Low weight and high durability soft body armor composite using silicone-based topical treatments

ES 2 445 656 T3

DESCRIPTION

Composite material for soft, lightweight and highly durable body armor using silicone-based topical treatments

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

This invention relates to bullet resistant articles with improved abrasion resistance.

DESCRIPTION OF THE RELATED TECHNIQUE

Bullet resistant articles containing high strength fibers having excellent projectile properties are well known. Items such as bulletproof vests, helmets, vehicle panels, and structural members of military equipment are typically made from fabrics comprising high-strength fibers. Conventionally used high strength fibers include polyethylene fibers, aramid fibers such as poly (phenylenediamine terephthalamide), graphite fibers, nylon fibers, glass fibers, and the like. For many applications such as vests or vest parts, the fibers can be used in a woven or knitted fabric. For other applications, the fibers can be encapsulated or embedded in a polymeric matrix material to form rigid or flexible, woven or non-woven fabrics. Preferably, each of the individual fibers that make up the fabrics of the invention are substantially coated or encapsulated by the binder (matrix) material. From US 6063473 an abrasion resistant composite material is known comprising at least one fibrous substrate having a multilayer coating thereon.

Various bullet resistant structures are known to be useful for the formation of hard or soft armor articles such as helmets, panels and vests. For example, US Pat. 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 describe composite materials bullet resistant including high strength fibers made from materials such as ultra-high molecular weight extended chain polyethylene. These composite materials exhibit varying degrees of resistance to penetration by high velocity impact from projectiles such as bullets, shells, shrapnel, and the like.

For example, US Patents 4,623,574 and 4,748,064 describe simple composite structures comprising high-strength fibers embedded in an elastomeric matrix. US Patent 4,650,710 describes a flexible article of manufacture comprising a plurality of flexible layers made up of high strength extended chain polyolefin (ECP) fibers. The fibers of the net are coated with a low modulus elastomeric material. US Patents 5,552,208 and 5,587,230 describe an article and a method for producing an article comprising at least one high-strength fiber network and a matrix composition that includes a vinyl ester and diallyl phthalate. US Pat. US 6,642,159 describes a rigid impact resistant composite material having a plurality of fibrous layers comprising a network of filaments arranged in a matrix, with elastomeric layers in between. The composite material is bonded to a hard plate to increase protection against armor-piercing projectiles.

Hard or rigid body armor provides good resistance to bullets, but can be too stiff and bulky. Accordingly, garments with body armor, such as bulletproof vests, are preferably formed from flexible materials or soft armor. However, even though these types of flexible or soft materials exhibit excellent bullet resistance properties, they also generally exhibit poor abrasion resistance, which affects the durability of the armor. It is desirable in the art to provide soft and flexible bullet resistant materials that have improved durability. The present invention provides a solution to this need.

SUMMARY OF THE INVENTION

The invention provides an abrasion resistant composite material comprising at least one fibrous substrate having a multilayer coating thereon, wherein said fibrous substrate comprises one or more fibers having a toughness of about 7 g / denier or more and a tensile modulus of about 150 g / denier or more; said multilayer coating comprising a layer of a non-silicon-containing material on a surface of said one or more fibers, and a topical layer of a material containing silicon

ES 2 445 656 T3 in silicon on the layer of non-silicon-containing material.

The invention also provides a method of forming an abrasion resistant composite material, comprising:

i) providing at least one coated fibrous substrate having a surface; wherein said at least one fibrous substrate comprises one or more fibers having a tenacity of about 7 g / denier or more and a tensile modulus of about 150 g / denier or more; the surfaces of each of said fibers being substantially coated with a non-silicon-containing material; and ii) applying a silicon-containing material over at least a portion of said at least one coated fibrous substrate.

The invention further provides a method of forming an abrasion resistant composite material, comprising:

i) providing a plurality of nonwoven fiber layers, each of the fiber layers comprising a plurality of fibers having a tenacity of about 7 g / denier or more and a tensile modulus of about 150 g / denier or more, the surfaces of each of said fibers being substantially coated with a non-silicon-containing material;

ii) applying an uncured silicon-containing coating over at least a portion of said fiber layers;

^Y iii) subjecting said plurality of nonwoven fiber layers and said uncured silicon-containing coating to conditions sufficient to consolidate said fiber layers into a monolithic fabric composite material and optionally curing the silicon-containing coating .

DETAILED DESCRIPTION OF THE INVENTION

The invention features composite materials and fibrous articles with superior abrasion resistance and durability. In particular, the invention provides fibrous composites formed by applying a multilayer coating of the invention over at least one fibrous substrate. A "fibrous substrate", as used herein, can be a single fiber or a fabric, including felt, that has been formed from a plurality of fibers. Preferably, the fibrous substrate is a fabric comprising a plurality of fibers that are bonded together in the form of a monolithic structure, including woven and non-woven fabrics. Coatings of the non-silicon-containing material or both the non-silicon-containing material and the silicon-containing material can be applied on a plurality of fibers that are arranged in the form of a fiber web or other arrangement, which may or may not be considered as a fabric at the time of coating. The invention also provides fabrics formed from a plurality of coated fibers, and articles formed from such fabrics.

The fibrous substrates of the invention are coated with a multilayer coating comprising at least one layer of two different coating materials, wherein a layer of a non-silicon-containing material is applied directly to a surface of one or more of the fibers, and a topical coating of a silicon-containing material is applied over the top of the layer of non-silicon-containing material.

As used herein, a "silicon-containing" material describes non-polymeric materials and polymers containing silicon atoms, including both cured and uncured silicon-based polymers, as well as non-polymeric low molecular weight materials. As used herein, "silicone" is defined as a polymeric organic siloxane, specifically organic compounds comprising alternating silicon and oxygen atoms bonded to organic radicals, as is well known in the art. Silicone-based materials are derived from silicone. The silicon-containing coating preferably comprises a cured thermosetting polymer, a non-reactive thermoplastic polymer, or an uncured, silicon-based fluid or liquid. Most preferably, the silicon-containing material is uncured, which allows the silicon-containing material to serve as a lubricant, uniformly coating the substrate with a thin layer of the silicon-containing material and achieving the greatest improvement in performance. abrasion resistance.

For the purposes of the invention, a liquid polymer includes polymers that combine with a solvent or other liquid capable of dissolving or dispersing a polymer, molten polymers that do not combine with a solvent or other liquid, as well as uncured flowable polymers. In preferred embodiments, the silicon-containing material is an uncured, silicone-based fluid that is applied in the form of a silicone-based fluid and remains as a silicone-based fluid in the finished product on the surface of the fabric. made of composite material. A silicone-based fluid will act as a lubricant for the surface of the fabric material.

ES 2 445 656 T3 composite and will improve the abrasion resistance of the composite material.

Alternatively, a curable, liquid silicone-based fluid can be applied to the fibrous substrate and subsequently cured. However, cured or solid silicone polymers, as opposed to uncured silicone fluids, do not normally act as lubricants and may not provide the same abrasion resistance as uncured silicone-based fluids. Other non-silicon-containing lubricants can provide a similar abrasion resistance benefit, but silicone-based materials have low surface energy and are uniquely capable of providing a lubricating effect, while remaining essentially on the substrate. A cured silicone-based coating will add another layer of protection to the fibrous substrate, but a cured silicone-based coating by itself can wear away while the fluids cannot wear away. Thus, uncured silicone-based coatings are most preferred.

In preferred embodiments of the invention, the silicon-containing material comprises an uncured silicone-based fluid or liquid, an uncured silicone-based antifoam agent, an uncured silicone-based lubricant, or an uncured silicone-based release coating. cured. Preferably, the silicone-based fluid comprises a polymeric organic siloxane. Dialkyl silicone fluids are preferred, particularly polydimethylsiloxane, as well as more polar amino functional, silanol functional and polyether functional silicones. Suitable dialkyl silicone fluids are described, for example, in US Patent 4,006,207. Other suitable silicone fluids include DOW CORNING 200® fluids, commercially available from Dow Corning of Midland, MI, preferably its non-reactive silicone fluids, including DOW CORNING 200® (DC200) 10 centistokes (cst) silicone fluid, up to 1000 cst DC200; Dow Corning silicone release agents, including DOW CORNING® HV-495 Emulsion (HV-495) and DOW CORNING® 36 Emulsion (DC-36); and Dow Corning defoaming / antifoaming agents such as DOW CORNING® Antifoam 1410 Emulsion (DC-1410). Useful silicone-based fluids also include commercially available silicone additives from Byk-Chemie of Wesel, Germany, and Wacker-Belsil® DM polydimethylsiloxane fluids, commercially available from Wacker Chemical Corp. of Adrian, Michigan. Also useful are Wacker Chemical Corp's silicone release agents such as Wacker Silicone Release Agent TN and WACKER® TNE 50. Liquid silicone polymers described in US Patents 4,780,338 and 4,929,691 are also useful. Useful silicone antifoam agents are described, for example, in US Patents 5,153,258, 5,262,088.

Preferably, the silicon-containing material comprises a silicone-based fluid having a weight average molecular weight of from about 200 g / mole to about 250,000 g / mole, more preferably from about 500 g / mole to about 80,000 g / mole, plus preferably from about 1000 g / mol to about 40,000 g / mol, and most preferably from about 2000 g / mol to about 20,000 g / mol. Lower molecular weight silicon-containing materials may not be considered polymers, but for the silicon-containing material layer, polymeric silicon-containing materials are preferred. Preferably, the silicon-containing material comprises a silicone-based fluid having a viscosity of from about 1 cst to about 100,000 cst at 25 ° C, more preferably from about 10 cst to about 10,000 cst, and most preferably from about 10 cst. up to about 1000 cst at 25 ° C. The most preferred silicone-based fluids will have a viscosity of from about 10 cst to about 1000 cst at 25 ° C with a corresponding weight average molecular weight of from about 1000 g / mol to about 20,000 g / mol. These preferences are not intended to be limiting, and silicone-based liquids with higher / lower molecular weights and higher / lower viscosities can also be used.

The coated fibrous substrates of the invention are particularly intended for the production of fabrics and articles with superior resistance to bullet penetration. For the purposes of the invention, articles having superior resistance to bullet penetration describe those that exhibit excellent properties against deformable projectiles and against the penetration of fragments such as shrapnel. For the purposes of the present invention, a "fiber" is an elongated 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 can vary widely. These can be circular, flat or oblong in cross section. Accordingly, the term fiber includes filaments, tapes, strips and the like with a regular or irregular cross section. They may also be of an irregular or regular multi-lobular 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 be single lobe and have a substantially circular cross section.

ES 2 445 656 T3

As stated above, multilayer coatings can be applied over a single polymeric fiber or a plurality of polymeric fibers. A plurality of fibers may be present in the form of a web of fibers, a woven fabric, a nonwoven fabric, or a yarn, where a yarn is defined herein as a strand consisting of multiple fibers and a fabric comprises a plurality of bonded fibers. In embodiments that include a plurality of fibers, multilayer coatings can be applied either before the fibers are laid into a fabric or yarn, or after the fibers are laid into a fabric or yarn.

The fibers of the invention can comprise any type of polymeric fiber. More preferably, the fibers comprise high tensile modulus, high strength fibers that are useful for the formation of bullet resistant materials and articles. As used herein, a "high tensile modulus, high strength fiber" is one that has a preferred toughness of at least about 7 g / denier or more, a preferred tensile modulus of at least about 150 g / denier. denier or more and preferably an energy at break of at least about 8 J / g or more, each of which is measured by ASTM D2256. 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 "toughness" refers to tensile stress expressed as force (grams) per unit linear density (denier) of an unstressed sample. 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 toughness, expressed in grams-force per denier (g / d) to the change in stress, expressed as a fraction of the original fiber length (inch / inch).

The polymers that form the fibers are preferably fibers of high strength and high tensile modulus, suitable for the manufacture of bulletproof fabrics. High tensile modulus, high strength fiber materials that are particularly suitable for the formation of bullet resistant materials and articles include polyolefin fibers including high density and low density polyethylene. Particularly preferred are chain-extended polyolefin fibers such as high molecular weight, highly oriented polyethylene fibers, particularly ultra-high molecular weight polyethylene fibers, and polypropylene fibers, particularly ultra-high molecular weight polypropylene fibers. Also suitable are aramid fibers, particularly para-aramid fibers, polyamide fibers, poly (ethylene terephthalate) fibers, poly (ethylene naphthalate) fibers, extended chain poly (vinyl alcohol) fibers, polyacrylonitrile fibers. chain-extended, polybenzazole fibers, such as polybenzoxazole (PBO) and polybenzothiazole (PBT) fibers, liquid crystal copolyester fibers, and rigid rod fibers such as M5® fibers. Each of these types of fibers is conventionally known in the art. Also suitable for producing polymeric fibers are copolymers, block polymers and blends of the above materials.

Most preferred fiber types for bullet resistant fabrics include polyethylene, particularly extended chain polyethylene fibers, aramid fibers, polybenzazole fibers, liquid crystal copolyester fibers, polypropylene fibers, particularly highly extended chain polypropylene fibers oriented, polyvinyl alcohol fibers, polyacrylonitrile fibers and rigid rod fibers, particularly M5® fibers.

In the case of polyethylene, preferred fibers are chain-extended polyethylenes with molecular weights of at least 500,000, preferably at least one million, and more preferably between two million and five million. Chain-extended polyethylene (ECPE) fibers of this type can be developed in solution spinning processes as described in US Pat. 4,137,394 or 4,356,138 or can be spun from solution to form a gel structure as described in US Patents 4,551,296 and 5,006,390. A particularly preferred type of fiber 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 US Pat. US 4,623,547 and 4,748,064.

Also particularly preferred are aramid (aromatic polyamide) or para-aramid fibers. These are commercially available and are described, for example, in US Patent 3,671,542. For example, useful poly (p-phenylene terephthalamide) filaments are commercially produced by Dupont Corporation under the trademark KEVLAR®. Also useful in the practice of this invention are poly (m-phenylene isophthalamide) fibers commercially produced by Dupont under the trademark NOMEX®, and fibers commercially produced by Teijin under the trademark TWARON®; aramid fibers produced commercially by Kolon Inustries, Inc. from Korea under the trademark HERACRON®; SVM ™ and RUSAR ™ p-aramid fibers that are commercially produced by Kamensk Volokno JSC of Russia and ARMOS ™ p-aramid fibers commercially produced by JSC Chim Volokno of Russia.

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Polybenzazole fibers suitable for the practice of this invention are commercially available and are described, for example, in US Patents 5,286,833, 5,296,185, 5,356,584, 5,534,205 and 6,040,050. Liquid crystal copolyester fibers suitable for the practice of this invention are commercially available and are described, for example, in US Patents 3,975,487; 4,118,372 and 4,161,470.

Suitable polypropylene fibers include highly oriented extended chain polypropylene (ECPP) fibers as described in US Patent 4,413,110. Suitable polyvinyl alcohol (PVOH) fibers are described, for example, in US Patents 4,440,711 and 4,599,267. Suitable polyacrylonitrile (PAN) fibers are described, for example, in US Patent 4,535,027. Each of these types of fiber is conventionally known and widely available commercially.

Other types of fiber suitable for use in the present invention include rigid rod fibers such as M5® fibers and combinations of all of the above materials, all of which are commercially available. For example, fibrous layers can be formed from a combination of SPECTRA® fibers and Kevlar® fibers. M5® fibers are formed from pyridobisimidazole-2,6-diyl (2,5-dihydroxy-p-phenylene) and are manufactured by Magellan Systems International of Richmond, Virginia, and are described, for example, in US patents USA 5,674,969, 5,939,553, 5,945,537 and 6,040,478. Specifically preferred fibers include M5® fibers, SPECTRA® polyethylene fibers, Kevlar® aramid fibers, and TWARON® aramid fibers. The fibers can be any suitable denier such as, for example, from 50 to about 3000 denier, more preferably from about 200 to 3000 denier, still more preferably from about 650 to about 2000 denier, and most preferably from about 800 to about 1500 denier. Selection is governed by ballistic efficiency and cost considerations. Finer fibers are more expensive to manufacture and knit, but can produce a higher ballistic efficiency per unit weight.

The most preferred fibers for the purposes of the invention are high tensile modulus, high strength extended chain polyethylene fibers or high tensile modulus, high strength para-aramid fibers. As stated above, a high tensile modulus, high strength fiber is one that has a preferred toughness of about 7 g / denier or more, a preferred tensile modulus of about 150 g / denier or more, and a preferred breakage of approximately 8 J / g or more, each 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, most preferably about 1000g / denier or more and most preferably about 1500g / denier or more. The fibers of the invention also have a preferred energy at 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 a energy at break of approximately 40 J / g or more.

These combined high strength properties can be obtained using well known procedures. US 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 formation of high-strength, chain-extended polyethylene fibers. , preferred used in the present invention. Such methods, which include gel fiber or solution development processes are well known in the art. Methods for forming each of the other preferred fiber types, including para-aramid fibers, are also conventionally known in the art, and the fibers are commercially available.

The silicon-containing material is applied onto a fibrous substrate that has already been coated with a non-silicon-containing material, also known in the art as a polymeric matrix or polymeric binder material. Accordingly, the fibrous substrates of the invention are coated with multilayer coatings comprising a layer of a non-silicon-containing material on a surface of said one or more fibers, and a topical layer of a silicon-containing material on the layer of material that does not contain silicon.

The layer of non-silicon-containing material preferably comprises at least one material that is conventionally used in the art as a matrix or polymeric binder material, which bonds a plurality of fibers together by means of their inherent adhesive characteristics or after having been subjected to well known heat and / or pressure conditions. These materials include both low modulus elastomeric materials and high modulus rigid materials. Preferred low modulus elastomeric materials are those that

ES 2 445 656 T3 have an initial tensile modulus of less than about 6,000 psi (41.3 MPa) as measured at 37 ° C by ASTM D638. Preferred high modulus rigid materials generally have a higher initial tensile modulus. As used throughout this specification, the term "tensile modulus" means the modulus of elasticity as measured by ASTM 2256 for a fiber and by ASTM D638 for a polymeric binder material. Generally, a polymeric binder coating is necessary to effectively melt, that is, consolidate, a plurality of layers of nonwoven fibers. The non-silicon-containing material can be applied over the entire surface area of ​​the individual fibers, or only over a partial surface area of ​​the fibers. Most preferably, the coating of the non-silicon-containing material is applied over essentially the entire specific surface area of ​​each of the individual fibers that form a woven or non-woven fabric of the invention. In cases where the fabrics comprise a plurality of yarns, each of the fibers that forms a single yarn strand is preferably coated with the non-silicon-containing material.

An elastomeric polymeric binder (non-silicon containing material) can comprise a variety of materials. A preferred elastomeric binder material comprises a low modulus elastomeric material. For the purposes of this invention a low modulus elastomeric material has a tensile modulus, measured at approximately 6,000 psi (41.4 MPa) or less according to the test procedures of ASTM D638. Preferably, the tensile modulus of the elastomer is about 4,000 psi (27.6 MPa) or less, more preferably about 2,400 psi (16.5 MPa) or less, more preferably 1,200 psi (8.23 MPa) or less. , and most preferably about 500 psi (3.45 MPa) or less. The glass transition temperature (Tg) of the elastomer is preferably about 0 ° C or less, more preferably about -40 ° C or less, and most preferably about -50 ° C or less. The elastomer also has a preferred elongation at break of at least about 50%, more preferably at least about 100%, and most preferably has an elongation at break of at least about 300%.

A wide variety of low modulus materials and formulations can be used for the non-silicon coating. Representative examples include polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymers, ethylene-propylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, chlorosulfonated polyethylene, polychloroprene, plasticized poly (vinyl chloride), poly (vinyl chloride) acryl-butadiene elastomers, (isobutylene-co-isoprene), polyacrylates, polyesters, polyethers, ethylene copolymers and combinations thereof, and other low modulus polymers and copolymers. Also preferred are mixtures of different elastomeric materials, or mixtures of elastomeric materials with one or more thermoplastic materials.

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 can be hydrogenated to produce thermoplastic elastomers having saturated hydrocarbon elastomer segments. The polymers can be simple three-block copolymers of the ABA type, multi-block polymers of the (AB) n type (n = 2-10) or radial configuration copolymers of the R- (BA) x (x = 3-150) type. ; where A is a block of a polyvinyl aromatic monomers, and B is a block of a conjugated diene elastomer. Many of these polymers are commercially produced by Kraton Polymers of Houston, TX and are described in the bulletin "Kraton Thermoplastic Rubber", SC-68-81. Most preferred low modulus polymeric binder materials comprise styrenic block copolymers, particularly polystyrene-polyisoprene-polystyrene block copolymers, sold under the trademark KRATON®, commercially produced by Kraton Polymers and HYCAR® acrylic polymers, commercially available from Noveon, Inc. from Cleveland, Ohio.

Preferred high modulus rigid polymers useful for the non-silicon-containing material include polymers such as a vinyl ester polymer or a styrene-butadiene block copolymer, and also polymer blends such as vinyl ester and diallyl phthalate or phenol. -formaldehyde and polyvinyl-butyral. A particularly preferred high modulus material is a thermosetting polymer, preferably soluble in saturated carbon-carbon solvents, such as methyl ethyl ketone, and possessing a high tensile modulus when cured at at least about 1 x 10⁵ psi (689.5 MPa) as measured by ASTM D638. Particularly preferred rigid materials are those described in US Patent 6,642,159.

In preferred embodiments of the invention, the layer of non-silicon-containing material comprises a polyurethane polymer, a polyether polymer, a polyester polymer, a polycarbonate polymer, a polyacetal polymer, a polyamide polymer, a polyamide polymer, polybutylene, an ethylene-vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, an ionomer, a styrene-isoprene copolymer, a styrene-butadiene copolymer, a styrene-ethylene / butylene copolymer, a styrene-ethylene / propylene copolymer, a

ES 2 445 656 T3 polymethyl-pentene polymer, a hydrogenated styrene-ethylene / butylene copolymer, a maleic anhydride functionalized styrene-ethylene / butylene copolymer, a carboxylic acid functionalized styrene-ethylene / butylene copolymer, an acrylonitrile polymer, an acrylonitrile-butadiene-styrene copolymer, a polypropylene polymer, a polypropylene copolymer, an epoxy polymer, a novolac polymer, a phenolic polymer , a vinyl ester polymer, a nitrile rubber polymer, a natural rubber polymer, a cellulose acetate butyrate polymer, a polyvinyl butyral polymer, an acrylic polymer, an acrylic copolymer, or an acrylic copolymer incorporating non-acrylic monomers.

The stiffness, impact, and ballistic properties of articles formed from the fibrous composites of the invention are affected by the tensile modulus of the binder polymers that coat the fibers. For example, US Pat. 4,623,574 discloses that fiber-reinforced composites constructed with elastomeric matrices that have tensile moduli less than about 6,000 psi (41,300 kPa) have superior ballistic properties compared to both higher modulus polymer composites, as well as compared with the same fiber structure without one or more coatings of a polymeric binder material. However, low tensile modulus polymeric binder polymers also provide lower stiffness composites. Furthermore, in certain applications, particularly those where a composite material must function in both anti-ballistic and structural modes, there is a need for a superior combination of ballistic resistance and stiffness. Accordingly, the most appropriate type of non-silicon-containing material 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 non-silicon containing material may also comprise a combination of both low modulus and high modulus materials. Each of the polymer layers can also include fillers such as carbon black or silica, can be oil extended, or can be vulcanized by sulfur, peroxide, metal oxide, or radiation curing systems, if appropriate, as described. knows well in the art.

To produce a fabric article having sufficient ballistic resistance properties, the proportion of fibers that make up the fabric preferably comprises from about 50% to about 98% by weight of the fibers, plus the weight of the combined coatings, more preferably about 70% to about 95%, and most preferably from about 78% to about 90% by weight of the fibers, plus the coatings. Thus, the total weight of the combined coatings preferably comprises from about 1% to about 50% by weight, more preferably from about 2% to about 30%, more preferably from about 10% to about 22%, and most preferably from about 14% to about 17% by weight of the fibers, plus the weight of the combined coatings, where 16% is most preferred for nonwovens. A low binder / matrix content is appropriate for woven fabrics, where a binder content greater than zero but less than 10% by weight of the fibers, plus the weight of the combined coatings, is most preferred. The weight of the topical silicon-containing coating preferably ranges from about 0.01% to about 5.0% by weight, more preferably from about 0.1% to about 3.0%, and most preferably from about 0.2 % to about 1.5% by weight of the fibers, plus the weight of the combined coatings.

When forming nonwovens, the non-silicon-containing coating is preferably first applied to a plurality of fibers, whereby the fibers are coated onto, impregnated with, embedded in, or otherwise applied with the coating. The fibers are arranged in one or more fiber layers, and the layers are then consolidated following conventional techniques. In another technique, the fibers are coated, randomly arranged, and consolidated to form a felt. When woven fabrics are formed, the fibers can be coated with the non-silicon-containing coating either before or after weaving, preferably after. Techniques of this type are well known in the art. Articles of the invention may also comprise combinations of woven fabrics, nonwoven fabrics formed from layers of unidirectional fibers, and nonwoven felt fabrics.

Thereafter, the topical coating of the silicon-containing material is applied on at least one surface of the consolidated fabric over the layer of non-silicon-containing material. Preferably, the two outer surfaces of the fabric are coated with the silicon-containing material to improve the overall durability of the fabric, but coating only one side of the fabric with the silicon-containing material will provide improved abrasion resistance and add less. weight. The multilayer coating is preferably applied over the top of any pre-existing fiber finish such as a spin finish, or a pre-existing fiber finish can be at least partially removed prior to applying the coatings. The silicon-containing material only needs to be on one or both of the outer surfaces of the composite fabric, and

ES 2 445 656 T3 individual fibers need not be coated therewith.

For the purposes of the present invention, the term "coated" is not intended to limit the method by which layers of polymers are applied to the surface of the fibrous substrate. Any appropriate application method can be used in which the layer of non-silicon-containing material is first applied directly onto the fiber surfaces, followed by subsequent application of the layer of silicon-containing material onto the layer of material that does not contain silicon.

For example, the non-silicon-containing layer can be applied as a solution by spraying or roller coating a solution of the polymeric material onto the fiber surfaces, wherein a part of the solution comprises the desired polymer (s) and a part of the solution comprises the solvent capable of dissolving the polymer or polymers, followed by drying. Another method is to apply a pure polymer of the non-silicon-containing material (s) to the fibers in the form of a liquid, a sticky solid or suspended particles or as a fluid bed. Alternatively, the non-silicon-containing material can be applied in the form of a solution, emulsion or dispersion in a suitable solvent that does not adversely affect the properties of the fibers at the application temperature. For example, the fibers can be transported through a solution of the polymeric binder material and substantially coated with a non-silicon-containing material, and then dried to form a coated fibrous substrate. The resulting coated fibers are then arranged in the desired configuration and thereafter coated with the silicon-containing material. In another coating technique, the layers of unidirectional fibers or woven fabrics can be arranged first, followed by immersion of the layers or fabrics in a bath of a solution containing the non-silicon-containing material dissolved in a suitable solvent, so that each of the individual fibers is at least partially coated with the polymer and then dried through evaporation or volatilization of the solvent, and subsequently the layer of silicon-containing material can be applied by the same method. The dipping process can be repeated several times as required to dispose a desired amount of each of the polymeric coatings on the fibers, preferably coating or encapsulating substantially each of the individual fibers and covering all, or essentially all of the specific surface area of ​​the fibers with the non-silicon-containing material. The silicon-containing material can also be applied so as to cover all or essentially all of the layer of non-silicon-containing material on the fibers. In preferred embodiments of the invention, the topical coating of the silicon-containing material is only partially applied on the coated fibers or coated fabric, that is, only the outer surfaces of the fabric need to be coated.

Other techniques can be used to apply the non-silicon coating, including the high modulus precursor (gel fiber) coating, to the fibers before the fibers are subjected to a high temperature drawing operation, either before or after solvent removal from the fiber (if using a gel spinning fiber forming technique). The fiber can then be stretched at elevated temperatures to produce the coated fibers. The gel fiber can be passed through a solution of the appropriate coating polymer under conditions to achieve the desired coating.

Crystallization of the high molecular weight polymer in the gel fiber may or may not take place before the fiber is introduced into solution. Alternatively, the fibers can be extruded into a fluid bed of a suitable polymer powder. In addition, if a stretching operation or other manipulation process is performed, e.g. ex. solvent exchange, drying or the like, the non-silicon-containing material can be applied to a precursor material for the final fibers.

The silicon-containing material is applied to the fibrous substrate on top of the non-silicon-containing material in the liquid state. In one embodiment of the invention, the silicon-containing material is applied as an uncured liquid, while the non-silicon-containing material is also applied in the liquid state or when in the solid state. Most preferably, the silicon-containing material is applied in the form of an uncured liquid over a material that does not contain cured or otherwise solidified silicon. Subsequently, the uncured liquid can optionally be cured through conventional techniques, but curing is not preferred for optimal abrasion resistance.

The coated fibers can be formed into nonwoven fabrics comprising a plurality of nonwoven and overlapping fibrous layers that are consolidated into a single layer monolithic element. Most preferably, each of the layers comprises an arrangement of non-overlapping fibers that are aligned in a unidirectional, essentially parallel arrangement. This type of fiber arrangement is known in the art as a "uni tape" (unidirectional tape) and is referred to herein as a "single layer". As used in this

In specification, an "arrangement" describes an ordered arrangement of fibers or yarns, and a "parallel arrangement" describes an ordered parallel arrangement of fibers or yarns. A "layer" of fibers describes a planar array of woven or nonwoven fibers or yarns that include one or more layers. As used herein, a "single layer" structure refers to a monolithic structure composed of one or more layers of individual fibers that have been consolidated into a single unitary structure. By "consolidate" is meant that the polymeric binder coating together with each of the fiber layers are combined into a single unitary layer. Consolidation can occur through drying, heating, pressure, or a combination thereof. Heat and / or pressure may not be necessary, since the fibers or fabric layers can be glued together, as is the case in a wet lamination process. The term "composite material" refers to combinations of fibers with one or both of the coatings and an abrasion resistant composite which will include the silicon-containing coating. This is conventionally known in the art.

A preferred nonwoven fabric of the invention includes a plurality of overlapping, stacked fiber layers (plurality of ribbons), wherein the parallel fibers of each of the individual layers (ribbons) are positioned orthogonally (0 ° / 90 °) with relative to the parallel fibers of each of the adjacent single layers relative to the longitudinal direction of the fibers of each of the single layers. The stack of overlapping nonwoven fiber layers is consolidated under heat and pressure, or by adhering the coatings of individual fiber layers to form a single layer monolithic element also referred to in the art as a single layer, network consolidated in the that a "consolidated network" describes a consolidated (fused) combination of layers of fibers with a polymeric binder / matrix. The terms "polymeric binder" and "polymeric matrix" are used interchangeably herein and describe a material that binds fibers together. These expressions are conventionally known in the art. For the purposes of this invention, in cases where the fibrous substrate is a consolidated nonwoven fabric formed as a consolidated, single layer network, the fibers are coated with the polymeric coating that does not contain silicon, but only the outer surface. of the monolithic fabric structure is coated with the silicon-containing coating to provide the desired abrasion resistance, not each of the component fiber layers.

As is conventionally known in the art, excellent ballistic resistance is achieved when individual fiber layers intersect such that the fiber alignment direction of one layer is rotated at an angle relative to the alignment direction of the fiber of another layer. Most preferably, the fiber layers intersect orthogonally at angles of 0 ° and 90 °, but adjacent layers can be aligned at virtually any angle between about 0 ° and about 90 ° relative to the longitudinal fiber direction of another layer. . For example, a five-layer nonwoven structure can have layers oriented at 0 ° / 45 ° / 90 ° / 45 ° / 0 ° or at other angles. Rotated unidirectional arrays of this type are described, for example, in US Patents 4,457,985; 4,748,064; 4,916,000; 4,403,012; 4,623,573; and 4,737,402.

Most typically, nonwoven fabrics include 1 to about 6 layers, but can include as many as about 10 to about 20 layers as desired for various applications. The higher the number of layers, this translates into greater ballistic resistance but also in greater weight. Accordingly, the number of layers of fibers that form a fabric or article of the invention varies depending on the end use of the fabric or article. For example, in bulletproof vests for military applications, in order to form a composite material of an article that achieves a desired density of 1.0 pounds per square foot of area (4.9 kg / m²), a total of about 20 layers (or layers) may be required to about 60 individual layers (or layers), where the layers / layers can be woven, knitted, felted or non-woven fabrics (with parallel oriented fibers or other arrangements ), formed from the high-strength fibers described herein. In another embodiment, bulletproof vests for security forces may have a certain number of layers / layers, based on the National Institute of Justice (NIJ) Threat Level. For example, for an NIJ Threat Level IIIA vest, there may be a total of 22 layers / layers. For a lower NIJ Threat Level, fewer layers / strata can be used.

Consolidated nonwovens can be constructed using well known methods, such as by the methods described in US Patent 6,642,159. As is well known in the art, consolidation is accomplished by placing the individual fiber layers on top of each other under conditions of sufficient heat and pressure to cause the layers to combine into a unitary fabric. Consolidation can be performed at temperatures ranging from about 50 ° C to about 175 ° C, preferably from about 105 ° C to about 175 ° C, and at pressures ranging from about 5 psig (0.034 MPa) to about 2,500 psig ( 17 MPa), for about 0.01 seconds to about 24 hours, preferably about 0.02 seconds to about 2 hours.

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When heated, non-silicon polymeric binder coatings may be caused to stick or flow without completely melting. However, generally, if the polymeric binder materials are caused to melt, relatively little pressure is required to form the composite, whereas if the binder materials are only heated to a point of tack, typically more pressure is required. As is conventionally known in the art, consolidation can be performed in a calender assembly, a flat bed mill, a press, or in an autoclave.

Alternatively, consolidation can be achieved by molding under heat and pressure in a suitable molding apparatus. Generally, molding is done at a pressure of from about 50 psi (344.7 kPa) to about 5,000 psi (34,470 kPa), more preferably from about 100 psi (689.5 kPa) to about 1,500 psi (10,340 kPa), most preferably from about 150 psi (1,034 kPa) to about 1,000 psi (6,895 kPa). Molding can alternatively be performed at elevated pressures from about 500 psi (3,447 kPa) to about 5,000 psi, more preferably from about 750 psi (5,171 kPa) to about 5,000 psi, and more preferably from about 1,000 psi to about 5,000 psi. The molding step can last from about 4 seconds to about 45 minutes. Preferred molding temperatures range from about 200 ° F (~ 93 ° C) to about 350 ° F (~ 177 ° C), more preferably at a temperature of about 200 ° F to about 300 ° F (~ 149 ° C), and most preferably at a temperature of from about 200 ° F to about 280 ° F (~ 121 ° C). The pressure under which the fabrics of the invention are molded has a direct effect on the stiffness or flexibility of the resulting molded product. In particular, the higher the pressure at which the tissues are molded, the greater the stiffness, and vice versa. In addition to molding pressure, the amount, thickness, and composition of fabric layers and polymeric binder coating types also directly affect the stiffness of articles formed from the fabrics of the invention. Most commonly, a plurality of orthogonal fiber webs are "glued" together with the matrix polymer and run through a flat bed mill to improve bond strength and uniformity.

While each of the molding and consolidation techniques described herein are similar, each of the processes is different. In particular, molding is a batch process and consolidation is a continuous process. Furthermore, molding typically involves the use of a mold such as a shaped mold or a related die when forming a flat panel, and does not necessarily result in a flat product. Typically consolidation is performed on a flat bed mill, calender holding assembly, or as a wet mill to produce soft (flexible) body armor fabrics. Molding is typically reserved for the manufacture of hard armor, e.g. ex. rigid plates. In the context of the present invention, consolidation techniques and the formation of soft body armor are preferred.

In any process, suitable temperatures, pressures, and times generally depend on the type of non-silicon-containing polymeric binder coating materials, polymeric binder content (of combination coatings), the process used, and the type of fiber. Fabrics of the invention can optionally be calendered under heat and pressure to smooth or polish their surface. Calendering methods are well known in the art.

Woven fabrics can be formed using techniques that are well known in the art, using any fabric fabric, such as plain weave, houndstooth weave, basket weave, satin weave, twill weave, and the like. Plain weave is the most common, in which the fibers are woven together in a 0 ° / 90 ° orthogonal orientation. In another embodiment, a hybrid structure can be assembled in which one or both woven and nonwoven fabrics are combined and interconnected such as by consolidation. Prior to weaving, the individual fibers of each of the woven fabric materials may or may not be coated with the layer of non-silicon-containing material. The layer of silicon-containing material is most preferably coated on the woven fabric.

The thickness of the individual fabrics will correspond to the thickness of the individual fibers. A preferred woven fabric will have a preferred thickness of from about 25 µm to about 500 µm per layer, more preferably from about 50 µm to about 385 µm, and most preferably from about 75 µm to about 255 µm per layer. A preferred nonwoven fabric, i.e. a consolidated, single ply nonwoven web, will have a preferred thickness of from about 12 pm to about 500 pm, more preferably from about 50 pm to about 385 pm, and most preferably from about 75 pm. pm to about 255 pm, where a consolidated single layer network typically includes two consolidated layers (ie, two uni-strips). While thicknesses of this type are preferred, it is to be understood that other thicknesses can also be produced to meet a particular need and will still fall within the scope of the present invention.

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Fabrics of the invention will have a preferred areal density of about 50 grams / m2.² (gsm) (0.01 lb / ft² (psf)) to about 1,000 gsm (0.2 psf). More preferred surface densities for the fabrics of the invention will range from about 70 gsm (0.014 psf) to about 500 gsm (0.1 psf). The most preferred areal density for fabrics of this invention will range from about 100 gsm (0.02 psf) to about 250 gsm (0.05 psf). Articles of the invention, comprising multiple individual layers of fabric stacked on top of one another, will further have a preferred areal density of from about 1,000 gsm (0.2 psf) to about 40,000 gsm (8.0 psf), more preferably about 2,000 gsm (0.40 psf) to about 30,000 gsm (6.0 psf), more preferably about 3,000 gsm (0.60 psf) to about 20,000 gsm (4.0 psf), and most preferably from about 3,750 gsm (0.75 psf) to about 10,000 gsm (2.0 psf).

The composites of the invention can be used in various applications to form a variety of different bullet resistant articles using well known techniques. For example, suitable techniques for forming bullet resistant articles are described, for example, in US 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. Composite materials are particularly useful for the formation of soft and flexible articles of armor that include clothing such as vests, pants, hats or other articles of clothing, and covers or blankets used by military personnel to protect against a number of ballistic threats such as a 9mm jacketed bullet (FMJ) and a variety of fragments generated due to exploding hand grenades, artillery shells, Improvised Explosive Devices (IEDs) and other such devices encountered on military and peacekeeping missions.

As used herein, "soft" or "flexible" armor is armor that does not retain its shape when subjected to a significant amount of stress. The structures are also useful for the formation of rigid hard armor articles. By "hard" armor is meant an article such as helmets, panels for military vehicles or protective shields that have sufficient mechanical strength so that they maintain their structural rigidity when subjected to a significant amount of stress and are capable of being maintained. without collapsing. The structures can be cut into a plurality of discrete sheets and can be stacked to form an article or can be formed into a precursor that is subsequently used to form an article. Techniques of this type are well known in the art.

Garments of the invention can be formed by methods conventionally known in the art. Preferably, a garment can be formed by joining the bullet resistant articles of the invention with an article of clothing. For example, a vest can comprise a generic fabric vest that is attached to the bullet resistant structures of the invention, whereby the structures of the invention 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 "bond" or "bonded" are intended to include fixing such as by stitching or adhering and the like, as well as unattached coupling or juxtaposition with other fabric, so that bullet resistant articles can optionally be easily separated from the vest or other article of clothing. Articles used to form sensitive structures such as flexible sheets, vests and other clothing are preferably formed by using a low tensile modulus binder material. Hard articles such as helmets and armor are preferably, but not exclusively, formed using a high tensile modulus binder material.

Ballistic resistance properties are determined using standard test processes that are well known in the art. In particular, the protective power or resistance to penetration of a bullet resistant composite material is normally expressed by citing the speed of impact at which 50% of the projectiles penetrate the composite material, while 50% are stopped by the composite material, also known as V50 value. As used herein, the "penetration resistance" of an article is the resistance to penetration by a designated threat such as physical objects, including bullets, shards, shrapnel, and the like. For composites of equal surface density, which is the weight of the composite divided by its area, the higher the V50, the better the ballistic resistance of the composite. The ballistic resistance properties of the articles of the invention will vary depending on many factors, in particular the type of fibers used to make the fabrics, the percentage by weight of the fibers in the composite material, the suitability of the physical properties of the coating materials, the number of layers of the fabric that constitute the composite material and the total surface density of the composite material.

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The following Examples serve to illustrate the invention:

EXAMPLES

Various tissue samples were tested as exemplified below. Each of the samples comprised TWARON® Type 2000 1000 denier aramid fibers and polymeric binder material that did not contain silicon and included 45 layers of fibers. For Samples A1-A4, the non-silicon-containing coating is an unmodified, water-based polyurethane polymer. For Samples B1-B4, the non-silicon-containing coating is a fluorocarbon modified, water-based acrylic polymer (84.5% by weight acrylic copolymer sold as HYCAR® 26-1199, commercially available from Noveon, Inc. from Cleveland, Ohio; 15% by weight of NUVA® NT X490 fluorocarbon resin, commercially available from Clariant International, Ltd of Switzerland; and 0.5% Dow TERGITOL® TMN-3 nonionic surfactant, commercially available from Dow Chemical Company of Midland, Michigan). For Samples C1-C4, the non-silicon-containing coating is a fluoropolymer / nitrile rubber blend (84.5% by weight nitrile rubber polymer sold as TYLAC® 68073 from Dow Reichhold of North Carolina; 15% by weight of NUVA® TTH U fluorocarbon resin; and 0.5% of Dow TERGITOL® TMN-3 nonionic surfactant). For Samples D1-D7, the non-silicon-containing coating is a fluoropolymer / acrylic blend (84.5% by weight acrylic polymer, sold as HYCAR 26477 from Noveon Inc. of Cleveland, Ohio; 15% by weight resin NUVA NT X490 fluorocarbon; and 0.5% Dow TERGITOL TMN-3 nonionic surfactant). For Samples E1-E8, the non-silicon-containing binder material is a fluorocarbon modified polyurethane polymer (84.5% by weight of polyurethane polymer sold as SANCURE® 20025, from Noveon, Inc .; 15% by weight of NUVA® NT X490 fluorocarbon resin; and 0.5% Dow TERGITOL® TMN-3 non-ionic surfactant). Each of the fabric samples were non-woven and consolidated fabrics with a two-layer (two-tie), 0 ° / 90 construction. The fabrics had an areal weight and total areal density (TAD) (areal density of fabrics, including fibers and polymeric binder material), as shown in Table 2. The fiber content of each of the fabrics was approximately 85%, with the remainder 15% being the identified non-silicon-containing polymeric binder material.

Samples A2, B2, C2, D3, D6, E3, and E6 were coated with R300B release strap silicone fluid (250 cst estimate), commercially available from Reliant Machinery, Ltd., of Bedfordshire, UK, at a flat bed mill, which consisted of 0.7% by weight of the sample. Samples D2, D5, E2, E5, A4, B4 and C4 were coated with 1000 cst DOW CORNING 200® silicone fluid in a flat bed laminator, consisting of 2.5% by weight of the sample. Samples A3, B3, C3, D4, and E4 were run through the dry flatbed laminator without a silicone coating to determine the effect, if any, of processing. Samples A1, B1, C1, D1, D7, E1, E7, and E8 are control samples without topical silicone coating or laminator processing. Sample A4 was equivalent to sample A2, but was coated with DOW CORNING 200® 1,000 cst silicone fluid (2.5% by weight) instead of R300B fluid. Sample B4 was equivalent to Sample B2, but was coated with DOW CORNING 200® 1,000 cst silicone fluid (2.5% by weight) instead of R300B fluid. Sample C4 was equivalent to Sample C2, but was coated with 1,000 cst DOW CORNING 200® silicone fluid (2.5% by weight) instead of R300B fluid.

EXAMPLES 1-15

Each of the five types of fabric described above was tested for abrasion resistance in accordance with the Inflated Diaphragm test method of ASTM D3886. The tissues tested for each sample type were the control samples that were not coated with the silicon-based coating, as well as the samples coated with ~ 2,500 cst R300B fluid and 1,000 cst DC200 fluid. Results are quantified as Pass or Fail based on the OTV requirement for "non-broken surface characteristics" after 2,000 cycles (5 pound top load weight and 4 psi diaphragm pressure). Both the sample and the abrasive are identical for each of the examples. Table 1 summarizes the results.

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TABLE 1

<td colspan="4">Abrasion resistance Modified ASTM D3886 Standard * - Inflated Diaphragm Method</td>

<td>EXAMPLES</td><td>SAMPLE / ABRASIVE AGENT</td><td>COATING</td><td>OUTCOME</td>

<td> 1</td><td>A1</td><td>N / A</td><td>HAPPENS</td>

<td> 2</td><td>D1</td><td>N / A</td><td>FAILURE</td>

<td> 3</td><td>B1</td><td>N / A</td><td>FAILURE</td>

<td> 4</td><td>E1</td><td>N / A</td><td>FAILURE</td>

<td> 5</td><td>C1</td><td>N / A</td><td>FAILURE</td>

<td> 6</td><td>A2</td><td>R300B</td><td>HAPPENS</td>

<td> 7</td><td>D6</td><td>R300B</td><td>HAPPENS</td>

<td> 8</td><td>D2</td><td>R300B</td><td>HAPPENS</td>

<td> 9</td><td>E3</td><td>R300B</td><td>HAPPENS</td>

<td> 10</td><td>C2</td><td>R300B</td><td>HAPPENS</td>

<td> 11</td><td>A4</td><td>DC200</td><td>HAPPENS</td>

<td> 12</td><td>D2</td><td>DC200</td><td>HAPPENS</td>

<td> 13</td><td>B4</td><td>DC200</td><td>HAPPENS</td>

<td> 14</td><td>E2</td><td>DC200</td><td>HAPPENS</td>

<td> 15</td><td>C4</td><td>DC200</td><td>HAPPENS</td>

* Amended By: Top Load Weight (Over Abrasive Agent) Set At 5 Pounds (2.27kg) And Number Of Cycles Set At 2000

These data illustrate the overall improvement in fabric abrasion resistance imparted by the silicone-based coating, compared to the uncoated control sample.

EXAMPLES 16-39

Each of the samples was tested for V50 against 9mm, 124-grain bullets, following the standardized test conditions of MIL-STD-662F. Bullet resistant armor articles can be designed and constructed to achieve a desired V50 by adding or subtracting individual layers of bullet resistant fabric. For the purpose of these experiments (and for Examples 1-15), the construction of the articles 15 was standardized by stacking a sufficient number of fabric layers (45) so that the total areal density (TAD) (areal density of the fabrics including fibers and polymeric binder material) of the article was 1.01 + 0.03 psf. Table 2 summarizes the results.

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TABLE 2

<td>EXAMPLE</td><td>Show</td><td>Area Weight</td><td>TAD</td><td>Silicone Type</td><td>Processed in the laminator</td><td>V50 (ft / s)</td>

<td> 16</td><td>A1</td><td> 1,532</td><td> 0,98</td><td>N / A</td><td>N</td><td>1690 (515 m / s)</td>

<td> 17</td><td>A2</td><td> 1,550</td><td> 0,99</td><td>R300B</td><td>S</td><td>1790 (546 m / s)</td>

<td> 18</td><td>A3</td><td> 1,534</td><td> 0,98</td><td>N / A</td><td>S</td><td>1724 (525 m / s)</td>

<td> 19</td><td>B1</td><td> 1,590</td><td> 1,02</td><td>N / A</td><td>N</td><td>1693 (516 m / s)</td>

<td> 20</td><td>B2</td><td> 1,547</td><td> 0,99</td><td>R300B</td><td>S</td><td>1722 (525 m / s)</td>

<td> 21</td><td>B3</td><td> 1,545</td><td> 0,99</td><td>N / A</td><td>S</td><td>1648 (502 m / s)</td>

<td> 22</td><td>C1</td><td> 1,544</td><td> 0,99</td><td>N / A</td><td>N</td><td>1673 (510 m / s)</td>

<td> 23</td><td>C2</td><td> 1,555</td><td> 1,00</td><td>R300B</td><td>S</td><td>1734 (529 m / s)</td>

<td> 24</td><td>C3</td><td> 1,542</td><td> 0,99</td><td>N / A</td><td>S</td><td>1729 (527 m / s)</td>

<td> 25</td><td>D1</td><td> 1,569</td><td> 1,00</td><td>N / A</td><td>N</td><td>1671 (509 m / s)</td>

<td> 26</td><td>D2</td><td> 1,623</td><td> 1,04</td><td>DC200</td><td>S</td><td>1713 (522 m / s)</td>

<td> 27</td><td>D3</td><td> 1,566</td><td> 1,00</td><td>R300B</td><td>S</td><td>1737 (529 m / s)</td>

<td> 28</td><td>D4</td><td> 1,564</td><td> 1,00</td><td>N / A</td><td>S</td><td>1704 (519 m / s)</td>

<td> 29</td><td>D5</td><td> 1,618</td><td> 1,04</td><td>DC200</td><td>S</td><td>1800 (549 m / s)</td>

<td> 30</td><td>D6</td><td> 1,568</td><td> 1,00</td><td>R300B</td><td>S</td><td>1768 (539 m / s)</td>

<td> 31</td><td>D7</td><td> 1,562</td><td> 1,00</td><td>N / A</td><td>N</td><td>1719 (524 m / s)</td>

<td> 32</td><td>E1</td><td> 1,588</td><td> 1,02</td><td>N / A</td><td>N</td><td>1729 (527 m / s)</td>

<td> 33</td><td>E2</td><td> 1,586</td><td> 1,02</td><td>DC200</td><td>S</td><td>1814 (553 m / s)</td>

<td> 34</td><td>E3</td><td> 1,625</td><td> 1,04</td><td>R300B</td><td>S</td><td>1799 (548 m / s)</td>

<td> 35</td><td>E4</td><td> 1,586</td><td> 1,02</td><td>N / A</td><td>S</td><td>1723 (525 m / s)</td>

<td> 36</td><td>E5</td><td> 1,584</td><td> 1,01</td><td>DC200</td><td>S</td><td>1774 (541 m / s)</td>

<td> 37</td><td>E6</td><td> 1,619</td><td> 1,04</td><td>R300B</td><td>S</td><td>1741 (531 m / s)</td>

<td> 38</td><td>E7</td><td> 1,589</td><td> 1,02</td><td>N / A</td><td>N</td><td>1688 (515 m / s)</td>

<td> 39</td><td>E8</td><td> 1,586</td><td> 1,02</td><td>N / A</td><td>N</td><td>1670 (509 m / s)</td>

Quite unexpectedly, a regression analysis of the above data found that the presence of a silicone coating increased the 9mm V50 by approximately 65 ft / second (~ 20 m / s). Thus, the materials of the invention desirably achieve both improved abrasion resistance and improved ballistic penetration resistance.