JPH04506325A - Cut resistant composite article - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Vital point resistant composite article The present invention relates to vital point resistant articles. More specifically, the present invention provides improved vital point protection. relating to such articles having protection.

Conventional technology Construction of bulletproof vests, helmets, helicopters and other military equipment containing high-strength fibers critical points such as structural elements, car panels, briefcases, raincoats and umbrellas. Resistant articles are known. Commonly used fibers include poly(phenylenediamine) 　Terebutalamide), graphite fiber, nylon fiber, ceramic fiber, glass fiber Including fiber etc. For many applications, such as vests or parts of vests, the fibers are woven. Used as cloth or knitted fabric. For many other uses (in which fibers are composite materials) Enclosed or embedded in the food.

“The Application of High Modulus Fibers for Vital Area Protection.

n of High Modulus Fibers to Ba1listi c Protection) J, R, C, La1bl e) etc., J, Macromo, Cychem (J, Macromo 1.Sc f-Chem, ) A7 (1), 295-322 (1973), 2 The fourth requirement on page 98 is that the textile material has a high degree of heat resistance; e.g. A polyamide material with a melting point of 255C has comparable tensile properties and a lower melting point. It has been shown to have better impact resistance in critical areas than polyolefin fibers. Ru. NTl5 Publication, AD-A018 958r New Materials for Improved Helmet Construction (New Materials in Con5truction for I mproved Helmets) J, -Ui, L, Allen (A, L, Al es f), etc., a multilayer highly oriented polypropylene film called rXPJ The material (without matrix) is made of aramid fibers (phenol/polyvinyl butylene) (including resin matrix). Aramid type combat helmet determined to have the most promising combination of good performance and minimal problems for development of has been done. U.S. Patent Nos. 4.457.985 and 4.403.012 are Molecular weight polyethylene or polypropylene structure and olefin polymer and copolymer Curable below the melting point of polymers, unsaturated polyester resins, epoxy resins and fibers A vital point resistant composite article is disclosed that includes a matrix of other resins.

"Modified phenolic resin" such as A, L, La5tnik (A, L, La5tnik) etc. The effect of concentration increase and lamination pressure on Kevlar fabric bonded by ffect of Rising Concentration and Lam initiating Pressures on KEVLARFabricBon ded with Modified Phenolic Re5in) J, Te Technical report (Technical Re, port) NATICK/T R-841030, June 8, 1984, during the encapsulation and bonding of fabric fibers. It is disclosed that the interstitial resin reduces vital point resistance of the resulting composite article.

U.S. Pat. No. 4.623.574 and U.S. Pat. No. 4.748.064 We describe a simple composite structure consisting of high-strength fibers embedded in lix. This simple Simple composite structures offer better vital protection than simple composites with rigid matrices. The results are disclosed in the patent. U.S. Patent No. 4,413.110 Using ultra-high molecular weight polyethylene and polypropylene as disclosed in Simple complexes are particularly effective.

U.S. Pat. Nos. 4,737,402 and 4,613,535 disclose elastomeric Ultrasonic acid as disclosed in U.S. Pat. No. 4,413,110 embedded in Trix A network of high strength fibers such as high molecular weight polyethylene and polypropylene, Contains one additional hard layer on the main surface of the matrix for improved impact resistance A complex rigid composite article is disclosed. These composites have improved environmental hazards. protection, improved impact resistance and vital point resistance such as protective clothing or helmets. It has been disclosed that it is unexpectedly effective as a product.

Summary of the invention The present invention is a complex vital point resistant composite with improved impact resistance. relating to body manufactured articles. The article consists of two or more layers, at least one of the layers has a tenacity of at least about 7 g/denier, at least about a tensile modulus of 160 g/denier and an energy to break of at least about 8 joules/g High strength with energy-to-break in the matrix material a fibrous layer consisting of a network of force filaments, at least one of the layers comprising: a rigid material that is harder than the fibrous layer; The relative weight percent of the layer and the relative position of the layer are approximately 2 ．． Mass efficiency (mass efficiency) (EJ) of 5 or more It is a value. The "mass efficiency" of the complex used in ++ is calculated from the following formula: rADJE of protective clothing grade steel required to overcome the threat = rADJE of protective clothing grade steel required to overcome the threat rADJ formula for the substance in question, where AD is the protective clothing in kg/m” or lbs/ft” Or is the areal density of the substance.

Mass efficiency measures the threat of a specified projectile at a specified impact velocity between (1) armor grade steel and (2) Measure the AD required to overcome the target substance and calculate E from the above formula. determined by. Surprisingly, high tenacity fibers and stiff hard materials in the matrix the relative amount of te) the relative order in which these layers are assembled and the mass efficiency of the composite and the resulting abrupt break. It has been found that this has an effect on the degree of resistance.

Compared to conventional vital point resistant body armor constructions, the composite articles of the present invention require a lower amount of protection. quality can be used to provide a certain level of vital point protection. Or the article of the present invention compared to normally constructed composite body armor of equal or substantially equal weight. Can provide vital point protection.

Brief description of the drawing The invention will be more fully understood by reference to the following detailed description of the invention and the accompanying drawings. Figures 1-8. 2A and 2B are cross-sectional views of various embodiments of the present invention, showing various representative structural configurations.

Detailed description of the invention It is a hard hard layer made of hard material. The special structure of the complex varies greatly Vine. For example, the two layers can be in contact or separated by a void space. be able to. A complex is two or more parts that are in contact or separated by a void space. a top fibrous layer and two or more rigid layers, or one or more fibrous layers and only one rigid layer. or one or more hard hard layers and only one fibrous layer. It can be in the form of a composite. Various specific forms of the invention are illustrated in the drawings.

Figure 1 shows a 1 with three layers, a hard ceramic layer 1, a hard metal layer 2 and a fiber composite layer 3. An embodiment is shown. This implementation uses ceramic as the first layer exposed to threats. The layer 1 functions to weaken or distort the projectile. Ceramic layer 1 and metal layer 2 , and the contacted layers 1 and 2 are separated from the fibrous layer 3 by a void space 4 .

In FIG. 2, a metal or fiber bag is shown separated from the fiber layer 3 by a void space 4. 1 shows an embodiment of the invention consisting of a hard ceramic layer 1 with a king layer 5; Figure 2 In the embodiment, the hard ceramic layer 1 is the first layer exposed to the threat; acts to weaken or distort the projectile, thereby increasing the effectiveness of the fiber layer 3 .

FIG. 3 shows an exemplary embodiment of the invention in which metal layer 2 is the first layer exposed to the threat. show. Layer 2 is separated by a void space 4 from ceramic layer 1 in contact with fiber layer 3. It will be done.

FIG. 4 shows a multi-layer/multi-void space embodiment of the present invention. The embodiment of Figure 4 is a threat The metal layer 2 is first exposed to the ceramic layer 2 which is in contact with the backing layer 5. The layer 1 is separated by a void space 4. Ceramic layer 1 and backing in contact The fiber layer 5 is separated from the fiber layer 3 by a void space 4'. Figure 5 shows Figure 2 shows an embodiment of the invention with multiple metal layers consisting of exposed layers 2 and 2°. layer 2 and 2° are manufactured from metals with different hardness, and the fiber layer 3 is separated by the void space 4. separated from

FIG. 6 shows an embodiment consisting of only two layers. Layer 1 is directly exposed to the threat, fibrous layer 3 The ceramic layer 1 is in contact with the ceramic layer 1.

Figure 7 has a ceramic layer 1 with a contact backing layer 5 directly exposed to threats. 1 illustrates one embodiment of the invention. layer 1 is separated from metal layer 2 by a void space 4; The metal layer 2 is separated from the fiber layer 3 by a void space 4'.

FIG. 8 shows an embodiment of the invention with three contact layers. Cerami exposed to direct threat The adhesive layer 1 is in contact with the metal layer 2, which is also bonded to the fiber layer 3.

In a preferred embodiment of the present invention, the composite includes, in addition to the wood-like fiber layer, Contains at least two rigid rigid layers. In these preferred embodiments, the various layers It is preferable that the keys are placed against the threats in the vital points in order of decreasing hardness, for example, Directly to! Behind the exposed ceramic layer is a metal layer and then a fiber layer.

In a particularly preferred embodiment of the invention, one or more layers of hard material and one layer of fibrous material are provided. A void space exists between the layers. The size and shape of the space can be determined by, for example, the thickness of protective clothing. depending on various factors such as the limitations of the Varies widely. In general, the larger the space, the better the clearance of vital threat debris. Dispersion (divergence) and rotation take place, which makes the complex more effective in overcoming threats. Ru. Conversely, if the space is small, the dispersion and rotation of the vital threat debris will be small and the threat Complexes become less effective in overcoming power. The width of the space is usually about 0.5cm to approx. 3Qcm, preferably from about Icm to about 20cm, more preferably from about 15cm to about 1 0 cm, most preferably in the range of about 2.5 cm to about 7.5 cm.

The relative weight percentages of the fibrous layer and stiff rigid layer in the composite can vary over a wide range. in general , the amount of either the fibrous layer or the rigid rigid layer ranges from about 20% to about 80% by weight of the composite. can occupy the surrounding area. In a preferred embodiment of the invention, the amount of fibrous layer is from about 20% to about 80% by weight of the composite, and the amount of stiff hard layer is about 8% by weight of the composite. In a particularly preferred embodiment of the invention, the amount of fiber layer is within the range of 0% by weight. The amount of stiff hard layer is within the range of about 20-60% by weight of the composite, based on the weight of the composite. in the range of about 60 to about 40% by weight. Particularly preferred embodiments of these in which the amount of fibrous layer is within the range of about 25 to about 50% by weight of the composite, and Most preferred are embodiments in which the amount of mass layer is within the range of about 75% to about 50% by weight of the composite. stomach.

The structure of the fibrous layer can vary within a wide range. In the composite article of the present invention, the fiber layer The filaments inside are arranged in networks of various shapes. For example, multiple The filaments are brought together to form twisted or untwisted yarn bundles of various orientations. Form. In a preferred embodiment of the invention, the filaments in each layer are substantially flat. Individual filaments of matrix material filament arranged unidirectionally in rows to substantially cover. The filament or yarn can be prepared in any of the usual ways. Thus, it can be formed as felt or knitted or woven into a tissue [ Plain weave, basket weave, satin weave, tallophyte weave (CrOfeetwe) a, v, e), etc.], or these are made into a non-woven fabric or arranged in parallel rows, Laminated or formed into fabric. Among these methods, for vital point resistance applications, Using modifications commonly used in the manufacture of aramid fabrics for vital point resistant articles. is preferable. For example, U.S. Patent No. J1G4,181,768 and M.R. Jiei, Makomol, Sai such as Siquist (M, R, Si 1yquist) etc. , Kem.

(J, Macromol Sci, Chem,), A7 (1), 203 pages and below The method described in Reference (1973) is particularly suitable.

The type of filament used to manufacture the fibrous layer of the article of the invention can vary widely. metal filament, metalloid filament, inorganic filament and/or can be an organic filament. Preferred filaments for use in practicing the invention The agent has a tensile strength of about 10 g/d or more, a tensile modulus of about 150 g/d or more, and about 8 di The filament has a breaking energy of Yule/g or more. Especially preferred The filament has a strength of about 20 g/d or more, a tensile modulus of about 500 g/d or more, and The filament has a breaking energy of about 30 Joules/g or more. these In particularly preferred embodiments, the tenacity of the filament is greater than or equal to about 25 g/d; The elastic modulus is about 1000 g/d or more and the breaking energy is about 35 joules/g or more. energy is about 40 joules/g or more.

The filaments for use in the fiber layer may be metallic, semimetallic, inorganic and/or organic. sell. Examples of useful inorganic filaments are S-glass, silicon carbide, and asbestos. , Basa 1T, E-glass, alumina, alumina-silica quartz, zirconia-silica, ceramic filament, boron filament It is a filament formed from carbon filament, carbon filament, etc. useful metal or semi- Examples of metal filaments are filaments made of boron, aluminum, steel and titanium. filament. Specific examples of useful organic filaments include aramids (aromatic polyamides). poly(m-xylylene adipamide), poly(p-xylylene adipamide) ), poly(2,2,2-trimethylhexamethylene terephthalamide), poly( biverazine sebaamide), poly(metaphenylene isophthalamide) (Nome x), poly(p-phenylene terephthalamide) (Kevlar), and fat and cycloaliphatic polyamides, such as hexamethylene diammonium isophthalate 3 Copolyamide of 0% and 70% hexamethylene diammonium adipate, 30 Bis-(-amidocyclohexyl)methylene and terephthalic acid and caprola up to % ctam copolyamide, polyhexamethylene adipamide (nylon 66), poly (Petitrolacta phantom (nylon 4), poly(9-aminononanoic acid) (nylon 9) ), poly(enantlactam) (nylon 7), poly(capryllactam) (na nylon 8), polycaprolactam (nylon 6), poly(p-phenylene tereph) talamide), polyhexamethylene sebacamide (nylon 6.10), polyamide Noundecanamide (nylon 11), polycaprolactam (nylon 12), Polyhexamethylene isophthalamide, polycaproamide, poly(nonamethylene azelamide) (nylon 9.9), poly(decamethylene azelamide) (nylon 9.9), Poly (decamethylene sebaamide) (Nylon 10.10), Poly (decamethylene sebaamide) (Nylon 10.10) Li [bis(4-aminocyclohexyl)methane 1,10-decanedicarboxer Midoko (Qiana) () Lance), or a combination thereof; and Aliphatic, cycloaliphatic and aromatic polyesters, such as poly(1,4-cyclohexyl) dendimethyl-eneterephthalate) cis and trans, poly(ethylene-1 , 5-naphthalate), poly(ethylene-2,6-naphthalate), poly(1, 4-cyclohexane dimethylene terephthalate) (trans), poly(decamethyl) lenterephthalate), poly(ethylene terephthalate), poly(ethylene iso phthalate), poly(ethyleneoxybenzoate), poly(bara-hydroxy) benzoate), poly(α,β-thiamethylpropiolactone), poly(decame Filament composed of poly(ethylene succinate), poly(ethylene succinate), etc. It is

A specific example of a useful organic filament is the formula:% formula% [In the formula, R1 and R2 are the same or different, hydrogen, hydroxy,)1 0gen, alkylcarbonyl, carboxy, alkoxycarbonyl, heterocyclic group or unsubstituted or alkoxy, cyano, hydroxy, alkyl and ary Alkyl substituted with one or more substituents selected from the group consisting of is an aryl] From long-chain polymers formed by α, β-unsaturated It is also a filament composed of α, β-unsaturated unsaturated polymers such as -Specific examples of polystyrene, polyethylene, polypropylene, poly(1-octa) decene), polyisobutylene, poly(l-pentene), poly(2-methylstyrene) poly(4-methylpentene), poly(1-butene), poly(3-methyl-1-butene) ), poly(3-phenyl-1-propene), polyvinyl chloride, polybutylene Polyacrylonitrile, Poly(methylpentene-1), Poly(vinyl alcohol) poly(vinyl acetate), poly(vinyl acetate), poly(vinyl acetate), poly(vinyl acetate), poly(vinyl acetate) chloride), poly(vinylidene chloride), vinyl chloride-vinyl acetate Chloride copolymer, poly(vinylidene chloride), poly(methyl acrylate) ), poly(methyl methacrylate), poly(methacrylonitrile), poly(methacrylonitrile), poly(acrylamide), poly(vinyl alcohol), poly(vinyl formal) ), sen), poly(vinylcyclobenkune), poly(vinylcyclohexane), Poly(a-vinylnaphthalene), poly(vinyl methyl ether), poly(vinyl ethyl ether), poly(vinylpropyl ether), poly(vinyl carbazole) ), poly(vinylpyrrolidone), poly(2-chlorostyrene), poly(4-chlorostyrene), poly(vinylpyrrolidone), poly(2-chlorostyrene), lorostyrene), poly(vinyl formate), poly(vinyl butyl ether), Poly(vinyl octyl ether), poly(vinyl methyl ketone), poly(methyl isopropenylketone), poly(4-phenylstyrene), etc.

In a most preferred embodiment of the invention, all or part of the fibrous layer is a filament network. high molecular weight polyethylene filament, high molecular weight polypropylene filament, aramid filament, high molecular weight polyvinyl alcohol filament filaments, high molecular weight polyacrylonitrile filaments or mixtures thereof. Ru. U.S. Pat. No. 4,457,985 generally describes such high molecular weight polyethylene. and polypropylene filaments, the disclosure of which is hereby incorporated by reference. It is related to the extent that it does not contradict this. In the case of polyethylene, use a suitable filament. The agent has a molecular weight of at least 150.00, preferably at least 1 million, and more. Preferably, it has a molecular weight of 2 million to 5 million. Such a long chain Liethylene (E CP E) filament is manufactured by Meihuzen etc. No. 4,137.394 or issued Oct. 26, 1982. As described in U.S. Pat. No. 4,356.138 to Kavesh et al. Vines grown in solution as shown in 3,004.699 and British Patent No. 2051667, in particular 1 Application No. 572,60 of Kavesh et al., filed January 20, 1984. No. 7 (see European Patent Application No. 64,167, published November 10, 1982) ), filaments spun from solution form a gel structure. do.

The term polyethylene as used herein refers primarily to modified polyethylene per 100 main chain carbon atoms. Contains a small amount of branched or monomer units of up to 5 units, mixed with about 50% by weight % or less of one or more polymeric additives, such as alkene-1-polymers, especially low-density polyethylene, polypropylene or polybutylene as the main monomer Special Table Sen4-506325 (4) Copolymers containing diolefins, oxidized polyolefins, grafted polyolefins copolymers and polyoxymethylene, or low molecular weight additives such as antioxidants, Lubricants, UV blockers, colorants, etc. (these are generally relevant here for reference) means a linear polyethylene material that may also contain Molding method, stretching ratio, temperature, etc. Depending on other conditions, these filaments are given different properties. Fi The strength of the lament is at least 15 g/denier, preferably less (both 20 g/denier) denier, more preferably at least 25g/denier, most preferably less than Both are 30g/denier. Similarly, measured by Instron tensile testing machine The tensile modulus of the filament is low (both 300 g/denier, preferably (at least 500 g/denier, more preferably at least 1000 g/denier) denier, more preferably at least 1.200 g/denier. tension These highest values of modulus and strength are generally achieved by solution-grown processes or gel filaments. can only be obtained by using a process.

Similarly, at least 200,000. Preferably at least 1 million, more preferably Alternatively, highly oriented polypropylene filaments with a molecular weight of 2 million are used. be able to. Such high molecular weight polypropylenes are described in the various references cited above. In particular, the patent application filed on January 20, 1984 by Kabesh et al. and by the method described in commonly assigned U.S. Application No. 572.607. and formed into reasonably well oriented filaments. Polypropylene like this Ren is a much less crystalline material than polyethylene and contains pendant methyl groups. strength values obtained with polypropylene are generally comparable to those of polyethylene. substantially lower than the value. Therefore, a suitable strength is at least 8g/denier. , the preferred tenacity is at least 11 g/denier. polypropylene tensile The modulus of elasticity is low (both 160 g/denier and preferably at least 200 g/denier). It's Neil.

High molecular weight polyvinyl alcohol filaments with high tensile modulus are Y, Kw is hereby referred to as a reference to the extent consistent with the above.

No. 4,440,711 to n) et al. polyvinyl aluminum In the case of cole (PV-OH), a pv of molecular weight of at least about 200,000 -OH filament. Particularly useful PV-OH filaments are small (approximately 300 g/denier modulus of at least about 7 g/denier (preferably at least about 10 g/denier, more preferably at least about 14 g/denier, most preferably strength of at least about 17 g/denier) and at least about 8 joules/g should have a breaking energy of small (with a weight average of about 200,000 Molecular weight, strength of at least about 10 g/denier, at least about 300 g/denier Pv having a modulus of elasticity of 100 joules and an energy of rupture of at least about 8 joules/g. -OH filaments are more useful in making vital point resistant articles. This kind of property A PV-OR filament having a Manufactured by the method shown.

In the case of polyacrylonitrile (PAN), at least about 400,000 min. molecular weight PAN filament. Particularly useful PAN filaments are at least about 10 g/denier and a breaking energy of at least about 8 joules/g. Should. molecular weight of at least about 400,000, at least about 15 to about 2 0 g/denier and a breaking energy of at least about 8 Joules/g. PAN filaments are most useful for making vital point resistant articles; Filaments are disclosed, for example, in US Pat. No. 4,535,027.

In the case of aramid filaments, as a rule they are formed from aromatic polyamides Suitable aramid filaments are those described in U.S. Pat. No. 3,671,542. and this patent is incorporated herein by reference. Preferred aramid filament has a tensile modulus of at least about 8 joules and a tensile modulus of about 400 g/d. and an energy to break of at least about 8 joules/g; The filament is small (both about 20g/denier strong, at least about 480g/denier) It has a modulus of elasticity of d and a low energy to break of about 20 joules/g.

The most preferred aramid filaments are strong, raw materials of at least about 20 g/denier. It has new energy. For example, Kevlar! DuPont Co. with the product names 29 and 49 - Commercially manufactured by Boresian (DuPont Corporation) poly(phenylenethia mintilef) with moderately high elastic modulus and strength values. Alamide) filaments are particularly useful in making vital point resistant articles. (That's it As for the elastic modulus value and strength value, Kevlar 29 has 500 g/denier and 22 g/denier. Kevlar 49 has 1000g/denier and 22g/denier ).

Poly( Metaphenylene inphthalamide) filaments are also useful in the practice of this invention.

In the fibrous layer, the filaments are arranged in a network that can take various forms.

For example, multiple filaments are brought together to form twisted or untwisted yarns. can do. The filament or yarn is prepared by any of the conventional methods. may be formed as felt or knitted or woven into a network. [plain weave, basket weave, satin weave, crofe weave etc.] or formed into a network. Preferred embodiments of the present invention In embodiments, the filament is an untwisted monofilament yarn; The components are parallel and unidirectionally aligned. For example, the filament can be Therefore, it is formed into a nonwoven fabric layer.

In the fibrous layer, the filaments are most preferably dispersed in a continuous phase of matrix material. and the matrix material favors each filament contained in the filament bundle. or substantially covered. The manner in which the filaments are dispersed can vary widely.

The filaments may be arranged substantially parallel, unidirectionally, or the filaments may be arranged in multiple directions. The filaments are arranged in the (multidirectional) direction, and the filaments are mutually aligned. Arranged in multiple directions at various angles. In a preferred embodiment of the invention, each The filaments of the layer are manufactured by pultruded 5 unidirectionally arranged substantially parallel as in heet).

The matrix materials used can vary widely and include metals, metalloid materials, It can be organic and/or inorganic. The matrix material is flexible (low It can be hard (high modulus) or hard (high modulus). Useful high modulus or hard matrices Examples of carbonaceous materials include polycarbonate, polyether, etherketone, and polyaryl. - Ren sulfide, polyarylene oxide, polyester carbonate, poly Thermoplastic resins such as esterimides and polyimides, e.g. epoxy resins, Phenolic resin, modified phenolic resin, allyl resin, alkyd resin, unsaturated polyester esters, aromatic vinyl esters, e.g. vinyl aromatic monomers (e.g. styrene) condensation of bisphenol A and methacrylic acid diluted in vinyltoluene). synthetic products, urethane resins, amino (melamine and area) resins, or It can be a mixture of these. The main criterion is that such substances is to hold together and maintain the geometric integrity of the fiber layers under favorable conditions. .

In a preferred embodiment of the invention, the matrix material is a low modulus elastomeric material. It is. Preferred embodiments of the invention utilize a variety of elastomeric materials and compositions. can be done. of suitable nidistomeric materials for use in forming the matrix. A typical example is Encyclavesia of Polymer Science. ropedia of Polymer 5science), 5 volumes, elastomer - Synthetics (Elastmers-8 synthetics) (John Wie) The structure and properties are summarized together with the crosslinking method in Lee & Sons, 1964). It has quality and composition. For example, use any of the elastomeric materials listed below. I can be there. Polybutadiene, polyisoprene, natural rubber, ethylene rubber Ropylene copolymer, ethylene-propylene-diene, terpolymer, polysulfate fido polymer, polyurethane elastomer, chlorosulfonated polyethylene, using polychloroprene, octyl phthalate and other plasticizers well known in the art. Plasticized polyvinyl chloride, butadiene acrylonitrile elastomer, poly( isobutylene-coisobrene), polyacrylate, polyester, polyether elastomer, fluoroelastomer, silicone elastomer, thermoplastic elastomer , ethylene copolymer.

A particularly useful elastomer is a block copolymer of a conjugated diene and a vinyl aromatic monomer. It's Rimmer. Butadiene and isoprene are the preferred conjugated diene elastomers. Ru. Conjugated aromatic monomers preferably include styrene, vinyltoluene, and t-butylstyrene. It's Ma. Hydrogenation of block copolymers containing polyisoprene to produce saturated hydrocarbons It is possible to produce thermoplastic elastomers with elementary elastomer segments. Ru. The polymer is a simple triblock copolymer of type A-B-A, (AB), (n= 2-10) type multiblock copolymers or R-(BA), (x=3-150) A is a radical-shaped copolymer of the type, where A is a polyvinyl aromatic monomer polymer. B is a block from a conjugated diene elastomer. These ports Many of the remers are manufactured by Shell Chemical Co. Manufactured commercially by and published in the booklet ``Craton Thermoplastic Rubber ( Kraton Thermoplastic Rubber) JSC-58-8 1.

Most preferably, the elastomeric matrix material comprises at least one of the above elastomers. also consists essentially of one species. Low modulus elastomeric matrices are e.g. carbon Preferably fillers such as black, silica, glass microballoons etc. up to no more than about 50% by volume, more preferably about 40% by weight of the stomer material. The amount can be increased by adding oil, for example, halogen. can include flame retardants such as paraffin nitrides and methods well known to rubber engineers. Can be cured using sulfur, peroxide, metal oxide, or radiation curing systems. I can do it. Blends of various elastomeric materials can also be used together or One or more thermoplastic resins may also be blended with one or more elastomeric materials. Wear. High-density, low-density, and linear low-density polyethylene are crosslinked to have appropriate properties. The matrix materials can be obtained alone or as blends. in all cases The elastic modulus of the elastomeric matrix material is approximately 6,000 psi (41,3 QQkPa), preferably about 5. 0OOps i (3 4,5QQkPa), more preferably less than 1,000 ps i (6900 kP a), most preferably less than about 500 ps i (3450 kPa).

In a preferred embodiment of the invention, the matrix material is a low modulus elastomeric material. It is. The low modulus elastomer material has a pressure of approximately 6,000 psi (41,300 kP a) has a tensile modulus measured at about 23°C of less than a). Get more improved performance Therefore, preferably the tensile modulus of the elastomeric material is about 5,0 OOpsi ( 34,500 kPa), more preferably less than 1.000 psi (6900 kP a), most preferably less than about 500 ps i (3450 kPa).

The glass transition temperature (Tg) of an elastomeric material (the rapid decrease in ductility and elasticity of the material) thus demonstrating) is below about 0°C. The Tg of the elastomeric material is preferably about -4 Below 0°C, more preferably below about -50°C. Elastomeric materials are at least It also has an elongation at break of about 50%. The elongation at break of the elastomeric material is preferably is at least about 100%, more preferably at least about 300%.

The ratio of matrix to filament in the fiber layer is not critical; whether the substance has its own vital point resistance (generally does not have this condition) Many factors including stiffness, shape, heat resistance, abrasion resistance, flame retardancy and composite article It can vary widely depending on other properties desired. Generally, the matrix in the composite The ratio of matrix to filament is such that the amount of matrix is about 10% by volume of the filament. from a relatively small amount of matrix up to about 90% by volume of the filament. It can vary up to a relatively large amount. In a preferred embodiment of the invention, about 15 to about 80 volumes % matrix amount is used. All volume percentages are based on the total volume of the composite.

In a particularly preferred embodiment of the invention, the vital point resistant article of the invention has a vital point resistant Because it is almost entirely due to the filaments, a relatively small amount (e.g. about 10 to 100% of the complex) In particularly preferred embodiments of the invention, the The proportion of matrix during coalescence ranges from about 10% to about 30% by weight of the filament weight. It is within.

The fibrous layer can be manufactured using many methods. Generally, the layers are matrix Shaping the combination of material and filament in the desired form and amount by exposing it to heat and pressure. Manufactured by

The filament can be preformed by exposing it to heat and pressure. ECPE filament The molding temperature ranges from about 20°C to about 150°C, preferably from about 80°C to about 145°C, - More preferably about 100 to about 135°C, even more preferably about 110 to about 130°C is within the range of The pressure is approximately Lops i (69kPa) ~ approximately 10.0OOp si (69,000 kPa). Approximately 10 ps (69 kPa) Pressure within the range of ~10 Opsi (690 kPa) and temperature below approximately 100°C for a time of less than about 1.0 minutes to easily attach adjacent filaments. can be set. Approximately Loops i (6900kPa) ~ Approximately 10,0OO psi (69,000kPa) and a pressure in the range of about 100 to about 155℃ When used in combination with a temperature within the range and a time within the range of about 1 to about 5 minutes, the filament It can be deformed and compressed together (generally into a film-like shape). Approximately 100ps i (690kPa) to approximately 10,000psi (69,000kPa) When the pressure within the surrounding area is within the range of about 150 to about 155°C and the temperature is within the range of about 1 to about 5 minutes. When used in combination, the filament can be made translucent or transparent.

For polypropylene filaments, the upper end of the wet carbon range is higher than for ECPE filaments. The temperature increases by about 10 to about 20°C.

In a preferred embodiment of the invention, the filament (preformed if desired) is , with a preferred matrix material before placing into the network or mold as described above. Can be pre-coated. The coating layer can be applied to the filament in various ways. and methods well known to those skilled in the art for filament coating can be used.

For example, one method involves adding a matrix material to a drawn high modulus filament as a liquid. and applied as sticky solids or particles in suspension, or as fluidized beds. It is to clothe. Alternatively, the matrix material can be applied to the filament at the application temperature. Applied as a solution or emulsion in a suitable solvent that does not adversely affect the properties. can be done. In these specific embodiments, the matrix material may be melted. Alternatively, a dispersing liquid can be used. However, the matrix material is elastomeric. In preferred embodiments of the invention which are tomeric materials, the preferred group of solvents is water, para Fin oil, ketones, alcohol solvents, aromatic solvents, hydrocarbon solvents, or mixtures thereof. Contains specific solvents such as paraffin oil, xylene, toluene and octane. Contains tongue. The method used to dissolve or disperse the matrix in a solvent is It is a commonly used method for applying similar elastomeric materials to a variety of substrates.

Other methods of applying the coating layer to the filament can be used, including High modulus precursor ( Gel filament) is applied. The filament is then drawn at high temperature to A filament can be formed. Gel filament in a suitable matrix Enamels dissolved in quality solutions, e.g. paraffin oil, aromatic or aliphatic solvents. The lastomeric material can be passed under conditions such that the desired coating layer is obtained.

Crystallization of the polymer in the gel filament before the filament reaches the cooling solution may or may not occur. Alternatively, the filament can be powdered into a suitable matrix. It can also be extruded into a fluidized bed of trix material.

The proportion of the coating layer on the coated filament or fabric is relatively small (e.g. from 1% by weight of the filament to relatively large amounts (e.g. 150% by weight of the filament). The substance has its own impact resistance or vital point resistance (generally in this state (not) and stiffness, shape, heat resistance, abrasion resistance, flame retardancy and composites It may vary depending on other desired properties of the article. Generally coated filaments of the invention The vital point resistant article containing the filament is characterized in that the vital point resistance is almost entirely due to the filament. and a relatively small amount (e.g., about 10 to about 30% by volume of the filament) of the matrix. including. Nevertheless, using coated filaments with a high coating layer content Can be done. However, in general, the coating component is about 60% (based on filament volume). As the filaments grow larger, they combine with similar coated filaments to form matrices.

A simple complex is formed without the use of additional alcohol.

Additionally, the filament may undergo a drawing operation or other treatment such as solvent exchange, drying, etc. coating on the precursor of the final filament if it obtains its final properties only after processing It is contemplated that layers could also be applied. In such cases, the filament Adding desirable and favorable tenacity, modulus, and other properties to coated filament precursors Continue the treatment process on the filament precursor in a manner consistent with the method used. It should be determined by Thus, for example, U.S. patent application no. Applying a coating layer to the xerogel filaments described in No. 572.607, Next, when drawing the coated xerogel filament at a constant temperature and drawing ratio, , ・Filament strength and filament elasticity values were similarly stretched for uncoated xero Measure with gel filament.

To produce fibrous layers with improved impact protection and/or maximum vital point resistance It is preferred according to the invention that each filament is substantially coated with matrix material. It is in a bad condition. Substantially coat the filament using any of the above coating processes. overturning or coating by said process (e.g. using known high pressure molding methods) Other methods that can produce filaments that are coated to essentially the same extent as those coated with The process can be used to coat the filament.

The filament and network produced from this are described as ``simple composite fiber layer''. to form. As used herein, the term "simple composite" consists of one or more layers, each layer The layer is a filament as described above, a filler, a lubricant, etc. as described above. consisting of a single primary matrix material containing small amounts of other materials. shall mean a complex. Simple composite elastomeric matrix materials: The proportion of filaments is variable, with matrix material comprising about 5 to about 50% of the filaments. 150% by volume, which represents a wide general range. Within this range, relatively high A composite with a filament content, e.g. a matrix material, is or more preferably about 10% to about 50% by volume of the matrix material. It is preferred to use a composite comprising about 10 to about 30% by volume of.

In other words, the network of filaments covers various proportions of the total volume of the simple complex. occupy However, the filament network consists of at least about 30 simple complexes. It is preferable that it accounts for % by product. Filament network for vital point protection accounts for at least about 50% by volume, preferably accounts for about 70% by volume, most preferably The matrix occupies at least about 75% by volume, and the matrix occupies the remaining volume.

Preferred composites of the invention are comprised of substantially parallel, unidirectionally aligned filaments. A particularly effective method of producing a fibrous layer for use in coalescence is to use a matrix material, preferably or through a bath containing a solution of elastomeric matrix material. is the process of drawing out a filament bundle: and forming it into a suitable shape, e.g. a cylinder. Circle this filament into a single sheet-like layer along the filament bundle around the long object. Including the process of wrapping around. Then, once the solvent has evaporated, it can be removed from the cylinder shape. A sheet-like layer of filaments embedded in the matrix is left behind, which can be . Alternatively, multiple filaments or filament bundles may be placed in a solution of matrix material. or simultaneously drawn from the bath containing the dispersion and deposited on a suitable surface substantially flat with each other. They can be placed closely spaced in rows. When the solvent evaporates, the matrix material sheet-like material coated with fibers and arranged substantially parallel and in a common filament direction A layer is left behind. Sheets can be laminated to other sheets to form composites containing two or more layers. Suitable for the following processing.

Groups of filament bundles are drawn through a dispersion or solution of matrix material and individually separated. each of the filaments and then evaporate the solvent to form the coated yarn. By forming, simple composites of yarn type can be produced.

The yarns are then used to form fabrics, for example, and the fabrics are then used to make more complex composites. Can form body structure. In addition, the coated yarn can be wound using conventional filament winding. For example, a simple composite can be Composite yarns formed in overlapping filament layers can be included.

The number of layers included in the fibrous layer can vary widely depending on the use of the composite.

The number of layers depends on the number of factors including the desired degree of vital point protection and a person skilled in the field of vital point protection. and other factors known in the art. For this application, a large degree of protection is generally desired. The higher the weight, the greater the number of layers included in the fibrous layer for a given weight article.

The geometry of the fiber layer is characterized by the morphology of the filaments, and The trix material also fills some of the void space left by the filament network. It is convenient to indicate whether or not the area occupies all of the area. One of these suitable arrangements In one, the coated filaments are arranged in sheet-like rows along a common filament direction. A plurality of filament layers arranged parallel to each other. coated like this The unidirectional filament is the previo can be rotated with respect to the uS) layer. An example of such a laminate structure is Based on the first layer +: L, T+45', -45', 90' and the second rotated O'OO, A composite comprising the third, fourth and fifth layers (not necessarily in this order; other An example is an example in which adjacent layers are oriented OD/90t' with respect to their common filament direction. The coating comprises a fibrous layer consisting of a layer of homogeneous filaments.

One method of forming a fibrous layer, including two or more layers, is to form a covering fiber into a preferred network structure. The process of placing the filament and then bonding the entire structure and heat curing the coating to flow. and filling the residual void space to form a continuous matrix. others The method involves forming layers or other structures of coated or uncoated filaments into various shapes (e.g. (e.g. film) and then the entire The structure is bonded and heat cured. In the above case, the matrix material is completely removed. It is possible to make it stick and flow without completely melting it. In general, the matrix When melting materials, little pressure is required to form a complex, but the matrix If a substance is to be heated only to the sticking point, high pressure is generally required. vinegar That is, the pressure and temperature used to cure the composite and obtain optimum properties are generally depends on the nature of the substance (chemical composition and molecular weight) and processing temperature.

The complex composite of the present invention (collplex coIIposit, e) is impact resistant. Contains at least one hard layer, preferably containing a hard material with useful impact resistance. Examples of materials are steel plates, composite protective clothing plates, and ceramic reinforced metal composites. , ceramic plates, concrete and high strength filament composites [e.g. S-glass, E-glass or aramid filament and high modulus resin matrix e.g. epoxy or phenolic resin vinyl esters, unsaturated polyesters thermoplastic resin, nylon 6, nylon 6.6, or polyvinylidene halide Doreen]. Preferably, the hard impact layer is made of e.g. ceramic vital point resistively effective layers, such as plates or ceramic-reinforced metal composites; . Preferred embodiments of the invention include, for example, aluminum oxide, boron carbide, silicon carbide, etc. A layer of ceramic such as ion, titanium boride, barium oxide, etc. and/or Made from metals such as stainless steel, copper, aluminum, titanium, etc. layer that at least partially deforms the initial impact surface of the projectile, or [Additionally useful hard layers include: See Laible, supra, chapters 5-7].

In a preferred embodiment of the invention, the complex complex is, for example, aluminum oxide, carbide at least one of ceramic materials such as iron, boron carbide and titanium diboride. also includes one hard layer. Various ceramic materials differ in purity, density, hardness, strength, etc. processing of raw materials into different grades with desirable different physical properties such as modulus of elasticity etc. Manufactured using engineering and manufacturing methods.

Usually from ceramic materials with relatively high purity, high density, high hardness, high modulus and high toughness , good vital point performance is obtained and such materials are included in the most preferred embodiment of the invention. used.

The shapes of ceramic materials vary widely. In the most preferred embodiment of the invention In this case, the ceramic layer is formed from flat ceramic tiles of various sizes.

Ceramic materials for use in the present invention are of types well known to those skilled in the ceramic art. It can be manufactured by various methods. Ceramic powders are typically ground from raw materials and sieving. The resulting powder is subjected to specific treatments and admixtures known in the art. It is further processed by addition of additives to obtain good processability in the next process.

The produced processed powder is then molded into any desired shape at room temperature by pressing or molding, The compacted powder is then compacted by sintering or hot pressing at elevated temperatures. be In some cases, the compacted product may be finished by cutting with diamond or other means. give.

In a further preferred embodiment of the invention, the composite comprises at least three layers, one of which is a fibrous layer, e.g. of high molecular weight polyethylene, in a polymer matrix. , a ceramic layer, a glass or glass reinforced layer. These composites are made of steel It is preferable to also include such a metal layer. In the most preferred embodiment, the metal layer It is a hole. The hole tilts and rotates the projectile, preferably breaking it into small pieces, and the pieces are It is more effectively stopped by the fibrous layer. Tilt or rotation of the projectile causes the projectile to become fibrous The composite body receives the impact over a wide area because it collides with the side of the body rather than its nose. The vital point resistance performance is improved. Porosity can vary over a wide range; Preferably at least about 20% by volume based on the total volume of the metal layer, and Preferably at least about 70% by volume based on the total volume of the metal layer, most preferably - Preferably at least about 30-60% by volume based on the total volume of the metal layer.

Generally, the spacing and size of the pores in the metal layer can vary over a wide range. of a threatening projectile The larger the size, the greater the impact on the mass efficiency of the composite The spacing and size of the holes in the metal layer increases. Figure 9 shows an example of a perforated steel plate. show. The size of the pores can vary within a wide range. In general, the size is faced with the specific depending on the vital threat, typically sized to tilt and/or rotate the projectile. be. The shape of the pores can also vary within a wide range. Such holes can be circular, rectangular or square. , rectangle, etc. In a preferred embodiment of the invention, the holes are rectangular.

The composite of the invention may be used, for example, in the hull of a landing craft, in other types of protective clothing, in helmets, etc. It is useful in the production of vital point resistant articles. The protective power of a structure is determined by its mass efficiency (E, ) is expressed by The mass efficiency of the present invention is a good mass efficiency of at least about 2.5. rate. In preferred embodiments of the invention, the mass efficiency is at least about 3; In particularly preferred embodiments, it is at least about 3.5. These particularly preferred Among the embodiments, those in which the mass efficiency is at least about 4.0 are most preferred. preferable.

Typically, composite body armor has a shell or plate geometry. shell and The specific gravity of the plate is expressed as areal density (AD). Areal density is the unit area of the structure equivalent to the weight of In the case of filament-reinforced composites, their vital point resistance depends primarily on the filament, another useful weight property is the filament of the composite. is the areal density of the material. This term refers to the filament reinforcement per unit area of the composite. Corresponds to the weight of the material (AD).

The following examples are included to provide a more complete understanding of the invention. To explain the invention The specific methods, conditions, materials, ratios, and reported data described above are examples, and the present invention should not be construed as infringing on the scope of

Mouth Leighton D1107 thermoplastic elastomer (containing 14% by weight styrene, polyester) Styrene-polyisoprene-block copolymer, a product of Shell Chemical) Impregnated Spectoday 900 unidirectional high strength long chain polyethylene (E CP E )・Produce vital point resistant panels by forming multiple sheets of yarn. Built. This yarn has a strength of 30g/denier and an elasticity of 1,200g/denier. It had a breaking energy of 55 units/g. The elongation at break of the yarn is 4%. Denier is 1.200, individual filament denier is 10 or 118 filament It was a lament/yarn end. Each filament is 0.0014” (0,00 36 cm). Using a total of 360 yarns, with O’/90° yarn orientation. Stacked or laminated, each layer has a length relative to the filament length of the adjacent layer. It has a vertical filament length.

Laminate composite panel then 24” (61cm) x 24” (61cm) temperature of 124 °C and 420 ps i (2900 k Molding was carried out for 40 minutes at a pressure of Pa). After molding, the panel was molded for 30 minutes. Allowed to cool to room temperature. Molded panel is 24” (61cm) x 24” (6 layers cm) xO,93” (2,36 cm) in size and has an areal density of 24 kg/m2. Ta.

Titanium diboride tile [4” (10,1 cm) with areal density of 97 kg/m” ) x 4” (10,1cm)] xo, 85B” (2,18cm) [Ceraro Cera Joy 225, CeradyneS Inc. , )] and composite vital point resistance using fiber panels containing Spectra 1 polyethylene fibers. A resistant panel was produced. The titanium diboride tile was contacted with the textile panel. Combined emergency The edge surface density of the resistive article was 121 kg/m2.

This composite vital point resistant article was tested using a prescribed projectile using conventional test methods. In addition, to overcome this projectile, approximately 400 kg/m” roll-hardened protective clothing is required. (RHA) was required. The impact velocity of the projectile is 3.069 ft/s (935 m/sec). In this test, the projectile penetrated titanium diboride tiles, but , is only partially transparent to fiber composites formed from Spectra 3 fibers; 12 kg/m” of Tora 3 composite was not penetrated. The E of the article was approximately 3.3. It was.

Example ■ Using the method of Example ■, a composite vital point resistant article having the structural characteristics listed in Table 1 was manufactured. did. Features are listed in the order in which they are exposed to the projectile during testing.

(a) Aluminum oxide tile [4” (10,1cm) x 4” (10,1on)] Riryo Earth Ceramic Co., Ltd. Obtained 49k g/m2 (b) RHA sheet panel 20” (50,8cm) x 20” (50,8cm) 0.9cm x 2.1cm 19kg/m” (c) void space 3in (7.6cm) (d ) Spectra Rub et al. fiber composite 24” (61cm) x 24” (61cm) 1 and Ml with In 4 5 k g/m2 The edge surface density of the article is 113 kg/m''. It was.

Using the method of Example 2, a projectile is delivered to a composite article at an impact velocity of 3,425 ft/sec (95 ft/sec). 3 m/sec). The projectile penetrated the aluminum oxide layer and the steel layer, but 12 kg/m'' of fiber Spectra 3 fiber was not penetrated. E of complex composite.

was about 3.5.

flood Using the method in Example ■, manufacture a composite vital point resistant article having the structural characteristics listed in Table ■. did. Features are listed in the order in which they are exposed to the projectile during testing.

Sac and Layer composition: Honey! (a) Aluminum oxide tile [4” (10,1cm) x 4” (10,1cm) from Kokuearth Ceramic Company Obtained 49kg/m” (b) Glass fiber reinforced panel 7-Chin Obtained from Mariefta 20’ (50,8C!1)X20” (50,8CI11) 19k g/m” (c) Void space 3” (7,5) (d) Spectra-1 loose to fiber composite 24” (61c+a) x 24” ( 61cm) #11 and II to I! ! 4 5 k g/m2 The total density of the article is 12 2kg/m”.

Using the method of Example I, a projectile is applied to a composite article at an impact velocity of 3.058 ft/sec (93 ft/sec). 2 m/sec). The projectile penetrates the aluminum oxide layer and the glass reinforcement layer. However, 21 kg/m' of fiber Spectra 1 composite was not transmitted. complex complex The E of the body was approximately 3.3.

Example ■ Using the method of Example I to produce a composite vital point resistant article having the structural characteristics listed in Table ■ did. Features are listed in the order in which they are exposed to the projectile during testing.

(a) Perforated RHA copper plate 20” (50,8cm) x 20’ (50,8cm) Detroit Punch Anne E Manufactured by Retainer 19kg/m” (b) Aluminum oxide tile [4” (10,1cm) x 4° (10,1Cw)] From Kokuearth Ceramic Co. Obtained 49k g/m2 (c) glass fiber reinforced panel Manpower from Martin Marieta 20” (50,8c+a) x 20” (50,8cm) 28k g/m” (d ) Spectra-1 male hull fiber composite 24” (61cm) x 24” (61cm) Even 1 piece of silk 24k g/m” The total image density of the article was 120 kg/m''.

Using the method of Example I, a projectile was delivered to a composite article at an impact velocity of 3,047 ft/sec (92 ft/sec). 9 m/sec). The projectile has a steel layer, an aluminum oxide layer and a glass reinforced layer 2 k g/m'' of the fiber Spectra 8 composite was not transmitted.

E of the complex complex was approximately 3.3.

Example V Using the method of Example I to produce a composite vital point resistant article having the structural characteristics listed in Table ■ did. Features are listed in the order in which they are exposed to the projectile during testing.

(a) RHA steel plate 20" (50,8cm) x 20" (50,8cm) 0.9CIIK2.1CI Detroit punch 77F with rectangular hole, obtained from Retainer, 19k g/m” (b) Gap - 2in (5.1cm) (C) Aluminum oxide tile [4” (10,1cm) x 4” (10,1cm) from Kokuearth Ceramic Company Obtained 49k g/m” (d) Glass fiber reinforced panel 20" (50,8C11) x 20" (50,8CIl) 45 k g / m”(e) Gap 1” (2,54cm) (f) Fiber composite 12” (30,5c+a) x 12” ( 30,5cm) 10k g/m2 Example 1 and same production The total density of the article was 123 kg/m''.

Using the method of Example I, a projectile is delivered to a composite article at an impact velocity of 3,104 ft/sec (94 ft/sec). 6 m/sec). The projectile has a steel layer, an aluminum oxide layer and a glass reinforced layer 2 kg/m” of fiber Spectra 8 composite was not transmitted. The E of the complex was approximately 3.2.

FIG, I FIG, 2 FIG, 3 FIG, 4 FIG, 5 FIG, 6 Translation submission form of amendment (Article 184-8 of the Patent Act)

Claims (10)

[Claims] 1. Next element: (a) at least one rigid rigid layer comprising one or more rigid rigid substances; and (b) a tensile modulus of at least about 160 g/denier and at least at least a network of filaments having a tenacity of about 7 g/denier. also one fiber layer a composite article comprising: a relative weight percentage of said fibrous layer and said stiff hard layer; , the relative positions of the layers are such that the article has a mass efficiency of about 2.5 or greater. The said articles as specified. 2. Is the hard hard material a group consisting of ceramics, metals and fiber-reinforced polymers? The article according to claim 1, which is selected from the following. 3. An article according to claim 1, comprising at least two rigid rigid layers. 4. Claim 1, wherein at least one of said rigid layers is a porous metal layer. Items listed. 5. a portion of the article comprising at least one of the fibrous layers and a portion of the stiff hard layer; Claim 1 further comprising a void layer between the at least one portion of the article. Items listed in section. 6. The strength is about 20 g/d or more, and the elastic modulus is about 500 g/d or more. The article of claim 1, wherein the breaking energy is about 15 J/g or more. . 7. the network of filaments comprises at least two sheet-like filaments; rows, in each row the filaments are aligned with each other along a common filament direction. The lengths of parallel filaments arranged substantially in parallel, with adjacent rows included in said rows. 2. A method according to claim 1, wherein the method is arranged obliquely to the axis. 8. Claim 1: The network of filaments comprises a non-woven or woven fabric. Items listed. 9. The filament is an aramid filament, a polyethylene filament, or Claims that are a combination of aramid filaments and polyethylene filaments Articles described in paragraph 1. 10. Claim 2, wherein the filament is a polyethylene filament. Articles listed.