Transaction card
09665815 ยท 2017-05-30
Assignee
Inventors
Cpc classification
B42D25/382
PERFORMING OPERATIONS; TRANSPORTING
Y10S977/773
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
B82Y30/00
PERFORMING OPERATIONS; TRANSPORTING
B42D25/00
PERFORMING OPERATIONS; TRANSPORTING
G06K19/02
PHYSICS
International classification
G06K19/06
PHYSICS
G06K19/02
PHYSICS
B42D25/00
PERFORMING OPERATIONS; TRANSPORTING
B42D25/382
PERFORMING OPERATIONS; TRANSPORTING
C23C14/00
CHEMISTRY; METALLURGY
Abstract
This invention relates to a transparent or translucent transaction card having a base comprising a core of substantially transparent or translucent material with a plurality of coats, including optically recognizable ink comprising one or more infrared blocking dyes and other nanoparticles, such as rare earth nanophosphors and other metal nanoparticles, and/or optically recognizable film comprising nanoparticles, such as rare earth nanophosphors, and other metal oxide and/or non-oxide complexes, and methods for their preparation.
Claims
1. An identification card comprising: a card body adapted to substantially transmit radiation in a visible light wavelength region; card issuer identification information disposed on said card body, card user identification information disposed on said card body, and optionally a graphic image, a design or photograph disposed on or within said card body; said card body comprising an optically recognizable material selected from at least one of an infrared ink and/or an infrared film, wherein said at least one infrared ink comprises at least one infrared blocking dye and the same or different nanoparticles, wherein said at least one infrared film comprises the same or different nanoparticles and other metal oxide and/or non-oxide complexes sputtered on a substrate, wherein said at least one infrared ink and said at least one infrared film block transmission of incident infrared radiation, and wherein said same or different nanoparticles are selected from rare earth nanophosphors comprising a plurality of monodisperse particles having: a single pure crystalline phase of a rare earth-containing lattice, a uniform three-dimensional size, and a uniform polyhedral morphology.
2. The identification card of claim 1, wherein said at least one infrared blocking dye is selected from pthalocyanine dyes, benz[e]indol cyanines, dibutyl amino thpenyl benzenes, and hexa antimonte dyes, and mixtures thereof.
3. The identification card of claim 2, wherein said rare earth nanophosphors are selected from LaF.sub.3, CeF.sub.3, NdF.sub.3, PmF.sub.3, SmF.sub.3, GdF.sub.3, YbF.sub.3 LuF.sub.3, NaGdF.sub.3, Gd.sub.2OS.sub.2, CeO, GdOCl, Y.sub.2O.sub.3, Y.sub.2O.sub.2S:Sm, Y.sub.2O.sub.2S:Yb, YVO.sub.4, Y,Gd.sub.2:O.sub.3:Mg, Y.sub.2O.sub.3:Nd,Ho, Sr.sub.2S:Sm,Er, Gd.sub.2O.sub.3:Yb, and NaYF.sub.4:NdTm, and mixtures thereof.
4. The transaction identification card of claim 1, wherein said at least one infrared blocking dye has infrared absorption peaks ranging from about 800-1000 nm.
5. The identification card of claim 1, wherein said rare earth nanophosphors are selected from LaF.sub.3, CeF.sub.3, NdF.sub.3, PmF.sub.3, SmF.sub.3, GdF.sub.3, YbF.sub.3 LuF.sub.3, NaGdF.sub.3, Gd.sub.2OS.sub.2, CeO, GdOCl, Y.sub.2O.sub.3, Y.sub.2O.sub.2S:Sm, Y.sub.2O.sub.2S:Yb, YVO.sub.4, Y,Gd.sub.2:O.sub.3:Mg, Y.sub.2O.sub.3:Nd,Ho, Sr.sub.2S:Sm,Er, Gd.sub.2O.sub.3:Yb, and NaYF.sub.4:NdTm, and mixtures thereof.
6. The identification card of claim 1, wherein said at least one infrared blocking dye further comprises other metal oxide and/or non-oxide complexes.
7. The transaction identification card of claim 1, wherein said metal oxide and non-oxide complexes are selected from silicon dioxide, strontium titanate, yttrium oxide, magnesium oxide, copper oxide, CaS, LiNbO.sub.3, SrS, SrTiO.sub.3, gadolinium oxide, lithium niobate, sodium yttrium fluoride, neodymium oxide, ytterbium oxide, vanadates, fluorides, chlorides, and garnets, and mixtures thereof.
8. The identification card of claim 1, wherein said at least one infrared film further comprises at least one dopant.
9. The identification card of claim 8, wherein said at least one dopant is selected from niobium pentoxide, silicon dioxide, and gadolinium/yttrium/strontium oxide particles activated with either neodymium, magnesium, holmium, erbium, and samarium, and mixtures thereof.
10. The identification card of claim 1, wherein said card has an optical density less than 0.5 between about 450-750 nm, an optical density greater than 1.3 between about 775-950 nm, and an optical density greater than 1.1 between about 950-1000 nm.
11. The identification card of claim 1, wherein said card has a chromaticity distance of less than 0.005 from the color of a while-light source.
12. The identification card of claim 1, wherein said at least one infrared ink, said at least one infrared film, or mixtures thereof further comprises at least one binder.
13. The identification card of claim 1, wherein said infrared blocking dye and nanoparticle is present in said at least one infrared ink in an amount ranging from about 0.25%-25.0% by weight.
14. The identification card of claim 1, wherein said substrate is a polyethylene substrate.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The following figures, which are described below and which are incorporated in and constitute a part of the specification, illustrate exemplary embodiments according to the invention and are not to be considered limiting of the scope of the invention, for the invention may admit to other equally effective embodiments. The figures are not necessarily to scale, and certain features and certain views of the figures may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.
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DETAILED DESCRIPTION
(19) In general, the present invention allows for the identification and detection of various articles, wherein the articles include materials having optically recognizable (i.e., infrared) inks and/or films. The articles include, for example, transaction cards, documents, papers and/or the like. The materials include, for example, coatings, films, threads, plastics, inks, fibers, paper, planchettes, and/or the like.
(20) In an exemplary embodiment, the optically recognizable inks contain near-infrared blocking (i.e., absorbing, refracting, diffusing, reflecting, or otherwise blocking) ingredients, including infrared dyes and absorbers, and nanoparticles (e.g., RE nanophosphors and other metal nanoparticles). In another exemplary embodiment, the optically recognizable films contain infrared blocking (i.e., absorbing, refracting, diffusing, reflecting, or otherwise blocking) ingredients, including nanoparticles, such as RE nanophosphors and other metal oxide and/or non-oxide complexes, which are, for example, sputtered on a substrate, such as a PET substrate. The optically recognizable inks and films may be invisible, visible, or colored to produce a desired effect and/or they may contain other detectable compounds, such as, for example, UV-Fluorescent or IR-Fluorescent and/or phosphorescent features. The optically recognizable inks and films preferably have good stability, resistance properties, durability, and other physical properties, such as good appearance, flexibility, hardness, solvent resistance, water resistance, corrosion resistance, and exterior stability. Moreover, the use of such inks and films typically does not interfere with UV compounds that may be present in many substrates. The optically recognizable ink comprises any dye, absorber, and/or the like, and RE nanophosphors, the combination of which is recognizable by a sensor. In an exemplary embodiment, the optically recognizable ink is an infrared dye and/or absorber, and RE nanophosphor, which blocks, absorbs, diffuses, refracts, or reflects most infrared light, but transmits most other wavelengths of light. The optically recognizable film comprises nanoparticles, such as the same or different RE nanophosphors and one or more metal oxide and non-oxide complexes, the combination of which is recognizable by a sensor. In an exemplary embodiment, the optically recognizable film is an RE nanophosphor and other metal oxide or non-oxide complex, which blocks, absorbs, or reflects most infrared light, but transmits most other wavelengths of light.
(21) In an exemplary embodiment, the optically recognizable ink is incorporated into a material in the form of a film, plastic, fiber, ink, concentrate, thermoplastic or thermoset matrix, thread, planchette, and/or other medium which contains in the range of about 0.001 to 40.0 wt. % of a compound derived from organic or inorganic materials. The infrared ink may be applied to a transaction card by, for example, a screen printing process or any other printing or coating means such as lithography, gravure, flexo, calendar coating, curtain coating, roller coating, and/or the like. An exemplary screen printing process utilizes a screen press equipped with drying equipment (UV curable or convection heat) and a screen with a specific mesh size of about 80 lines/cm. The optically recognizable ink is printed across any portion of the card surface of plastic using a silk screen press, as described below. The ink may be diluted to any desired amount, for example, 10-150 fold dilution.
(22) In a preferred embodiment, the clear card stack (i.e., the subassembly layers that comprise the completed transaction card) will include (1) a single- or double-sided, vapor-deposited thin film of nanoparticles (e.g., RE metals and other metals and oxide and non-oxide metals) on a PET substrate and (2) a single- or double-pass of commercially-available NIR blocking ink modified with synthesized RE nanophosphor colloidal suspensions (e.g., Sunstone Upconverting Nanocrystals UCP 475, Sunstone Upconverting Nanocrystals UCP 545, Sunstone Upconverting Nanocrystals UCP 538), silk-screened on an inner layer, polyvinyl chloride (PVC) film in the card stack. In other embodiments, one or more layers of the films and/or one or more layers of the inks of the invention may be included in the clear card stack. The invention developed is a flexible thin film optical filter that can be tuned to absorb, reflect, or transmit various wavelengths of light within the visible and infrared spectrum.
(23) IR blocking physical vapor deposition (PVD) film comprises various ratios and combinations of RE and transition metal activators doped into the crystals for the sputtered PET thin films in order to shift the absorption/transmission up or down the electromagnetic spectrum. For some embodiments of the transparent transaction card, dopants with high absorption cross-sections in the NIR region (800-1000 nm) may be utilized. See, e.g., PCT/US11/054593, filed Oct. 3, 2011, the disclosure of which is incorporated herein. Alternating layers of niobium pentoxide (Nb.sub.2O.sub.5), silicon dioxide (SiO.sub.2), and gadolinium/yttrium/strontium oxide particles activated with either neodymium (Nd-1%), magnesium (Mg-2%), holmium (Ho-2%), erbium (Er-0.2%), and samarium (Sm-0.4%) may be sputtered onto the PET substrates. The resultant thin film yields a visibly transparent filter capable of reflecting and absorbing 70-80% of NIR light at 860 nm and 950 nm while still retaining near complete transparency in the visible regions of the electromagnetic spectrum (>98%).
(24) Because the relative eye sensitivity of an ordinary observer for a specified level of illumination is between around 400-770 nm, infrared ink and film at over 770 nm is preferable because it is invisible to the human eye in normal white light. As such, the infrared inks and films will not substantially obscure the transparent surface of the transaction card. For example, in one embodiment, the transparent transaction card should have an optical density of <0.5 between about 450-750 nm. Additionally, the exemplary ink and film withstands card production temperatures of about 200 F. to 450 F. and includes a light fastness period (which is the resistance of the ink and film to fade or degrade in the presence of any light, and specifically, UV light) of about at least three years under normal credit card usage conditions. Moreover, the exemplary ink and film blocks, absorbs, or reflects the spectral output of IRED's, such as, for example, the Sankyo Seiki LED's, which is about 800-1000 nm. In one embodiment, the transparent transaction card should have an optical density of >1.3 between about 775-950 nm, and an optical density of >1.1 between about 950-1000 nm. The exemplary ink also limits the light reaching the phototransistors, so the presence of a clear card having the ink is detected in a transaction machine, such as, for example, a card grabbing-type ATM machine. Furthermore, in another embodiment, the exemplary ink and film should result in a transparent transaction card having an acceptably low color tint, e.g., a chromaticity distance of less than 0.005 from the color of a white-light source. Chromaticity is measured on the CIE chromaticity diagram. The target coordinates for the chromaticity values are centered at 0.522, 0.4169 (halogen white light source) with acceptable deviations in any direction of 0.005.
(25) An approximate quantitative measure of the degree of coloration is the distance of a particular sample's chromaticity coordinates from the lamp source alone. For this reason, it is suitable to define the coloration specification in terms of chromaticity distance. The resulting card should have an acceptably low color tint. Targets for the overall appearance of the card may be based on the final transparency in the visible wavelengths and any apparent color or tinting of the cards was set according to specified chromaticity diagram coordinates, as discussed above.
(26) The inks or films of the invention can be mixed with a binder to form infrared compounds for use in threads, fibers, coatings, and the like. Binders that can be incorporated in the present invention include, but are not limited to, conventional additives such as waxes, thermoplastic resins, thermoset resins, rubbers, natural resins, or synthetic resins. Non-limiting examples of such binders are, polypropylene, nylon, polyester, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyethylene, chlorinated rubber, acrylic, epoxy, butadiene-nitrile, shellac, zein, cellulose, polyurethane, polyvinylbutyrate, vinyl chloride, silicone, polyvinyl alcohol, polyvinyl methyl ether, nitrocellulose, polyamide, bismaleimide, polyimide, epoxy-polyester hybrid, and/or the like. As discussed below, films that can be used as a substrate for the PVD of the metal and non-metal ions include, but are not limited to, PET, PVC, polypropylene, polyethylene, acrylic, polycarbonate, and/or the like. As discussed below, any film can be laminated or adhered to common card articles using heat, adhesives, or a combination of both.
(27) If the content of the optically recognizable ink and/or film is too low, adequate blocking may not be achieved and the phototransistor may not send the proper signal to the capture device, which will mean that the card will not be detected. Therefore, the infrared blocking dyes and nanoparticles in the inks and/or films are usually present in the composition at a total amount from about 1 ppm to 80.0 wt. (%), and preferably from about 0.25%-25.0% by weight. Moreover, the present invention contemplates that other materials such as, for example, UV absorbers, reflectors, antioxidants, and/or optical brighteners, may be added in order to achieve better resistance properties, aesthetics, or longevity of the materials.
(28) Particularly, other materials may be added to allow for color shifts from one color to another color after stimulation. Commonly employed materials such as dyes, pigments, fluorescent dyes, luminous pigments, and/or the like, can be used to promote reversible color changes from one color state to another color state. Such materials can be incorporated directly with the infrared inks and films during initial processing or may be added after the infrared inks and films have been processed. The use of materials such as solvents, water, glycols, and/or the like can be added to adjust rheological properties of the material. Also, the use of surfactants, defoamers, release agents, adhesion promoters, leveling agents, and/or the like may be added to the formulations for improved processing properties. Optical brightening materials may also be added to ensure whiteness in a colorless state and to maintain a low level of contrast between many substrates where infrared inks and films are located.
(29) In an embodiment of the present invention, an infrared ink and/or film may be printed onto one or more layers of a transaction card. The inks of the invention comprise a combination of one or more infrared dyes and other absorbers (i.e., blockers, refractors, reflectors, diffusers, etc.), and the same or different nanoparticles (e.g., RE nanophosphors). The films of the invention comprise nanoparticles, such as RE nanophosphors and other metal oxide and/or non-oxide complexes, which are preferably sputtered on a substrate (e.g., PET).
(30) The infrared dye or absorber utilized in the inks possess high spectral coverage from 800-1000 nm, blocking at least about 97% of infrared light in that region. Exemplary infrared dyes and absorbers include, but are not limited to, pthalocyanine dyes, benz[e]indol cyanines, dibutyl amino thpenyl benzenes, hexa antimonte dyes, and the like, available commercially from HW Sands, Adams Gate Company, Epolin, Avecia. The dyes can be found commercially under the following commercial names MSA4800, MSB4833, and MSD3600 from HW Sands, EPOLIGHT 4148 from Epolin, Inc., and IR Dye 5630 from Adam Gates Company. One of skill in the art would recognize that any infrared dye or absorber having infrared absorption peaks from 800-1000 nm may be utilized to provide a broad range of infrared absorption in the invention. Preferably, one or more infrared dyes and/or absorbers having infrared absorption peaks at 850 nm and 1000 nm are utilized. A combination of two or more dyes and absorbers are preferably used. Moreover, the dyes and other absorbers (nanoparticles) of the present invention may be present in an amount between about 0.0001 wt. % and about 20 wt. %, either alone or in combination, depending on the desired transparency and chromaticity in the visible region.
(31) The infrared inks further comprise nanoparticles (e.g., RE nanophosphors and other metal nanoparticles). The RE activated crystal absorbers that may be used in the ink include, but are not limited to, LaF.sub.3, CeF.sub.3, NdF.sub.3, PmF.sub.3, SmF.sub.3, GdF.sub.3, YbF.sub.3LuF.sub.3, NaGdF.sub.3, Gd.sub.2OS.sub.2, CeO, GdOCl, Y.sub.2O.sub.3, Y.sub.2O.sub.2S:Sm, Y.sub.2O.sub.2S:Yb, YVO.sub.4, Y,Gd.sub.2:O.sub.3:Mg, Y.sub.2O.sub.3:Nd,Ho, Sr.sub.2S:Sm,Er, Gd.sub.2O.sub.3:Yb, and NaYF.sub.4:NdTm. PCT/US11/054593, filed Oct. 3, 2011, the disclosure of which is incorporated herein, discloses preferable RE nanophosphors that may be used in inks of the invention. PCT/US11/054593 also discloses methods for making the preferable RE nanophosphors. The RE nanophosphors disclosed in PCT/US11/054593 have high degrees of tunability over various parameters, such as optical signatures (absorption/emission), morphology, and size. Preferable RE nanophosphors include, but are not limited to, a plurality of monodisperse particles having: a single pure crystalline phase of a rare earth-containing lattice, a uniform three-dimensional size, and a uniform polyhedral morphology. Various compositions of RE nanophosphors and other metal composite crystal absorbers may be utilized in the present invention to enhance the optical density in the NIR regions from 775-1000 nm. The RE nanophosphors of the invention provide for broad absorption in the NIR (see
(32) Table 1 describes exemplary nanoparticles (e.g., RE nanophosphors and other metal nanoparticles (e.g., MgO, CuO)) and their chemical compositions. Besides enhancing the optical density in the NIR regions from 775-1000 nm, the crystal absorbers may also be incorporated as a forensic tag, for example, for identification of manufactured materials to ensure authenticity of the product as well as overall quality and function (see, e.g., Table 1). When the crystal absorbers are excited under UV light, a unique spectral peak arising at 1.5 microns can be observed utilizing NIR spectroscopy. The RE nanophosphors may be present in the inks in an amount between about 0.01 wt. % and about 5 wt. %, and may be used either alone or in combination. Depending on the type of tinting needed, various levels of transparency and chromaticity may be obtained by adjusting the types and/or amounts of the components in the ink composition.
(33) TABLE-US-00001 TABLE 1 Rare Earth/Other Metal crystals Combined in various ratios for enhancement of NIR Blocking Inks Std Name Formula Avg. Size Function Strontium Titanate SrTiO.sub.3 200 nm NIR Blocker Lithium Niobate LiNbO.sub.3 200 nm NIR Blocker Yttrium, Gadolinium Y,Gd.sub.2:O.sub.3:Mg 100 nm NIR Blocker Magnesium Oxide Magnesium Oxide MgO 150 nm NIR Blocker Yttrium Oxide Y.sub.2O.sub.3:Nd,Ho 200 nm NIR Blocker Strontium Sulfide Sr.sub.2S:Sm,Er 200 nm Forensic Gadolinium Oxide Gd.sub.2O.sub.3:Yb 200 nm Forensic Sodium Yttrium Fluoride NaYF.sub.4:NdTm 250 nm NIR Blocker
(34) In another embodiment of the present invention, in addition to or alternatively to the infrared ink, discussed above, an optically recognizable film may be printed onto one or more layers of a transaction card. The optically recognizable film comprises infrared blocking ingredients, including nanoparticles, such as the same or different RE nanophosphors, discussed above for the ink composition, and other metal oxide and/or non-oxide complexes (e.g., vanadates, fluorides, chlorides, garnets, etc.), which are preferably sputtered on a substrate (e.g., PET). Exemplary films that can be used as a substrate for the PVD of the metal and non-metal ions include, but are not limited to, PET, PVC, polypropylene, polyethylene, acrylic, polycarbonate, and/or the like.
(35) The films of the invention comprise RE-activated crystal absorbers, including, for example, the same nanoparticles and RE nanophosphors described above for the ink composition (see, e.g., PCT/US11/054593). The RE nanophosphors and other metal nanoparticles may be present in the films in an amount between about 0.01 wt. % and about 5 wt. %, and may be used either alone or in combination.
(36) The films of the invention also comprise other metal oxide and non-oxide complexes. The metal oxide and non-oxide complexes include, but are not limited to, silicon dioxide, strontium titanate, yttrium oxide, magnesium oxide, copper oxide, gadolinium oxide, lithium niobate, sodium yttrium fluoride, neodymium oxide, ytterbium oxide, vanadates, fluorides, chlorides, and garnets. See, e.g., PCT/US11/054593.
(37) In an embodiment of the invention, a multilayer sputtering technique utilizing nanoparticles (e.g., RE nanophosphors) and other metal oxide and non-oxide complexes on flexible substrates (e.g., PET, PVC) may be utilized. The number of layers in the coating may range from a single thin film layer for simple antireflection or barrier coatings to multilayer stacks of thin films having numerous coatings for applications such as the blocking of infrared and transmission of visible light. As with substrate materials, the coating materials and the physical and optical thicknesses are selected to attain the desired optical properties, although the chemical and physical properties of the thin films may be a concern. Composition and microstructure-dependent properties such as mechanical stress, moisture content, crystallization, and surface morphology of the thin films may affect the reliability and performance of the material. For example, crystallization can cause stress-induced cracking and rough morphology resulting in optical scattering and loss of mechanical and optical integrity of the coatings. Preferably, a thin film optical coating capable of blocking infrared while still limiting the visible light scatter occurs during the initial synthesis of the RE and other metal oxide and non-oxide complexes. Preferably, nanoparticles of high uniformity and monodispersity with narrow size distributions may be used. To this effect, nanoparticle synthesis procedures capable of producing highly uniform optically active metal oxides and halides for incorporating into PVD Sputtering of thin films may be used.
(38) Sputtering produces very high quality coatings, and can be done over very large areas (e.g., targets can be 6-10 feet long). It is used for architectural glass, electronics, and, more recently, tools and decorative finishes (watchstraps, bezels, automotive lights, pens, etc.). Sputtered coatings are generally high quality (although they may contain trapped particles similar to macroparticles). Sputtering can be done at low temperatures (although close process control and good cleaning may be required), and almost any material can be sputtered, including complex materials (such as hydroxyapatitebone) that can be RF (radio frequency) sputtered. Traditionally, sputtering has always been the slowest deposition method, but High Rate Reactive Sputtering (HRRS) has improved deposition rates (although not to the speed of evaporation). In order to sputter coatings reactively at high rates, good control of the partial pressure of the active gas to prevent its poisoning the cathode, which reduces the deposition rate by an order of magnitude, should be kept. (Oxide coatings may be especially difficult in this respect.) The process may be controlled by partial pressure monitoring with closed loop feedback control, which may be an additional complication. For high volume production, the cost of sputter targets is the primary cost factor in the process, and difficulties in obtaining sufficiently strong targets of brittle materials such as chrome may be encountered.
(39) Other methods known to those of skill in the art may be used to sputter the nanoparticles (e.g., RE nanophosphors) and other metal oxide and non-oxide complexes on flexible substrates, including, for example, evaporation (e.g., ion plating, e-beam PVD, hollow cathode), other sputtering methods (e.g., balanced magnetron, unbalanced magnetron (UBM), DC, RF), arc (e.g., cathodic, anodic, random, steered, confined, ducted), and ion-assisted (e.g., sputtering evaporation, ion sputtering, metamode).
(40) Sputtering of RE and Metal Thin Films on PET
(41) The three major commercial hard coating technologies all draw their ions from a plasma formed in the gas in the chamber (which is usually at a pressure of a few millitorr). Most hard coatings are compounds that are deposited reactively, by combining the metal with active gas (N or C) at the surface of the growing coating.
(42) Evaporation PVD (Ion Plating)
(43) This technique has proven to yield the greatest success and best functioning IR blocking films. The highest quality coatings are produced by the electron beam evaporation methods. The major advantages of this method are its high quality and the low cost of evaporation materials.
(44) The inks and films described above may be combined together with binders, resins, catalysts, and other compounds useful for creating an ink from the materials. Preferably, solvent may be utilized, including preferably, 2-ethoxy-ethyl propionate, ethyl acetate, n-propyl acetate, ethyl alcohol, n-propanol, and methyl ethyl ketone. The solvent may be present in an amount between about 5 wt. % and about 60 wt. %. Moreover, the infrared dyes and/or absorbers may be loaded in a liquid vehicle, at approximately 1% loading. An exemplary water-based liquid vehicle used is Sericol Mixing Clear. Other solvent based liquid vehicles can be obtained commercially from Sericol as well as Apollo Colour and HW Sands. Resins useful for the present invention include VMCH, VMCA, polyamide, polyester, linseed alkyl resins and acrylic, and may be present in an amount between about 8 wt. % and about 35 wt. %. A silane-type catalyst may be used to help bond the infrared dye and/or absorber to the resin. Specifically, the silane-type catalyst may be used to ring-open the infrared dye and/or absorber molecule and help the molecule bind to the resin, such as, for example, acrylic. A preferable silane-type catalyst includes 3-amino-propyl triethoxy silane, although the present invention should not be limited, as stated herein. The silane-type catalyst may be present in an amount between about 0.005 wt. % and about 2.00 wt. %. Most preferably, the silane-type catalyst is present at about 500 ppm.
(45) The infrared inks and films of the invention may be printed on one or more layers of a transaction card by methods known to those of skill in the art. The printing method is typically chosen based on the composition of the various formulations outlined above. Various printing methods may preferably include gravure, silkscreen, and lithographic processes, although ink-jet, roll-coating, and flexographic methods may be utilized as well. The infrared inks, infrared films, and/or substrates of the exemplary embodiments and their placement and thickness can vary to accommodate different types of core substrates and thicknesses thereof. In addition, PVC is preferably utilized as a printable substrate. However, other substrates such as PETG, polycarbonate, and PET may be utilized provided there are at least slight differences in refractive index between the infrared ink, infrared film, and the substrate.
(46) The present invention allows for the easy production of IR-blocking and/or absorbing transaction cards without adhesives and/or subassemblies. For example,
(47) The transaction card shown in
(48) As discussed above, various compositions of RE and other metal composite crystal may be utilized to enhance the optical density in the NIR regions from 775-1000 nm. Table 1 above describes the various crystal and their chemical compositions. Additionally, one crystal composition is incorporated as a forensic tag for identification of our manufactured materials to ensure authenticity of the product as well as overall quality and function. When the material is excited under UV light a unique spectral peak arising at 1.5 microns can be observed utilizing NIR spectroscopy.
(49) The printed adhesive layers A preferably comprise polyester-based adhesive. Specifically, a preferable material that may be used as the polyester-based adhesive is Bemis Associates Inc. 5250 Adhesive Film. Alternatively, another preferably material that may be used as the polyester-based adhesive is Transilwrap Company, Inc. Trans-Kote Core Stock KRTY.
(50) After placing the layers of the transaction card shown in
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(52) After placing the layers of the transaction card shown in
(53) After the card sheets in
(54) In a further embodiment of the present invention, fibers of various materials are used either in a continuous manner or single fibers can be incorporated into a wide variety of materials. The present invention contemplates, for example, natural fibers, synthetic fibers, copolymer fibers, chemical fibers, metal fibers, and/or the like. Examples of these fibers may be nylon, polyester, cotton, wool, silk, casein fiber, protein fiber, acetalyated staple, ethyl cellulose, polyvinylidene chloride, polyurethane, acetate, polyvinyl alcohol, triacetate, glass, wood, rock wool, carbon, inorganic fibers, and/or the like. Such fibers can be incorporated or mixed into other types of materials such as paper pulp, plastic label stock, plastic materials, and the like. Such materials can be used alone in a continuous manner or can be used as mono- or di-filaments in other materials.
(55) Moreover, the infrared inks and films that are incorporated into plastics can be used with a wide variety of materials, such as, for example, nylon, acrylic, epoxy, polyester, bismaleimide, polyamide, polyimide, styrene, silicone, vinyl, ABS, polycarbonate, nitrile, and/or the like. As such, the compounds that are incorporated into fibers, plastics, film and/or the like, may be processed directly to a suitable form in a single- or multi-process application. Such infrared inks and films can be added into a formulation in the form of a single ingredient or in the form of a master-batch that is then processed in a similar manner to normal processing operations of compounds. Processing of such compounds includes the use of continuous mixers, two- or three-roll mills, extrusion, and/or other melt-compounding methods of dispersion. While in an exemplary embodiment, the thread can be woven or non-woven, the infrared materials may be extruded directly into a thermoplastic matrix and drawn directly into the form of a thread that can be used in a continuous manner or sectioned in the form of a fiber or plastic film.
(56) The exemplary infrared inks and films are deposited onto films of various compositions and can be used in most card applications. Moreover, the infrared inks and films in accordance with the present invention can be used alone or blended with other materials at ranges from 0.001 to 50.0 parts by weight, but most preferable from 1.0 to 15.0 parts by weight.
(57) In a further exemplary embodiment, the optically recognizable inks and films block light which is detectable by machines. More particularly, the machines suitably detect the presence of a card via infrared interference at one or several wavelengths. In an exemplary embodiment, detection of materials may include the production of a visual effect when the materials are interrogated with invisible infrared radiation from the proper instrument, and when such radiation contacts the infrared material, a visual effect, such as a colored light, can be seen. Alternatively, the materials may be detected by a remote detector that will indicate the presence of the materials. Detection or authentication of the materials occurs above and below the stimulation wavelength of the reading device. As such, once the optically recognizable ink or film has been detected, the detection device may then provide the user with a positive identification signal, which is preferably located on or near the detection device.
(58) In an exemplary embodiment, the detection of infrared materials triggers the sensors in ATM machines. In particular, the present invention allows for the passage of a greater percentage of visible light (from about 400-700 nm), which allows the card to appear transparent or translucent in nature, while allowing for the blockage of certain light (from about 700 nm and above) to allow the phototransistors in ATM's to detect that a card has been inserted into the carriage mechanism. As discussed above, an exemplary ATM sensing device includes an IRED, a filter, and a phototransmitter.
(59) In addition to triggering the sensors in ATM machines, translucent or transparent transaction cards of the invention can be used with any magnetic stripe or smart card reader. The reader system can include a card reader/writer, a point-of-sale terminal, ATM, or any other acceptance device. In an exemplary embodiment, a transaction card of the invention is used in conjunction with a reader which, not only detects the existence of the card, but also illuminates the transparent portion of the transaction card when the card is inserted into the reader. The illumination source can be either an incandescent or solid state source (infrared emitting diode or laser). In operation, when the card is inserted into the acceptance device, the edge of the card presses against the illumination assembly (or activates a switch, interrupts a beam, etc.). Depending upon the application of the card, the illumination source can be under the control of the acceptance device or external software. Thus, the illumination source can flash or display a particular color if directed by the external software program. Additionally, depending on the structure of the card, the illumination source could be used to excite an embedded design useful for security or product enhancement.
(60) The present invention will now be illustrated in greater detail with reference to the following examples, comparative examples, test examples, and use examples. As disclosed in the examples, tests and graphs herein, the resulting inks sufficiently block IR radiation from phototransistor detection. It is understood that the present invention is not limited thereto. For example, one skilled in the art will appreciate that, in any of the examples, the ink may contain other materials for different optical effects or authentication purposes.
EXAMPLES
Ink Formulation Preparation
(61) For the examples described herein, specially designed ratios of IR absorbing inks and RE nanophosphors were evaluated for effectiveness and overall aesthetic appeal. The RE nanophosphors were synthesized via thermal decomposition in a high temperature salt bath. The RE nanophosphors were prepared using the methods disclosed in PCT/US11/054593. 2.6 mmol of niobium acetate was weighed and dissolved in a 1:1 ratio of 1-octadecene (ODE) and oleic acid (OA) in a 100 ml, 3-neck flask. The mixture was heated at 110 C. under vacuum for 45-60 min until a clear solution was obtained. The solution was then transferred to a molten salt bath, maintained at a steady temperature of 341-343 C. for the entirety of the reaction, while purging with N.sub.2 gas. The solution reacted for 45 min while stirred. Upon completion of the 45 min reaction, the flask was removed from the salt bath and the solution was quenched with room temperature ODE.
(62) The particles were precipitated with a hexane/acetone solution (1:1) and centrifuged at 8300 rpm for 3 min. The collected particles were washed once more with hexane/acetone and re-suspended in water.
(63) The examples sought to identify preferable compositions giving sufficient blocking in the infrared regions while still maintaining an overall transparent appearance with a slight hue within the acceptable aesthetic limits of visible transparency and chromaticity. The required specifications are described below:
(64) Specifications: The optical properties of the solution meet the ISO specifications only for wavelengths from 775-1000 nm. Visible Transparency: The resulting card has an optical density of <0.5 in the wavelength range from 450-750 nm. Color Tint: The resulting card has a low color tint, which can be further optimized to reduce the tinting or adjust the hue. NIR Opacity: The resulting card possesses optical density of >1.3 in the wavelength range from 775-950 nm, and an optical density of >1.1 in the wavelength grange from 950-1000 nm. *all commercial IR absorber ink ratios used are listed as follows: H.W. Sands: Amer. Dye: Adam's Gate
(65) Film PreparationSynthesis of Thin Film PVD of Oxide Precursors
(66) Conventional PVD and Direct Current (DC) sputtering was used for depositing SiO and other conductive layers, while pulse-modulated DC technique was used for depositing Nb.sub.2O.sub.5, RE.sub.2O.sub.3, and other insulating layers. PET films (9-mil in thickness) were purchased pre-coated with acrylic anti-abrasion layer and used as substrates. The PET film substrate was placed on a glass plate and adhered to the plate using polyimide tape. An RF electrode was located in the back side of the glass plate. Before the sputter deposition, RF plasma treatment was carried out in different gas atmospheres. Argon and nitrogen as well as oxygen gas were introduced into the chamber through mass flow controllers. The gas composition and treatment time were varied and the effects on the adhesion strength were monitored.
(67) The underlying layer was deposited on the plasma-treated film substrate in order to improve the adhesion of the inorganic layer (SiO) on the organic substrate. After these pre-treatments, the metal oxide layers were sputter deposited on the PET substrate.
(68) Optical properties of the samples were measured by an Ocean Optics spectrophotometer (USB6000). Additional layers of the IR reflection coating were sputtered and re-read on the spectrophotometer until the infrared blocking reached 90%.
(69) RE oxides and Niobium and Silicon oxides were prepared via thermal decomposition route (see, e.g., PCT/US11/054593). Alternating layers of niobium pentoxide (Nb.sub.2O.sub.5) and various RE oxides (RE.sub.2O.sub.3) are applied using the Ulvac ULDis Meta Mode 3000. The combination of the electron Hall current confinement and the central ion flow creates a dense plasma with charged particle densities approaching 10.sup.12 charged particles per cm.sup.3. Each layer was determined to be approximately 50-100 nm thick, measured using UV-Vis spectroscopy. A sputtering temperature of 90 C. was maintained throughout the entire coating process for each layer. The flow rate of the metal oxide IR blockers was set at 50-sccm (Std. Cubic Centimeters/Min). A base layer of Silicon oxide is sputtered onto the PET surface to achieve optimum adhesion of the metal ions. The final, multilayer thin film coating was sputtered on 5-mil PET substrate using the Ulvac ULDis Meta Mode yielding a total thickness of 9-mil. Additionally, a separate layer of binding adhesive was screen printed on the opposite surface of the optical barrier coating for future incorporation into the pre-designed card stack and lamination.
(70) TABLE-US-00002 TABLE 2 IR Blocking Example Solution (Ink/Film) (Oberthur*) Visible Tint 1 Ink 6.8 yellow/grey (faint) 2 Ink 5.8 yellow/grey (dark) 3 Ink 6.0 grey (faint) 4 Ink 6.8 blue/grey (faint) 5 Ink 6.3 grey 6 Ink 6.4 yellow/grey 7 Ink 5.4 grey 8 Ink 4.6 blue (dark) 9 Ink 4.6 blue 10 Ink 2.7 blue (faint) 11 Ink 4.5 clear/grey 12 Film 6.2 clear 13 Film 6.0 clear 14 Film 5.9 clear 15 Film 6.0 clear 16 Film 5.4 clear/grey 17 Film 8.0 clear 18 Film 6.0 clear *IR ISO specifications met if Oberthur reading <6.2
Example 1
Silk Screen Ink (65% Nanophosphor Loading/Ink Absorber Ratio 5:1:1)
(71) A single pass coating of IR absorber ink was applied to the PVC inner layer. The sample was near infrared absorption/blocking specification; however, there was a significant yellow tint to the card. See
(72) Oberthur IR Spectrometer Readout of Example 1 (Pass6.0, 94% Blocking in the IR)6.8
Example 2
Silk Screen Ink (65% Nanophosphor Loading/Ink Absorber Ratio 6:2:1)
(73) A single pass coating of infrared absorber ink was applied to the PVC inner layer. The sample was at infrared absorption/blocking specification; however, there was a significant tint to the card not meeting ISO specifications. See
(74) Oberthur IR Spectrometer Readout5.8
Example 3
Silk Screen Ink (65% Nanophosphor Loading/Ink Absorber Ratio 5:2:1)
(75) A single pass coating of infrared absorber ink was applied to the PVC inner layer. The coating met the infrared absorption/blocking specification, but there was a slight grey tint to the card. See
(76) Oberthur IR Spectrometer Readout6.0
Example 4
Silk Screen Ink (65% Phosphor Loading/Absorber Ratio 4.0:1:1)
(77) A double pass coating of infrared absorber ink was applied to both sides of the PVC inner layer. The visible tint to the card was decreased, but the infrared blocking was also decreased. See
(78) Oberthur IR Spectrometer Readout6.8
Example 5
Silk Screen Ink (65% Phosphor Loading/Absorber Ratio 4.0:1:1)
(79) A single pass coating of infrared absorber ink was applied to both sides of the PVC inner layer. The visible tint to the card was decreased, but the infrared blocking was borderline for meeting the infrared specification. See
(80) Oberthur IR Spectrometer Readout6.3
Example 6
Silk Screen Ink (40% Phosphor Loading/Absorber Ratio 5.5:1:1)
(81) A single pass coating of infrared absorber ink was applied to the PVC inner layer. The visible tint to the card was decreased substantially but the infrared blocking fell below the acceptable limit. See
(82) Oberthur IR Spectrometer Readout6.4
Example 7
Silk Screen Ink (30% Phosphor Loading/Absorber Ratio 5.5:1:1)
(83) A single layer of infrared absorber was applied to both sides of the inner PVC layer. An increase in infrared blocking and slight decrease in visible transparency was observed. See
(84) Oberthur IR Spectrometer Readout5.4
Example 8
Silk Screen Ink (30% Phosphor Loading/Absorber Ratio 4:1:1)
(85) Three coatings of infrared absorber ink were incorporated into the card stack, two inner layer PVC films were utilized, one with both sides coated and a single coating on a second PVC film. There was an increase in infrared blocking to the required specifications; however, the cards possessed a cloudy appearance due to the triple coatings. See
(86) Oberthur IR Spectrometer Readout4.6
Example 9
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1:1)
(87) A layer of infrared absorber was applied to both sides of the inner PVC layer. Overall improvement in both the infrared blocking as well as the transparency of the card was observed; however, a blue tint was still present. See
(88) Oberthur IR Spectrometer Readout4.6
Example 10
Silk Screen Ink (40% Phosphor Loading/Absorber Ratio 5.5:1)
(89) Increased concentration of the Phosphor based absorber in silkscreen ink by 10% and included 10% doping of additional RE compounds (Ytterbium, Samarium) for total IR blocker concentration of 40%. A layer of infrared absorber was applied to both sides of the inner PVC layer. There was a slight improvement in infrared blocking; however, the transparency in the visible region was degraded. See
(90) Oberthur IR Spectrometer Readout2.7
Example 11
Silk Screen Ink (40% Phosphor Loading/Absorber Ratio 4.5:1:1)
(91) Increased concentration of the RE absorber in silk screen ink by 10% and increased Ytterbium Phosphor absorbers by 10% from previous run. A layer of infrared absorber was applied to both sides of the inner PVC layer. An overall improvement in both the infrared blocking as well as the transparency of the card meeting the ISO specifications for infrared blocking and visible transparency was observed. See
(92) Oberthur IR Spectrometer Readout4.5
(93) IR Blocking Film and Ink
Example 12
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PET Film
(94) A second and separate thin film layer of Nb/Ta absorbers vapor deposited on PET film was added into the card stack. A layer of infrared absorber phosphor-based ink was applied to both sides of the inner PVC layer. There was a slight decrease in infrared blocking from previous run; however, the overall transparency in the visible region clearly met specification.
(95) Oberthur IR Spectrometer Readout6.2
Example 13
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PET Film
(96) Two thin films of Nb/Ta absorbers vapor deposited on PET film were added into the card stack. A separate coating of infrared absorber phosphor-based ink was applied to one side of the inner PVC layer. Cards did not laminate and no bonding was observed. An additional layer of outer laminate with adhesive was required to utilize the two sheets of Nb/Ta PET film.
(97) Oberthur IR Spectrometer Readout6.0
Example 14
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PET Film
(98) Two thin films of Nb/Ta absorbers vapor deposited on PET film were added into the card stack with adhesive on both sides of the two films. The A layer of infrared absorber phosphor-based ink was applied to both sides of the inner PVC layer. Bonding was successful and cards passed required bond tests. An additional layer of outer laminate with adhesive was incorporated into the card stack on opposite sides of the PET layer. Infrared blocking specifications were achieved. The transparency was of acceptable tinting, but further optimization was performed to enhance the transparency.
(99) Oberthur IR Spectrometer Readout5.9
Example 15
Silk Screen Ink (10% Phosphor Loading/Absorber Ratio 7:1:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PET Film
(100) Two thin films of Nb/Ta absorbers vapor deposited on PET film were added into the card stack with adhesive on both sides of the two films. A layer of infrared absorber phosphor-based ink at 10% was applied to one side of the inner PVC layer. Bonding was successful and cards passed required bond tests. An additional layer of outer laminate with adhesive was incorporated into the card stack on opposite sides of the PET layer. Infrared blocking specifications were achieved and the transparency in the visible regions met specifications.
(101) Oberthur IR Spectrometer Readout6.0
Example 16
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PET Film
(102) Two thin films of Nb/Ta absorbers vapor deposited on PET film were added into the card stack with adhesive on both sides of the two films. A layer of infrared absorber phosphor-based ink was applied to both sides of the inner PVC layer. Bonding was successful and cards passed required bond tests. An additional layer of outer laminate with adhesive was incorporated into the card stack on opposite sides of the PET layer. Infrared blocking specifications were acceptable; however, the tinting still needed to be decreased.
(103) Oberthur IR Spectrometer Readout5.4
Example 17
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PVC Film
(104) Two thin films of Nb/Ta absorbers vapor deposited on PVC film were added into the card stack with adhesive on both sides of the two films. A layer of infrared absorber phosphor-based ink was applied to both sides of the inner PVC layer. Bonding was successful and cards passed required bond tests. An additional layer of outer laminate with adhesive was incorporated into the card stack on opposite sides of the PVC layer. Infrared blocking specifications were below specification. See
(105) Oberthur IR Spectrometer Readout8.0
Example 18
Silk Screen Ink (20% Phosphor Loading/Absorber Ratio 5.5:1:1)+Niobium/Tantalum IR-Blockers Vapor Deposited on PET Film
(106) Two thin films of Nb/Ta absorbers vapor deposited on PET film were added into the card stack with adhesive on both sides of the two films. A layer of infrared absorber phosphor-based ink was applied to both sides of the inner PVC layer. Bonding was successful and cards passed required bond tests. An additional layer of outer laminate with adhesive was incorporated into the card stack on opposite sides of the PVC layer. Infrared blocking specifications were below specification.
(107) Oberthur IR Spectrometer Readout6.0
(108) The present invention has been described above with reference to exemplary embodiments. However, those skilled in the art having read this disclosure will recognize that changes and modifications may be made to the exemplary embodiments without departing from the scope of the present invention. These and other changes or modifications are intended to be included within the scope of the present invention, as expressed in the following claims.