DESCRIPTION OF THE PREFERRED EMBODIMENTS
Embodiments of the invention are particularly suitable for marking goods during the manufacturing process and enabling detection/cross-validation of the marks so that the goods are uniquely identified and tracked throughout the stream of commerce. The markings, which preferably contain source information sufficient to enable product authentication, identification, and tracking, are not readily reproducible and/or detectable with commonly available devices.
Although the invention is particularly suitable for marking products and/or product containers, the invention is suitable for marking information on any substrate which would benefit from having such information encoded thereon in a latent format. Thus, the invention is also suitable for marking substrates such as, e.g., collectibles, money, legal documents, tickets, credit cards, etc. Non-limiting examples of materials from which suitable substrates can be made include paper, wood, synthetic polymers and metals.
The substrate is marked with a latent marking agent. The expression latent marking agent denotes a material that emits a detectable signal only after being activated. The expression latent marking agent encompasses invisible inks and pigments. It is particularly preferred that the latent marking agent be activated by electromagnetic radiation (EMR), preferably narrow bandwidth EMR (defined herein as EMR not more than 10 nm in width), more preferably EMR having a bandwidth of 5 nm or less, even more preferably single wavelength EMR. In embodiments, the activation or excitation wavelength is preferably at least 900 nm. In further embodiments, the activation or excitation wavelength is 915 nm to about 990 nm and/or 1550 nm to 1800 nm.
The EMR is preferably provided by a laser. In embodiments, the laser is a component of a detection apparatus dedicated to the task of screening substrates for latent marks of the invention. The apparatus can include features and components generally known to those of ordinary skill in the art. See, example, U.S. Pat. No. 4,540,595. Thus, the system can include a transport means for transporting the items to the reading means, which includes a source of radiation having the appropriate wavelength and intensity. The reading means includes a photodetector which reads the fluorescent emission. If necessary, the system can include optical filters to eliminate or minimize undesired radiation, and any pattern recognition circuitry appropriate to the particular code patterns recorded.
Non-limiting examples of materials suitable for use as latent marking agents include rare earth metals, such as, e.g., europium, dysprosium, samarium or terbium, combined with a chelating agent, such as, e.g., an organic ligand, to form a biketonate, acetonate or salicylate. Additional examples include yttria phosphors, inorganic phosphors, Ciba Geigy Cartax CXDP and UV visible Eccowhite series from Eastern Color and Chemical. The marking agent preferably comprises an inorganic pigment, and in certain embodiments, the marking agent is free of organic dyes. The selection of the marking agent is largely dictated by the desired excitation wavelength and emission wavelength. In certain embodiments, it is preferred that the excitation wavelength be longer than the emission wavelength.
The method for affixing the marking agent to the substrate is not particularly limited. The term affix as used herein is intended to denote a durable (but not necessarily permanent or unremovable) association between the marking agent and the substrate. Preferably, the association between the marking agent and the substrate is sufficiently durable to remain functionally intact through the stream of commerce. The marking agent can be affixed to the substrate directly (e.g., via adsorption and/or absorption) or indirectly (e.g., via an adhesive).
The marking agent is preferably provided in a marking composition. Marking compositions generally comprise a marking agent and a solvent, with the marking agent provided at a concentration of about 2 to about 10 grams/liter of solvent, depending upon the marking agent used. Preferred solvents include methyl ethyl ketone, ethanol and isopropanol. A solvent soluble resin, such as a Lawter resin, can be used if the marking agent is smaller than two microns to avoid precipitation of the marking agent for solution.
The marking compositions can further comprise additives, stabilizers, and other conventional ingredients of inks, toners and the like. In embodiments, various varnishes or additives, such as polyvinyl alcohol, Airvol 203 and/or MM14 (Air Products and Chemicals, Inc., Allentown, Pa.), propylene carbonate, Joncry wax varnishes, and Arcar overprint varnishes, can be added to the marking composition to reduce absorption into the substrate and ensure that the marking agent remains on the surface of the substrate.
Suitable marking means include, e.g., printers, including inkjet, flexographic, gravure and offset printers, pens, stamps, and coaters.
In a particularly preferred embodiment, the marking agent is luminescent pigment Z, K, S, ZH and/or GE (available from Stardust Material, New York, N.Y.), which is dispersed in an aqueous or organic varnish at a 2% to 5% ratio and applied to a substrate via printing or coating. This mark visibly fluoresces when exposed to a specific infrared light range. The illuminated color can vary depending upon the type of pigment utilized.
The illuminated color can also vary when used in conjunction with a colored plastic film or a translucent colored coating or varnish. The colored translucent layer can be printed or laminated on top or under the marking agent. The amounts of possible illuminating colors are virtually endless due to the numerous different translucent colored layers available.
When used in conjunction with the translucent colored layer, one specific marking agent can give virtually endless different illuminating colors, when excited by the appropriate EMR.
In embodiments, a first latent marking agent is adapted to emit a first signal at a first emission wavelength after being irradiated with infrared radiation at a first excitation wavelength, and a second latent marking agent is adapted to emit a second signal at a second emission wavelength after being irradiated with infrared radiation. The infrared radiation which excites the second latent marking agent to fluoresce can be the same as or different from the infrared radiation which excites the first latent marking agent. In either case, the first emission wavelength and the second emission wavelength differ, preferably by at least 5 nm, more preferably by at least 50 nm. These embodiments are useful, e.g., to provide multiple or redundant levels of protection or authentication, wherein authorized users having low-level clearance can detect only the first signal and are not informed of the second signal, whereas users having a higher level clearance are aware of, and can verify the presence of the second signal.
Such a system guards against security breaches from within an organization.
The signal emitted by the latent marking agent is preferably a fluorescent emission. In certain embodiments, the emission wavelength is about 915 nm to about 1800 nm. In certain embodiments, the signal is a fluorescent emission at a visible wavelength.
Thus, products can be authenticated through the stream of commerce by irradiating any marking agent affixed to the product with EMR of a predetermined excitation wavelength and monitoring a predetermined emission wavelength for a signal, confirming the presence of the latent marking agent on the substrate.
In embodiments, the monitoring is accomplished by a detector exclusively tuned to the emission wavelength. The expression exclusively tuned indicates that the detector detects only a narrow band of wavelengths within 5 nm of the emission wavelength.
In certain embodiments, the latent marking agent must be exposed to ultraviolet radiation before it can emit the signal in response to being irradiated with infrared radiation. These embodiments can be useful for a variety of purposes, including demonstrating that a document has been photocopied, since photocopiers expose originals to ultraviolet radiation.
A product package can be marked with a first marking agent designed to emit fluorescent radiation at a first emission wavelength detected by the detector specifically focused on the first emission wavelength.
After a period of time, counterfeiters may figure out how to duplicate the authentication certificate, making it advisable to alter the authentication protocol periodically or after there is a suspicion that the certificate has been compromised. The instant invention provides for such a strategy. For example, the exciting radiation generating means can be replaced or tuned to another wavelength and a different marking agent can be used to provide a signal differing from the compromised signal. If the original marking agent is used along with the updated marking agent, counterfeiters who have compromised the original signal may not realize until it is too late that the original signal has been replaced by an updated signal.
The invention will be illustrated in more detail with reference to the following Examples, but it should be understood that the present invention is not deemed to be limited thereto.
EXAMPLE
Flexographic/Gravure Ink
1. Disperse Stardust Materials Product Z (CAS 68585-88-6) at a ratio of 2% to 5% in a solution of Polyvinyl Alcohol, water and 0.5% to 2% Surfynol 104PG surfactant with standard mixing equipment.
2. Pass mixture through a wet micronizer to reduce the pigment size to between 3 microns to 8 microns.
3. Then wetting agents, dispersing agents and color dyes or pigments (omit if colorless is desired) are added to the mixture.
4. Adjust viscosity by either increasing water content or adding a viscous PVA MM14 additive.
5. Once the mixture has ideal viscosity and suspension of solids, then this mixture or ink is ready to print by standard flexographic/gravure press.
6. Print ink on a white or clear substrate such as paper or film via flexographic/gravure printing press.
To the naked eye, the printed ink will have no noticeable difference than any other ink. When the printed ink is excited at a wavelength of 980 nm, which is delivered by a hand-held laser apparatus, a noticeable color will fluoresce, and when the apparatus is removed, the ink will appear as before. If no colored dye or pigment is added to the ink, the color will be a bright glowing green, with red dye/pigment the color will be a bright glowing light, and with black dye/pigment the color will be green. When the laser apparatus is used in total darkness, the fluorescence will appear brighter. When the same ink is excited at 1550 nm, a different color will fluoresce (in colorless it will appear yellow).
In a further preferred embodiment of the present invention, the following testing was performed: Fifteen percent of inorganic, upconverting pigment with a mean particle size of 2.3 um was dispersed via a high speed mixer during the manufacturing process of flexographic ink, available as Rub & Reveal from Nocopi Technologies, Inc.
The ink has a high solids content (35% to 55%); thus, adding e.g., 15% of an upconverting pigment to the ink would create a very viscous, high solids ink which would provide inadequate printing. In order to make a well-dispersed ink with the appropriate viscosity, the upconverting pigment should be mixed during the making of the ink. The ink contains two components (leucodye and Lewis acid activator); when both are scratched/rubbed together or heat is applied, a color appears. Both components are made separately with a wet micronizer (reduced particle size), and then mixed together, in order to create the final ink. The ratio of Lewis acid activator to leucodye in the ink is about 2:1. Given the upconverting pigment is relatively hard and abrasive, premature color activation can occur if it was dispersed via high sheer mixer into the ink, with both components present. In order to avoid this problem, from about 5-15% upconverting pigment was dispersed via a high speed air mixer with the Lewis acid activator, after it has been wet micronized; the use of about 15% upconverting pigment is particularly preferred. The upconverting pigment does not require particle size reduction; 2.3 um is a suitable size for a flexographic ink. Leucodyes are more sensitive to premature color activation when mixed with hard or abrasive pigment. In the final formula for the ink with upconverting pigment, the ratio of 2:1 Lewis acid activator to leucodye was maintained, and the overall solids content was only increased by about 5%.
The finished ink was then printed successfully with a small web (Mark Andy) flexographic press onto an uncoated, pressure sensitive label stock.
In order to assess finished inks as described above, a hand held 980-nm laser was aimed directly at the printed ink, and a green signal (550 nm to 600 nm) was visible. The printed sample was then scratched with a fingernail, and the ink turned from colorless to red. A 980-nm laser was again directed at the scratched red ink, and a green signal was still present. The two illuminated colors were different in that colors will absorb some of the IR light and the visible color will differ from white or clear to a color-printed sample.
A density measurement was made with a densitometer before scratching, and after scratching the ink. In order to obtain a readable sample, IR light was directed through the pressure sensitive label sample from the opposite side, before and after scratching. This resulted in a lighter illumination of a visible color, but still would allow for the observation of differences.
Results are found in Table I, below:
TABLE I
|
IR 980 nm:IR 980 nm:Scratched Red Color:
No Scratch ColorScratched Red ColorNo IR
|
|
C0.370.410.25
Y0.340.390.23
K0.300.410.33
M0.270.460.36
|
Units in Absolute Density
Key: C CYAN, Y YELLOW, K BLACK, M MAGENTA
From the results noted above, it is apparent that the green color after scratched has a stronger magenta present; (0.27 versus 0.46). A stronger black presence is also shown; (0.30 versus 0.41). Note that if a spectrometer reading were taken comparing the percentage of reflectance to wavelength, a more detailed difference would be observed.
The leucodye in the flexographic ink tested determines the color; in the above example, the leucodye was a red color. Leucodyes are available to produce a variety of colors, such as; red, blue, yellow, green, black, etc. Each leucodye has its own unique color, and it will absorb IR 980 light differently, and provide different visible colors, before and after these colors are scratched. This allows for the use of a myriad of colors from the before and after scratched with directed IR 980 light.
Thus, the final ink contains multiple security features: When exposed to 980 nm or 1550 nm light, the ink gives two different visible responses, and when scratched, the ink gives a visible color change. Furthermore, activated ink (scratched to a color) results in a different (versus not activated) visible response when exposed to 980 nm or 1550 nm. In preferred embodiments, the ink displays differing visible responses before and after rubbing or scratching the substrate containing the ink, when the substrate is exposed to light with wavelengths of e.g., from about 915 to 990 nm or 1550 to 1800 nm.
While the invention has been described in detail and with reference to specific examples thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.