Multilayered material sheet and process for its preparation

(54) Title: MULTIPLE LAYER MATERIAL SHEET AND PROCESS FOR ITS PREPARATION (30) Unionist Priority: 26/04/2006 ep 06008600.6,

06/29/2006 EP 06013452.5, 12/22/2006 EP 06026723.4, 12/22/2006 US 60 / 876.545, 12/22/2006 EP 06026723.4, 4/26/2006 EP

06008600.6, 06/29/2006 EP 06013452.5, 12/22/2006 EP 06026723.4, 12/22/2006 EP 06026723.4, 12/22/2006 US 60 / 876.545, 26/04/2006 EP 06008600.6, 06/29/2006 EP 06013452.5 (73) Holder (s): DSM IP Assets BV

(72) Inventor (s): Alexander Volker Peters, David Vanek, Gijsbertus Hendrikus Maria Calis, Jacobus Johannes Mencke, Jean Hubert Marie Beugels, Johann Van Elburg, Joseph Arnold Paul Maria Simmelink, Marko Dorschu, Reinard Jozef Maria Steeman, Roelof Marissen, Steen Tanderup (74) Attorney (s): Flavia Salim Lopes (57) Summary: multilayered material sheet AND PROCESS FOR YOUR PREPARATION. The invention relates to a sheet of multilayer material comprising a consolidated stack of unidirectional monolayers of stretched polymer, whereby the direction of stretching of two subsequent monolayers in the stack differs. At least one monolayer comprises a plurality of unidirectional strips of the stretched polymer, aligned in the same direction, so that adjacent strips do not overlap. The invention also relates to a process for preparing the multilayer material sheet, and to a ballistic resistance article comprising the multilayer material sheet.

(86) International Order: pct EP2007003684de

26/04/2007 (87) International Publication: wo 2007 / 122009de

01/11/2007

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1/29

MULTIPLE LAYER MATERIAL SHEET AND PROCESS FOR YOUR

PREPARATION

The invention relates to the sheet of multilayer material comprising a consolidated pile of unidirectional monolayers of stretched polymer, and its preparation process. The invention also relates to an article of ballistic resistance comprising the sheet of multilayer material.

A sheet of multilayer material comprising a consolidated stack of drawn polymer unidirectional monolayers is known from EP 1627719 A1. This publication discloses a sheet of multilayer material comprising several unidirectional monolayers; consisting of ultra-high molecular weight polyethylene, and essentially devoid of bonding matrices, so it differs the stretching direction of two subsequent monolayers in the stack. A monolayer of the multilayer material disclosed in EP 1627719 A1 is produced by positioning a plurality of polyethylene tapes of ultra-high molecular weight adjacent to each other so that adjacent positioned tapes overlap at least partially along their side edges . Without overlapping, known multi-layer material cannot be produced. In addition, in order to obtain good anti-ballistic properties, the material sheet of EP 1627719 A1 makes use exclusively of ultra-high molecular weight polyethylene, essentially free of the binding matrices.

Although the multi-layer material sheet of

2/29 according to EP 1627719 Al show a satisfactory ballistic performance, this performance can be further improved.

The aim of the present invention is to provide a sheet of multilayer material having at least similar anti-ballistic properties as the known material, and the sheet of which can be easily produced.

This objective is achieved according to the invention by providing a sheet of multilayer material comprising a consolidated stack of unidirectional monolayers of stretched polymer, whereby the direction of stretching of two subsequent monolayers in the stack differs, so that at least one monolayer comprises at least one unidirectional strip of the stretched polymer, each strip comprises longitudinal edges; with which the monolayer is free of overlap, or free of an area of ​​high thickness, adjacent to the longitudinal edges, and along the substantial length thereof. Preferably, the monolayer is free of overlapping, or free of the adjacent high-thickness area and over at least 50%, 60%, 70%, 80%, 90% or 95% of the length of the longitudinal edges of at least one tape unidirectional. More preferably, the monolayer is free of overlapping, or free of an area of ​​high thickness along and adjacent to the total length of the longitudinal edges of at least one unidirectional tape.

The formation of monolayers that are free of overlap or excessive levels of binders allows the monolayers to be easily stacked and compressed into a sheet of multilayer material

3/29 with uniform sand density resulting in a more homogeneous antiballistic performance across the sheet of multilayer material.

In one embodiment of the present invention, that objective is achieved by means of a sheet of multilayer material and a process for producing such sheet of multilayer material, the sheet comprising a consolidated stack of unidirectional stretched polymer monolayers, with which differs from two subsequent monolayers in the stack, with which at least one monolayer comprises a unidirectional plurality of the stretched polymer, aligned with ribbons in the same

It is found that a sheet of multilayer material according to the invention, that is, a sheet in which areas of high thickness adjacent and along the longitudinal edges of the unidirectional tapes, for example, longitudinal overlaps of tapes or extensively bonded tapes together with overlapping binder material are substantially absent, not only improving the antiballistic properties of the sheet, but doing so to an unexpectedly high extent.

Preferably, the monolayer is free of an area of ​​high thickness that extends along (more properly, transversely) and adjacent to the longitudinal edges of at least one unidirectional tape. The occurrence of areas of high thickness that extend along the longitudinal edges of the unidirectional tape or unidirectional tapes, and adjacent to them, makes it more difficult to form a homogeneous consolidated pile in

4/29 so aligned that they form a woven structure.

A sheet of multilayer material particularly preferred according to comprises a stack of monolayers, whereby each monolayer is constructed of a plurality of unidirectional strips of the stretched polymer aligned thereon do not overlap. A sheet of material according to the invention is more homogeneous than the sheet of known material. In reality, in overlapping locations, the sheet of known material will have areas of greater sand density. These zones are absent or occur to a lesser extent on the material sheet of the invention. This feature surprisingly improves the anti-ballistic properties.

A monolayer of the sheet of multilayer material of the invention is preferably produced by positioning a plurality of tapes with their edges as close as possible to each other, and preferably in proximity to touch. However, in order to be able to produce a monolayer on an industrial scale at economical speeds, it would be desirable to allow a sheet between the adjacent tapes (that is, the adjacent tapes in a monolayer are not in contact along their longitudinal edges - clearance greater than 0 %). Preferably, the sheet of material according to the invention is characterized in that the gap between adjacent tapes in a monolayer is

5/29 less than 10% of the width of the adjacent unidirectional tapes and, even more preferably, less than 5%, even more preferred 3% of the width of the adjacent unidirectional tapes. More preferably, the gap between adjacent tapes in a monolayer is less than 1%.

A sheet of material according to this preferred embodiment is easily produced and yet has anti-ballistic properties of a level similar to that of sheets of material without gap. Although a monolayer according to the invention is preferably produced by positioning a plurality of tapes with their longitudinal edges against each other, monolayers constructed from just one tape (wide enough) of sufficient width are also within the scope of invention, since such a monolayer does not show adjacent areas of high thickness and along the length of the longitudinal edges of at least one unidirectional tape.

By aligning the various polymer strips, it is drawn in such a way that each strand is oriented in parallel with adjacent strands, and in such a way that a substantial amount, that is, at least 90% of the adjacent strands do not overlap, an improved anti-ballistic performance is achieved through known materials. According to the prior art, as described in EP 1627719 A1, the unidirectional monolayers comprise a plurality of high strength unidirectional polyethylene tapes, oriented in parallel in a plane, but partially overlapping, the overlap area being of the order of 5 mm to 40 mm wide. According to a

6/29 alternatively, a narrow polymeric film, approximately 5 to 20 mm wide, is placed over the contact area and placed over the contact area between two adjacent strips. An additional advantage of the multilayer material sheet of a preferred embodiment of the present invention is that there is no need for such additional polymeric films to obtain good anti-ballistic properties. In addition, due to the fact that tapes are free from areas of high thickness, as defined in the present invention, the subsequent stacking and consolidation of the monolayers under pressure will result in a more homogeneous sand density or thickness in the multi-layer material sheet in comparison with the state of the art.

A particularly preferred embodiment of the multilayer material sheet according to the invention is characterized in that the polymer from which it is made is selected from the group consisting of polyolefins, polyesters, polyvinyl alcohols, polyacrylonitriles, polyamides, especially poly (p-phenylene) terephthalamide), liquid crystalline polymers and polymers similar to the ladder, such as polybenzimidazole or polybenzoxazole, especially poly (1,4-phenylene-2,6-benzobisoxazole), or poly (2,6-diimidazo [4,5-b-4 ', 5'-e] pyridinylene-1,4 - (2,5dihydroxy) phenylene). Unidirectional and monolayer tapes from these polymers are preferably highly oriented by means of stretching material forms, for example, films, at a suitable temperature. By means of unidirectional and monolayer tapes we mean in the context of this request monolayer tapes that show a

7/29 preferred orientation of the polymer chains in one direction, that is, in the direction of the stretch. Such tapes and monolayers can be produced by stretching, preferably by means of uniaxial stretching, and will have anisotropic mechanical properties.

The sheet of a multi-layer material of the invention allows the use of stretched polymers with relatively low strength and, therefore, ultra-high molecular weight polyethylene is not required to obtain adequate anti-ballistic performance. However, a preferred embodiment comprises ultra-high molecular weight polyethylene. Ultra high molecular weight polyethylene can be linear or branched, although preferably linear polyethylene is used. Linear polyethylene is understood here to mean polyethylene with less than one side chain per 100 to 100 carbon atoms, and preferably with less than one side chain per 300 carbon atoms; a side chain or branch usually containing at least 10 carbon atoms. The chains suitably by means of the compression molding of 2 mentioned, for example, on the sides can be measured by FTIR in a mm thick film, according to EP 0269151. Linear polyethylene can additionally contain up to 5 mol% of one or more different alkenes which are copolymerizable with the same, such as propene, butene, pentene, 4-methylpentene, octene. Preferably, linear polyethylene is of high molar mass with an intrinsic viscosity (IV, as determined in decalin solutions at 135 ° C) of at least 4 dl / g; more preferably at least 8 dl / g, more

8/29 preferably at least 10 dl / g. Such polyethylene is also referred to as ultra high molecular weight polyethylene. Intrinsic viscosity is a measure for molecular weight that can be more easily determined than effective molar mass parameters such as Mn and Mw. Such a polyethylene film produces particularly suitable anti-ballistic properties.

The tapes according to the invention can be prepared in the form of films. A preferred process for forming such films or tapes comprises feeding a polymeric powder between a combination of endless belts, compression molding the polymeric powder at a temperature below its melting point, and laminating the resulting compression-molded polymer followed by stretching. Such a process, for example, is described in EP 0 733 460 A2, which is incorporated herein by reference. If desired, before feeding and compression molding the polymer powder, the polymer powder can be mixed with a suitable liquid organic compound having a boiling point greater than the melting point of the polymer. Compression molding can also be performed by temporarily retaining the polymer powder between the endless belts while transporting it. This can be done, for example, by providing press plates and / or rollers in connection with endless belts. The UHMWPE polymer used in this process needs to be stretchable in the solid state.

Another preferred process for forming films comprises feeding a polymer to an extruder, extruding a film at a temperature above its melting point and stretching the polymer film

9/29 extruded. If desired, before feeding the polymer to the extruder, the polymer can be mixed with a suitable liquid organic compound, for example, to form a gel, as is preferably the case when using ultra high molecular weight polyethylene.

Stretching, preferably uniaxial stretching, of the films produced can be carried out by means known in the art. Such means comprise extrusion stretching and tensile stretching in suitable stretching units. To obtain increased mechanical strength and stiffness, stretching can be carried out in multiple stages. In the case of preferred ultra high molecular weight polyethylene films, the drawing is typically performed uniaxially in a number of drawing steps. The first stretching step may, for example, comprise stretching up to a stretching factor of 3. Multiple stretching can typically result in a stretch factor of 9 for stretch temperatures up to 120 ° C, a stretch factor of 25 for stretch temperatures up to 140 ° C, and a stretch factor of 50 for stretch temperatures of up to 150 ° C and above. Through multiple stretching at increasing temperatures, stretching factors of approximately 50 and above can be achieved. This results in high strength tapes so that for ultra high molecular weight polyethylene tapes, resistances of 1.5 GPa to 1.8 GPa and higher can be obtained.

The resulting drawn tapes can be used as such to produce a monolayer, or they can be cut to your desired width, or divided along the

10/29 stretch direction. Preferably, the monolayer is produced from non-slit tape. The width of the unidirectional tapes thus produced is limited only by the width of the film from which they are produced. The width of the tapes is preferably greater than 2 mm, more preferably greater than 5 mm and even more preferably greater than 30 mm. The sand density of tapes or monolayers can be varied across a wide range, for example, between 5 and 200 g / m². Preferred sand density is between 10 and 120 / m², most preferred between 15 and 80 g / m² and most preferred between 20 and 60 g / m².

Another particularly preferred sheet of multilayer material according to the invention comprises at least one monolayer, preferably all monolayers, constructed from a plurality of unidirectional tapes of the stretched polymer, aligned in such a way that they form a woven structure. Such tapes can be manufactured by applying textile techniques, such as weaving, interlacing, etc. of small strips of stretched polymer instead of fibers, which is usually done. Although in this modality the polymer strips have areas of high thickness where the strips partially overlap at the crossing points, the areas of high thickness cross the longitudinal edges of the unidirectional tape, rather than extending along and adjacent to the longitudinal edges. Each ribbon (being a braided fabric of small strips) is positioned in such a way that there is no overlap between adjacent ribbons, aligned in the same direction. By stacking the tapes in such a way that the splice lines

11/29 in different monolayers are staggered with respect to each other, anti-ballistic properties are further improved.

In some embodiments, the monolayer may include a binder which is applied locally to bond and stabilize the various unidirectional tapes in such a way that the monolayer structure is maintained during handling and manufacture of unidirectional sheets. Suitable binders are described, for example, in EP 0191306 Bl, EP 1170925 Al, EP 0683374 Bl and EP 1144740 Al. The binder can be applied in several ways and modes; for example, as a transverse strip (transverse to unidirectional tapes). The application of the binder during the formation of the monolayer advantageously stabilizes the tapes, thereby enabling faster production cycles to be achieved while avoiding overlaps between adjacent tapes.

In one embodiment, a binder is applied to firmly touch adjacent unidirectional strips along its longitudinal edges. As the function of the binder is to temporarily retain and stabilize the plurality of unidirectional tapes during handling and manufacture of unidirectional sheets, localized application of the binder is preferred. Local application of the binder is an application that is limited to the immediate vicinity of the longitudinal edges and may include intermittent localized application (application of points along the longitudinal edges).

Preferably, the application of the binder results in a maximum high monolayer thickness (embossed edge) of 150% of the average thickness of the unidirectional tapes

12/29 forming the monolayer. More preferably, the application of the binder results in a maximum high thickness of 120%, 110% or 105% of the average thickness of the plurality of unidirectional tapes forming the monolayer. In another embodiment, the application of the binder results in an increase in the monolayer thickness adjacent to the longitudinal edges of the unidirectional tapes of less than 4 micrometers, more preferably less than 3, 2 or 1 micrometer.

In modalities with intermittent localized application of the binder, the proportion of the longitudinal edges comprising binder is preferably less than 50%, 30%, 20%, 10%, 5% or 2%. Similarly, the proportion of the longitudinal edges (or areas adjacent to the longitudinal edges) of the unidirectional tape which is in relief due to the application of the binder is preferably less than 50%, 30%, 20%, 10%, 5% or 2%. Preferably, the binder comprises less than 20%, 10%, 5%, 2%, 1%, 0.5% or 0.2% of the weight of the consolidated or monolayer stack.

In alternative embodiments, an agglutination medium, such as ultrasonic welding, can be used to intermittently fuse the sections of the longitudinal edges of the adjacent unidirectional tapes together.

With adjacent unidirectional tapes within a monolayer intermittently linked along contiguous longitudinal edges, the adjacent unidirectional tapes are kept in a parallel arrangement. The application of the binder allows the adjacent unidirectional tapes to be close together without substantially overlapping the contiguous longitudinal edges. The localized variation in thickness

13/29 of the monolayer is advantageously reduced monolayers (compared to conventional ones with overlapping longitudinal edges or with continuous, overlapping, polymeric agglutination strips) which contributes to a consolidated pile resulting from monolayers with a more homogeneous thickness and, therefore,

The thickness of the monolayers or tapes of the multilayered material sheet can, in principle, be selected within wide ranges. Preferably, however, the sheet of multilayer material according to at least one mono and a layer exceeds

120 gm, plus μπι, and more preferably it is between and 2 9 μπι. Particularly suitable anti-ballistic properties are obtained if the thickness of all monolayers in the stack does not exceed 120 μπι, more preferably it does not exceed 50 μπι, and most preferably it is between 3 and 2 9 μπι. A sheet of additional preferred multilayer material according to the invention is characterized in that the thickness of at least one monolayer greater than 10 exceeding μπι, preferably

100 μτη or more thickness of at least one of the monolayers in the pile at the claimed thickness, sufficient monolayered anti-ballistic properties are surprisingly obtained even with the most properly limited resistances.

The strength of the tapes in the sheet of multilayer material depends largely on the polymer from

14/29 (uniaxial). The resistance of tapes (and monolayers) is at least

<td>less 0.7 5 GPa,</td><td colspan="6">preferably at least 0.9 GPa,</td><td>more</td>

<td>preferably</td><td>in</td><td>to</td><td>any less</td><td> 1.2</td><td>GPa,</td><td>still</td><td>more</td>

<td>preferably</td><td>in</td><td>to</td><td>any less</td><td> 1.5</td><td>Gpa,</td><td>still</td><td>more</td>

<td>preferably</td><td>in</td><td>to</td><td>any less</td><td> 1.8</td><td>GPa, and</td><td>still</td><td>more</td>

preferably at least 2.1 GPa, and more preferably at least 3 GPa. The unidirectional monolayers are preferably sufficiently interconnected to each other, meaning that the unidirectional monolayers do not come off under conditions of normal use such as, for example, at room temperature.

The sheet of multilayer material according to the invention comprises at least two unidirectional, unidirectional monolayers, preferably at least 4 monolayers more preferably at least 6 monolayers even more preferably at least 8 unidirectional monolayers and more preferably at least 10 unidirectional monolayers. Increasing the number of unidirectional monolayers on the multilayer material sheet of the invention simplifies the manufacture of articles from these material sheets, for example, anti-ballistic sheets.

In an embodiment of the present invention, a process is provided for preparing a sheet of multilayer material comprising:

(a) positioning a first unidirectional tape of at least one polymer stretched on a mobile substrate thereby forming a first monolayer, whereby the monolayer is free of an area of ​​adjacent high thickness and along the substantial length of the edges

Longitudinal 15/29 of at least one unidirectional tape;

(b) holding the first monolayer on the mobile substrate;

(c) positioning a second unidirectional strip of at least one stretched polymer on the first monolayer, thereby forming a second monolayer, whereby the direction of the second monolayer makes an angle α with respect to the first; and (d) compressing the stack thus formed to consolidate its monolayers. The consolidated stack of monolayers has a more homogeneous thickness / sand density compared to the prior art, due to the reduction or absence of areas of high thickness along and adjacent to the longitudinal edges of at least one unidirectional tape, preferably in each of the monolayers .

In a preferred embodiment of the present invention, a process is provided for preparing a sheet of multilayer material of the claimed type. The process according to the invention comprises the steps of:

(a) providing a plurality of strips of stretched polymer, aligned in such a way that each strip is oriented parallel to the adjacent strips, and so that the adjacent strips do not substantially overlap;

(b) positioning the various strands of stretched polymer on a mobile substrate thereby forming a first monolayer;

(c) holding the first monolayer on the mobile substrate;

(d) positioning a plurality of strands of stretched polymer over the first monolayer, thereby forming

16/29 a second monolayer, so the direction of the second monolayer makes an angle α with respect to the first; and (e) compressing the stack thus formed to consolidate its monolayers.

Step (a) can optionally include the application of a binder or agglutination medium to retain or stabilize the adjacent tapes, such that increased production speeds can be achieved. With the claimed process, a sheet of multilayer material substantially devoid of overlapping regions, i.e., regions with greater sand density, can be easily produced. Sheets of material thus produced have improved anti-ballistic properties over a sheet of material with overlapping regions.

Preferably, the plurality of strands of stretched polymer is unwound from a unwinding station and step (d) is carried out by folding the various strands of polymer stretched at least partially on them. More specifically, the various strips of stretched polymer are positioned in such a way that the first monolayer forms an angle β with respect to the direction of movement of the substrate, and the folding is carried out in such a way that the fold line extends approximately parallel to the direction of movement of the substrate. The process according to the invention is further characterized in that the angle β is between 40 and 50 degrees, whereby the most preferred angle β is approximately 45 degrees.

Another preferred process according to the invention is characterized in that the second monolayer is at least

17/29 partially adhered to the first monolayer. This can be easily accomplished through ultrasonic welding, adding a low-melting film, an adhesive, or by any other method of joining the layers. The adhesion of the second monolayer to the first monolayer is preferably strong enough to allow transport of the monolayer assembly, without substantial, relative movement, of the separate tapes and / or monolayers.

According to the process of the invention, a sheet of multilayer material is produced in which the direction of removal of two subsequent monolayers in the pile differs by an angle a. For the preferred process in which the fold line extends approximately parallel to the movement of the substrate, the angle a - 2β. Although angle α can be selected within wide ranges, angle α is preferably between and 135 °, more preferably between 65 and

115 ° and even more preferably between 80 and 100 °. In the preferred range mentioned last, a particularly preferred angle α is approximately according to this modality

90 °. A material preferably produced is denoted as a transverse layer in the art.

The sheet of multilayer material according to the invention is particularly useful in the manufacture of ballistic resistant articles, such as suits or armored plates. Ballistic applications comprise applications with ballistic threat of projectiles of various types including so-called AP, armor-piercing projectiles, and hard particles such as fragments and shrapnel from

18/29 shrapnel.

The ballistic resistance article according to comprises at least two unidirectional monolayers, preferably at least 10 unidirectional monolayers, more preferably at least unidirectional monolayers, even more preferably at least 30 unidirectional monolayers and most preferably at least 40 unidirectional monolayers. The drawing direction of two subsequent monolayers in the stack differs by an angle α. The angle α is preferably between 45 and 135 °, more preferably between 65 and 115 ° and more preferably between 80 and 100 °.

Preferably the ballistic resistance article according to the invention comprises an additional sheet of inorganic material selected from the group consisting of ceramics; metal, preferably aluminum, magnesiotitanium, nickel, chromium and iron or their alloys; glass; graphite, or combinations thereof. Particularly preferred is metal. In such a case the metal in the metal sheet preferably has a melting point of at least 350 ° C, more preferably at least 500 ° C, more preferably at least 600 ° C. Suitable metals include aluminum, magnesium, titanium, copper, nickel, chromium, beryllium, iron and copper including their alloys such as steel and stainless steel and aluminum alloys with magnesium (so-called 5000 series aluminum), and alloys of aluminum with zinc and magnesium or with zinc, magnesium and copper (so-called 7000 series aluminum). In alloys, the amount, for example, of aluminum, magnesium, titanium and iron is preferably at least 50% by weight. Metal Sheets

Preferred 19/29 comprising aluminum, magnesium, titanium, nickel, chromium, beryllium, iron including its alloys. More

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r nickel, aluminum, preferably

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your leagues

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good anti-ballistic article results in a

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light alloys with

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its preferably more

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any less

500. Most preferably the metal sheet is based on aluminum, magnesium, titanium, and their alloys . This results in the lightest anti-ballistic article with the highest durability. Durability in this order means the useful life of a compound under conditions of exposure to heat, moisture, light and UV irradiation. Although the additional sheet of material can be positioned anywhere on the monolayer stack, the preferred ballistic resistance article is characterized in that the additional sheet of material is positioned on the outside of the monolayer stack, more preferably at least on its face. impact.

The ballistic resistant article according to the invention preferably comprises an additional sheet of the inorganic material described above having a maximum thickness of 100 mm. Preferably the maximum thickness of the additional sheet of inorganic material is 75 mm, more preferably 50 mm, and most preferably 25 mm. This results in the best balance between weight and anti-ballistic properties. Preferably, in the case of

<td>additional sheet of</td><td>material</td><td>inorganic</td><td>to be</td><td>a sheet of</td>

<td>metal, thickness</td><td>of leaf</td><td>of metal, is</td><td>in</td><td>at least 0.25</td>

<td colspan="2">mm, more preferably and</td><td>at least</td><td> 0,5</td><td>mm, and more</td>

preferably at least 0.75 mm. This results in a

20/29 even better anti-ballistic performance.

The additional sheet of inorganic material can optionally be pretreated to improve adhesion with the sheet of multilayer material. Adequate pretreatment of the additional sheet includes mechanical treatment, for example, roughening or cleaning of its surface by sanding or grinding, chemical engraving with, for example, nitric acid and lamination with polyethylene film.

In another embodiment of the ballistic resistance article a bonding layer, for example, an adhesive, can be applied between the additional sheet and the sheet of multilayer material. Such an adhesive may comprise an epoxy resin, a polyester resin, a polyurethane resin or a resin and vinyl ester. In another preferred embodiment, the bonding layer may further comprise a woven or non-woven layer of inorganic fiber, for example, glass fiber or carbon fiber. It is also possible to fix the additional sheet to the sheet of multilayer material by mechanical means, such as, for example, screws, pins and pressure fittings. In the event that the ballistic resistance article according to the invention is used in ballistic applications where threat of AP projectiles, fragments or improvised explosive devices can be found the additional sheet is preferably comprised of a metal sheet covered with a ceramic layer . In this way an anti-ballistic article is obtained with a layered structure as follows: ceramic layer / metal sheet / at least two unidirectional sheets with the direction of the fibers in the sheet

21/29 unidirectional at an angle α relative to the direction of the fibers in an adjacent unidirectional sheet. Suitable ceramic materials include, for example, alumina oxide, titanium oxide, silicon oxide, silicon carbide and boron carbide. The thickness of the ceramic layer depends on the level of ballistic threat, but generally varies between 2 mm and 30 mm. This ballistic resistance article is preferably positioned in such a way that the ceramic layer faces the ballistic threat.

In an embodiment of the present invention, a process is provided for manufacturing a ballistic resistance article comprising:

(a) stacking at least two unidirectional stretched polymer monolayers, each monolayer comprising at least one unidirectional tape, whereby the stretching direction of the subsequent 2 monolayers in the stack differs, so that at least one layer is free of an area of ​​high thickness adjacent and along the substantial length of the longitudinal edges of the at least one unidirectional tape; and a sheet of material selected from the group consisting of ceramics, steel, aluminum, titanium, glass and graphite, or combinations thereof; and (b) consolidating the stacked sheets under temperature and pressure.

In a preferred embodiment of the present invention, a process is provided for the manufacture of a ballistic resistance article comprising the steps of:

(a) stacking at least two unidirectional stretched polymer monolayers, so the stretching direction of the subsequent two monolayers in the stack differs, so

22/29 at least one monolayer, and preferably all monolayers, comprises a plurality of unidirectional strips of the stretched polymer, aligned in the same direction, so that adjacent strips do not overlap, and an additional sheet of inorganic material selected from the group consisting of ceramics , steel, aluminum, titanium, glass and

<td>graphite,</td><td>or</td><td>combinations thereof; and</td><td></td><td></td><td></td>

<td>(B)</td><td colspan="2">consolidate the stacked sheets</td><td>under</td><td colspan="2">temperature and</td>

<td>pressure.</td><td></td><td></td><td></td><td></td><td></td>

<td>In</td><td>one</td><td>alternative battery process</td><td>in</td><td>at least</td><td>two</td>

<td colspan="2">monolayers</td><td colspan="2">unidirectional polymer</td><td>stretched</td><td>was</td>

manufactured in a separate process, as described above. This prefabricated pile is then combined with the additional sheet of material selected from the group consisting of ceramics, steel, aluminum, titanium, glass and graphite, or combinations thereof, in step (a) of the process.

Consolidation for all the processes described above can be done properly in a hydraulic press. Consolidation is meant to mean that the monolayers are fixed relatively firmly to one another to form a unit. The temperature during consolidation is usually controlled by the temperature of the press. A minimum temperature is generally chosen in such a way that a reasonable rate of consolidation is achieved. In this regard, 80 ° C is a suitable lower temperature limit, preferably that lower limit is at least 100 ° C, more preferably at least 120 ° C, more preferably at least 140 ° C. A maximum temperature is chosen below the temperature at which the stretched polymer monolayers lose their high properties

Mechanical 23/29 due, for example, to fusion. Preferably the temperature is at least 10 ° C, preferably at least 15 ° C and even more preferably at least 20 ° C below the melting temperature of the stretched polymer monolayer. In the event that the stretched polymer monolayer does not exhibit an evident melting temperature, the temperature at which the stretched polymer monolayer begins to lose its mechanical properties should be read instead of the melting temperature. In the case of the preferred ultra high molecular weight polyethylene, a temperature below 145 ° C will generally be chosen. The pressure during consolidation is preferably at least 7 MPa, more preferably at least 15 MPa. In this way, a rigid anti-ballistic article is obtained. The optimum time for consolidation generally ranges from 5 to 120 minutes, depending on conditions such as temperature, pressure and thickness of the part and can be verified through a routine experiment. In the event that curved anti-ballistic articles are to be produced, it may first be advantageous to pre-shape the additional sheet of material in the desired shape, followed by consolidation with the monolayers and / or sheet of multilayer material.

Preferably, in order to obtain a high ballistic resistance, cooling after high temperature compression molding is also carried out under pressure. Pressure is preferably maintained at least until the temperature is low enough to prevent relaxation. This temperature can be set by those skilled in the art. When a ballistic resistance article comprising polyethylene monolayers of molecular weight

24/29

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temperatures

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115

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preferably

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typical vary

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vary

100

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preferably 100

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in between

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more preferably

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<img file="BRPI0710941A2_D0022.tif" />

<img file="BRPI0710941A2_D0023.tif" />

bars while

<img file="BRPI0710941A2_D0024.tif" />

times

<img file="BRPI0710941A2_D0025.tif" />

between 40 to 180 minutes.

<img file="BRPI0710941A2_D0026.tif" />

material

<img file="BRPI0710941A2_D0027.tif" />

multiple

<img file="BRPI0710941A2_D0028.tif" />

article

<img file="BRPI0710941A2_D0029.tif" />

advantageous present particularly

<img file="BRPI0710941A2_D0030.tif" />

<img file="BRPI0710941A2_D0031.tif" />

<img file="BRPI0710941A2_D0032.tif" />

materials previously

<img file="BRPI0710941A2_D0033.tif" />

that known articles at a significantly lower weight,

<img file="BRPI0710941A2_D0034.tif" />

<img file="BRPI0710941A2_D0035.tif" />

performance

<img file="BRPI0710941A2_D0036.tif" />

improved in equal weight compared to the article

<img file="BRPI0710941A2_D0037.tif" />

<img file="BRPI0710941A2_D0038.tif" />

<img file="BRPI0710941A2_D0039.tif" />

<img file="BRPI0710941A2_D0040.tif" />

effective

<img file="BRPI0710941A2_D0041.tif" />

<img file="BRPI0710941A2_D0042.tif" />

mode

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terms

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cost. As polymers

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can be used to produce the multilayer material sheet of the invention, the properties can be optimized according to specific application. In addition to ballistic resistance, properties include, for example, thermal stability, shelf life, resistance to deformation, ability to bond with other sheets of material, modeling property, and so on.

The invention will now be explained further by means of figures 1-4 below, without however being limited to them.

Figure 1 schematically represents an embodiment of an apparatus for carrying out the process according to the invention.

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Figure 2 schematically represents a sheet of multilayer material.

Figure 3 schematically represents a monolayer of woven tapes.

Figure 4 schematically represents a sheet of multilayer material.

With reference to Figure 1, an apparatus 1 for producing a sheet of multilayer material of the claimed type is shown. The apparatus comprises means 2 to provide a plurality of strands of stretched polymer 10. The means 2 may, for example, comprise a unwinding station for rolls of strands of polymer 10. The strands of polymer 10 are aligned in such a way that each strand 10 is oriented in parallel to the adjacent strips 10. The apparatus 1 further comprises a movable substrate 3, which, in the embodiment shown is a belt, driven by two cylindrical rollers 4. The belt 3 is movable at a speed V3 in the direction shown by the arrow. The various tapes 10 are positioned on the substrate 3 by passing the tapes 10 through a set of pass rolls (5a, 5b).

The various tapes 10 are secured on the substrate 3 by means of retention, for example, by perforating the substrate 3, and providing a space 6, which can be placed under vacuum by the pump 7 below the substrate3.

Behind the movable substrate 3, a belt press 20 is positioned, comprising two heated surfaces (21, 22), driven by the cylindrical rollers 23.

The process according to the invention comprises unwinding a plurality of polymer strips non-axially stretched 10 from the unwinding station 2

26/29 at a VI speed. The tapes 10 are positioned in such a way that adjacent tapes do not overlap substantially, and there are substantially no gaps (typically less than 2 mm) between adjacent tapes. The tapes 10 are then fed through the set of pass rolls (5a, 5b). As shown in Figure 1, the unwinding device assembly 2 and pass roll assembly (5a, 5b) moves up and down of the substrate 3 in the transverse direction at a speed V2. The vacuum belt substrate 3 moves at a speed V3 in a direction essentially perpendicular to the transverse direction. The ratio between V2 and V3 is chosen such that the various tapes 10 are positioned on the mobile substrate 3 at an angle of approximately 45 degrees with respect to the direction of movement of the substrate 3, thereby forming a first monolayer. The first monolayer is secured on the mobile substrate 3 by means of the suction produced by the vacuum medium (6, 7). When the unwinding device 2 reaches the side of the moving substrate 3, its direction of movement is reversed, and the unwinding device 2 moves in the opposite direction. In this way, the various strands of stretched polymer 10 are partially folded over themselves. More specifically, the various strands of stretched polymer 10 are folded in such a way that the fold line extends approximately parallel to the direction of movement of the substrate 3. In this way, a second monolayer is positioned on the first monolayer, so the direction of the second monolayer is at an angle of approximately 90 degrees with respect to the first monolayer. To ensure that

27/29 the first and second monolayer set can be transported without relative movement of the separate and / or monolayer tapes, the second monolayer of tapes is adhered to the first monolayer at least partially. Suitable means of doing this include, but are not limited to, ultrasonic welding, addition of a low melting film, an adhesive, a hot melt adhesive, or any other method of bonding the layers.

Finally, the thus formed set of monolayers is fed to a belt press or calender 20 for final consolidation of the sheet of multilayer material. In the belt press or calender 20 the various stacked tapes are connected at a temperature close to the melting point of the tapes. The resulting multilayer material is, in the described embodiment, a two-layer material, of transverse folds, made of tapes, with the direction of the tapes at an angle of approximately 45 degrees with respect to the direction of movement of the substrate 3.

The width of the various tapes 10 in the device 2 is determined by the width of the multilayer material on the substrate 3 which must be positioned on the belt press or calender 20. In the case where the angle β of the tapes with the direction of movement of the substrate 3 is 45 ° C, the width of the various tapes 10 is the width ^ 2 * of the multilayer material.

With reference to Figure 2, a graphical presentation of the sheet of multilayer material according to the invention is shown comprising a consolidated stack of two unidirectional monolayers of stretched polymer, whereby the drawing direction of two subsequent monolayers in the

The stack is rotated by 90 °, so that each monolayer comprises a plurality of unidirectional strips of the stretched polymer aligned in the adjacent do not overlap.

For the sake of clarity, the individual tapes extend at the edges of the sheet of multilayer material.

With reference to Figure 3, a graphical presentation of a monolayer according to the invention is shown, whereby the monolayer is constructed of a plurality of unidirectional tapes of the stretched polymer, aligned so that they form a woven structure.

With reference to Figure 4, a graphical presentation of a sheet of multilayer material according to the invention is shown comprising the monolayer of Figure 3 denoted by numeral 1 (in solid lines), with below it a second monolayer of woven tapes denoted by the numeral 2 (in dotted lines). The second monolayer is positioned in such a way that the seam lines of the respective monolayers are aligned and staggered in shape.

The test methods as referred to in this application are as follows • Intrinsic (IV) viscosity is determined according to the PTC-179 method (Hercules Inc. Rev. 29 April 1982) at 135 ° C in decal, the time of dissolution being 16 hours, with DBPC as antioxidant in an amount of 2 g / 1 of solution, through extrapolation of viscosity

<td>as measured</td><td>in</td><td>many different</td><td>concentrations</td><td>for</td>

<td>zero concentration;</td><td></td><td></td><td></td><td></td>

Traction properties (measured at

25 ° C):

29/29 tensile strength (or strength), tension modulus (or modulus) and elongation at break (or eab) are defined and determined on multi-filament yarns as specified in ASTM D885M, using a standard 5 fiber length and 5 00 mm, a crosshead speed of 50% / minute. Based on the measured stress-strain curve, the modulus is determined as the gradient between 0.3 and 1% stress. To calculate the module and resistances, the measured tensile forces are divided by the titration, as determined by weighing 10 meters of fiber; GPa values ​​are calculated assuming a density of 0.97 g / cm³ .

The tensile properties of these films are measured according to ISO 1184 (H).

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