A surface treated yarn and fabric with enhanced physical and adhesion properties and the process of making.

(54) Title: A THREAD TREATED ON THE SURFACE AND FABRIC WITH IMPROVED PHYSICAL AND ADHESION PROPERTIES AND THE MANUFACTURING PROCESS.

(54) Title: A SURFACE TREATED YARN AND FABRIC WITH ENHANCED PHYSICAL AND ADHESION PROPERTIES AND THE PROCESS OF MAKING.

(57) Summary

Methods for modifying high tenacity fibers without reducing the physical strength properties of the fibers. Very particularly, methods for modifying fibers with a plasma treatment or a corona treatment without reducing the physical strength properties of the fibers.

(57) Abstract

Methods for modifying high tenacity fibers without reducing the physical strength properties of the fibers. More particularly, methods for modifying fibers with a plasma treatment or a corona treatment without reducing the physical strength properties of the fibers.

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Institute

Mexican Property

Industrial

PATENT TITLE NO. 347124

Owner (s): HONEYWELL INTERNATIONAL INC.

Address: Patent Services M / S AB / 2B, 101 Colombia Road. PO Box 2245, Morristown, New

Jersey, 07962-2245, USA

D nomination: A SURFACE AND FABRIC TREATED YARN WITH IMPROVED ADHESION AND PHYSICAL PROPERTIES AND THE MANUFACTURING PROCESS.

Classification: lnt.CI.8: D06M10 / 02; D06M15 / 37

Inventor (s): THOMAS YIU-TAI TAM; RALF KLEIN; HENRY GERARD ARDIFF; JOHN

ARMSTRONG YOUNG; MARK TALLENT

REQUEST

Number: International filing date:

MX / a / 2014/002565 September 5, 2012

PRIORITY

<td>Country:</td><td>Date:</td><td>Number:</td>

<td>US</td><td>September 6, 2011</td><td> 61/531,302</td>

<td>US</td><td>December 2, 2011</td><td> 61/566,320</td>

<td>US</td><td>September 4, 2012</td><td> 13/602,381</td>

Validity: Twenty years

Expiration Date: September 5, 2032

The reference patent is granted based on articles 1, 2^or fraction V, 6^or Section III, and 59 of the Industrial Property Law.

In accordance with article 23 of the Industrial Property Law, this patent has a validity of twenty years Non-derogable, counted from the date of presentation of the international application and will be subject to the payment of the fee to keep the rights in force. . .....

Whoever signs this title does so based on the provisions of articles 6 ° sections III and 7 ° bis 2 of the Industrial Property Law (Official Gazette of the Federation (DOF) 06/27/1991, amended on 02 / 08/1994, 10/25/1996, 12/26/1997, 05/17/1999, 01/26/2004, 06/16/2005, 01/25/2006, 05/06/2009, 06/01 / 2010, 06/18/2010, 06/28/2010, 01/27/2012 and 04/09/2012), articles 1, 3rd section V subsection a), 4th and 12th sections I and III of the Regulations of the Mexican Institute of Industrial Property (DOF 12/14/1999, amended on 07/01/2002, 07/01/2004, 07/28/2004 and 09/07 2007); items 1^or, 3^or, 4^or, 5^or Section V subsection a), 16 sections I and III and 30 of the Organic Statute of the Mexican Institute of Industrial Property (DOF 12/27/1999, amended on 10/10/2002, 07/29/2004, 08/04/2004 and 09/13/2007); 1^or, 3^orand 5^or Subsection a) of the Agreement that delegates powers to the Deputy General Directors, Coordinator, Divisional Directors, Heads of the Regional Offices, Divisional Deputy Directors, Departmental Coordinators and other subordinates of the Mexican Institute of Industrial Property. (DOF 12/15/1999, amended on 02/04/2000, 07/29/2004, 08/04/2004 and 09/13/2007).

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MX / 2017/31813

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A THREAD TREATED ON THE SURFACE AND FABRIC WITH PROPERTIES

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IMPROVED PHYSICAL AND ADHESION AND THE MANUFACTURING PROCESS

Cross Reference to Related Application 'This application claims the benefit of the United States provisional application co-pending with Serial No. 61 / 531,302, filed on September 6, 2011, the description of which is incorporated herein by reference in its entirety. This application also claims the benefit of the United States provisional application co-pending with No. No. 61 / 566,320, filed December 2, 2011, the description of which is incorporated herein by reference in its entirety.

Field of the invention

The invention relates to methods for modifying high tenacity fibers, without reducing the physical strength properties of the fibers. Very particularly, the invention relates to methods for modifying fibers with a plasma treatment or corona treatment without reducing the physical strength properties of the fibers.

Description of Related Art

Many different techniques are known for the manufacture of high tenacity fibers and filaments,

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Mexican IMPI wiTmno DE LA PROniBAD INDUSTRIAL including fibers and high molecular weight polyethylene filaments. Furthermore, bullet resistant articles made from mixed materials comprising high tenacity synthetic fibers are well known. Items such as bullet resistant vests, helmets, vehicle panels and structural members of military equipment are typically made of fabrics comprising high tenacity fibers such as SPECTRA® polyethylene fibers or KEVLAR® aramid fibers.

For many applications, high tenacity fibers can be used in a knitted or woven fabric. For other applications, the fibers can be encapsulated or embedded in a polymeric matrix material and formed into nonwoven fabrics. For example, US patents 4,403,012, 4,457,985, 4,613,535, 4,623,574, 4,650,710,

4,737,402, 4,748,064, 5,552,208, 5,587,230, 6,642,159,

6,841,492, 6,846,758, all of which are incorporated herein by reference, describe bullet resistant mixed materials that are formed from high tenacity fibers, such as extended chain ultra-high molecular weight polyethylene (UHMW PE) fibers. Each type of high tenacity fiber has its own unique characteristics and properties, and mixed bullet resistant materials made from high tenacity fibers exhibit varying degrees of resistance to projectile penetration and transmitted impact energy (BFS).

Impact energy

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Transmitted, also known in the art as transmitted impact energy deformation or trauma transmitted impact energy, is the measurement of the depth of deflection of the body armor that results from a projectile impact.

A defining characteristic of a fiber is the ability of the fiber to bond or adhere to surface coatings, including resin coatings. The strong adhesion of polymeric binder materials is important in the manufacture of bullet resistant fabrics. Poor adhesion of polymeric binder materials on fiber surfaces can reduce fiber-fiber bond strength and fiber-binder bond strength and therefore cause the bonded fibers to peel from each other and / or cause the binder will de-laminate from the fiber surfaces. This reduces the bullet resistance properties, also known as bulletproof performance, of such mixed materials and can result in catastrophic product failure. For example, as described in co-pending application Ser. No. 61 / 531,233; 61 / 531,255; 61 / 531,268; 61 / 531,302; and 61 / 531,323, there is a direct correlation between the transmitted impact energy and the tendency of the component fibers of a mixed material

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IMPI, Ν ^ ΤΤυΤΟ MEXICANO DE LA MÍDA · INBUSTUAl bullet resistant to delaminating each other and / or delaminating from fiber surface coatings as a result of a projectile impact.

By improving the bond between a fiber surface and a fiber surface coating, the effect of fiber-fiber decoupling and / or fiber-coating delamination is reduced, thus increasing friction on fibers and increasing projectile coupling with fibers. . This improvement in bond strength results in improved structural properties of the mixed material, allowing the energy of a projectile impact to be dissipated in a manner that reduces a transmitted impact energy deformation of the mixed material.

As is known in the art, the ability of a fiber to bond with or adhere to surface coatings can be enhanced by corona treatment or plasma treatment of the fibers. Corona treatment is a process in which a fiber is passed through a corona discharge station, thus passing the fiber ribbon through a series of high voltage electrical discharges, which tend to act on the surface. of the fiber web in a variety of forms, including dimpling, roughness, and introduction of polar functional groups through partial oxidation of the fiber surface. A plasma treatment is similar to a treatment

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mainly in that a plasma treatment is conducted in a controlled, reactive gas atmosphere, while in the corona treatment the atmosphere is air. These treatments modify the fibers, such as by ablation of the fiber surface, dimpling and roughness of the fiber surface, removal of contaminants from the fiber surface, oxidation of the fiber surface, polarization of the fiber. fiber surface, causing chain cleavage and molecular weight reduction of polymer molecules on the fiber surface, and / or by interlacing polymer chains near the fiber surface through free radical bonding. As a result of these modifications, the ability of post-applied materials to adsorb to, adhere to, or bond to the fiber surface is increased, thus reducing the tendency of fiber surface coatings to delaminate, and thus reducing the energy deformation of the fiber. transmitted impact of mixed material under the impact of the projectile.

However, it has now been recognized that the adverse conditions of plasma treatment and corona treatment are destructive of fiber toughness. Data has been shown that the fiber toughness pretreatment is significantly higher than the fiber toughness pretreatment. This is undesirable fiber penetration resistance

INSTITUTE MUK-ANÜ DI LA mOnSDAD,,. , INOUITWAL 7¹· -----'-- because it is exactly proportional to the physical resistance of the fibers that form the mixed material, so that a reduction in physical resistance is correlated with a decrease in speed V₅₀/ and obtaining the desired improvements in BES entails a sacrifice of resistance to penetration. Accordingly, there is a need in the art for a method of producing bullet resistant composite materials that have reduced transmitted impact energy without sacrificing ballistics performance properties V₅₀ superiors. The invention provides a solution to this need.

Summary of the invention

The invention provides a process for producing a modified high tenacity fiber that has been modified by plasma treatment or modified by corona treatment, said modified high tenacity fiber having a tenacity of at least about 33 g / denier at temperature environment, said process comprising the steps of:

a) providing a high tenacity fiber having a tenacity of at least about 33 g / denier at room temperature, wherein said fiber has fiber surfaces and wherein said surfaces are at least partially covered by a surface finish of fiber

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or wherein said fiber is substantially free of finish from

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INSTITUTO MEXICANO ΠΕ LA PMiniDAD INDUSTRIAL fiber surface;

b) wherein said fiber surfaces are still less partially covered by a fiber surface finish, removing at least a portion of the fiber surface finish from the fiber surfaces; and

c) subjecting the high tenacity fiber to plasma treatment or corona treatment within a chamber maintained at a non-vacuum pressure under conditions effective to modify the high tenacity fiber;

thus producing a modified high tenacity fiber which has been modified by plasma treatment or modified by corona treatment, said modified high tenacity fiber has a tenacity of at least about 33 g / denier at room temperature.

The invention also provides a process for producing a modified polymeric fiber that has been modified by a plasma treatment or modified by a corona treatment, said process comprising the steps of:

a) providing a polymeric fiber wherein said fiber has fiber surfaces and wherein said surfaces are at least partially covered by a fiber surface finish or wherein said fiber is

IMPIAS

MEXICAN INSTITUTE

DI LA PHOniDAD _ INDUSTRIAL substantially free of a fiber surface finish;

b) wherein said fiber surfaces are at least partially covered by a fiber surface finish, removing at least a portion of the fiber surface finish from the fiber surfaces; and

c) subjecting the polymeric fiber to plasma treatment or corona treatment within a chamber maintained at a non-vacuum pressure under conditions effective to modify the high tenacity fiber;

thus producing a modified fiber that has been modified by a plasma treatment or modified by a corona treatment.

The invention also provides a process to produce a modified polymeric fiber that has been modified by a plasma treatment or modified by a corona treatment, said process comprising the steps of:

a) providing a polymeric fiber having surfaces that are at least partially free of a fiber surface finish such that at least part of the fiber surface is exposed and not covered by a fiber surface finish; and

c) subjecting the polymeric fiber to plasma treatment or corona treatment within a chamber maintained at a non-vacuum pressure under conditions effective to modify the polymeric fiber;

<img file="MX347124B_D0008.tif" />

producing in this way a modified fiber that

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Detailed description of the invention

For the purposes of the invention, articles having superior bullet penetration resistance describe those that exhibit excellent properties against deformable projectiles, such as bullets, and against fragment penetration, such as fragmentary grenades.

For the purposes of the present invention, a fiber is an elongated body whose long dimension is much greater than the transverse dimensions of width and thickness. The cross sections of fibers for use in this invention can vary widely, and can be circular, flat, or oblong in cross section. Therefore, the term fiber includes filaments, slats, strips, and the like that have a regular or irregular cross section, but it is preferred that the fibers have a substantially circular cross section. As used herein, the term yarn is defined as a single strand consisting of multiple fibers. A single fiber can be formed from just one filament or from multiple filaments. A fiber made up of only one filament is referred to herein as either a single filament fiber or a monofilament fiber, and a fiber

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A fiber layer, as used herein, may comprise a single layer of unidirectionally oriented fibers, a plurality of unconsolidated layers of unidirectionally oriented fibers, a plurality of consolidated layers of unidirectionally oriented fibers, a woven fabric, a plurality of woven fabrics consolidated, or any other fiber structure that has been formed from a plurality of fibers, including felts, mats and other structures, such as those comprising randomly oriented fibers. A layer describes a generally flat arrangement. Each fiber layer will have both an upper outer surface and a lower outer surface. A single layer of unidirectionally oriented fibers comprises an arrangement of non-overlapping fibers that are aligned in a substantially parallel, unidirectional arrangement. This type of fiber arrangement is also known in the art as a uni tape, unidirectional tape, UD or UDT. As used herein, an arrangement describes an ordered arrangement of fibers or yarns, which is unique to woven fabrics, and a parallel arrangement describes an orderly parallel arrangement of fibers or yarns. The term oriented as used in the context of oriented fibers refers to the alignment of the fibers in the term fabric.

<img file="MX347124B_D0009.tif" />

opposition to stretching of the fibers. He describes structures that can include one or more layers of fibers, with or without molding or consolidation of the layers. For example, a woven fabric or felt can comprise a single layer of fibers. A nonwoven fabric formed from unidirectional fibers typically comprises a plurality of layers of fibers stacked on top of each other and consolidated. When used herein, a single layer structure refers to a monolithic fibrous structure comprising one or more individual layers or individual layers that have been fused, i.e. consolidated by low pressure lamination or high pressure molding, into a single unitary structure together with polymeric binder material. By consolidation thereof it is meant that the polymeric binder material together with each fiber layer is combined into a single unitary layer. Consolidation can occur by drying, cooling, heating, pressing, or a combination thereof. Heating and / or pressure may not be necessary, since the fibers or fiber layers can be glued together, as is the case in a wet lamination process. The term "mixed material" refers to combinations of fibers with at least one polymeric binder material. A complex mixed material, as used herein, refers to a consolidated combination of a plurality of layers of fibers. As used here, fabrics not

<img file="MX347124B_D0010.tif" />

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INSTITUI or msmcanc • t LA VAOFIIDAO INDUSTRIAL Woven fabrics include all fabric structures that are not formed by weaving. For example, non-woven fabrics can comprise a plurality of webs that are at least partially coated with a polymeric binder material, stacked / overlapped and consolidated into a single layer, monolithic element, as well as a felt or mat comprising random fibers oriented, not parallel, which are preferably coated with a polymeric binder composition.

A fiber surface finish is applied. typically to all fibers to facilitate their processability. To allow direct plasma or corona treatment of fiber surfaces, it is necessary that existing fiber surface finishes be at least partially removed from the fiber surfaces, and preferably completely removed from substantially all or some. of the fiber surfaces of some or all of the component fibers that form a fibrous mixed material. This fiber finish removal will also serve to improve fiber-fiber friction and to allow direct bonding of resins or polymeric binder materials to fiber surfaces, thereby increasing fiber-coating bond strength. The at least partial removal of the fiber surface finish 25 will preferably begin once all the steps of

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IMPI stretching / extension have been completed. The washing step

INDUSTRIAL of the fibers or otherwise removal of the fiber finish will remove enough of the fiber finish that at least some of the underlying fiber surface is exposed, although different removal conditions should be expected to remove different amounts of the finish. For example, factors such as the composition of the washing agent (e.g., water), mechanical attributes of the washing technique (e.g., the force of the water making contact with the fiber; agitation of a bath of washing, etc.), will affect the amount of finish that is removed. For purposes herein, minimal processing to achieve minimal removal of the fiber finish will generally expose at least 10% of the surface area of ​​the fiber. Preferably, the fiber surface finish is removed such that the fibers are predominantly free of a fiber surface finish. As used herein, fibers that are predominantly free of a fiber surface finish are fibers that have had at least 50% by weight of their finish removed, most preferably at least about 75% by weight of their finish removed. . It is even more preferred that the fibers are substantially free of a fiber surface finish. Fibers that are substantially free of a fiber finish are fibers that have had at least about 90% by weight of their

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MEXICAN INSTITUTE

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removed finish, and most preferably at least about 95% by weight of its removed finish, thereby exposing at least about 90% or at least about 95% of the fiber surface area that was previously covered by the fiber finish. fiber surface. Most preferably, any residual finish will be present in an amount less than or equal to about 0.5% by weight based on the weight of the fiber plus the weight of the finish, preferably less than or equal to about 0.4% by weight, most preferably less than or equal to about 0.3% by weight, most preferably less than or equal to about 0.2% by weight and most preferably still less than or equal to about 0.1% by weight based on the weight of the fiber plus the weight of the finish.

Depending on the surface tension of the fiber finish composition, a finish may have a tendency to spread over the fiber surface, even if a substantial amount of the finish is removed. Therefore, a fiber that is predominantly free of a fiber surface finish may still have a portion of its surface area covered by a very thin coating of the fiber finish. However, this remaining fiber finish will typically exist as residual finishing patches rather than a continuous coating. Accordingly, a fiber having surfaces that are predominantly free of a fiber surface finish preferably has its surface at least partially exposed and not covered by a fiber finish, where preferably less than 50% of the fiber surface area It is covered by a fiber surface finish. The fibrous composite materials of the invention comprising fiber surfaces that are predominantly free of fiber finish are then coated with a polymeric binder material. Where the removal of the fiber finish has resulted in less than 50% of the fiber surface area being covered by a fiber surface finish, the polymeric binder material will therefore be in direct contact with more than 50% of the area. fiber surface.

Most preferably, the fiber surface finish is substantially completely removed from the fibers and the fiber surfaces are substantially fully exposed. In this regard, a substantially complete fiber surface finish removal is at least about 95% removal, most preferably at least about 97.5% and most preferably at least about 99.0% fiber surface finish removal , and therefore the fiber surface is at least about 95% exposed, very

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INSTITUTE MWUCANC

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preferably at least about 97.5% exposed and most preferably still at least about 99.0% exposed. Ideally, 100% of the fiber surface finish is removed, thus exposing 100% of the fiber surface area. After removing the fiber surface finish, it is also preferred that the fibers be rinsed of any removed finish particles prior to the application of a polymeric binder material, resin or other adsorbate on the exposed fiber surfaces. Since processing the fibers to achieve minimal removal of the fiber finish will generally expose at least about 10% of the surface area of ​​the fiber, a comparable mixed material that has not been similarly washed or treated to remove at least a portion of the fiber finish will have less than 10% of the exposed fiber surface area, with zero percent surface exposure or substantially no fiber surface exposure.

Increasing the bond strength of the coating fiber also reduces the amount of binder required to properly bond the fibers together. This reduction in the amount of binder allows a greater number of fibers to be included in a fabric, potentially producing lighter ballistic materials that have improved strength. This also leads to

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INSTITUTE MUICANU DE LA noriEBAD INDUSTRIAL

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Improved stab resistance of the resulting mixed fabric materials.

Any conventionally known method of removing fiber surface finishes is useful within the context of the present invention, including both mechanical and chemical technical means. The method required generally depends on the composition of the finish. For example, in the preferred embodiment of the invention, the fibers are coated with a finish that is capable of being washed with only water. Typically, a fiber finish will comprise a combination of one or more lubricants, one or more non-ionic emulsifiers (surface active agents), one or more antistatic agents, one or more wetting and cohesive agents, and one or more antimicrobial compounds. The finished formulations preferred here can be washed with water only. Mechanical means can also be used in conjunction with a chemical agent to improve the efficiency of chemical removal. For example, the finish removal efficiency using deionized water can be enhanced by manipulating the force, steering speed, etc., of the water application processes.

Most preferably, the fibers are washed and / or rinsed with water as a ribbon of fibers, preferably using deionized water, with optional drying of the fibers after washing, without using any other chemical compounds.

<img file="MX347124B_D0014.tif" />

In other modalities where the finish is not soluble in

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INSTITUTO MEXICANO Dt LA MtOMlDAD INDUSTRIAL water, the finish can be removed or washed, for example, with an abrasive cleaner, chemical cleaner or enzyme cleaner. . For example, US patents 5,573,850 and 5,601,775, which are incorporated herein by reference, teach passage of yarns through a bath containing a non-ionic surfactant (HOSTAPUR® CX, commercially available from Clariant Corporation of Charlotte, NC), trisodium phosphate and hydroxide of sodium, followed by rinsing the fibers. Other useful chemical agents include, but are not limited to, alcohols, such as methanol, ethanol, and 2-propanol; aliphatic and aromatic hydrocarbons such as cyclohexane and toluene; chlorinated solvents such as dichloromethane and trichloromethane. Fiber washing will also remove any other surface contaminants, allowing more intimate contact between the fiber and resin or other coating material.

The preferred means used to clean the fibers with water are not intended to be limiting except for the ability to substantially remove the fiber surface finish from the fibers. In a preferred method, removal of the finish is accomplished by a process comprising passing a ribbon of fiber through nozzles of pressurized water to wash (or rinse) and / or physically remove the finish from the fibers. Fibers

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INSTITUTO MEXICANO US LA rkOrilBAD INDUSTRIAL can be optionally pre-soaked in a water bath before passing the fibers through the pressurized water nozzles, and / or soaked after passing the fibers through the pressurized water nozzles, and They can also be optionally rinsed after any of the optional soaking steps by passing the fibers through additional pressurized water nozzles. The washed / soaked / rinsed fibers are also preferably dried after the wash / soak / rinse is complete.

The equipment and means used to wash the fibers are not intended to be limiting, except that it must be capable of washing individual multifilament fibers / multifilament yarns rather than fabrics, i.e. before they are woven or formed into layers or strata of non-woven fibers.

The fiber surface finish removal prior to fabric formation is specially designed here for the production of nonwoven fabrics that are formed by consolidating a plurality of fiber layers comprising a plurality of unidirectionally aligned fibers. In a typical process for forming unidirectionally aligned nonwoven fiber layers, bundles of fibers are supplied from a spool and driven through guides and one or more spreader bars to a collimating comb, followed by coating the fibers with a polymeric binder material. Alternately, the

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INSTITUTO MEXICANO DE LA LÍOHiDA · INDUSTRIAL fibers can be coated before finding the bars

<img file="MX347124B_D0015.tif" />

spreaders, or they can be clad between two sets of spreader bars, one before and one after the cladding section. A bundle of ΐίρϊοο fibers (eg, a yarn) will have about 30 to about 2000 individual filaments, each fiber typically including, but not limited to, about 120 to about 240 individual filaments. The spreader bars and collimating comb disperse and distribute the packed fibers, rearranging them from side to side in a coplanar fashion. The ideal fiber distribution results in individual fibers, or even individual filaments, being placed next to each other in a single fiber plane, forming a parallel, substantially unidirectional arrangement of fibers with a minimal amount of fibers overlapping each other. . The removal of the fiber surface finish before or during this distribution step can intensify and accelerate the distribution of the fibers in said parallel arrangement due to the physical interaction of the cleaning agent (e.g., water) with which fibers / filaments interact. After fiber distribution and collimation, fibers in such a parallel distribution will typically contain about 3 to 16 fiber ends per 2.54 centimeters (1.2 to 6.3 ends per cm), depending on the

IMPI iNSTrnrro Mexican Γ ». ΙΛ mummy »a · __ INDUSTRIAL fiber thickness. Accordingly, removal of fiber surface finish achieves a twofold benefit of enhancing fiber distribution and improves bond strength of subsequently applied materials / adsorbates on fiber surfaces.

After the fiber surface finish is removed to the desired degree, the fibers are subjected to either a plasma treatment or a corona treatment. Both plasma treatment and corona treatment will modify the fibers on the fiber surfaces, thus further enhancing the adsorption / binding capacity of a subsequently applied adsorbate (eg, polymer / resin) on the fiber surfaces. The removal of the fiber finish allows these additional processes to act directly on the fiber surface and not on the fiber surface finish or surface contaminants. Plasma treatment and corona treatment are each desirable to optimize the interaction between the bulk fiber and the fiber surface coatings to improve the anchoring of the coatings to the fiber surfaces. This interaction

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Modified can easily be seen in BFS enhancements.

Corona treatment is a process in which a fiber is passed through a corona discharge station, thus passing the fiber tape through

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INDUSTRIAL a series of high-voltage electrical discharges, which tends to act on the surface of the fiber web in a variety of ways, including dimpling, roughness, and introduction of polar functional groups through partial oxidation of the surface of the fiber. fiber. Corona treatment typically oxidizes the surface of the fiber and / or adds polarity to the surface of the fiber. Corona treatment also works by burning small dimples or holes in the surface of the fiber. When fibers are oxidizable, the degree of oxidation depends on factors such as power, voltage, and frequency of corona treatment. The residence time within the corona discharge field is also a factor, and this can be manipulated by a corona treatment design or by the line speed of the process. Suitable corona treatment units are available, for example, from Enercon Industries Corp., Menomonee Falls, Wis., From Sherman Treaters Ltd., Thame, Oxon., UK or from Softal Corona &amp; Plasma GmbH &amp; Co of Hamburg, Germany .

In a preferred embodiment, the fibers are subjected to a corona treatment of approximately 21.55 watts / m²/ min at approximately 1077.6 watts / m²/ min, most preferably about 53.88 watts / m²/ min at approximately 538.8 watts / m²/ min, and most preferably about 215.52 watts / m²/ min at approximately 538.8

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INDUSTRIAL watts / m²/ min. The lowest energy corona treatments of approximately 10,776 watts / m²/ min at approximately

53.88 watts / m²/ min are also useful but may be less effective. In addition to applying a load to the fiber surface, a corona treatment can roughen the surface by dimpling the fiber surface.

In a plasma treatment, the fibers, typically as a fiber ribbon, are passed through an ionized atmosphere in a chamber that is filled with an inert or non-inert gas, such as oxygen, argon, helium, ammonia, or other. Appropriate inert or non-inert gas, including combinations of the above gases, to thereby bring the fibers into contact with a combination of neutral molecules, ions, free radicals, as well as ultraviolet light. On fiber surfaces, surface collisions with charged particles (ions) result in both the transfer of kinetic energy and the exchange of electrons, etc. Furthermore, collisions between surfaces and free radicals will produce similar chemical rearrangements. Chemical changes to the fiber substrate are also caused by bombardment of the fiber surface by ultraviolet light, which is emitted by excited atoms, and by molecules that relax to lower states. As a result of these interactions, plasma treatment can modify both the chemical structure of the fiber and the topography of the fibers.

<img file="MX347124B_D0018.tif" />

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Mexican INSTITUTE M LA nOPIWAB. , INDUSTRIAL fiber surfaces. For example, like corona treatment, a fiber and / or plasma surface treatment also adds polarity to the oxidized fiber surface portions. Plasma treatment can also serve to increase the surface energy of the fiber, reduce the contact angle, modify the density of entanglement of the fiber surface, thus increasing the hardness, melting point and mass anchoring of subsequent coatings. and it can add chemical functionality to the fiber surface and potentially ablate the fiber surface. These effects probably depend on the chemistry of the fiber, and also depend on the type of plasma used.

Gas selection is important for the desired surface treatment because the chemical structure of the surface is modified differently using different plasma gases. That would be determined by one skilled in the art. It is known, for example, that amine functionalities can be introduced to a fiber surface using ammonia plasma, while carboxyl and hydroxyl groups can be introduced using oxygen plasma. Accordingly, the reactive atmosphere may comprise one or more of argon, helium, oxygen, nitrogen, ammonia, and / or other gas known to be suitable for plasma treatment of fabrics. The reactive atmosphere

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For example, an atomic form in an array may comprise one or more of those ionic, molecular or free radical gases. By the preferred continuous process of the invention, fibers are passed through a controlled reactive atmosphere that preferably comprises argon atoms, oxygen molecules, argon ions, oxygen ions, oxygen free radicals, as well as other trace species. In a preferred embodiment, the reactive atmosphere comprises both argon and oxygen at concentrations of about 90% to about 95% argon and from about 5% to about 10% oxygen, with concentrations of 90/10 or 95/5 argon / oxygen being preferred. In another preferred embodiment, the reactive atmosphere comprises both helium and oxygen at concentrations of from about 90% to about 95% helium and from about 5% to about 10% oxygen, with concentrations of 90/10 or 95/5 helium / oxygen being preferred. Another useful reactive atmosphere is a zero gas atmosphere, that is, ambient air comprising about 79% nitrogen, about 20% oxygen, and small amounts of other gases, which is also useful for corona treatment to some degree.

A plasma treatment differs from a corona treatment mainly in that a plasma treatment is conducted in a controlled, reactive gas atmosphere.

IMPI

ΙΗΓΤΓΠΠΟ MUICANO DE LA NORIPAD INDUSTRIAL whereas in corona treatment the reactive atmosphere is air. The atmosphere in plasma treatment can be easily controlled and maintained, allowing surface polarity to be achieved in a more controllable and flexible way than corona treatment. The electrical discharge is by radio frequency energy (RF) that dissociates the gas into electrons, ions, free radicals and metastable products. Electrons and free radicals created in plasma collide with the fiber surface, breaking covalent bonds and creating free radicals on the fiber surface. In a batch process, after a predetermined reaction time or temperature, the process gas and RF energy are turned off and the remaining gases and other by-products are removed. In a continuous process, which is preferred herein, an array of fibers is passed through a controlled reactive atmosphere comprising atoms, molecules, ions and / or free radicals of the selected reactive gases, as well as other trace species. The reactive atmosphere is constantly generated and refilled, probably reaching a steady state composition, and is not quenched or quenched until the coating machine is stopped.

The plasma treatment can be carried out using any useful commercially available plasma treatment machine, such as

IMPI

INSTmjTU MEXICANO M LA PkOHiDAD INDUSTRIA!

<img file="MX347124B_D0020.tif" />

plasma treatment available from Softal Corona &amp; Plasma GmbH &amp; Co of Hamburg, Germany, 4^or. Belmont California State, Inc; Plasmatreat US, Elgin Illinois LP; Enercon Suface Treating Systems of Milwaukee, Wisconsin. The plasma treatment can be conducted in a chamber maintained under a vacuum or in a chamber maintained under atmospheric conditions. When using atmospheric systems, a fully enclosed chamber is not mandatory. Plasma treatment or corona treatment of fibers in a non-vacuum environment, that is, in a chamber that is not maintained in either full or partial vacuum, can increase the potential for fiber degradation. This is because the concentration of the reactive species is proportional to the pressure of the treatment. This increased potential for fiber degradation can be counteracted by reducing the residence time in the treatment chamber. Treatment of fibers under a vacuum, together with the need to treat fibers through their fiber surface finish, results in the need for long treatment residence times. This undesirably causes a typical loss of fiber strength properties, such as fiber toughness, of about

15% to 20%. The aggressiveness of the treatments can be reduced by reducing the energy flow of the treatment, but this sacrifices the effectiveness of the treatments by

IMPI

MEXICAN INSTITUTE

FROM THE FKOHBPAT industrial

<img file="MX347124B_D0021.tif" />

increasing adsorbate binding limits improvements in BFS. However, on fibers, it has also been unexpectedly found that when conducting fiber treatments after at least partially removing the fiber finish, the fiber tenacity loss is less than 5%, typically less than 2% or less than 1%, often with no loss at all, and in some cases the strength properties of the fiber are actually increased, This is due to the increased entanglement density of the polymeric fiber due to the direct treatment of the fiber surfaces. When fiber treatments are conducted after at least partially removing the finish from the fiber, the treatments are much more effective and can be conducted in non-vacuum, less aggressive environments at various levels of energy flow without sacrificing increased performance. liner bonding and BFS. In the most preferred embodiments of the invention, the high tenacity fibers are subjected to plasma treatment or corona treatment in a chamber maintained at approximately atmospheric pressure or above atmospheric pressure. As a secondary benefit, atmospheric pressure plasma treatment allows treatment of more than one fiber at a time, while vacuum treatment is limited to treating one fiber at a time.

A preferred plasma treatment process is

INSTITUTO MEXICANO DE LA nonUAD iNBurrtiAi leads to approximately atmospheric pressure, that is, 1 atm (760 mm Hg (760 torr)), with a chamber temperature of approximately room temperature 21.1 ° C-22.2 ° C. The temperature within the plasma chamber can potentially change due to the treatment process, but the temperature is generally not independently cooled or heated during treatments, and is not believed to affect the treatment of the fibers as they rapidly pass through the plasma treatment machine. The temperature between the plasma electrodes and the fiber tape is typically about 100 ° C. The plasma treatment process is preferably conducted under RE power at about 0.5 kW to about 3.5 kW, most preferably from about 1.0 kW to about 3.05 kW, and most preferably still the plasma treatment is conducted using a plasma treatment machine. Atmospheric set to 2.0 kW. This power is distributed over the entire width of the plasma treatment zone (or the length of the electrodes) and this power is also distributed along the entire length of the substrate or fiber tape at a speed that is inversely proportional to the speed of line to which the fiber tape passes through the reactive atmosphere of the plasma treatment machine. This energy per unit area per unit time (Watts per square meter / minute or W / m²/ min) or energy flow, is a useful way to compare treatment levels. The effective values ​​for power flow are preferably from about 5.39 to about 2155.2 W / m²/ min, most preferably from about 10,776 to about 1077.6 W / m²/ min, most preferably still from about 10,776 to about 862.08 W / m²/ min, most preferably still from about 21.55 to about 431.04 W / m²/ min, and most preferably still from about 21.55 to about 215.52 W / m²/ min. The total gas flow rate is approximately 16 liters / min, but is not intended to be strictly limiting.

As the total gas flow rate is distributed across the width of the plasma treatment zone, additional gas flow may be required with increments to the length / width of the plasma treatment zone of the plasma treatment machine. plasma treatment. For example, a plasma treatment machine that has a treatment zone width of 2x may need twice as much gas flow compared to a plasma treatment machine that has a treatment zone width of lx. The plasma treatment time (or residence time) of the fiber is also relative to the dimensions of the plasma treatment machine used and is not intended to be strictly limiting. In a system

<img file="MX347124B_D0022.tif" />

Atmospheric preferred, the fibers are plasma treated with a time from about b second to about

<img file="MX347124B_D0023.tif" />

residence of three seconds, with an average residence time of approximately 2 seconds. A more appropriate measure is the amount of plasma treatment in terms of RF power applied to the fiber per unit area or over time.

Furthermore, the mixed materials and fabrics of the invention may comprise some fibers that are treated and some fibers that are not treated. For example, the mixed materials here can be made of some fibers that are treated by and some fibers that are plasma treated. Each of these illustrative processes, through their action on the fiber surface, can be used to modify, enhance or reduce the interaction between the bulk fiber and subsequent coating materials, depending on the fiber chemistry. The various treatment steps of the invention can be used as a recipe for manipulating the fibers in order to place the mixed material within the desired range for transmitted impact energy or other properties. If the BFS test determines that a particular mixed material has a worse than desired BFS, which is indicative that additional fiber washing and / or additional surface treatment should be conducted to further increase said

<img file="MX347124B_D0024.tif" />

properties to fall within the desired range.

IMPI

OWTmrro MEXICAN

O £ THE INDUSTRIAL PWRITY

Plasma and corona treatments will be conducted after at least partial removal of the fiber surface finish but before the application of any binder / matrix resins or other adsorbates / surface coatings. Treatment of exposed fiber surfaces immediately prior to coating the lined fiber tape with a polymeric binder material or resin is most preferred because it causes the least disruption to the fiber manufacturing process and will leave the fiber in a modified state. and unprotected for the shortest period. It is ideal to remove fiber surface finish and treat exposed fiber surfaces immediately after unwinding fibers from a fiber reel (wound fiber bundle) and aligning the fibers on a fiber tape, followed by immediately coating or impregnating the fibers with a polymer / resin coating. This will also leave the fibers in a treated and uncoated state for the shortest time if there are considerations about the shelf life or decomposition rate of the fiber surface modification. However, this is ideal primarily for causing the least disruption to the overall manufacturing process, and not necessarily for achieving improved performance of

BFS of the mixed material.

<img file="MX347124B_D0025.tif" />

Fibrous mixed materials

IMPI produced according to the methods described here

<img file="MX347124B_D0026.tif" />

excellent properties of transmitted impact energy. The transmitted impact energy is a measure of the depth of deflection of either the soft armor or the hard armor in a backing material or in the body of a user due to a projectile impact. Very specifically, BFS, also known in the art as transmitted impact energy deformation, impact energy transmitted by trauma or blunt force trauma, is a measure of how much impact a projectile leaves under armor once the armor stops the projectile. so that it does not penetrate, indicating the potential blunt trauma experienced by the body under the armor. The reduction in transmitted impact energy deformation results from modifying the component fibers of fibrous composite materials to enhance fiber-fiber coupling and / or reduce the tendency for fiber-cladding delamination.

The reduction in fiber-fiber coupling and / or fiber-cladding delamination under projectile impact is optimized by plasma treatment or corona treatment of the fibers after at least partially removing the pre-existing fiber surface finish. of the fibers prior to processing the fibers into a fabric, wherein forming a fabric includes interconnecting

IMPI

MIXICAN INSTITUTE

M INDUSTRIAL PROBITY fibers to form woven fabric layers, non-woven fabric layers or non-woven fiber layers. The removal of fiber surface finishes before the formation of non-woven fabric layers or non-woven fiber layers, or before the weaving of woven fabrics, has hitherto been known because the fiber surface finish is generally known as a necessary processing aid as described above. In the manufacture of nonwovens, a fiber surface finish is generally required to reduce static build-up, prevent fiber entanglement, lubricate the fiber to allow it to slide over the loom components, and improve fiber cohesion during processing. , including during fiber stretching steps. Plasma treatment or corona treatment of the fibers after removing at least a portion of the pre-existing fiber surface finish from the fibers allows the exposed fiber surfaces to be treated directly, thus modifying the fiber surfaces more to conduct the treatments on the fiber finish. The reduction in fiber-fiber decoupling and / or fiber-coating delamination produces mixed materials having correspondingly superior transmitted impact energy performance against high velocity projectiles.

The improvement in transmitted impact energy is

IMPI iNímvru mejucanc

Ot THE INDUSTRIAL NOTICE

<img file="MX347124B_D0027.tif" />

particularly evident when the component fibers are polyethylene fibers, which are naturally superior to other fibers in their bullet resistance capabilities but not necessarily in their structural properties. Treatment of polyethylene fiber surfaces as described above prior to the manufacture of polyethylene-based fabrics formed therefrom achieves a combination of structural properties, bullet penetration resistance, and impact energy resistance properties. that are comparatively superior to any other type, including aramid fibers.

. In this regard, the fibrous mixed materials of the invention have a preferred transmitted impact energy of less than about 6 mm as measured for a mixed material having an areal density of 9.8 kg / m²when hit with an 8035.2 mg FMJ RN 9 mm projectile, fired at a velocity of approximately 427 m / s to approximately 445 m / s, measured at room temperature. Not all fibrous mixed materials or articles of the invention will have an areal density of 9.8 kg / m², not all fibrous mixed materials or articles of the invention will have a BFS of 6 mm against said FMJ RN projectile at that speed. That only identifies that mixed materials

ΙΜΡΙΛ?

MEXICAN INSTITUTE,

OS LA SMPKDAO industrial manufactured according to the processes of the invention are characterized because when they are manufactured in a panel of 9.8 kg / m², that panel of 9.8 kg / m² It will have a BFS of less than about 6mm against an FMJ RN projectile at that velocity when measured at about room temperature (about 21.1 ° C-22.2 ° C).

It should also be understood that the terms BFS, transmitted impact energy deformation, trauma transmitted impact energy, and blunt force trauma are not measurements of depth of depression of the mixed material due to projectile impact, but rather are measurements of the depth of depression in the backing material or in the body of a user due to a projectile impact. This is particularly relevant for the study of hard armor, particularly hull armor. Helmet BFS is typically tested by placing a prototype helmet over a metal head form, where the helmet is held onto the head form by a suspension system that separates the helmet from. the head shape by 1.27 cm. Sections of the head shape are filled with clay, and the depth of depression in those clay areas is measured as the BFS without including the 1.27 cm depth of separation in the measurement. This is done for the purpose of correlating the laboratory BFS test with BFS experienced by a soldier in use at the

<img file="MX347124B_D0028.tif" />

IMPI

MEXICAN INSTITUTE

M LA FROHIOac industrial field, where a typical helmet incorporates a 1.27 cm offset from the head, due to internal helmet padding or a suspension / harness retention system. The BFS or soft shield, on the other hand, is conventionally tested by placing the shield directly on the clay surface without separation, which is consistent with its position in actual field use. Consequently, BFS depth measurements are relative to the test method used, and when comparing BFS depth measurements, it is necessary to identify whether or not the test method used required placement of the test sample directly on the backing material. or separate from the backing material. In this regard, all transmitted impact energy data in this application was measured using an apparatus described in co-pending patent application No. standard 61 / 531,233 with a 1.27 cm gap between the 9.8 kg / m sample² and a clay backing material. In preferred embodiments of the invention, the fibrous composite materials of the invention have a more preferred transmitted impact energy of less than about 5mm when struck with a 9mm, 8035.2mg FMJ projectile fired at a velocity of about 427m / s at about 445 m / s under NIJ Standard 0101.04 projectile firing conditions, most preferably less than about 4mm, very

<img file="MX347124B_D0029.tif" />

IMPI

MEXICAN INSTITUTE

OF THE INDUSTRIAL FWOHITY preferably less than about 3 mm, most preferably less than about 2 mm, and most preferably still having a transmitted impact energy of less than about 1 mm when struck with an 8035.2 mg FMJ RN 9 mm projectile ( a bullet comprising approximately 90% copper and 10% zinc excluding the base) fired at a velocity of approximately 427 m / s to approximately 445 m / s, when measured approximately at room temperature. The BFS test against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity of about 427 m / s to about 445 m / s is common in the art.

Said fibrous mixed materials that achieve these BFS values ​​each comprise a plurality of layers of fibers together, each layer of fibers comprising fibers having surfaces that are at least partially covered with a polymeric material, wherein said fibers are predominantly free of a fiber surface finish such that said polymeric material is predominantly in direct contact with the fiber surfaces. Such mixed fibrous materials that achieve these BFS values ​​also preferably exhibit a V₅₀ against a 1036.8 mg Right Circular Cylinder (RCC) projectile of at least about 975.36 m / s, most preferably at least about 1005.84 m / s, very

<img file="MX347124B_D0030.tif" />

preferably still at least

IMPI

ΙΝΓΠΠΓΓ · MEXICAN

Say LA noniDAU

INDUSTRIAL about 1036.32 m / s, minus about 1066.8 at least V values₅₀that have a 9.76 kg / m² (ksm).

fibrous mixtures or areal density most preferably still about 1097.28 m / s and most preferably still about 1097.28 m / s. All of the above are for armor panels with mixed area density of approximately Same as with BFS, not all material articles of the invention will have a particular, nor will all mixed fibrous materials or articles of the invention have a V₅₀ against an RCC projectile of

1036.8 mg of at least about 1005.84 m / s. These only identify that mixed materials manufactured according to the procedures of the invention are characterized because when they are manufactured in a 9.8 kg / m panel², that panel of 9.8 kg / m² will have a V₅₀ against a 1036.8 mg RCC projectile of at least about 975.36 m / s.

In a preferred embodiment of the invention, the fibrous mixed materials of the invention have a V₅₀against a 1036.8 mg RCC projectile of at least about 975.36 m / s or at least about 1005.84 m / s, in addition to a BFS of about 5 mm or less against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity from about 427 m / s to about 445 m / s, most preferably a V50 against a 1036.8 mg RCC projectile of at least about

<img file="MX347124B_D0031.tif" />

975.36 m / s or at least about 1005.84 m / s plus a BFS of about 4 mm or less against an 8035.2 mg FMJ RN 9mm projectile fired at a velocity of about 427 m / s to about 445 m / s, and most preferably still a V₅₀ against a 1036.8 mg RCC projectile of at least about 975.36 m / s or at least about 1005.84 m / s, plus a BFS of about 3 mm or less, about 2 mm or less, or about 1 mm or less against An 8035.2 mg 9mm FMJ RN projectile fired at a velocity of approximately 427 m / s to approximately 445 m / s, when measured at approximately room temperature. In a more preferred embodiment of the invention, the fibrous mixed materials of the invention have a V₅₀ against a 1036.8 mg RCC projectile of at least about 1036.32 m / s or at least about 1066.8 m / s, in addition to a BFS of about 5 mm or less against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity from about 427 m / s to about 445 m / s, most preferably a V₅₀against a 1036.8 mg RCC projectile of at least about 1036.32 m / s or at least about 1066.8 m / s in addition to a BFS of about 4 mm or less against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity from about 427 m / s to about 445 m / s, and most preferably still a V₅₀ against a projectile

IMPI INSTITUTO MEXICANO Oí LA FMOHIDAD INDUSTRIAL

<img file="MX347124B_D0032.tif" />

RCC of 1036.8 mg of at least about 1005.84 m / s, plus a BFS of about 3 mm or less, about 2 mm or less, or about 1 mm or less against an 8035.2 mg FMJ RN projectile fired at a speed of about 427 m / s to about 445 m / s, when measured at about room temperature. In a more preferred embodiment of the invention, the fibrous mixed materials of the invention have a V₅₀against a 1036.8 mg RCC projectile of at least approximately 1097.28 m / s, in addition to a BFS of approximately 5 mm or less against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity of approximately 427 m / s to approximately 445 m / s, most preferably a V₅₀against a 1036.8 mg RCC projectile of at least approximately 1097.28 m / s in addition to a BFS of approximately 4 mm or less against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity of approximately 427 m / s at approximately 445 m / s, and most preferably still a V₅₀ against a 1036.8 mg RCC projectile of at least approximately 1097.28 m / s in addition to a BFS of approximately 3 mm or less, approximately 2 mm or less, or approximately 1 mm or less against an 8035.2 mg 9mm FMJ RN projectile fired at a velocity of approximately 427 m / s to approximately 445 m / s, when measured at approximately room temperature. As before, these data from

IMPI tNSWTUTOMMICANC; otiAr «oru * AO! N» &lt;«T1UAI

<img file="MX347124B_D0033.tif" />

BFS were measured using an apparatus described in co-pending patent application Serial No. 61 / 531,233 with a 1.27 cm gap between a 9.8 kg / m sample² and a clay backing material, measured at room temperature.

The high tensile, high tensile modulus polymeric fibers that form the fiber and mixed material layers of the invention can be of any fiber toughness as long as the fiber toughness after plasma / corona treatment is about 95% at 100% of the original fiber toughness before plasma / corona treatment (that is, fiber toughness loss due to treatment is less than 5%), most preferably it is from about 98% to 100% of the original fiber toughness (i.e. loss of fiber toughness due to treatment is less than 2%), most preferably still it is from about 99% to 100% of the toughness of original fiber (i.e. fiber tenacity loss due to treatment is less than 1%), most preferably still 'wherein the fiber toughness after plasma / corona treatment is equal to the original fiber toughness before plasma / corona treatment (i.e. there is no loss of fiber toughness due to treatment), and very preferably still where the fiber toughness after plasma / corona treatment is greater than the fiber toughness

<img file="MX347124B_D0034.tif" />

IMPI

INÍTnVTOMWUCAN ·

BF INDUSTRIAL HORITY fiber say original before plasma / corona treatment (fiber toughness increases due to treatment).

Accordingly, the fiber and mixed material layers formed herein are preferably bullet resistant mixed materials formed from high strength, high tensile modulus polymeric fibers having a pre-plasma / corona toughness of at least about 20 g / denier, as well as a toughness after plasma / corona treatment of at least about 20 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 25 g / denier as well as a post-plasma / corona toughness of at least about 25 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 30 g / denier, as well as a post-plasma / corona toughness of at least about 30 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 33 g / denier, as well as a post-plasma / corona toughness of at least about 33 g / denier. Most preferably, the fibers have a toughness prior to plasma / corona treatment

4

INSTITUTO MEXICANO DE LA PROPIEDAD INDUSTRIAL of at least approximately 35 g / denier, as well as a toughness after plasma / corona treatment of at least approximately 35 g / denier. Still most preferably, the fibers have a pre-plasma / corona toughness of at least about 37 g / denier, as well as a post-plasma / corona toughness of at least about 37 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 39 g / denier, as well as a post-plasma / corona toughness of at least about 39 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 45 g / denier, as well as a post-plasma / corona toughness of at least about 45 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 50 g / denier, as well as a post-plasma / corona toughness of at least about 50 g / denier. Most preferably, the fibers have a pre-plasma / corona toughness of at least about 55 g / denier, as well as a post-treatment toughness of. plasma / corona of at least about 55 g / denier. Most preferably still,

IMPI ^

INJTTTUTO MEXICANA DE LA FEOHEUAD, INDUSTRIAL ~ * fibers have a toughness prior to plasma / corona treatment of at least about bü g / denier, as well as a toughness after plasma / corona treatment of at least about 60 g / denier . Still most preferably, the fibers have a pre-plasma / corona toughness of at least about 65 g / denier, as well as a post-plasma / corona toughness of at least about 65 g / denier. All toughness measurements identified here are measured at room temperature. 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 the tensile stress expressed as force (grams) per unit linear density (denier) of an unstressed specimen and is measured by ASTM D2256. 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 strain, expressed as a fraction of the original fiber length (cm / cm). The tensile modulus of the fibers is also affected by plasma and corona treatments such as the toughness of the fiber. However, plasma or corona treatment of fibers under pressure

<img file="MX347124B_D0035.tif" />

atmospheric after removing the surface finish from

IMPI

MEXICAN INSTITUTE

FROM THE »ONI * to £ INDUSTRIAL fiber currently it has been found that the modulus increases due to an increase in the density of entanglement due to the direct treatment of the fiber surfaces.

The fiber-forming polymers are preferably high-strength, high-tensile modulus fibers, suitable for making bullet resistant blends / fabrics. Suitable high-strength, high-tensile modulus fiber materials that are particularly suitable for the formation of mixed materials and bullet resistant articles include polyolefin fibers, including high-density and low-density polyethylene. Particularly preferred are extended chain polyolefin fibers, such as highly oriented, high molecular weight 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, polyethylene terephthalate fibers, polyethylene naphthalate fibers, extended chain polyvinyl alcohol fibers, extended chain polyacrylonitrile fibers, polybenzazole fibers, such as polybenzoxazole (PBO) and polybenzothiazole (PBT) fibers, glass copolyester fibers

<img file="MX347124B_D0036.tif" />

liquid and other rigid rod fibers,

IMPI

INSTITUTO MEXICANO M LA PROHIJAD INDUSTRIAL such as fibers

M5®. Each of these types of fiber is conventionally known in the art. Also suitable for producing polymeric fibers are copolymers, block polymers, and blends of the above materials.

The most preferred fiber types for bullet resistant fabrics include polyethylene, particularly extended chain polyethylene fibers, aramid fibers, polybenzazole fibers, 1-0 liquid crystal copolyester fibers, polypropylene fibers, particularly chain polypropylene fibers. highly oriented extended, polyvinyl alcohol fibers, polyacrylonitrile fibers and other rigid rod fibers, particularly M5® fibers. Specifically most preferred fibers are aramid fibers.

In the case of polyethylene, preferred fibers are chain-extended polyethylenes having molecular weights of at least 500,000, preferably at least one million, and most preferably between two million and five million. Such extended chain polyethylene (ECPE) fibers can be grown in solution centrifugation processes as described in US Pat. 4,137,394 or 4,356,138, which are incorporated herein by reference, or can be centrifuged from solution to form a gel structure, as shown

IMPI

ΙΝΓΠΤυΤ · MEXICANO M LA nontlMD iNtxisnuAi described in US Patents 4,551,296 and 5,006,390, which are incorporated herein by reference. A type of fiber

<img file="MX347124B_D0037.tif" />

Particularly preferred 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 Patents 4,623,547 and 4,748,064. In addition to polyethylene, another type of useful polyolefin fibers is polypropylene (fibers or tapes), such as TEGRIS® fibers commercially available from Milliken &amp; Company of Spartanburg, South Carolina.

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 under the trademark KEVLAR®. Also useful in the practice of this invention are poly (m-phenyleneisophthalamide) 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 Industries, Inc. of Korea under the trademark HERACRON®; SVM ™ and RUSAR ™ p-aramid fibers that are commercially produced by Kamensk Volokno JSC of

<img file="MX347124B_D0038.tif" />

IMPI

INSTITUTO MMUCANO os la noraoAD

INWUSTRIAL

Russia and ARMOS ™ p-aramid fibers commercially produced by JSC Chim Volokno of Russia.

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, each of which is incorporated herein by reference. Liquid crystal copolyester fibers suitable for the practice of this invention are commercially available and are described, for example, in US Pat. 3,975,487; 4,118,372 and 4,161,470, each of which is incorporated herein by reference. Suitable polypropylene fibers include highly oriented extended chain polypropylene (ECPP) fibers as described in US Patent 4,413,110, which is incorporated herein by reference. Suitable polyvinyl alcohol (PV-OH) fibers are described, for example, in US Patents 4,440,711 and 4,599,267 which are incorporated herein by reference. Suitable polyacrylonitrile fibers (PAN) are described, for example, in US Patent 4,535,027, which is incorporated herein by reference. Each of these types of fibers is conventionally known and widely commercially available.

M5® fibers are formed from pyridobisimidazole-2,6-diyl (2,5-dihydroxy-p-phenylene) and are

<img file="MX347124B_D0039.tif" />

manufactured by Magellan Systems International of Richmond,

IMPI

MEXICAN INSTITUTE OF INDUSTRIAL PROPERTY

Virginia, and are described, for example, in US Patents 5,674,969, 5,939,553, 5,945,537, and 6,040,478, each of which is incorporated herein by reference. Also suitable are combinations of all of the above materials, all of which are commercially available. For example, fibrous layers can be formed from a combination of one or more aramid fibers, UHMWPE fibers (e.g., SPECTRA® fibers), carbon fibers, etc., as well as fiberglass and others. inferior performance materials. However, the values ​​of BES and V₅₀they can vary by type of fiber.

The fibers can be of any suitable denier useful to achieve fibers having tenacity as described above. Selection is governed by ballistics cost and effectiveness considerations. Finer fibers are more expensive to manufacture and weave, but can produce greater ballistic effectiveness per unit weight. Ultra-high molecular weight polyethylene fibers having a tenacity of at least about 37 g / denier can be obtained, for example, using the process of co-pending application Ser. No. 13 / 173,919, filed on 30 June 2011.

Other known processes for the manufacture of high strength fibers are described, for example, in US patents 4,413,110, 4,440,711, 4,535,027,

4,457,985, 4,623,547,

4,650,710 and 4,748,0 which are incorporated herein by reference to the extent consistent therewith. Such methods, including solution growth or gel fiber processes, are well known in the art. Methods of 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.

After removing at least a portion of the fiber surface finish from the fiber surfaces as desired, and after the fiber surfaces are optionally treated under conditions effective to enhance the adsorption capacity of an adsorbate subsequently applied to to the fiber surfaces, an adsorbate is then optionally applied onto at least a portion of at least some of the fibers. To this end, an adsorbate can be any solid, liquid, or gas, including polymeric binder materials and resins, and adsorption includes any form of attachment of the materials to fiber surfaces. The definition of adsorbate expressly includes all polymers useful as polymeric binder materials, resins, or polymeric matrix materials, but the class of useful adsorbates expressly excludes materials that do not have binding properties including

IMPI

IMSTTTUT · MEXICAN 1% LA nOHUAD iNoumu-M

<img file="MX347124B_D0040.tif" />

Fiber surface finishing substances such as spin finishing materials, which are non-binding materials that have bonding properties. In contrast, finished fiber surface materials are specifically removed from fiber surfaces in accordance with the invention. The term adsorbate also expressly includes inorganic materials, such as silicon oxide, titanium oxide, aluminum oxide, tantalum oxide, hafnium oxide, zirconium oxide, titanium aluminate, titanium silicate, hafnium aluminate, hafnium silicate. , zirconium aluminate, zirconium silicate, boron nitride, or a combination thereof, as described in commonly owned US patent application publication no. 2008/0119098, the description of which is incorporated herein by reference.

The term adsorption (or adsorbability or adsorb) is broadly designed to encompass both physisorption and chemisorption of any material (solid, liquid, gaseous or plasma) onto the fiber surface, where physisorption is defined here as the physical attachment of a material on a fiber surface and chemisorption is defined herein as the chemical binding of a material on. the fiber surface, where a chemical reaction occurs at the exposed fiber surface (i.e., the

IMPI • NSTrtUTO MEXICANO t * la rionwAD • NPUSTEML

<img file="MX347124B_D0041.tif" />

assorbant). The term adsorption as used herein is designed to include any possible means of fixation, adhesion or attachment of a material to a substrate surface, physically or chemically, without limitation, including means to increase the wetting / adhesion of the fiber fibers in polymer matrices. This expressly includes the adhesion or coating of any solid, liquid or gaseous material on the surfaces of the fiber, including any monomer, oligomer, polymer or resin, and including the application of any organic material or inorganic material on the surfaces of the fiber.

It is more preferred here that the fibers forming the woven or nonwoven materials of the invention are coated with or impregnated with a polymeric binder material. The adsorbent of polymeric binder material, such as a resin, either partially or substantially coats the individual fibers of the fiber layers, preferably substantially covering each of the individual fibers of each fiber layer. The polymeric binder material is also commonly known in the art as a polymeric matrix material, and these terms are used interchangeably herein. These terms are conventionally known in the art and describe a material that binds fibers together either by means of its inherent adhesive characteristics or after being subjected to well known conditions of heat and / or pressure.

IMPI

INSTITUTO MEXICANO Dt LA nUSHWAD INDUSTRIAL

<img file="MX347124B_D0042.tif" />

Said polymeric matrix material or polymeric binder also provide a fabric with other desirable properties, such as resistance to abrasion and resistance to adverse environmental conditions, so it may be desirable to coat the fibers with such a binder material when its binder properties they are not important, such as woven fabrics.

Suitable polymeric binder materials include both low modulus elastomeric materials and high modulus rigid materials. As used herein, 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. A low or high modulus binder can comprise a variety of polymeric and non-polymeric materials. A preferred polymeric binder comprises a low modulus elastomeric material. For the purposes of this invention, a low modulus elastomeric material has a tensile modulus measured at approximately 41.4 MPa or less according to the test procedures of ASTM D638. A low modulus polymer preferably has the elastic modulus of the elastomer at about 27.6 MPa or less, most preferably about 16.5 MPa or less, most preferably 8.23 ​​MPa or less, and most preferably still

IMPI '

Mexican INSTITUTE t

INDUSTRIAL about 3.45 MPa or less. The glass transition temperature (Tg) of the elastomer is preferably less than about 0 ° C, most preferably less than about -40 ° C, and most preferably less than about -50 ° C. The elastomer also has a preferred elongation at break of at least about 50%, most preferably at least about 100%, and most preferably has an elongation at break of at least about 300%. .

A wide variety of materials and formulations that have a low modulus can be used as the polymeric binder. Representative examples include polybutadiene, polyisoprene, natural rubber, ethylene-propylene copolymer, ethylene-propylene-diene terpolymers, polysulfide polymers, polyurethane elastomers, chlorosulfonated polyethylene, polychloroprene, plasticized polyvinyl chloride, poly (butadiene-acryl elastomers, acrylonitrile) elastomers. isobutylene-co-isoprene), polyacrylates, polyesters, polyethers, fluoroelastomers, silicone elastomers, ethylene copolymers, polyamides (useful with some types of fibers), acrylonitrile-butadiene-styrene, polycarbonates, and combinations thereof, as well as other low modulus polymers and copolymers curable below the melting point of the fiber. Also preferred are mixtures of

<img file="MX347124B_D0043.tif" />

IMPI

INSTITUTO MEXICANO E LA PROPIEDAD INDUSTRIAL different elastomeric materials, or mixtures of elastomeric materials with one or more thermoplastics.

Particularly useful are block copolymers of conjugated dienes and vinyl aromatic monomers. Butadiene and isoprene are preferred conjugated diene elastomers. Styrene, vinyl toluene, and t-butyl styrene are preferred conjugated aromatic monomers. Block copolymers incorporating polyisoprene can be hydrogenated to produce thermoplastic elastomers having saturated hydrocarbon elastomer segments. The polymers can be simple tri-block copolymers of the ABA type, multi-block copolymers of the (AB) type_n (n = 2-10) or R- (BA) type radial configuration copolymers_X (x = 3-150); wherein A is a block of a polyvinyl aromatic monomer 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 Kraton Thermoplastic Rubber bulletin, SC-68-81. Also useful are styrene isoprene-styrene block copolymer (SIS) resin dispersions sold under the trademark PRINLIN® and commercially available from Henkel Technologies, based in Dusseldorf, Germany. Particularly preferred low modulus polymeric binder polymers comprise styrenic block copolymers sold under the trademark KRATON® commercially produced by Kraton

IMPI

Polymers. A particularly preferred polymeric binder material comprises a polystyrene-polyisoprene-polystyrene block copolymer sold under the trademark

KRATON®.

ΙΝΓΠΤυΤΟ MEXICAN DEIA nQHUMD INDUSTRIAL

Although low modulus polymer matrix binder materials are more useful for the formation of flexible armor, such as bullet resistant vests, rigid high modulus materials useful for forming hard armor articles, such as helmets, are particularly preferred herein. Preferred high modulus rigid materials generally have an initial tensile modulus higher than 421.8 kg / cm². Preferred high modulus rigid polymeric binder materials useful herein include polyurethanes (both ether-based and ester-based), epoxies, polyacrylates, phenolic / polyvinyl butyral (PVB) polymers, vinyl ester polymers, styrene-block copolymers. butadiene, as well as polymer blends such as vinyl ester and diallyl phthalate or phenol formaldehyde and polyvinyl butyral. A particularly preferred rigid polymeric binder material for use in this invention is a thermoset polymer, preferably soluble in carbon-carbon saturated solvents such as methyl ethyl ketone, and processing a high stress modulus when cured of at least about 6895 MPa as It is measured by ASTM D638.

<img file="MX347124B_D0044.tif" />

IMPI mwcanu institute

M THE FIORSITY

INDUSTRIAL

Particularly preferred rigid polymeric binder materials are those described in US Patent 6,642,159, the disclosure of which is incorporated herein by reference. The polymeric binder, either a low modulus material or a high modulus material, can also include fillers such as carbon black or silica, can be extended with oils, or can be vulcanized by sulfur, peroxide, metal oxide, carbon systems. radiation healing as is well known in the art.

Very particularly preferred are polar resins or polar polymers, particularly polyurethanes within the range of soft and rigid materials at a tensile modulus ranging from. about 13.79 MPa to about 55.16 MPa. Preferred polyurethanes are applied as aqueous polyurethane dispersions which are most preferably, but not necessarily, co-solvent free. These include aqueous anionic polyurethane dispersions, aqueous cationic polyurethane dispersions, and aqueous nonionic polyurethane dispersions. Particularly preferred are aqueous anionic polyurethane dispersions; Aqueous aliphatic polyurethane dispersions, and more preferred are the aqueous anionic aliphatic polyurethane dispersions, all of which are preferably co-solvent-free dispersions. These include polyester-based polyurethane dispersions

IMPI INSTITUTO MEXICANO LA MONEDAD

INDUSTRIAL anionic aqueous; polyurethane dispersions based on

<img file="MX347124B_D0045.tif" />

aqueous aliphatic polyesters, and aqueous anionic aliphatic polyester-based polyurethane dispersions, all of which are preferably co-solvent-free dispersions. These also include aqueous anionic polyether polyurethane dispersions; aqueous aliphatic polyether based polyurethane dispersions; and aqueous anionic, aliphatic, polyether-based polyurethane dispersions, all of which are preferably cosolvent-free dispersions. Similarly preferred are all corresponding variations (polyester based; aliphatic polyester based; polyether based; aliphatic polyether based, etc.) of aqueous cationic and nonionic aqueous dispersions. Highly preferred is an aliphatic polyurethane dispersion having a modulus at 100% elongation of approximately 49.21 kg / cm² or more, with a particularly preferred range of 49.21 kg / cm² at about 210.9 kg / cm². Highly preferred are aliphatic polyurethane dispersions having a 100% modulus at elongation of approximately 70.3 kg / cm² or more, and most preferably still about 77.33 kg / cm² or more. Highly preferred is an aliphatic, polyether-based anionic polyurethane dispersion having a modulus of 70.3 kg / cm² or more, preferably 77.33 kg / cm² or more.

The stiffness, impact and ballistics properties of

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INDUÍTRIAL&gt;

Articles formed from the mixed materials of the invention are affected by the tensile modulus of the polymeric binder polymer coating the fibers.

For example, US Patent 4,623,574 describes fiber reinforced mixed materials constructed with elastomeric matrices that have a tensile modulus less than about 41,300 kPa, have superior ballistic properties compared to conventional mixed materials. with higher modulus polymers and also compared to the same fiber structure without a polymeric binder material. However, low tensile modulus polymeric binder material polymers also produce lower stiffness mixed materials. Furthermore, in certain applications, particularly those where a mixed material must perform in both antiballistic and structural modulus, there is a need for a superior combination of bullet resistance and stiffness.

Accordingly, the most appropriate type of polymeric binder polymer to be used will vary depending on the type of article to be formed from the mixed materials of the invention. To achieve a compromise in both properties, a suitable polymeric binder combines both low modulus and high modulus materials to form a single polymeric binder.

Polymeric binder material can be applied

<img file="MX347124B_D0046.tif" />

either simultaneously or sequentially to a plurality of

IMPI

INSTITUTO MUICANfc Di LA FHOHUMD INDUSTRIAL fibers arranged as a ribbon of fibers (e.g., a parallel arrangement or a felt) to form a coated ribbon, applied to a woven fabric to form a coated woven fabric, or as another arrangement, to thus impregnating the fiber layers with the binder. As used herein, the term "impregnated with" is synonymous with embedded in as well as coated with or otherwise applied with the coating wherein the binder material diffuses into the fiber layer and is not simply on the surface of the fiber layers. . The polymeric material can also be applied over at least one fiber array that is not part of a fiber ribbon, followed by weaving the fibers into a woven fabric or followed by formulation of a non-woven fabric following the methods described above. here. The techniques of forming layers, strata, and woven and non-woven fabrics are well known in the art.

Although not required, the fibers that form layers of woven fibers are at least partially coated with a polymeric binder, followed by a consolidation step similar to that conducted with layers of non-woven fibers. Said consolidation step can be conducted to fuse multiple layers of woven fibers with one another, or to fuse the binder with the fibers and said woven fabric. For example, a plurality of layers of woven fibers do not necessarily have to be consolidated, and can be attached by other means, such as with conventional adhesive, or by basting.

Generally, a coating of polymeric binder is necessary to efficiently fuse, ie, consolidate, a plurality of layers of nonwoven fibers. The polymeric binder 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 polymeric binder material is applied over substantially the entire surface area of ​​each individual fiber that forms a layer of fibers of the invention. Wherein a fiber layer comprises a plurality of yarns, each fiber forming a single yarn strand is preferably coated with the polymeric binder material.

Any suitable application method can be used to apply the polymeric binder material and the term "coated" is not intended to limit the method by which it is applied over the filaments / fibers. The polymeric binder material is applied directly to the fiber surfaces using any appropriate method that is readily determined by one of ordinary skill in the art, and the binder is then typically diffused into the fiber layer as described herein. Most preferably still,

IMPI Mexican institute OI LA FROMIDAD INOUSTRIAl

<img file="MX347124B_D0047.tif" />

uses a method that at least partially coats each individual fiber with the polymeric material, preferably substantially coats or encapsulates each of the individual fibers, and covers all or substantially all of the surface area of ​​the filament / fiber with the polymeric binder material.

Although it is necessary for the fibers to be coated with the polymeric binder after at least partial removal of the fiber surface finish, and preferably after a surface treatment that increases the adsorption capacity and an adsorbent subsequently applied on the fibers. fiber surfaces, the fibers can be coated with the polymeric binder either before or after the fibers are arranged in one or more layers / strata, or before or after the fibers are woven into a woven fabric. Woven fabrics can be formed using techniques that are well known in the art using any fabric fabric, such as flat weave, houndstooth weave, basket weave, satin weave, twill weave, and the like. Flat weave is the most common, where the fibers are woven together in a 0 ° / 90 ° orthogonal orientation. Either before or after weaving, the individual fibers of each woven fabric material may or may not be coated with the polymeric binder material. Typically, the weave of fabrics

<img file="MX347124B_D0048.tif" />

IMPI

INSTITUTE Μ1ΧΚΛΝΟ O * LA nont * AI »iNVurnuAi is carried out before coating the fibers with the polymeric binder, where the woven fabrics are impregnated in this way with the binder. However, the invention is not designed to be limited by the stage at which the polymeric binder is applied to the fibers, nor by the means used to apply the polymeric binder.

Methods for the production of nonwovens are well known in the art. In preferred embodiments herein,. a plurality of fibers are arranged in at least one arrangement, typically being arranged as a ribbon of fibers comprising a plurality of fibers aligned in a substantially parallel unidirectional arrangement. As noted above, in a typical process for forming nonwoven unidirectionally aligned fiber layers, the fiber bundles are supplied from a spool and driven through guides and one or more spreader bars to a collimating comb, followed by coating of the fibers with a polymeric binder material. A typical fiber bundle will have from about 30 to about 2000 individual fibers. The spreader bars and collimating comb disperse and distribute the packed fibers, rearranging them side by side in a coplanar fashion. The ideal fiber distribution results in the individual filaments or individual fibers being positioned close to one another in a single fiber plane, forming a substantially unidirectional parallel arrangement of fibers without the fibers overlapping each other. At this point, the removal of the fiber surface finish before or during this distribution step can increase and accelerate the distribution of the fibers in said parallel arrangement.

After the fibers are coated with the binder material, the coated fibers are formed into layers of nonwoven fibers comprising a plurality of layers of overlapping nonwoven fibers that are consolidated into a single layer monolithic element. In a preferred nonwoven fabric structure of the invention, a plurality of stacked, overlapping webs are formed wherein the parallel fibers of each individual layer (uni tape) are positioned orthogonally to the parallel fibers of each adjacent individual layer relative to the longitudinal grain direction of each individual layer. The stack of overlapping nonwoven fiber layers is consolidated under heat and pressure, or by bonding the coatings of the individual fiber layers, to form a single-layer monolithic element also referred to in. the technique as a single layer consolidated network wherein a consolidated network describes a consolidated (fused) combination of fiber layers with the polymeric matrix / binder. Articles of the invention may also comprise

<img file="MX347124B_D0049.tif" />

IMPI INSTITUTO MEXICANO D £ LA raontOAD INDUSTRIAL hybrid consolidated combinations of adjoining woven fabrics and non-woven fabrics, as well as combinations of non-woven fabrics formed from layers of unidirectional fibers and non-woven felt fabrics.

Very typically, nonwoven fiber layers or fabrics include 1 to about 6 layers of attached fibers, but can include as many as about 10 to about 20 layers as desired for various applications. The greater number of layers translates into greater resistance to bullets, but also greater weight. Accordingly, the number of fiber layers that form a mixed material of fiber layers and / or mixed fabric material or an article of the invention varies depending on the end use of the fabric or article. For example, in body armor vests for military applications, in order to form a mixed article material that achieves an areal density of 4.9 kg / m² or less, a total of about 100 layers (or layers) to about 50 individual layers (or layers) may be required, where the layers / layers can be woven, knitted, felt or non-woven fabrics (with parallel oriented fibers or other arrangements) formed from the high strength fibers described herein. In another embodiment, body armor vests for law enforcement use may have a number of layers / layers based on the NIJ threat level.

UNHEAD?

MEXICAN INSTITUTE

I HEARD THE NOMEDAD

INeurriUAL

For example, for an NIJ threat level ΙΙΙΆ vest, there may be a total of 40 layers. For a lower NIJ threat level, fewer layers / strata can be used. The invention allows the incorporation of a greater number of layers of fibers to achieve the desired level of bullet protection without increasing the weight of the fabric compared to other known bullet resistant structures.

As is conventionally known in the art, excellent bullet resistance is achieved when individual fiber layers are cross-laid in such a way that the alignment direction of the fibers in a layer is rotated at an angle relative to the direction. fiber alignment of another layer. Most preferably, the fiber layers are orthogonally crossed at angles of 0 ° and 90 °, but the adjacent layers can be aligned almost at any angle between about 0^or and approximately

90 ° with respect to the longitudinal grain direction of another layer. For example, a five-layer nonwoven structure may have 0-oriented layers.⁰/45°/90⁰/ 45 ° / 0 ° or other angles. Such rotated unidirectional alignments are described, for example, in US Patents 4,457,985; 4,748,064; 4,916,000; 4,403,012; 4,623,574 and 4,737,402, all of which are incorporated herein by reference to the extent not incompatible therewith.

mixed are

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M THE IKOFIIIMD 'NDümUAl layers of r

<img file="MX347124B_D0050.tif" />

described in the

The consolidation methods are known to form layers of fibers and materials, such as by US Patent 6,642,159. Consolidation can occur by drying, cooling, heating, pressing, or a combination thereof. Heat and / or pressure may not be necessary, as the fibers or fiber layers can simply be glued together, as is the case in a wet lamination process. Typically, consolidation is done by placing the individual fiber layers one on top of the other under conditions of sufficient heat and pressure to cause the layers to combine into a unitary fabric. Consolidation can be done 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 0.034 MPa to about 17 MPa, for about 0.01 seconds to about 24 hours, preferably from about 0.02 seconds to about 2 hours. When heated, it is possible that the polymeric binder coating can be made to stick or flow without completely melting. However, generally, if the polymeric binder material (if it is one that is capable of melting) is melted, relatively little pressure is required to form the mixed material, whereas if the

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OF THE RWOniTY Jl¡f

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Binder material is only heated to one point of adhesion, typically more pressure is required. As is conventionally known in the art, consolidation can be conducted in a calendering assembly, a flat bed mill, a press or in an autoclave. Most commonly, a plurality of orthogonal fiber tapes are glued together with a binder polymer and run through a flat bed laminator to improve bond strength and uniformity. Furthermore, the consolidation and polymer application / bonding steps may comprise two separate steps or a single consolidation / laminating step.

Alternatively, consolidation can be achieved by molding under heat and pressure in a suitable molding apparatus. Generally, the molding is conducted at a pressure of from about 344.7 kPa to about 34.470 kPa, most preferably from about 689.5 kPa to about 20.680 kPa, most preferably still from about 1034 kPa to about 10.340 kPa. Staggered molding can be conducted at higher pressures from about 34,470 kPa to about 103,410 kPa, most preferably from about 5171 kPa to about 34,470 kPa; and most preferably from about 6890 kPa to about 34.470 kPa. The molding step can take from approximately 4 seconds to

IMPI ^

MEXICAN INSTITUTE

M LA r »OHl * AD, iÑournuAL approximately 45 minutes. Preferred molding temperatures range from about ~ 93 ° C to about -177 ° C), most preferably at a temperature from about -93 ° C to about 148.8 ° C and most preferably at a temperature from about -93 ° C to about 137.7 ° C. The pressure under which the fiber and mixed material layers of the invention are molded typically has a direct effect on the stiffness or flexibility of the resulting molded product. Molding at a higher pressure generally produces stiffer materials, up to a certain limit. In addition to molding pressure, the amount, thickness, and composition of fiber layers and type of polymeric binder coating also directly affect the stiffness of articles formed from the mixed materials.

Although each of the molding and consolidation techniques described here is similar, each process is different. In particular, molding is an intermittent process and consolidation is a generally continuous process. Additionally, molding typically involves the use of a mold, such as a shaped mold or a matching die mold when forming a flat panel, and does not necessarily result in a flat product. Consolidation is typically done on a flat bed mill, a calendering grip assembly, or as a

IMPI

INSTmn u MEXICANO M LA INDUSTRIAL PROPERTY

<img file="MX347124B_D0051.tif" />

wet lamination to produce soft (flexible) body armor fabrics. Molding is typically reserved for the manufacture of hard armor, eg, rigid plates. In any process, suitable temperatures, pressures and times generally depend on the type of polymeric binder coating materials, content of polymeric binder, process used and type of fiber.

To produce a fabric article having sufficient bullet resistance properties, the total weight of the binder / matrix coating preferably comprises from about 2% to about 50% by weight, most preferably from about 5% to about 30%, most preferably from about 7% to about 20%, and most preferably still from about 11% to about 16% by weight of the fibers plus the weight of the coating, where 16% is more preferred for nonwovens. A lower binder / matrix content is appropriate for woven fabrics, where a polymeric binder content greater than zero but less than 10% by weight of the fibers plus the weight of the coating is typically most preferred. This is not intended to be limiting. For example, phenolic / PVB-impregnated woven aramid fabrics are sometimes manufactured with a higher resin content of about 20% at

IMPIAS Mexican institute

Dt LA nOHUMD CMi about 30%, although a content of about ^^ nen ^ 12% is typically preferred. ————————

After weaving or consolidation of the fiber layers, an optional thermoplastic polymer layer can be attached to one or both of the outer surfaces of the fibrous composite material by conventional methods. Polymers suitable for the thermoplastic polymer layer non-exclusively include thermoplastic polymers non-exclusively which may be selected non-exclusively from the group consisting of polyolefins, polyamides, polyesters (particularly polyethylene terephthalate (PET) and PET copolymers. ), polyurethanes, vinyl polymers, ethylene-vinyl alcohol copolymers, ethylene-octane copolymers, acrylonitrile copolymers, acrylic polymers, vinyl polymers, polycarbonates, polystyrenes, fluoropolymers, and the like, as well as copolymers and blends thereof, including ethylene-vinyl acetate (EVA) and ethylene-acrylic acid. Also useful are natural and synthetic rubber polymers. Of these, the polyolefin and polyamide layers are preferred. The preferred polyolefin is a polyethylene. Non-limiting examples of useful polyethylenes are low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), linear medium density polyethylene (LMDPE), linear very low density polyethylene

<img file="MX347124B_D0052.tif" />

IMPI institute mmucano Ot LA MOM1DAD industrial (VLDPE), linear ultra low density polyethylene (ULDPE), high density polyethylene (HDPE) and co-polymers and mixtures thereof. Also useful are SPUNFAB® polyamide tapes commercially available from Spunfab, Ltd, of Cuyahoga Falls, Ohio (registered trademark for Keuchel Associates, Inc.), as well as web and film tapes, THERMOPLAST ™ and HELIOPLAST ™, commercially available from Protechnic SA from Cernay, France. The thermoplastic polymer layer can be bonded to the mixed material surfaces using well known techniques, such as thermal lamination. Typically, lamination is done by placing the individual layers one on top of the other under conditions of sufficient heat and pressure to cause the layers to combine into a unitary film. The individual layers are placed one on top of the other and the combination is then typically passed through the grip of a pair of heated lamination rolls by techniques well known in the art. The lamination heating can be conducted at temperatures ranging from about 95 ° C to about 175 ° C, preferably from about 105 ° C to about 175 ° C, at pressures ranging from about 0.034 MPa to about 0.69 MPa, for about 5 seconds to about 36 hours, preferably from about 30 seconds to about 24 hours.

IMPI iNrrrruTOMUucANb M LA rWPMIMP INOUmUAL

<img file="MX347124B_D0053.tif" />

The thickness of the individual fabrics / mixed materials / fiber layers will correspond to the thickness of the individual fibers and the number of fiber layers incorporated in a fabric. A preferred woven fabric will have a preferred thickness of from about 25 gm to about 600 gm per layer, most preferably from about 50 gm to about 385 gm, and most preferably still from about 75 gm to about 255 gm per layer. A preferred nonwoven fabric, that is, a consolidated, single layer, nonwoven web will have a preferred thickness of from about 12 gm to about 600 gm, most preferably from about 50 gm to about

385 gm and most preferably still from about 75 gm to about 255 gm, wherein a single layer consolidated network typically includes two consolidated layers (ie, two ribbons). Any thermoplastic polymer layers are preferably very thin, having preferred layer thicknesses from about 1 gm to about 250 gm, most preferably from about 5 gm to about 25 gm, and most preferably still from about 5 gm to about 9 gm. Discontinuous tapes such as SPUNFAB® nonwoven tapes are preferably applied at a basis weight of 6 grams / square meter (g / m²). Although such thicknesses are preferred, it is to be understood that other thicknesses can be produced for

IMPI

INSTITUTO M &amp; X1CANO DB LA ΡΗΟΕΙΒΔΛΟ INDUSTRIAL

<img file="MX347124B_D0054.tif" />

meet a particular need and yet fall within the scope of the present invention.

Fabrics / blends of the invention will have a preferred areal density prior to consolidation / molding of about 20 grams / m2² at about 1000 g / m². Most preferred area densities for the fabrics / blends of the invention prior to consolidation / molding will subsequently vary from about 30 g / m2² at about 500 g / m². The most preferred areal density for fabrics / blends of this invention will range from about 50 g / m2² at about 250 g / m² before consolidation / molding. Articles of the invention comprising multiple layers of fibers stacked on top of each other and consolidated will have a preferred mixed area density of about 1000 g / m² at about 40,000 g / m², most preferably about 2000 g / m² at about 30,000 g / m², most preferably about 3000 g / m² at about 20,000 g / m², and most preferably still about 3750 g / m² at about 15,000 g / m². A typical range for mixed items configured in helmets is approximately 7500 g / m² at about 12,500 g / m².

Fabrics of the invention can be used in various applications to form a variety of different bullet resistant articles using well known techniques,

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INSTITUTO MUUCANC t * la noniMo rv industrial&gt; ¡C!

including soft, flexible armor items as well as hard, rigid armor items. For example, techniques suitable 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, all of which are incorporated herein by reference to the extent that they are not incompatible therewith. Mixed materials are particularly useful for the formation of hard armor and shaped or unconformed subassembly intermediates formed in the hard armor manufacturing process. By hard armor is meant an item, such as helmets, panels for military vehicles, or protective armor, that has sufficient mechanical strength so that it maintains structural rigidity when subjected to a significant amount of stress and is capable of standing upright without collapsing. . Such articles are preferably, but not exclusively, formed using a high tensile modulus binder material.

The structures can be cut into a plurality of discrete sheets and stacked to form into an article or they can be formed into a precursor that is subsequently used to form an article. Such techniques are well known in the art. In an even more preferred embodiment of the invention, a plurality of fiber layers

IMPI ^

MEXICAN INSTITUTE

OF THE INDUSTRIAL PROBITY are provided, each comprising a consolidated plurality of fiber layers, wherein a thermoplastic polymer is bonded to at least one outer surface of each fiber layer either before, during or after the consolidation step that consolidates the plurality of layers of fibers, wherein the plurality of fiber layers are subsequently fused by another consolidation step that consolidates the plurality of fiber layers into an armor article or sub-assembly of an armor article.

The bullet resistance properties of the fibrous composite materials of the invention, including both bullet penetration resistance and transmitted impact energy, can be measured according to techniques well known in the art.

The following examples serve to illustrate the invention.

Examples 1-10

In Examples 1-10, the physical properties of ultra-high molecular weight polyethylene fibers were measured without being washed to remove their fiber finish and without being plasma treated. The fiber samples for all Examples 1-30 were selected from the same reel of ultra-high molecular weight polyethylene fibers. Fiber denier, fiber load at maximum strain (kilograms

<img file="MX347124B_D0055.tif" />

force, kgf), percent deflection at maximum load,

IMPI

INSTITUTO MEXICANO MunwwDxc INDUSTRIAL fiber tenacity (g / denier) and fiber initial tension modulus (g / denier) were measured for ten control fiber samples. The results are set forth in Table 1 where the fibers are identified as control fibers 1-10.

Table 1

<td>Ex.</td><td>Sample ID</td><td>Fiber denier</td><td>Maximum load (kgf)</td><td>Maximum deformation (%)</td><td>Fiber tenacity (g / denier)</td><td>Initial fiber modulus (g / denier)</td>

<td> 1</td><td>Control 1</td><td> 1290</td><td> 53.1634</td><td> 3.698</td><td> 41.2</td><td> 1288</td>

<td> 2</td><td>Control 2</td><td> 1290</td><td> 51.4382</td><td> 3.567</td><td> 39.8</td><td> 1285</td>

<td> 3</td><td>Control 3</td><td> 1290</td><td> 50.6664</td><td> 3.600</td><td> 39.3</td><td> 1265</td>

<td> 4</td><td>Control 4</td><td> 1290</td><td> 52.9818</td><td> 3.667</td><td> 41.0</td><td> 1270</td>

<td> 5</td><td>Control 5</td><td> 1290</td><td> 46.5804</td><td> 3.167</td><td> 36.1</td><td> 1280</td>

<td> 6</td><td>Control 6</td><td> 1290</td><td> 51.8014</td><td> 3.533</td><td> 40.1</td><td> 1295</td>

<td> 7</td><td>Control 7</td><td> 1290</td><td> 48.4872</td><td> 3.433</td><td> 37.5</td><td> 1247</td>

<td> 8</td><td>Control 8</td><td> 1290</td><td> 50.7572</td><td> 3.433</td><td> 39.3</td><td> 1298</td>

<td> 9</td><td>Control 9</td><td> 1290</td><td> 48.6234</td><td> 3.233</td><td> 37.7</td><td> 1286</td>

<td> 10</td><td>Control 10</td><td> 1290</td><td> 45.5362</td><td> 3.167</td><td> 35.3</td><td> 1245</td>

<td colspan="2">AVERAGE</td><td> 1290</td><td> 48.3056</td><td> 3.28</td><td> 37.4</td><td> 1276</td>

Examples 11-20

In Examples 11-20, the physical properties of ultra-high molecular weight polyethylene fibers were measured after being washed to substantially remove the fiber finish but without being plasma treated. The fiber samples for all Examples 1-30 were selected from the same reel of ultra-high molecular weight polyethylene fibers.

To remove the finish, the fibers were

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INDUSTRIAL ~~ directed through a pre-soaked water bath containing deionized water, with an approximate residence time of approximately 18 seconds. After exiting the pre-soak water bath, the fibers were rinsed through a set of 30 water nozzles. The water pressure of each water nozzle was approximately 2.95 kg / cm² with a water flow rate of approximately 1.89 liters per minute per nozzle. The water exiting the nozzles formed as a relatively flat stream and the contact angle of the water on the fibers was either 0^or or 30 ° in relation to the angle of incidence of the stream exiting the adjacent nozzles. The water temperature was measured at 28.9 ° C. The line speed through the set of water nozzles was approximately 3.66 meters / min. The water in the soak bath and the water supplied to the nozzles was deionized by first passing through a separate deionization system. The washed fibers were then dried and analyzed.

Fiber denier, fiber load at maximum strain, percent strain at maximum load, fiber tenacity, and initial fiber tension modulus were measured for ten washed fiber samples. The results are set forth in Table 2, where the fibers are identified as washed fibers 1-10.

<img file="MX347124B_D0056.tif" />

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Table 2

<td>Ex</td><td>Sample ID</td><td>Fiber denier</td><td>Maximum load (kgf)</td><td>Maximum deformation (%)</td><td>Fiber tenacity (g / denier)</td><td>Initial fiber modulus (g / denier)</td>

<td> 11</td><td>Washed 1</td><td> 1290</td><td> 50.25</td><td> 3.366</td><td> 38.9</td><td> 1303</td>

<td> 12</td><td>Washed 2</td><td> 1290</td><td> 49.89</td><td> 3.366</td><td> 38.6</td><td> 1317</td>

<td> 13</td><td>Washed 3</td><td> 1290</td><td> 45.94</td><td> 2.934</td><td> 35.6</td><td> 1303</td>

<td> 14</td><td>Washed 4</td><td> 1290</td><td> 45.89</td><td> 3.033</td><td> 35.6</td><td> 1299</td>

<td> 15</td><td>Washed 5</td><td> 1290</td><td> 45.62</td><td> 3.000</td><td> 35.3</td><td> 1301</td>

<td> 16</td><td>Washed 6</td><td> 1290</td><td> 45.25</td><td> 2.934</td><td> 35.1</td><td> 1286</td>

<td> 17</td><td>Washed 7</td><td> 1290</td><td> 45.15</td><td> 2.967</td><td> 35.0</td><td> 1301</td>

<td> 18</td><td>Washed 8</td><td> 1290</td><td> 41.97</td><td> 2.800</td><td> 32.5</td><td> 1275</td>

<td> 19</td><td>Washed 9</td><td> 1290</td><td> 44.54</td><td> 2.967</td><td> 34.5</td><td> 1280</td>

<td> 20</td><td>Washed 10</td><td> 1290</td><td> 50.12</td><td> 3.300</td><td> 38.8</td><td> 1289</td>

<td colspan="2">AVERAGE</td><td> 1290</td><td> 45.53</td><td> 3.02</td><td> 35.3</td><td> 1281</td>

Examples 21-30

In Examples 21-30, the physical properties of ultra-high molecular weight polyethylene fibers were measured after being washed to substantially remove the fiber finish and then subsequently also plasma treated. The fiber samples for all Examples 1-30 were selected from the same reel of ultra-high molecular weight polyethylene fibers.

The fiber finish was removed substantially in accordance with the process described in Examples 11-20. The plasma treatment was conducted by continuously passing the washed fibers through an atmospheric plasma treatment machine (model: Enercon Plasma3 Station Model APT12DF-150/2, from Enercon Industries Corp., having 73.66 cm wide electrodes) at a line speed of

<img file="MX347124B_D0057.tif" />

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Fiber denier, fiber load at maximum strain, percent strain at maximum load, fiber toughness, and initial fiber tensile modulus were measured for ten washed fiber samples. The results are set out in Table 3 where the fibers are identified as W&amp;P fibers (washed and plasma treated fibers) 1-10.

Table 3

<td>Ex.</td><td>Sample ID</td><td>Fiber denier</td><td>Maximum load (kgf)</td><td>Maximum deformation (%)</td><td>Fiber tenacity (g / denier)</td><td>Initial fiber modulus (g / denier)</td>

<td> 21</td><td>W&amp;P 1</td><td> 1290</td><td> 50.89</td><td> 3.336</td><td> 39.4</td><td> 1293</td>

<td> 22</td><td>W&amp;P 2</td><td> 1290</td><td> 47.21</td><td> 3.200</td><td> 36.6</td><td> 1268</td>

<td> 23</td><td>W&amp;P 3</td><td> 1290</td><td> 50.12</td><td> 3.233</td><td> 38.8</td><td> 1291</td>

<td> 24</td><td>W&amp;P 4</td><td> 1290</td><td> 50.21</td><td> 3.333</td><td> 38 . 9</td><td> 1325</td>

<td> 25</td><td>W&amp;P 5</td><td> 1290</td><td> 48.21</td><td> 3.100</td><td> 37.3</td><td> 1309</td>

<td> 26</td><td>W&amp;P 6</td><td> 1290</td><td> 49.16</td><td> 3.167</td><td> 38.1</td><td> 1297</td>

<td> 27</td><td>W&amp;P 7</td><td> 1290</td><td> 50.71</td><td> 3.366</td><td> 39.3</td><td> 1306</td>

<td> 28</td><td>W&amp;P 8</td><td> 1290</td><td> 45.80</td><td> 2.934</td><td> 35.5</td><td> 1293</td>

<td> 29</td><td>W&amp;P 9</td><td> 1290</td><td> 48.89</td><td> 3.133</td><td> 37.9</td><td> 1311</td>

<td> 30</td><td>W&amp;P 10</td><td> 1290</td><td> 51.52</td><td> 3.300</td><td> 39.9</td><td> 1328</td>

<td colspan="2">AVERAGE</td><td> 1290</td><td> 48.75</td><td> 3.12</td><td> 37.8</td><td> 1311</td>

<img file="MX347124B_D0058.tif" />

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Conclusions:

Collectively, Examples 1-30 illustrate that the fibers that were plasma treated after washing the fibers to substantially remove the fiber finish have approximately the same physical properties both before and after the treatments. In particular, the combined treatments resulted in approximately no loss in fiber tenacity and, in many cases, resulted in an increase in initial tensile modulus.

Based on the fiber property averages, the examples show a tenacity gain 'of about 1% and an increase in initial tensile modulus of about 2.7% when the fibers are washed prior to plasma treatment. Increases in toughness and initial tensile modulus can result, for example, from polymer chain entanglement on fiber surfaces due to plasma treatment directly on fiber surfaces and not through a fiber surface finish.

Comparative Examples 1-6

In Comparative Examples 1-6, the physical properties of the ultra-high molecular weight polyethylene fibers were measured after plasma treatment, but

3

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<img file="MX347124B_D0059.tif" />

unwashed to remove its fiber finish prior to plasma treatment. Fiber samples for all

Comparative Examples 1-6 were selected from the same reel of ultra-high molecular weight polyethylene fibers.

Fiber denier, fiber load at maximum strain, percent strain under maximum load, fiber toughness and initial fiber tension modulus were measured for three control fiber samples and three plasma samples. treated. The plasma treatment was carried out by continuously passing the washed fibers through a low pressure plasma treatment machine (Plasma Science Model PS 1010, commercially available from Plasmatreat US LP of Elgin, IL; modified to allow a single fiber to make multiple passes through the plasma atmosphere before exiting the chamber) at a line speed of approximately 10 m / min, with a residence time of the fibers within the treatment machine of plasma for approximately 1.4 minutes and with the plasma treatment machine set to a power of 250 W. The treatment was carried out at a pressure of 400 millitorr in an atmosphere of 90% argon gas and 10% oxygen. The results are summarized in Table 4 and Table 5.

<img file="MX347124B_D0060.tif" />

ΙΜΡΙ

Table 4

<td>Example</td><td>Sample ID</td><td>Treated with plasma</td><td>Line speed</td><td>Plasma gas</td><td>Plasma power</td>

<td>Comp. 1</td><td>Control A</td><td>No</td><td>N / A</td><td>N / A</td><td>N / A</td>

<td>Comp. 2</td><td>Control B</td><td>No</td><td>N / A</td><td>N / A</td><td>N / A</td>

<td>Comp. 3</td><td>Control C</td><td>No</td><td>N / A</td><td>N / A</td><td>N / A</td>

<td>Comp. 4</td><td>Plasma Ά</td><td>Yes</td><td>10 m / min</td><td>90% argon; 10% oxygen</td><td>250W</td>

<td>Comp. 5</td><td>Plasma B</td><td>Yes</td><td>10 m / min</td><td>90% argon; 10% oxygen</td><td>250W</td>

<td>Comp. 6</td><td>Plasma C</td><td>Yes</td><td>10 m / min</td><td>90% argon; 10% oxygen</td><td>250W</td>

Table 5

<td>Ex</td><td>Sample ID</td><td>Fiber denier</td><td>Maximum load (kgf)</td><td>Maximum deformation (%)</td><td>Fiber tenacity (g / denier)</td><td>Initial fiber modulus (g / denier)</td>

<td>Comp. 1</td><td>Control A</td><td> 1268</td><td> 49.30</td><td> 3.227</td><td> 38.9</td><td> 1269</td>

<td>Comp. 2</td><td>Control B</td><td> 1253</td><td> 49.25</td><td> 3.250</td><td> 39.3</td><td> 1281</td>

<td>Comp. 3</td><td>Control C</td><td> 1250</td><td> 48.26</td><td> 3.133</td><td> 38.6</td><td> 1284</td>

<td colspan="2">AVERAGE</td><td> 1257</td><td> 48.94</td><td> 3.20</td><td> 38.9</td><td> 1278</td>

<td>Comp. 4</td><td>Plasma A</td><td> 1274</td><td> 41.059</td><td> 2.563</td><td> 32.2</td><td> 1313</td>

<td>Comp. 5</td><td>Plasma B</td><td> 1262</td><td> 40.59</td><td> 2.567</td><td> 32.1</td><td> 1316</td>

<td>Comp. 6</td><td>Plasma C</td><td> 1274</td><td> 40.30</td><td> 2.470</td><td> 31.6</td><td> 1303</td>

<td colspan="2">AVERAGE</td><td> 1270</td><td> 40.63</td><td> 2.53</td><td> 32.0</td><td> 1311</td>

Conclusions:

Collectively, Comparative Examples 1-6 illustrate that fibers that were plasma treated without first washing the fibers to substantially remove the fiber finish experience a significant loss in fiber toughness due to plasma treatment, a loss of tenacity of approximately 17% based on fiber averages. This is particularly revealing in view of the substantially less aggressive plasma treatment level in Comparative Examples 1-6 (i.e. 15 250 W) at low pressure relative to the treatment level.

<img file="MX347124B_D0061.tif" />

plasma in Examples 1-30 (i.e. 1.5 kW) at nrpsign

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Example 31

A four-layer nonwoven mixed material was made incorporating four layers of substantially parallel, unidirectionally oriented, ultra-high molecular weight polyethylene fibers having a fiber tenacity of about 45 g / d.

Prior to layering, the fibers were washed to substantially remove their fiber finish and subsequently plasma treated and dried. To remove the finish, a plurality of multifilament fibers were unwound from a plurality of fiber spools (one spool per multifilament fiber) and then passed through a fixed collimating comb to organize the fibers on a fiber web evenly. separated. The fiber web was then directed through a pre-soak water bath containing deionized water, with a residence time of approximately 18 seconds. After exiting the pre-soak water bath, the fibers were rinsed by a set of 30 water nozzles. The water pressure of each water nozzle was approximately 2.95 kg / cm² with a water flow rate of approximately 1.89 liters

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INDUSTRIAL ^ C3 per minute per nozzle. The water exiting the nozzles formed as a relatively flat stream and the contact angle on the fibers was either 0^or or 30 ° in relation to the angle of incidence of the stream exiting adjacent nozzles. The water temperature was measured as 28.9 ° C. The line speeds through the pre-soak water bath and through the set of water nozzles ranged from about 4 m / min to about 20. m / min. The water in the soak bath and the water supplied to the nozzles was deionized by passing it through a separate deionization system. The washed fibers were then dried and transferred for further processing.

The plasma treatment was performed by continuously passing a 73.66 cm wide ribbon of washed fibers through an atmospheric plasma treatment machine (model: Enercon Plasma3 Station Model APT12DF150 / 2, from Enercon Industries Corp., which had electrodes of 73.66 cm wide) at a speed of approximately 3.66 meters / min, with a plasma treatment machine set at a power of 1.5 kW. This resulted in a power distribution over the fiber area, measured in watt density, of 2000W / (73.66 cm x 3.66 meters / min) or 721.99 watts / m²/ min applied to the fibers. The residence time of the fibers inside the treatment machine

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K Plasma NOFUDE was approximately 2.5 seconds. The trS ^ amien ^ TT was conducted under standard atmospheric pressure. The reHacldád UU fiber after plasma treatment was approximately 45 g / d.

Subsequently, the fibers were coated with an anionic, aliphatic polyurethane dispersion that had a modulus of 77.33 kg / cm². Each layer had a resin content of about 16% by weight of the layer. All four layers were oriented at 0 ° / 90 ° / 0⁰/ 90 ° in relation to the longitudinal grain direction of each layer. The four-layer mixed material had a fiber area density (per layer) of approximately 35 g / m² and a total areal density of each layer of approximately 42 g / m², which translates into a final product FAD and TAD of 140 g / m² and 167 g / m², respectively.

Example 32 '

The mixed material of Example 31 was made in a sample of 9.8 kg / m² consolidated and tested impact energy transmitted and V₅₀ at room temperature. The value of V₅₀ average against the RCC of 1036.8 mg at room temperature was 1104.4 meters / second. The average BFS at room temperature against the same 1036.8 mg RCC projectile was 3 mm as measured with a 1.27 cm air gap between the rear surface of the mixed material and the clay backing material.

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<img file="MX347124B_D0062.tif" />

Measurement of transmitted impact energy

The transmitted impact energy was measured using an apparatus described in co-pending patent application no. standard 61 / 531,233. The mixed material was separated from a clay block by 1.27 cm by inserting a custom machined spacer between the mixed material article and the clay block. The custom machined spacer element comprised an element having a boundary and an interior cavity defined by said boundary where the clay was exposed through the cavity, and where the spacer was placed in direct contact with the front surface of the clay. The projectiles were fired into the mixed material articles at target sites corresponding to the inner cavity of the separator. The projectiles struck the mixed material article at locations corresponding to the interior cavity of the separator, and each projectile impact caused a medial depression in the clay. The 3 mm BFS measurement refers to the depth of the depression in the clay according to this method without taking into account the depth of the spacer element, i.e. the BFS measurement does not include the actual distance between the mixed material and clay.

<img file="MX347124B_D0063.tif" />

The data of V₅₀ were acquired taken under

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V measurement₅₀ conventionally known standardized techniques, particularly in accordance with the Department of Defense MIL-STD-662F test method standard against a 1036.8 mg RCC projectile.

Examples 33-38

Examples 31 and 32 were repeated to make 9.8 kg / m samples² but with different binder resins. The mixed materials were tested for transmitted impact energy and V₅₀ at room temperature, and the results are set forth in Table 6. For Examples 36-38, the corona treatment was conducted instead of a plasma treatment as in Example 31. The corona treatment was performed by continuously passing a tape of fibers washed through a corona treatment machine having 76.2 cm wide electrodes at a speed of approximately 4.57 meters / min, with the corona treatment machine set to 2kW power. The residence time of the fibers within the corona field was approximately 2 seconds. The treatment was conducted under standard atmospheric pressure.

<img file="MX347124B_D0064.tif" />

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Table 6

<td>Example</td><td>Treatment</td><td>Resin</td><td>Resistance modulus at 100% elongation (kg / cm²)</td><td>v₅₀Prom.</td><td>BFS Avg.</td>

<td> 32</td><td>Washing and Plasma</td><td>Polyurethane based on aliphatic polyether</td><td> 77.33</td><td> 3621</td><td> 3.0</td>

<td> 33</td><td>Washing and Plasma</td><td>Aqueous polyurethane dispersion</td><td> 50.97</td><td> 3533</td><td> 6.75</td>

<td> 34</td><td>Washing and Plasma</td><td>Aqueous polyurethane dispersion</td><td> 203.87</td><td> 3487</td><td> 2.25</td>

<td> 35</td><td>Washing and Plasma</td><td>Polyurethane based on aliphatic polyether</td><td> 77.33</td><td> 3459</td><td> 3.5</td>

<td> 36</td><td>Wash and Crown</td><td>Aqueous polyurethane dispersion</td><td> 203.87</td><td> 3287</td><td> 3.75</td>

<td> 37</td><td>Wash and Crown</td><td>Aqueous polyurethane dispersion</td><td> 50.97</td><td> 3349</td><td> 5.25</td>

<td> 38</td><td>Wash and Crown</td><td>Polyurethane based on aliphatic polyether</td><td> 77.33 ·</td><td> 3223</td><td> 2.625</td>

Example 39

A plurality of mixed materials from Example 31 are cut into a plurality of 53.34 cm x 53.34 cm squares. A plurality of the frames are manufactured in one or more ballistic armor, and the ballistic armor is manufactured in improved combat helmets. Each ballistics cuirass weighs approximately 1.27 kg. There is a polymer-based or thick-film external surface coating 10 on the outside of the helmet, and a woven polyethylene-based fabric on the inside of the helmet (e.g., 903 style woven fabric incorporating S900 SPECTRA® polyethylene fibers 1200 denier; flat knit with a 53.34 x 53.34 end count 15 ends / 2.54 cm; area weight 217 grams / square meter (g / m².). The hulls were optionally finished with

<img file="MX347124B_D0065.tif" />

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Example 40

A four layer nonwoven mixed material was manufactured incorporating four layers of substantially parallel, unidirectionally oriented 45 g / d fibers. The fibers were washed to substantially remove their fiber finish and subsequently plasma treated and dried. The fiber toughness after plasma treatment was 45 g / d. Subsequently, the fibers were coated with an anionic, aliphatic polyurethane dispersion that had a modulus of 77.33 kg / cm². Each layer had a resin content of about 16% by weight of the layer. All four layers were oriented at 0 ° / 90 ° / 0⁰/90⁰ relative to the longitudinal grain direction of each layer. The four-layer mixed material had a fiber area density (per layer) of approximately 53 g / m² and a total areal density of each layer of approximately 64 g / m².

Although the present invention has been shown and described particularly with reference to preferred embodiments, those skilled in the art will readily appreciate that various changes and modifications can be made without departing from the essence and scope of the invention. The claims are intended to be interpreted to

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<img file="MX347124B_D0066.tif" />

cover the modality described, those alternatives that have been previously described and all the equivalents to them.