.

The above methods are preferably followed to form at least two unidirectional fiber layers whereby the fibers are substantially coated with the matrix

composition on all fiber surfaces. Thereafter, the fiber layers are preferably consolidated into a single-layer consolidated fiber network. This may be achieved by stacking the individual fiber layers one on top of another, followed by bonding them together under heat and pressure to heat setting the overall structure, causing the matrix material to flow and occupy any remaining void spaces. As is conventionally known in the art, excellent ballistic resistance is achieved when individual fiber layer are cross-plied such that the fiber alignment direction of one layer is rotated at an angle with respect to the fiber alignment direction of another layer. For example, a preferred structure has two fiber layers of the invention positioned together such that the longitudinal fiber direction of one layer is perpendicular to the longitudinal fiber direction of the other layer.

In the most preferred embodiment, two layers of unidirectionally aligned fibers are cross-plied in the 0°/90° configuration and then molded to form a precursor. The two fiber layers can be continuously cross-plied, preferably by cutting one of the layers into lengths that can be placed successively across the width of the other layer in a 0°/90° orientation, forming what is known in the art as unitape. U.S. patents 5,173,138 and 5,766,725 describe apparatuses for continuous cross- plying. The resulting continuous two-ply structure can then be wound into a roll with a layer of separation material between each ply. When ready to form the end use structure, the roll is unwound and the separation material stripped away. The two-ply sub-assembly is then sliced into discrete sheets, stacked in multiple plies and then subjected to heat and pressure in order to form the finished shape and cure the matrix polymer, if necessary. Similarly, when a plurality of yarns are arranged to form a single layer, the yarns may be arranged unidirectionally and cross-plied in a similar fashion, followed by consolidation. Suitable bonding conditions for consolidating the fiber layers into a single layer, consolidated network, or fabric composite, include conventionally known lamination techniques. A typical lamination process includes pressing the cross- plied fiber layers together at about 1 10⁰C, under about 200 psi (1379 kPa) pressure for about 30 minutes. The consolidation of the fibers layers of the invention is preferably conducted at a temperature from about 200⁰F ( -93⁰C) to about 350°F (~177°C), more preferably at a temperature from about 200⁰F to about 300°F (~149°C) and most preferably at a temperature from about 200⁰F to about 280⁰F (-121⁰C), and at a pressure from about 25 psi (-172 kPa) to about 500 psi (3447 kPa) or higher. The consolidation may be conducted in an autoclave, as is conventionally known in the art.

When heating, it is possible that the matrix can be caused to stick or flow without completely melting. However, generally, if the matrix material is caused to melt, relatively little pressure is required to form the composite, while if the matrix material is only heated to a sticking point, more pressure is typically required. The consolidation step may generally take from about 10 seconds to about 24 hours. However, the temperatures, pressures and times are generally dependent on the type of polymer, polymer content, process and type of fiber. The thickness of the individual fabric layers will correspond to the thickness of the individual fibers. Accordingly, preferred single-layer, consolidated networks of the invention will have a preferred thickness of from about 25 μm to about 500 μm, more preferably from about 75 μm to about 385 μm and most preferably from about 125 μm to about 255 μm. While such thicknesses are preferred, it is to be understood that other film thicknesses may be produced to satisfy a particular need and yet fall within the scope of the present invention. After formation of the fabrics, they may be used in various applications. The temperatures and/or pressures to which one or more sheets of said single layer, consolidated network of fibers are exposed for molding vary depending upon the type of high strength fiber used. For example, armor panels can be made by molding a stack of said sheets under a pressure of about 150 to about 400 psi (1 ,030 to 2,760 kPa) preferably about 180 to about 250 psi (1 ,240 to 1 ,720 IcPa) and a temperature of about 104°C to about 127⁰C. Helmets can be made by molding a stack of said sheets under a pressure of about 1500 to about 3000 psi (10.3 to 20.6 MPa) and a temperature of about 104⁰C to about 127°C.

Also suitable are the techniques suitable for forming articles described in, for example, U.S. patents 4,623,574, 4,650,710, 4,748,064, 5,552,208, 5,587,230, 6,642,159, 6,841,492 and 6,846,758.

The fabric composites of the present invention are particularly useful for the formation of flame resistant, ballistic resistant "hard" armor articles. By "hard" armor is meant an article, such as helmets, panels for military vehicles, or protective shields, which have sufficient mechanical strength so that it maintains structural rigidity when subjected to a significant amount of stress and is capable of being freestanding without collapsing. The fiber networks may individually retain the high flexibility characteristic of textile fabrics and preferably remain separate from each other, i.e. not being bonded together. Alternately, multiple layers of fabric may be stitched together or bonded together with adhesive materials or other thermoplastic or non-thermoplastic fibers or materials.

Accordingly, articles of the invention may comprise a plurality of non- woven, flame resistant fabrics that are assembled into a bonded or non-bonded array. The single layer, consolidated network can be cut into a plurality of discrete sheets and stacked for formation into an article or they can be formed into a precursor which is subsequently used to form an article. Such techniques are well known in the art.

Garments of the invention may be formed through methods conventionally known in the art. Preferably, a garment may be formed by adjoining the flame resistant fabrics of the invention with an article of clothing. For example, a vest may comprise a generic fabric vest that is adjoined with the flame resistant fabrics of the invention, whereby the inventive fabrics are inserted into strategically placed pockets. This allows for the maximization of ballistic protection, while minimizing the weight of the vest. As used herein, the terms "adjoining" or "adjoined" are intended to include attaching, such as by sewing or adhering and the like, as well as un-attached coupling or juxtaposition with another fabric, such that the flame resistant, ballistic resistant fabrics may optionally be easily removable from the vest or other article of clothing. Vests and other articles of clothing comprised of multiple layers of fabric constructed in accordance with the present invention have good flexibility and comfort coupled with excellent ballistic protection and flame resistance. Fabrics used in forming flexible structures like flexible sheets, vests and other garments are preferably formed from fabrics using a low tensile modulus matrix composition. Hard articles like helmets and armor are preferably formed from fabrics using a high tensile modulus matrix composition.

The flame resistance of the fabrics are determined using standard testing procedures that are well known in the art. For example, in test method ASTM El 354 (Cone Calorimeter Testing), intense heat and flame (equivalent to 50 KW of heat) is applied to a sample. A number of parameters are then recorded during the specimen burning.

The ballistic resistance properties are determined using standard testing procedures that are well known in the art. For example, screening studies of ballistic composites commonly employ a 22 caliber, non-deforming steel fragment of specified weight, hardness and dimensions (Mil-Spec.MIL-P- 46593A(ORD)). The protective power or penetration resistance of a structure is normally expressed by citing the impacting velocity at which 50% of the projectiles penetrate the composite while 50% are stopped by the shield, also known as the V₅₀ value. As used herein, the "penetration resistance" of the article is the resistance to penetration by a designated threat, such as physical objects including bullets, fragments, shrapnels and the like, and non-physical objects, such as a blast from explosion. For composites of equal areal density, which is the weight of the composite panel divided by the surface area, the higher the V₅o, the better the resistance of the composite. The ballistic resistant properties of the fabrics of the invention will vary depending on many factors, particularly the type of fibers used to manufacture the fabrics. However, it has been found that the

incorporation of a charring flame retardant into the matrix composition does not negatively affect the ballistic properties of the fabrics of the invention, as can be seen in the examples below. The following non-limiting examples serve to illustrate the invention.

EXAMPLE 1 (COMPARATIVE) A two-ply, 0°/90° cross-plied, non-woven composite was formed from layers of high modulus polyethylene fibers (HMPE)(SPECTRA® 1000, 1100 denier fibers). A first unitape of HMPE fibers was prepared by passing the fibers from several creels of fibers through a comb to form a unidirectional array. The fibers were coated with a matrix and then placed on a carrier web. The matrix polymer was a solution of Kraton® polymer dissolved in cyclohexane solvent. The coated fibers, having a 39 gsm fiber areal density, were then passed through an oven to evaporate the cyclohexane solvent. After drying, the fiber web was wound up on a roll. The width of this roll was 63". The polymer content on the fiber web was 20% by weight .

A second similar unitape was also prepared separately. Two fiber networks were cross-plied at 0°/90° and consolidated under heat and pressure to create a continuous roll of ballistic material. The total areal density of the cross-plied material was 98 gsm.

A 0.22" thick, 12" X 12" panel of the first unitape was molded by stacking 50 layers of cross-plied material. The molding conditions of the panel were 240°F heat and 500 psi pressure for 20 minutes. The panel was tested for ballistic resistance using the MIL-STD-662F test method utilizing a 17 grain Fragment Simulating Projectile (FSP) conforming to MIL-P-46593A. The V₅₀ of the panel was 1750 feet per second (fps). A 0.1" thick panel of the second unitape was molded by stacking 22 layers of cross-plied material. The molding conditions of this panel were the same as above. A 4" X 4" sample was cut from the above panel and tested for flame resistance. The ASTM E1354-Cone Calorimeter Test was used on the sample using 50 KW of heat energy. The average mass loss rate of his test sample was 12.269 kg/m², peak heat release rate was 645.17 KW/m², average heat release rate during burning was 325.43 KW/m², and time to peak rate of heat release was 110 seconds. EXAMPLE 2 (COMPARATIVE)

Example 1 was repeated, except an aqueous based Kraton® polymer emulsion was used to form both of the first and second unitapes. The polymer content was 16%. The cross-plied roll was made using four plies (0°, 90°, 0°, 90°)

configuration. The total areal density of this four-ply cross-plied roll was 250 gsm.

A 0.22" thick, 12" X 12" panel of the first unitape was molded by stacking 20 layers of cross-plied material. The molding conditions of panel were 240⁰F heat and 500 psi pressure for 20 minutes. The panel was tested for ballistic resistance using the MIL-STD-662F test method utilizing a 17 grain Fragment Simulating Projectile conforming to MIL-P-46593A. The V₅₀ of the panel was 1825 fps.

A 0.1" thick panel of the second unitape was molded stacking 9 layers of cross- plied material. The molding conditions of the panel were the same as above. A 4" X 4" sample was cut from the above panel and tested for flame resistance. The ASTM E1354-Cone Calorimeter Test was conduced on the sample using 50 KW of heat energy. The average mass loss rate of his test sample was 12.334 kg/m², peak heat release rate was 752.45 KW/m², average heat release rate during burning was 308.42 KW/m² and time to peak rate of heat release was 135 seconds. EXAMPLE 3

Example 1 was repeated, except 5%, by weight of the composite, of Budit® 3077 BG charring flame retardant blend was mixed with Kraton® polymer solution. The matrix composition comprised the following formulation which includes a charring flame retardant which comprises an intumescent blend containing ammonium polyphosphate and a melamine containing material:

Cyclohexane (Solvent) 79.48 wt. %

Budit® 3077 BG (Charring Flame retardant) 5.07 wt. %

Irganox™ 1010 (Anti-Oxidant Agent) 0.31 wt. %

Kraton polymer(Matrix Polymer) 15.14 wt. %

The two-ply cross-plied roll had a total areal density of 98 gsm. A 0.22" thick, 12" X 12" panel of the first unitape was molded by stacking 50 layers of flame retardant cross-plied material. The molding conditions of panel were 240⁰F heat and 500 psi pressure for 20 minutes. The panel was tested for ballistic resistance using the MIL-STD-662F test method utilizing a 17 grain Fragment Simulating Projectile conforming to MIL-P-46593A. The V₅o of the panel was 1795 fps.

A 0.1" thick panel of the second unitape was molded stacking 22 layers of cross- plied material. The molding conditions of panel were the same as above. A 4" X 4" sample was cut from the above panel and tested for flame resistance. The ASTM E1354-Cone Calorimeter Test was conduced on the sample in which intense heat and flame (50 KW of heat energy) is applied to the sample. The average mass loss rate of his test sample was 9.930 kg/m², peak heat release rate was 521.12 KW/m², average heat release rate during burning was 274.73 KW/m , and time to peak rate of heat release was 100 seconds.

These examples show that the addition of a charring type of flame retardant to the matrix composition of a ballistic resistant fabric adds flame retardance without reducing either the ballistic resistance or structural properties of the fabric.

The results from Examples 1-3 are summarized in the following table:

EXAMPLE 4

Example 3 is repeated using the following matrix formulation which includes a charring flame retardant which comprises an intumescent blend containing ammonium polyphosphate with a nitrogen containing synergist:

Cyclohexane (Solvent) 79.17 wt. %

Exolit® AP 752 (Charring Flame retardant) 6.85 wt . %

Irganox™ 1010 (Anti-Oxidant Agent) 0.28 wt. %

Kraton® polymer (Matrix Polymer) 13.70 wt. %

EXAMPLE 5

Example 3 is repeated using the following matrix formulation which includes a charring flame retardant which comprises an intumescent phosphorus containing blend: Cyclohexane (Solvent) 76.30 wt. %

Cirrasol® G 1096 (Surfactant) 2.30 wt. %

Intumax® (Charring Flame retardant) 7.80 wt. %

Irganox™ 1010 (Anti-Oxidant Agent) 0.40 wt. %

Kraton® polymer (Matrix Polymer) 13.20 wt. %

While the present invention has been particularly shown and described with reference to preferred embodiments, it will be readily appreciated by those of ordinary skill in the art that various changes and modifications may be made without departing from the spirit and scope of the invention. It is intended that the claims be interpreted to cover the disclosed embodiment, those alternatives which have been discussed above and all equivalents thereto.

Claims

What is claimed is:

1. A flame resistant, ballistic resistant fabric comprising:

b) a matrix composition comprising a charring flame retardant on the fibers.

2. The flame resistant, ballistic resistant fabric of claim 1 wherein the matrix composition comprises a charring flame retardant blended with a binder.

3. The flame resistant, ballistic resistant fabric of claim 1 wherein the matrix composition comprises a charring flame retardant on a binder.

4. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises a non-halogen emitting, intumescent material.

5. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises a non-halogen emitting, spumifϊc material.

6. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises a phosphorus containing material.

7. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises an ammonium polyphosphate containing material.

8. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises from about 1% to about 20% by weight of said fabric.

9. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises from about 3% to about 10% by weight of said fabric.

10. The flame resistant, ballistic resistant fabric of claim 1 wherein said charring flame retardant comprises from about 5% to about 7% by weight of said fabric.

11. The flame resistant, ballistic resistant fabric of claim 1 wherein said fibers comprise a material selected from the group consisting of extended chain polyolefin fibers, aramid fibers, polybenzazole fibers, polyvinyl alcohol fibers, polyamide fibers, polyethylene terephthalate fibers, polyethylene naphthalate fibers, polyacrylonitrile fibers, liquid crystal copolyester fibers, glass fibers, carbon fibers, and combinations thereof.

12. The flame resistant, ballistic resistant fabric of claim 1 wherein said fibers comprise polyethylene fibers.

13. The flame resistant, ballistic resistant fabric of claim 1 wherein said matrix composition has an initial tensile modulus measured at 37°C of about 6,000 psi or less.

14. The flame resistant, ballistic resistant fabric of claim 1 wherein said matrix composition has an initial tensile modulus measured at 37⁰C of at least about 300,000 psi.

15. A flame resistant, ballistic resistant fabric comprising at least one

consolidated network of fibers, said consolidated network of fibers comprising a plurality of cross-plied fiber layers, each fiber layer comprising a plurality of fibers arranged in a substantially parallel array; said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; said fibers having a matrix composition thereon, which matrix composition comprises a charring flame retardant; the plurality of cross-plied fiber layers being consolidated with said matrix composition to form said consolidated network of fibers.

16. The flame resistant, ballistic resistant fabric of claim 15 wherein the matrix composition comprises a charring flame retardant blended with a binder.

17. The flame resistant, ballistic resistant fabric of claim 15 wherein the matrix composition comprises a charring flame retardant on a binder.

18. The flame resistant, ballistic resistant fabric of claim 15 wherein each of said fiber layers are cross-plied at a 90° angle relative to the fiber direction of each adjacent fiber layer.

19. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises a non-halogen emitting, intumescent material.

20. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises a non-halogen emitting, spumific material.

21. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises a phosphorus containing material.

22. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises an ammonium polyphosphate containing material.

23. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises from about 1% to about 20% by weight of said fabric.

24. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises from about 3% to about 10% by weight of said fabric.

25. The flame resistant, ballistic resistant fabric of claim 15 wherein said charring flame retardant comprises from about 5% to about 7% by weight of said fabric.

26. The flame resistant, ballistic resistant fabric of claim 15 wherein said fibers comprise a material selected from the group consisting of extended chain polyolefin fibers, aramid fibers, polybenzazole fibers, polyvinyl alcohol fibers, polyamide fibers, polyethylene terephthalate fibers, polyethylene naphthalate fibers, polyacrylonitrile fibers, liquid crystal copolyester fibers, glass fibers, carbon fibers, and combinations thereof.

27. The flame resistant, ballistic resistant fabric of claim 15 wherein said fibers comprise polyethylene fibers.

28. The flame resistant, ballistic resistant fabric of claim 15 wherein said matrix composition has an initial tensile modulus measured at 37°C of about 6,000 psi or less.

29. The flame resistant, ballistic resistant fabric of claim 15 wherein said matrix composition has an initial tensile modulus measured at 37°C of at least about 300,000 psi.

30. A flame resistant, ballistic resistant article which comprises a flame resistant, ballistic resistant fabric, which flame resistant, ballistic resistant fabric comprises: a) a plurality of fibers arranged in an array, said fibers being united and forming a fabric, said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; and

b) a matrix composition comprising a charring flame retardant on the fibers.

31. The flame resistant, ballistic resistant article of claim 30 which comprises a molded panel.

32. The flame resistant, ballistic resistant article of claim 30 which comprises a garment and wherein said flame resistant, ballistic resistant fabric comprises a plurality of layers of said fibers consolidated into a single-layer network, wherein one or more of said networks are adjoined to said garment.

33. The flame resistant, ballistic resistant article of claim 30 wherein said charring flame retardant comprises a non-halogen emitting, intumescent material.

34. The flame resistant, ballistic resistant article of claim 30 wherein said charring flame retardant comprises a non-halogen emitting, spumific material.

35. The flame resistant, ballistic resistant article of claim 30 wherein said charring flame retardant comprises a phosphorus containing material.

36. The flame resistant, ballistic resistant article of claim 30 wherein said charring flame retardant comprises an ammonium polyphosphate containing material.

37. A method of producing a flame resistant, ballistic resistant fabric comprising: a) forming at least two fiber layers, each fiber layer being formed by arranging a plurality of fibers into a substantially parallel, unidirectional array; said fibers having a tenacity of about 7 g/denier or more and a tensile modulus of about 150 g/denier or more; said fibers being coated with a matrix composition comprising a charring flame retardant;

38. The method of claim 37 wherein said charring flame retardant comprises a non-halogen containing, intumescent material.

39. The method of claim 37 wherein said charring flame retardant comprises a non-halogen containing, spumific material.

40. The method of claim 37 wherein said charring flame retardant comprises a phosphorus containing material.