The present invention generally relates to tear-resistant paper and is more particularly directed to a paper/plastic film laminate wherein the polymeric film is biodegradable. The present invention also relates to materials that are electromagnetically opaque and, more particularly, to materials that provide electromagnetic shielding.
Durable papers are designed to perform well in challenging environments. One such paper employs at least one paper surface laminated to a sheet or film of polymeric material. In some instances the polymeric material is sandwiched between two pieces of paper. Such laminates offer superior tear resistance and durability.
RFID (“radio frequency identification”) device shielding is another area where paper has been employed. Increasingly, it has been easier to read important information from credit cards and/or passports that incorporate readable RFID devices simply by the card and/or passport being in proximity to an RFID card reader. In some instances the card and/or passport can be read while in the owner's bag, pocket or wallet. This can lead to such things as identity theft. To combat this, envelopes, sleeves and the like that incorporate RFID shielding have been used. Because such sleeves and envelopes may likely be used repeatedly over extended periods of time, the above-described paper/plastic material may provide a solution.
The present invention resides in one aspect in a paper/plastic laminate which contains a paper web having a first surface and a second surface, and a polymeric film having a first surface and a second surface. The polymeric film comprises a biodegradable polymeric material. The first surface of the polymeric film is adhered by an adhesive to the second surface of the paper web forming a paper/plastic laminate, the paper/plastic laminate being dimensionally stable.
The present invention resides in another aspect in a method of making a dimensionally stable paper/plastic laminate by providing a paper web having a second surface and providing a polymeric film having a first surface, the polymeric film comprising a biodegradable polymeric material. The paper web second surface is laminated to the polymeric film first surface using an adhesive. The paper web, polymeric film and the adhesive are selected such that the laminated combination is dimensionally stable.
Another aspect of the present invention resides an electromagnetic shielding laminate material that includes a first paper web, a polymeric film comprising a biodegradable polymeric material, and a conductive layer.
In another aspect, the invention provides an electromagnetic shielding material which includes a first paper web and a metalized polymeric film adhered to an adjacently positioned surface of the first paper web. The metalized polymeric film comprises a biodegradable polymeric material. There is a second paper web adhered to an adjacently positioned surface of the metalized polymeric film. The first paper web, the metalized polymeric film, and the second paper web form a laminate. When the laminate is interposed between a receiving antenna of an RFID smart chip and a transmitting antenna of an RFID signal generator, the laminate is capable of preventing the reading of the RFID smart chip.
Another aspect of the present invention resides in an electromagnetic shielding material that includes a paper web, a polymeric film comprising a biodegradable polymeric material, and a conductive material sandwiched between the paper web and the polymeric film. The paper web, the polymeric film and the conductive material form a laminate which, when interposed between a receiving antenna of an RFID smart chip and a transmitting antenna of an RFID signal generator, is capable of preventing the reading of said RFID smart chip.
Still another aspect of the invention resides in an electromagnetic shielding material that includes a polymeric film which has two sides and which comprises a biodegradable polymeric material, a first layer of conductive material on one side of the polymeric film, and a second layer of conductive material on the other side of the polymeric film. The electromagnetic shielding material, when interposed between a receiving antenna of an RFID smart chip and a transmitting antenna of an RFID signal generator, is capable of preventing the reading of said RFID smart chip.
The invention also provides a security device capable of electromagnetically shielding an RFID smart chip. The security device includes an electromagnetic shielding material having a polymeric film and at least one conductive layer. The polymeric film comprises a biodegradable polymeric material. The security device also includes at least one adjacently positioned substrate. When the electromagnetic shielding material is interposed between a receiving antenna of said RFID smart chip and a transmitting antenna of an RFID signal generator, the electromagnetic shielding material is capable of preventing the reading of said RFID smart chip.
In another aspect, the present invention relates to a method of electromagnetically shielding an RFID smart chip. The method includes providing an electromagnetic shielding material comprising at least a polymer film that comprises a biodegradable polymer material and a layer of conductive material. The electromagnetic shielding material is placed proximate an RFID smart chip; and the electromagnetic shielding material is interposed between the RFID smart chip and a transmitting antenna of an RFID signal generator.
In one aspect, the invention provides a paper/plastic laminate with a paper web laminated to a polymeric film that comprises a biodegradable polymeric material. The laminate is made using an adhesive and remains dimensionally stable in equipment employing heat set fuser toner adhesion as the method for fusing/binding ink to paper. Depending upon the desired application for the paper/plastic laminate, the paper web and the polymeric film can have a range of characteristics. In one embodiment, a second paper web is laminated to the other side of the polymeric film, sandwiching the polymeric film between two paper webs.
The paper/plastic laminate can be used similarly to regular paper in office midrange and high-speed traditional laser and digital copiers and digital printers, and other like equipment using heat set fuser toner adhesion as the method for fusing/bonding an ink to a paper. Alternatively, the paper/plastic laminate may have printed matter applied thereon by a variety of methods, including but not limited to, Gravure, Flexographic, Letter Press, or Direct Type processes. In some embodiments, printed images may be applied by ink jet or laser printing, as well. Suitable inks for printing the image include, but are not limited to, solvent or water-based inks, acrylic inks, soy inks and ultra-violet (“UV”) inks. In some embodiments, the paper/plastic laminate has an appearance and a texture consistent with regular papers. The polymeric film layer, however, gives the paper/plastic laminate resistance against tearing.
The paper web has a surface that permits writing or printing to be placed thereon using conventional writing implements, printing equipment and/or inks, and it is adapted to permit the paper/plastic laminate to be used with the equipment identified above. The characteristics of the paper web can be tailored, similarly to regular paper, by conventional processes well known to those skilled in the art of papermaking. Characteristics commonly adjusted are dimensional stability in the presence of heat, opacity, brightness, pH, water resistance, and acid content. The paper web should also be formulated to be compatible with the polymeric film and the laminating process discussed below. In the laminating process an adhesive is applied between the paper web and the polymeric film.
The polymeric film can be made with any biodegradable polymeric material. The polymeric film material is selected not only for its ability to be adhered to the paper web, but also for its dimensional stability, both shrinkage and distortion, in the presence of heat.
The laminating process positions an adhesive between the paper web and the polymeric film and then laminates the paper web to the polymeric film. In some embodiments, a paper/plastic laminate as described herein is made using a 100% solids adhesive. As used herein, a “100% solids adhesive” means an adhesive employing 100% solids adhesives technology as differentiated from solvated adhesives and waterborne adhesives. In one embodiment, a 100% solids adhesive comprises a tie layer of polyethylene that is laminated between, and adjacent to, the paper web and the polymeric film. Alternatively, the adhesive may be a curable urethane adhesive, as describe further below. Optionally, the paper/plastic laminate can be assembled in an extrusion lamination process in which the polymeric film and/or the adhesive layer are extruded during the process
As shown in
The paper web 12 can be formed from a fibrous web formulated with a blend of softwood Kraft, hardwood Kraft and/or recycled fiber. Brightness is a function of the application. A GE brightness value in excess of 83, per TAPPI test method T 452 om-92, is preferred for general writing paper. In premium writing paper, the GE brightness should be around 95, or higher. Conventional optical brightening additives can be used to achieve the desired level of brightness. As those skilled in the art of papermaking will appreciate, selection of the components of the fibrous web affects the brightness of the paper. While the paper 12 has been described as being formed from a fibrous web formulated from a blend of softwood Kraft hardwood Kraft and/or recycled paper, the present invention is not limited in this regard, as other materials known to those skilled in the art can be utilized instead of, or in combination with, the aforesaid papers.
The filler content in the paper web is adjusted to provide the opacity desired. For general paper applications, an opacity of at least about 77 percent is suitable, but a minimum opacity of 79 percent is desired. However, the present invention is not limited in this regard as any other desired opacity, including about 0% opacity, can be provided without departing form the broader aspects of the present invention. The caliper of the paper web can be selected by one of ordinary skill in the art to suit the intended use of the paper/plastic laminate and/or the paper handling capabilities of the laminating equipment.
In certain applications water resistance as well as wet strength may be desired. Water resistance can be achieved by use of a conventional internal sizing additive. A conventional wet strength additive may also be incorporated to increase wet rub resistance. Sizing methods and the amount of sizing, as well as wet strength additives are well understood in the art.
The polymeric film 14 comprises a biodegradable polymeric material. For example, a polymeric film in a laminate described herein may be made from a polylactide, e.g., a polylactic acid polymer (PLA) which is biodegradable. One suitable PLA film is available from BI-AX International, Inc., 596 Cedar Ave, Wingham, ON N0G 2WO Ontario, Canada, under the trade name Evlon. Other biodegradable polymer PLA films that can be used in the shielding material described herein are commercially available from SKC Inc., 1000 SKC Drive, Covington, Ga. 30014, USA, under the designations SKYWEL TE90, BC11C, TE75, and TE71C.
Alternatively, the polymeric material of the polymeric film may comprise a biodegradable polyolefin (e.g., polyethylene (PE) or polypropylene (PP)) or a biodegradable polyester, such as a polyolefin or polyester that includes a biodegradation additive to render the polymer material biodegradable. The biodegradation additive causes a reduction in the average molecular weight of the polymeric material to a molecular weight at which microbial biodegradation of the polymer material can occur, e.g., to a weight average molecular weight of about 10,000 grams per mole, or less. Biodegradation can occur in compost or in a landfill. One type of biodegradation additive comprises a catalyst which catalyzes the oxidative degradation of a polyolefin material to a reduced average molecular weight, at which biological processes can further break down the polyolefin material. Such a degradation process is referred to as oxobiodegradation. The effect of such a catalyst can be activated by ultraviolet (UV) light and/or heat. A number of such catalysts are commercially available under the trade designation “Reverte™” from Wells Plastics Ltd, Emerald Way, Stone Business Park, Stone, Staffordshire, ST15 0SR, UK, e.g., via the distributor Oxobioplast, Inc., which has a place of business at 120 Eglinton Ave. East, Suite 1100, Toronto, ON, Canada M4P 1E2. Masterbatch polymer materials that contain Reverte™ catalysts are commercially available, and the addition of about 1 to about 5% by weight of the masterbatch material to a standard polyolefin yields the biodegradation effect. Oxobiodegradable PP films are also commercially available, e.g., Envirosafe LCF 502E oxo-biodegradable PP, distributed by Multi Plastics, Inc., 777 North Central Drive, Lewis Center, Ohio 43035.
While UV/heat-activated biodegradation additives have been mentioned, the invention is not limited in this regard, and in other embodiments, the biodegradable polymeric material for the polymeric film may contain any other type of additive capable of rendering the polymeric material biodegradable.
Factors in the selection of polymeric film 14 material include dimensional stability, shrinkage, balance, and heat resistance. Polymeric film 14 properties generally vary by material gauge. Present polymeric films 14 employed in the manufacture of paper/plastic laminates of 25-lb. paper (500 sheets, 17 inch by 22 inch sheets) have gauges of about 118 (approx. 30 micron).
Optionally, the first surface 20 of the polymeric film 14 may include at least one printed image 32, as shown in
While any suitable adhesive may be employed to bond the layers of the paper/plastic laminate 10, in one embodiment, the laminating process used to adhere the paper web 12, 26 to the polymeric film 14 uses a 100% solids adhesive. The laminating process produces a destructive bond between the paper web 12, 26 and the polymeric film 14. A destructive bond is defined as a bond between the paper web 12, 26 and the polymeric film 14 that after curing under a T Peel Adhesion Test will not allow the paper web 12, 26 to be separated from the polymeric film 14 with the paper web 12, 26 remaining intact.
The 100% solids, or solventless, adhesive used in the present invention is a low temperature (flowable at room temperature at about 100 degrees F.) two-component adhesive or a warm one-component adhesive (an adhesive that is a gel at room temperature and that is heated to permit the adhesive to flow). The selection of adhesive is based on the adhesive penetration and holdout characteristics of the paper web. Generally, the warm temperature adhesive is used where the adhesive penetration and the holdout of the paper web is a concern. The low temperature adhesive is used when adhesive penetration and holdout of the paper web are less of an issue. Each adhesive properly used should produce the desired destructive bond.
Lamination is accomplished using standard lamination techniques. The adhesive can be applied directly to the paper web and/or the polymeric film prior to lamination. While the adhesive might be heated to enhance its flow characteristics, the paper web and the polymeric film are not heated, except incidentally by contact with the warmed adhesive, if any. The adhesive cures without the addition of heat. Where a second paper web is to be laminated to the other side of the polymeric film, some curing time for the first bond should be allowed for.
In a specific embodiment, the 100% solids adhesive comprises a curable two-component urethane laminating adhesive that is prepared by combining a polyol resin with an isocyanate cross-linking agent and a UV-initiated cross-linking catalyst or accelerator to provide a curable resin. The lamination process includes layering the polymeric film and the paper web with the curable resin between the paper web and the polymeric film, pressing the paper web, polymeric film and curable resin together, and exposing the laminate to UV light. Whereas prior art paper/plastic laminates could only be prepared using papers that exhibited low absorbency, the use of the described curable resin permits the manufacture of satisfactory paper/plastic laminates from papers that exhibit a wide range of absorbencies. In particular, the prior art (as seen, for example, in U.S. Pat. No. 6,673,465 and U.S. Pat. No. 6,926,968) required that the paper web 12 be resistant to adhesive penetration and allow sufficient holdout to degrees balanced to allow maximum surface contact, or wetting out. A sufficient level of surface sizing or coating applied through any of several conventional techniques was used to minimize the penetration of the adhesive into the paper web 12. Sizing or coatings such as starch, PVA or Latex. AKD (Alkyl Ketene Dimer) sizing in combination with starch sizing was found to provide suitable adhesion penetration and holdout for a non-acid paper web 12. However, by using a curable two-component urethane laminating adhesive as described herein to bond the paper web to the polymeric film, the choice of paper web need not be resistant to adhesive penetration and exhibit holdout as required by the prior art.
In operation, and as described above, the polymeric film 14 is laminated to a single paper web 12 or may be embedded between two layers of the paper web 12, 26, whereby the printed image 32, 34 is protected. As a result, the polymeric film 14 having a printed image 32, 34 thereon is not accessible to be altered without destroying the paper/plastic laminate 10. In addition, the differences between the original paper/plastic laminate 10 and a typical photocopy or digital scan is evident to the naked eye. Therefore, a document having security features can be created without alterations or special features being added to the paper.
To facilitate use of some embodiments of the paper/plastic laminate in office equipment using heat set fuser toner adhesion as the method for fusing/bonding an ink to a paper (e.g., in midrange and high-speed traditional laser and digital copiers and digital printers, and other like equipment), the paper and the polymeric film are selected for their thermal characteristics in addition to other criteria, because the ink binding processes in such equipment can generate significant heat, e.g., 375 degrees F. or higher. A paper web 12 suited for these applications will be one that can withstand the temperature extremes of the process while maintaining its dimensional properties. The paper may have a surface 16, 30 treated with a metal salt such as sodium salt and more specifically sodium nitrate or sodium chloride. In one embodiment, the paper web is treated with sodium nitrate at the rate of 50 pounds per 1000 pounds of starch, a rate approximately 30 percent greater than typical treatments for standard xerographic paper. Biodegradable polyester films are suitable for paper/plastic laminates to be used with such equipment, whereas the temperatures reached in the printing processes are sufficient to curl and/or to shrink paper/plastic laminates containing some other types of polymeric films. Therefore, the polymeric film is selected not only for its strength, but also for its thermal characteristics. In one embodiment, the polymeric film 14 may comprise a biodegradable polyester and may have a mechanical strength exceeding about 29,000 psi, approximately 20.4 Kg/mm2, in all directions measured using ASTM D 882. Thermal heat shrinkage should be less than about 2 percent using the SKC Method (this is an internal measurement of SKC, Inc. of Covington, Ga.), 150 degrees C. for 30 minutes.
In another broad aspect, the present invention provides an electromagnetic shielding material that comprises a polymeric film and that includes at least one layer of electrically conductive material. The polymeric film contains a biodegradable polymeric material as described further herein. Optionally, the electromagnetic shielding material is a laminate of the polymeric film with at least one paper web. The layer of conductive material may constitute a distinct ply that is adhered to the plastic film in a laminate. For example, the conductive material may be provided as a metal foil or a woven metal fabric, or deposited as a metalizing later on the polymeric material. Alternatively, the layer of conductive material may be provided as particles of conductive material that are incorporated into the polymeric film. Including a biodegradable material in the shielding material accelerates the biodegradation of the shielding material once the shielding material is discarded.
Referring to
Both the first paper web 42 and the second paper web 48 comprise fibrous web materials. In one embodiment, such web materials are formulated with but are not limited to one or more of natural fiber (such as cotton), synthetic fiber, and/or recycled fiber. Also, such web materials include fillers that are suitable to provide at least some of the desired opacity. Coloring may be added to one or both of the first paper web 12 and the second paper web 18 as desired. The paper may also be synthetic or artificial paper or the like. The paper may be coated or uncoated.
The conductive layer 46 comprises any suitable conductive material. In
In another embodiment, the conductive layer 46 may comprise metallic particles deposited onto one or more of the polymeric film 44 and the second paper web 48. The metallic particles may be aluminum (e.g., elemental aluminum), aluminum alloys, or aluminum-containing compounds, or they may comprise other metals (e.g., copper, silver, nickel, and the like). In still another embodiment, the conductive layer 46 may be woven or non-woven strands of metal.
In yet other embodiments, the conductive layer 46 may comprise a non-metallic material such as carbon, carbon-loaded matrix material, graphite, combinations of the foregoing, and the like. Carbon nanotubes may also be used either in single-walled form or double-walled form. In embodiments in which carbon nanotubes are used as the conductive layer 46, the carbon nanotubes can be deposited using any suitable technique such as chemical vapor deposition or the like to afford precise control of the thickness of the conductive layer.
In yet another embodiment, the adhesive 50 may be conductive in itself. In such an embodiment, the adhesive includes a suitable conductive material mixed therein. Such elements include, but are not limited to, metals in the forms of particles, powders, granules, beads, combinations of the foregoing, and the like. The metals may be aluminum (e.g., elemental aluminum), aluminum alloys, or aluminum-containing compounds, or they may be other metals (e.g., copper, silver, nickel, and the like).
The adhesive 50 used to adhere the first paper web 42, the polymeric film 44, the conductive layer 46, and the second paper web 48 into a laminated form may be a 100% solids adhesive. The present invention is not limited in this regard as other adhesives are within the scope of the present invention. In particular, the adhesive 50 may be solvent-based, water-based, a hot melt, ultraviolet radiation curable, electron beam curable, combinations of the foregoing, and the like.
When a 100% solids adhesive is used in laminating the first paper web 42, the polymeric film 44, the conductive layer 46, and the second paper web 48, a destructive bond is produced between the paper webs and the polymeric film. A destructive bond is one in which the paper web(s) and the polymeric film, after curing under a T Peel Adhesion Test, will not allow the paper web(s) to be separated from the polymeric film with the paper remaining intact.
Referring now to
In the electromagnetic shielding material 110, both the first paper web 112 and the second paper web 118 comprise fibrous web materials (similar to the previous embodiment), and the polymeric film 114 comprises a biodegradable polymeric material.
The conductive material 116 in the electromagnetic shielding material 110, however, comprises particles of suitable conductive material such as aluminum, copper, silver, nickel, alloys thereof, or the like in powder form. Non-metallic materials such as carbon, carbon-loaded matrix material, graphite, carbon nanotubes, combinations of the foregoing, combinations of the foregoing with metal, and the like may also be used. In such an embodiment, the conductive material 116 may be dispersed uniformly throughout the polymeric film 114 as shown in
Referring now to
Referring now to
Referring now to
To provide for effective shielding, the electromagnetic shielding material 10 is interposed between a transmitting antenna 54 and a receiving antenna 56. A signal generator 58 outputs an unmodulated sinusoidal RF signal at discrete frequencies into a power amplifier 60. The signal generator 46 is incremented at the discrete frequencies (13.56 MHz) with pre-determined amplitudes fed into the power amplifier 60 and through the transmitting antenna 54. The resulting planewave signal is field-propagated into the electromagnetic shielding material 40. Depending upon the exact configuration of a device into which the electromagnetic shielding material 40 is incorporated, the propagated signal is preferably not received by the receiving antenna 56 attached to an RFID receiving portion 62, which comprises a preamplifier 64 and an analyzer 66 located in a chip.
Referring now to
In addition to the electromagnetic shielding material 40, the security device includes an adjacently-positioned substrate 74. The substrate 74 may be the paper, cardboard, polymer, or other material of the envelope, sleeve, sheath, holder, wallpaper, or the like that contains or shields a smart chip 78 of an RFID system. When the security device 72 is wallpaper, the wallpaper may be backed with vinyl or the like. In any embodiment, the substrate 74 may be incorporated into the structure of another article 82. The article 82 may be a wallet, purse, handbag, pocket protector, article of clothing, suitcase, or computer bag. The article 82 may also be a room or an entire building. Also in any embodiment, the proximity of the electromagnetic shielding material 40 to the smart chip 78 provides effective shielding of the smart chip.
In another embodiment, as shown in
One advantage of the present invention is that personal information encoded into a device readable via RFID (e.g., an RFID smart chip) cannot be read without the authorization of the owner of the personal information. In particular, the proximity of the electromagnetic shielding material to the smart chip causes sufficient interference with the transmission and receiving of a planewave field-propagated signal to negate the ability of a reader to ascertain the information contained in the smart chip. By negating this ability, a person carrying the device into which an RFID smart chip is incorporated (e.g., a passport, an identification card, a credit card, a transit card or a pre-paid pass, a gift card, or the like) is able to feel confident in his ability to thwart the unauthorized reading of his information encoded onto the device. Codes or information cannot be read without the explicit permission of the user.
In embodiments in which the smart chip is in a small device that can be carried by a person (e.g., in the form of a document), the electromagnetic shielding material of the present invention may be in the form of an envelope, a folder, a sleeve, or a similar paper product in which the device having the RFID smart chip can be held. Additionally, or in the alternative, the electromagnetic shielding material may be in sheet form and held in proximity to the smart chip. In any embodiment, the paper of the envelope, folder, sleeve, or the like can be printed, embossed, colored, cut, perforated and/or folded in any configuration. The paper can also be coated or uncoated. Given the lightweight nature of the paper, most papers are suitable for use in the present invention. In embodiments in which the electromagnetic material is used in an envelope or other document holder, a clear or translucent window may be incorporated into the envelope of other document holder to allow documents to be manually read or viewed without being touched.
In embodiments in which the smart chip is in a device that is relatively large or not easily movable, the electromagnetic shielding material of the present invention may be used to shield packaging or even entire rooms. Particularly with regard to computer hard drives, computer media, and other types of electronics, the packaging thereof can be lined with, coated with, or otherwise incorporated with the electromagnetic shielding material. Such packaging includes, but is not limited to, computer cases, disc cases, boxes, and the like. Other packaging may include drums, totes, pallet wrapping devices, cargo containers, and the like. The electromagnetic shielding material may even be in the form of wallpaper or insulation or other paper that can be used to line ceilings and floors.
Referring to
Various arrangements of paper web material, nonbiodegradable polymeric film, and metal (in foil form or incorporated into the polymeric film) were constructed and tested for shielding effectiveness. The results are set forth in the following table.
Although the foregoing examples refer to laminates that do not contain biodegradable polymeric materials as described herein, it will be apparent to those of skill in the art that a paper/plastic laminate and a shielding material can be made using a polymeric film that comprises a biodegradable polymeric material as described herein pursuant to Example 1, and that the resulting shielding material would have substantially the same effectiveness as the samples in Example 2.
The terms “first,” “second,” and the like, herein do not denote any order, quantity, orientation or importance, but rather are used to distinguish one element from another. The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
Although this invention has been shown and described with respect to the detailed embodiments thereof, it will be understood by those of skill in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed in the above detailed description, but that the invention will include all embodiments falling within the scope of the appended claims.
This application is a continuation-in-part of U.S. patent application Ser. No. 11/803,773, filed May 16, 2007.
Number | Date | Country | |
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Parent | 11803773 | May 2007 | US |
Child | 12250606 | US |