WO2007068886A1 - Secure tag - Google Patents
Secure tag Download PDFInfo
- Publication number
- WO2007068886A1 WO2007068886A1 PCT/GB2006/004516 GB2006004516W WO2007068886A1 WO 2007068886 A1 WO2007068886 A1 WO 2007068886A1 GB 2006004516 W GB2006004516 W GB 2006004516W WO 2007068886 A1 WO2007068886 A1 WO 2007068886A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- secure tag
- carrier
- rare earth
- secure
- doped
- Prior art date
Links
- 230000005284 excitation Effects 0.000 claims abstract description 32
- 230000005855 radiation Effects 0.000 claims abstract description 28
- 230000004888 barrier function Effects 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 21
- -1 rare earth ions Chemical class 0.000 claims abstract description 19
- 230000000903 blocking effect Effects 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000000996 additive effect Effects 0.000 claims description 12
- 230000007704 transition Effects 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 239000004615 ingredient Substances 0.000 claims description 6
- 238000001228 spectrum Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 230000004044 response Effects 0.000 abstract description 8
- 239000002245 particle Substances 0.000 description 15
- 238000004020 luminiscence type Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910011255 B2O3 Inorganic materials 0.000 description 5
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229920001721 polyimide Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910016644 EuCl3 Inorganic materials 0.000 description 3
- 229910052693 Europium Inorganic materials 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 239000005388 borosilicate glass Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 3
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 230000000475 sunscreen effect Effects 0.000 description 3
- 239000000516 sunscreening agent Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MEZZCSHVIGVWFI-UHFFFAOYSA-N 2,2'-Dihydroxy-4-methoxybenzophenone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1O MEZZCSHVIGVWFI-UHFFFAOYSA-N 0.000 description 1
- WSSJONWNBBTCMG-UHFFFAOYSA-N 2-hydroxybenzoic acid (3,3,5-trimethylcyclohexyl) ester Chemical compound C1C(C)(C)CC(C)CC1OC(=O)C1=CC=CC=C1O WSSJONWNBBTCMG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- WYWZRNAHINYAEF-UHFFFAOYSA-N Padimate O Chemical compound CCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 WYWZRNAHINYAEF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 description 1
- 229960005193 avobenzone Drugs 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N cinnamic acid Chemical class OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- CMDKPGRTAQVGFQ-RMKNXTFCSA-N cinoxate Chemical compound CCOCCOC(=O)\C=C\C1=CC=C(OC)C=C1 CMDKPGRTAQVGFQ-RMKNXTFCSA-N 0.000 description 1
- 229960001063 cinoxate Drugs 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 229960004960 dioxybenzone Drugs 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 229960004881 homosalate Drugs 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 238000001748 luminescence spectrum Methods 0.000 description 1
- SOXAGEOHPCXXIO-DVOMOZLQSA-N menthyl anthranilate Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1OC(=O)C1=CC=CC=C1N SOXAGEOHPCXXIO-DVOMOZLQSA-N 0.000 description 1
- 229960002248 meradimate Drugs 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical group C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 229960000601 octocrylene Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 229960001173 oxybenzone Drugs 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- CXVGEDCSTKKODG-UHFFFAOYSA-N sulisobenzone Chemical compound C1=C(S(O)(=O)=O)C(OC)=CC(O)=C1C(=O)C1=CC=CC=C1 CXVGEDCSTKKODG-UHFFFAOYSA-N 0.000 description 1
- 229960000368 sulisobenzone Drugs 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
-
- G—PHYSICS
- G07—CHECKING-DEVICES
- G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
- G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
- G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
- G07D7/12—Visible light, infrared or ultraviolet radiation
- G07D7/1205—Testing spectral properties
-
- Y—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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
-
- Y—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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
Definitions
- the present invention relates to improvements in or relating to a secure tag.
- Secure tags are used for a number of different purposes. One of the primary uses of a secure tag is to prevent counterfeiting.
- One type of secure tag that has recently been developed is based on small particles of a rare earth doped host, such as glass. This type of secure tag is described in US patent application number 2004/0262547, entitled “Security Labelling," and US patent application number 2005/0143249, entitled “Security Labels which are Difficult to Counterfeit”.
- These rare earth doped particles (hereinafter "RE particles”) can be applied to valuable items in different ways.
- the secure tags can be incorporated in fluids which are applied (by printing, spraying, painting, or such like) to valuable items, or incorporated directly into a substrate (paper, rag, plastic, or such like) of the valuable items.
- RE particles In response to suitable excitation, RE particles produce a luminescence spectrum having narrow peaks because of the atomic (rather than molecular) transitions involved.
- Known readers for RE particles include (i) a suitable excitation source to stimulate transitions in the secure tag, and (ii) a detector to measure the luminescence emitted in response to the excitation.
- the suitable excitation source may be tuned (in the sense that the excitation is selected to optimize luminescence from one or more transitions in the rare earth ions), or high frequency (to stimulate all, or at least many, transitions in the rare earth ions and the host) .
- Tuned excitation is usually achieved using a narrowband source, such as an LED, in the visible region of the
- High frequency excitation may be achieved using a broadband source having a high intensity contribution from the ultra-violet or low-wavelength visible (for example, between 350nm and 400nm) portion of the electromagnetic spectrum.
- a broadband source having a high intensity contribution from the ultra-violet or low-wavelength visible (for example, between 350nm and 400nm) portion of the electromagnetic spectrum.
- .0 excitation may be achieved using a narrowband source emitting in the ultra-violet or low-wavelength visible portion (for example, at 395nm) of the electromagnetic spectrum.
- RE particles being responsive to excitation from a high frequency source is that low-cost L5 ultra-violet radiation excitation sources may be used for all types of RE particles, rather than having to use a different selective excitation source for each type of RE particle. This may reduce the security of the secure tags.
- a secure tag comprising: a carrier doped with one or more rare earth ions, and a barrier material associated with the carrier and substantially blocking low-wavelength radiation to shield the rare earth ions from low-wavelength 5 radiation.
- multiple secure tags of the same type may be used together to ensure that a strong luminescence signal can be obtained from the secure tags.
- the secure tags may be applied as a relatively dense coating in a secure tag area.
- the barrier material may be in the form of a highly reflective and/or scattering material, such as titanium dioxide or zinc oxide. Titanium dioxide blocks UVB (280nm to 320nm) primarily by absorption, and blocks UVA (320nm to 390nm) primarily by scattering.
- the barrier material may have a high coefficient of absorption for radiation between IOnm and 400nm, particularly for radiation between 300nm and 400nm.
- the coefficient of absorption for wavelengths between 300nm and 400nm is above 0.6, more preferably above 0.7, advantageously above 0.8. It is also preferable to have a coefficient of absorption of less than 0.4 (advantageously less than 0.2) for wavelengths above 450nm, and a coefficient of absorption of less than 0.2 (advantageously less than 0.1) for wavelengths above 500nm.
- An ideal barrier material would have characteristics similar to a bandpass filter that blocks all radiation having a wavelength between 250nm and 450nm, and allows all radiation above 450nm to pass through.
- the barrier material may encapsulate the doped carrier, for example, using microencapsulation techniques.
- Microencapsulation is a well known technique; one example is given in US 6,905,766 entitled "Encapsulation of discrete quanta of fluorescent particles”.
- Microencapsulating the secure tags ensures that little (or perhaps no) low-wavelength radiation reaches the rare earth ions to stimulate emission therefrom.
- the barrier material may be distributed throughout the secure tag.
- the carrier may comprise silica, such as a glass.
- the carrier may comprise a polymer.
- the barrier material may comprise a UV absorbing substance such as those substances used in coatings applied to sunglasses.
- a UV absorbing substance such as those substances used in coatings applied to sunglasses.
- One suitable substance is described in US patent number 5,949,518 entitled “Color-neutral UV blocking coating for plastic lens”. Such substances may be used to 10 microencapsulate the secure tags.
- Other well-known UV absorbing substances include cerium, polyimide, and other polycarbonates .
- the barrier material may be included in a liquid in which the secure tag is suspended.
- the barrier material may be included in a liquid in which the secure tag is suspended.
- L5 material may include common sunscreen additives.
- Sunscreen additives that absorb both UVA and UVB radiation include: avobenzone, Menthyl anthranilate, A&B oxybenzone (Benzophenones) , Homosalate, Dioxybenzone, Sulisobenzone, and Trolame Salicylate. Sunscreen additives that absorb primarily
- UVB radiation include: Octocrylene, PABA (para-aminobenzoic acid), Padimate-0 (Octyl dimethyl paba) , Cinnamates, and Cinoxate .
- a secure tag that shields rare earth ions within the tag from !5 low-wavelength radiation. This ensures that a low-wavelength radiation source cannot be used to excite all transitions in the secure tag, and requires a higher wavelength excitation source (for example 500nm) to selectively excite one or more transitions, thereby increasing the security of the secure tag.
- a secure tag comprising: a carrier doped with one or more rare earth ions, the carrier having barrier properties, including a high coefficient of absorption for low-wavelength radiation.
- a method of manufacturing a secure tag comprising a carrier doped with one or more rare earth ions, the method comprising: (i) ascertaining an excitation radiation wavelength that stimulates a plurality of transitions within the doped carrier; (ii) selecting an additive having a higher absorption coefficient at the ascertained excitation radiation wavelength than the carrier or the rare earth ions; and (iii) manufacturing a secure tag incorporating the selected additive .
- the step of ascertaining an excitation radiation wavelength may include ascertaining an excitation radiation wavelength that would stimulate the highest number and/or the strongest transitions within the secure tag. This enables the barrier material to be chosen with a view to ensuring certain transitions are not stimulated by a UV excitation source.
- the step of manufacturing a secure tag incorporating the selected additive may comprise encapsulating the doped carrier in the selected additive.
- the step of manufacturing a secure tag incorporating the selected additive may comprise including the additive as part of starting ingredients for the secure tag.
- Fig 1 is a schematic diagram illustrating manufacture of a secure tag according to one embodiment of the present invention.
- Fig 2 is a flowchart describing steps involved in the manufacture of the secure tag of Fig 1;
- LO Fig 3 is a table illustrating the luminescence peaks from a secure tag in response to different excitation wavelengths.
- Fig 1 is a schematic diagram of process 10 for manufacturing a secure tag according L5 to one embodiment of the present invention.
- Fig 2 is a flowchart 100 describing the steps involved in the manufacturing process 10.
- the process 10 is based on the melt and quench technique for glass production.
- the process 10 starts with preparing >0 starting ingredients 12 (step 102).
- 3mol% of Europium doped borosilicate glass is to be manufactured as a secure tag.
- the starting ingredients 12 for this secure tag are: SiO 2 51.79 wt%; Na 2 O 9.79 wt%; CaO 7.00 wt%; MgO 2.36 wt%/ Al 2 O 3 0.29 wt%; FeO, 25 Fe 2 O 3 0.14 wt%; K 2 O 0.07 wt%, B 2 O 3 28.56 wt%, and 3mol% of EuCl 3 .
- These ingredients are found in soda lime beads 12a, B 2 O 3 12b, and 3mol% of EuCl 3 12c, all in powder form. ⁇ 1
- the starting ingredients 12 are then mixed (step 104), so that 5g of the powdered soda lime beads, 2g of the B 2 O 3 and 3mol% of EuCl 3 , are ball milled together for a period of time (for example 3 minutes) to produce a finely mixed powder 14.
- the finely mixed powder 14 is then melted (step 106) into a glass by baking in a platinum crucible 16 in a furnace 18.
- the finely mixed powder 14 is first heated to 550C, left in the furnace at this temperature for approximately 30 minutes to ensure that the boric oxide (B 2 O 3 ) is completely melted.
- LO The furnace temperature is then increased to IIOOC for approximately 1 hour to produce a homogeneous melt. The temperature is again increased, this time to 1250C.
- step 108 is to pour the molten glass into a brass mould 20 maintained at room temperature.
- This L5 quenches (step 110) the glass to form a transparent, bubble free ingot 22 of borosilicate glass, doped with rare earth ions.
- the ingot 22 is then removed (step 112) from the mould 20.
- the ingot 22 is then iteratively ball milled (step 114) 20 and sieved (step 116) in a sonic sifter 24 to produce homogenous, small particles 26 (typically of 5 micron diameter) of Europium doped borosilicate glass.
- the next step is to encapsulate (step 118) the small particles 26 in a barrier material 28 to create a secure tag 5 30 that shields the particles 26 from low wavelength radiation.
- the barrier material 28 used in this embodiment comprises polyimide, which is dissolved in tetrahydrofuran (THF) . When applied to the beads the solution is heated to drive off the solvent and cross-link the polyimide for the purpose of encapsulating individual particles 26.
- THF tetrahydrofuran
- the secure tags 30 are applied to a document 32 (step 120) as a relatively dense coating in a secure tag area 34 of the document 32. This enables the document 32 to be validated either by detecting the presence of the secure tags 30, if high security is not required; or by measuring the response of the secure tags 30 to excitation, if high security is required.
- Measuring the response of the secure tags 30 to excitation can be achieved by a two-step process, and will be described with reference to Fig 3, which is a table showing the photoluminescence peaks for each of four different excitation wavelengths (395nm, 415nm, 465nm, and 535nm) .
- the photoluminescence peaks resulting from excitation at a particular wavelength can be ascertained prior to deciding which barrier material to use.
- the first step is to excite the secure tag area 34 with a UV source (corresponding to the 395nm excitation in Fig 3) , to measure the luminescence in response to the excitation, and to verify that the luminescence measured at 615nm is relatively weak.
- a UV source corresponding to the 395nm excitation in Fig 3
- the second step is to excite the secure tag area 34 with a source radiating at 465nm, to measure the luminescence in response to the excitation, and to verify that the luminescence measured at 615nm is relatively strong.
- a high energy excitation source (such as a 395nm source) will not stimulate strong luminescence from the secure tag area 34 because the secure tags 30 block the UV excitation due to the presence of the barrier material 28.
- a different barrier material may be used.
- particles of titanium dioxide and/or zinc oxide may be used as the barrier material. The smaller the primary particle size of the titanium dioxide or zinc oxide the greater the transparency.
- the secure tags 30 may be used individually, may be suspended in a fluid, may be incorporated in a substrate other than a document, or such like.
- the barrier material is dissolved in tetrahydrofuran (THF); whereas, in other embodiments, a polyimide barrier material may be dissolved in another suitable organic solvent.
- a combination of rare earth ions may be used in a secure tag. This combination may or may not include Europium.
- the secure tag may incorporate ions different to rare earth ions .
- a sol-gel process may be made to manufacture silica particles, instead of the melt and quench process described above.
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- Engineering & Computer Science (AREA)
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- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
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Abstract
A secure tag (30) comprising: a carrier doped with one or more rare earth ions, and a barrier material (28) associated with the carrier and substantially blocking low-wave length radiation to shield the rare earth ions from low-wave length radiation. This enables a secure tag to be fabricated that does not photoluminesce strongly in response to a low-wavelength excitation radiation source.
Description
SECURE TAG Background
The present invention relates to improvements in or relating to a secure tag. Secure tags are used for a number of different purposes. One of the primary uses of a secure tag is to prevent counterfeiting. One type of secure tag that has recently been developed is based on small particles of a rare earth doped host, such as glass. This type of secure tag is described in US patent application number 2004/0262547, entitled "Security Labelling," and US patent application number 2005/0143249, entitled "Security Labels which are Difficult to Counterfeit". These rare earth doped particles (hereinafter "RE particles") can be applied to valuable items in different ways. For example, the secure tags can be incorporated in fluids which are applied (by printing, spraying, painting, or such like) to valuable items, or incorporated directly into a substrate (paper, rag, plastic, or such like) of the valuable items.
In response to suitable excitation, RE particles produce a luminescence spectrum having narrow peaks because of the atomic (rather than molecular) transitions involved. Known readers for RE particles include (i) a suitable excitation source to stimulate transitions in the secure tag, and (ii) a detector to measure the luminescence emitted in response to the excitation.
The suitable excitation source may be tuned (in the sense that the excitation is selected to optimize luminescence from one or more transitions in the rare earth ions), or high
frequency (to stimulate all, or at least many, transitions in the rare earth ions and the host) .
Tuned excitation is usually achieved using a narrowband source, such as an LED, in the visible region of the
5 electromagnetic spectrum. High frequency excitation may be achieved using a broadband source having a high intensity contribution from the ultra-violet or low-wavelength visible (for example, between 350nm and 400nm) portion of the electromagnetic spectrum. Alternatively, high frequency
.0 excitation may be achieved using a narrowband source emitting in the ultra-violet or low-wavelength visible portion (for example, at 395nm) of the electromagnetic spectrum.
One disadvantage of the RE particles being responsive to excitation from a high frequency source is that low-cost L5 ultra-violet radiation excitation sources may be used for all types of RE particles, rather than having to use a different selective excitation source for each type of RE particle. This may reduce the security of the secure tags.
Summary
20 According to a first aspect of the invention there is provided a secure tag comprising: a carrier doped with one or more rare earth ions, and a barrier material associated with the carrier and substantially blocking low-wavelength radiation to shield the rare earth ions from low-wavelength 5 radiation.
In many applications of this aspect of the invention, multiple secure tags of the same type may be used together to ensure that a strong luminescence signal can be obtained from
the secure tags. The secure tags may be applied as a relatively dense coating in a secure tag area.
The barrier material may be in the form of a highly reflective and/or scattering material, such as titanium dioxide or zinc oxide. Titanium dioxide blocks UVB (280nm to 320nm) primarily by absorption, and blocks UVA (320nm to 390nm) primarily by scattering.
Alternatively, or additionally, the barrier material may have a high coefficient of absorption for radiation between IOnm and 400nm, particularly for radiation between 300nm and 400nm. Preferably, the coefficient of absorption for wavelengths between 300nm and 400nm is above 0.6, more preferably above 0.7, advantageously above 0.8. It is also preferable to have a coefficient of absorption of less than 0.4 (advantageously less than 0.2) for wavelengths above 450nm, and a coefficient of absorption of less than 0.2 (advantageously less than 0.1) for wavelengths above 500nm.
An ideal barrier material would have characteristics similar to a bandpass filter that blocks all radiation having a wavelength between 250nm and 450nm, and allows all radiation above 450nm to pass through.
The barrier material may encapsulate the doped carrier, for example, using microencapsulation techniques. Microencapsulation is a well known technique; one example is given in US 6,905,766 entitled "Encapsulation of discrete quanta of fluorescent particles". Microencapsulating the secure tags ensures that little (or perhaps no) low-wavelength radiation reaches the rare earth ions to stimulate emission therefrom.
Alternatively, the barrier material may be distributed throughout the secure tag.
The carrier may comprise silica, such as a glass. Alternatively, the carrier may comprise a polymer.
5 The barrier material may comprise a UV absorbing substance such as those substances used in coatings applied to sunglasses. One suitable substance is described in US patent number 5,949,518 entitled "Color-neutral UV blocking coating for plastic lens". Such substances may be used to 10 microencapsulate the secure tags. Other well-known UV absorbing substances include cerium, polyimide, and other polycarbonates .
The barrier material may be included in a liquid in which the secure tag is suspended. In such embodiments, the barrier
L5 material may include common sunscreen additives. Sunscreen additives that absorb both UVA and UVB radiation include: avobenzone, Menthyl anthranilate, A&B oxybenzone (Benzophenones) , Homosalate, Dioxybenzone, Sulisobenzone, and Trolame Salicylate. Sunscreen additives that absorb primarily
10 UVB radiation include: Octocrylene, PABA (para-aminobenzoic acid), Padimate-0 (Octyl dimethyl paba) , Cinnamates, and Cinoxate .
By virtue of this aspect of the invention, a secure tag is provided that shields rare earth ions within the tag from !5 low-wavelength radiation. This ensures that a low-wavelength radiation source cannot be used to excite all transitions in the secure tag, and requires a higher wavelength excitation source (for example 500nm) to selectively excite one or more
transitions, thereby increasing the security of the secure tag.
According to a second aspect of the invention there is provided a secure tag comprising: a carrier doped with one or more rare earth ions, the carrier having barrier properties, including a high coefficient of absorption for low-wavelength radiation.
According to a third aspect of the invention there is provided a method of manufacturing a secure tag comprising a carrier doped with one or more rare earth ions, the method comprising: (i) ascertaining an excitation radiation wavelength that stimulates a plurality of transitions within the doped carrier; (ii) selecting an additive having a higher absorption coefficient at the ascertained excitation radiation wavelength than the carrier or the rare earth ions; and (iii) manufacturing a secure tag incorporating the selected additive .
The step of ascertaining an excitation radiation wavelength may include ascertaining an excitation radiation wavelength that would stimulate the highest number and/or the strongest transitions within the secure tag. This enables the barrier material to be chosen with a view to ensuring certain transitions are not stimulated by a UV excitation source.
The step of manufacturing a secure tag incorporating the selected additive may comprise encapsulating the doped carrier in the selected additive. Alternatively, the step of manufacturing a secure tag incorporating the selected additive may comprise including the additive as part of starting ingredients for the secure tag.
These and other aspects of the present invention will be apparent from the following specific description, given by way of example, with reference to the following drawings.
Brief Description Of the Drawings
5 Fig 1 is a schematic diagram illustrating manufacture of a secure tag according to one embodiment of the present invention;
Fig 2 is a flowchart describing steps involved in the manufacture of the secure tag of Fig 1; and
LO Fig 3 is a table illustrating the luminescence peaks from a secure tag in response to different excitation wavelengths.
Detailed Description
Reference is first made to Fig 1, which is a schematic diagram of process 10 for manufacturing a secure tag according L5 to one embodiment of the present invention. Reference is also made to Fig 2, which is a flowchart 100 describing the steps involved in the manufacturing process 10.
The process 10 is based on the melt and quench technique for glass production. The process 10 starts with preparing >0 starting ingredients 12 (step 102).
In this example, 3mol% of Europium doped borosilicate glass is to be manufactured as a secure tag. The starting ingredients 12 for this secure tag are: SiO2 51.79 wt%; Na2O 9.79 wt%; CaO 7.00 wt%; MgO 2.36 wt%/ Al2O3 0.29 wt%; FeO, 25 Fe2O3 0.14 wt%; K2O 0.07 wt%, B2O3 28.56 wt%, and 3mol% of EuCl3. These ingredients are found in soda lime beads 12a, B2O3 12b, and 3mol% of EuCl3 12c, all in powder form.
~1
The starting ingredients 12 are then mixed (step 104), so that 5g of the powdered soda lime beads, 2g of the B2O3 and 3mol% of EuCl3, are ball milled together for a period of time (for example 3 minutes) to produce a finely mixed powder 14.
5 The finely mixed powder 14 is then melted (step 106) into a glass by baking in a platinum crucible 16 in a furnace 18. The finely mixed powder 14 is first heated to 550C, left in the furnace at this temperature for approximately 30 minutes to ensure that the boric oxide (B2O3) is completely melted. LO The furnace temperature is then increased to IIOOC for approximately 1 hour to produce a homogeneous melt. The temperature is again increased, this time to 1250C.
The next step (step 108) is to pour the molten glass into a brass mould 20 maintained at room temperature. This L5 quenches (step 110) the glass to form a transparent, bubble free ingot 22 of borosilicate glass, doped with rare earth ions. The ingot 22 is then removed (step 112) from the mould 20.
The ingot 22 is then iteratively ball milled (step 114) 20 and sieved (step 116) in a sonic sifter 24 to produce homogenous, small particles 26 (typically of 5 micron diameter) of Europium doped borosilicate glass.
The next step is to encapsulate (step 118) the small particles 26 in a barrier material 28 to create a secure tag 5 30 that shields the particles 26 from low wavelength radiation.
The barrier material 28 used in this embodiment comprises polyimide, which is dissolved in tetrahydrofuran (THF) . When
applied to the beads the solution is heated to drive off the solvent and cross-link the polyimide for the purpose of encapsulating individual particles 26.
Once the small particles 26 are encapsulated, they become secure tags 30. The secure tags 30 are applied to a document 32 (step 120) as a relatively dense coating in a secure tag area 34 of the document 32. This enables the document 32 to be validated either by detecting the presence of the secure tags 30, if high security is not required; or by measuring the response of the secure tags 30 to excitation, if high security is required.
Measuring the response of the secure tags 30 to excitation can be achieved by a two-step process, and will be described with reference to Fig 3, which is a table showing the photoluminescence peaks for each of four different excitation wavelengths (395nm, 415nm, 465nm, and 535nm) . The photoluminescence peaks resulting from excitation at a particular wavelength can be ascertained prior to deciding which barrier material to use.
The first step is to excite the secure tag area 34 with a UV source (corresponding to the 395nm excitation in Fig 3) , to measure the luminescence in response to the excitation, and to verify that the luminescence measured at 615nm is relatively weak.
The second step is to excite the secure tag area 34 with a source radiating at 465nm, to measure the luminescence in response to the excitation, and to verify that the luminescence measured at 615nm is relatively strong.
-Sl¬
it will now be appreciated that a high energy excitation source (such as a 395nm source) will not stimulate strong luminescence from the secure tag area 34 because the secure tags 30 block the UV excitation due to the presence of the barrier material 28.
Various modifications may be made to the above-described embodiments within the scope of the present invention, for example, in other embodiments a different barrier material may be used. In one embodiment, particles of titanium dioxide and/or zinc oxide may be used as the barrier material. The smaller the primary particle size of the titanium dioxide or zinc oxide the greater the transparency.
In other embodiments, the secure tags 30 may be used individually, may be suspended in a fluid, may be incorporated in a substrate other than a document, or such like.
In the above embodiment, the barrier material is dissolved in tetrahydrofuran (THF); whereas, in other embodiments, a polyimide barrier material may be dissolved in another suitable organic solvent.
In other embodiments, a combination of rare earth ions may be used in a secure tag. This combination may or may not include Europium.
In other embodiments, the secure tag may incorporate ions different to rare earth ions .
In other embodiments, a sol-gel process may be made to manufacture silica particles, instead of the melt and quench process described above.
Claims
1. A secure tag (30) comprising: a carrier doped with one or more rare earth ions, and a barrier material (28) associated with the carrier and substantially blocking low- wavelength radiation to shield the rare earth ions from low- wavelength radiation.
2. A secure tag (30) according to claim 1, wherein the barrier material (28) is a highly reflective and/or scattering material.
3. A secure tag (30) according to any preceding claim, wherein the barrier material has a high absorptivity in the ultra-violet region of the electromagnetic spectrum and a low absorptivity in the visible region of the electromagnetic spectrum.
4. A secure tag (30) according to any preceding claim, wherein the barrier material (28) microencapsulates the doped carrier.
5. A secure tag (30) according to any preceding claim, wherein the carrier comprises silica.
6. A secure tag (30) according to any preceding claim, wherein the barrier material (28) is included in a liquid in which the secure tag (30) is suspended.
7. A secure tag (30) comprising: a carrier doped with one or more rare earth ions, the carrier having barrier properties, including a high coefficient of absorption for low-wavelength radiation.
8. A method of manufacturing a secure tag (30) comprising a carrier doped with one or more rare earth ions, the method comprising: (i) ascertaining an excitation radiation wavelength that stimulates a plurality of transitions within the doped carrier; (ii) selecting an additive having a higher absorption coefficient at the ascertained excitation radiation wavelength than the carrier or the rare earth ions; and (iii) manufacturing a secure tag incorporating the selected additive.
9. A method according to claim 8, wherein ascertaining an excitation radiation wavelength includes ascertaining an excitation radiation wavelength that would stimulate the highest number of transitions within the secure tag (30) .
10. A method according to claim 8 or 9, wherein manufacturing a secure tag incorporating the selected additive comprises encapsulating the doped carrier in the selected additive .
11. A method according to any of claims 8 to 10, wherein manufacturing a secure tag incorporating the selected additive comprises including the additive as part of starting ingredients for the secure tag.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP06820402A EP1963446B1 (en) | 2005-12-13 | 2006-12-05 | Secure tag |
AT06820402T ATE517955T1 (en) | 2005-12-13 | 2006-12-05 | SAFETY LABEL |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/301,990 US7699230B2 (en) | 2005-12-13 | 2005-12-13 | Secure tag |
US11/301,990 | 2005-12-13 |
Publications (1)
Publication Number | Publication Date |
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WO2007068886A1 true WO2007068886A1 (en) | 2007-06-21 |
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ID=37669132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/GB2006/004516 WO2007068886A1 (en) | 2005-12-13 | 2006-12-05 | Secure tag |
Country Status (5)
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US (1) | US7699230B2 (en) |
EP (1) | EP1963446B1 (en) |
AT (1) | ATE517955T1 (en) |
ES (1) | ES2366737T3 (en) |
WO (1) | WO2007068886A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016015872A1 (en) | 2014-08-01 | 2016-02-04 | Giesecke & Devrient Gmbh | Security element, value document substrate, value document, method for producing said value document, and transfer belt |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010141869A1 (en) * | 2009-06-05 | 2010-12-09 | Spectra Systems Corporation | Ultraviolet-dull response in security taggants |
NL2004018C2 (en) | 2009-12-24 | 2011-06-27 | Vhp Ugchelen Bv | SAFETY FEATURE. |
US8517274B2 (en) * | 2010-10-15 | 2013-08-27 | Verrana Llc | Data word analysis by spectroscopy |
DE102012017710A1 (en) * | 2012-09-07 | 2014-03-13 | Polysecure Gmbh | Workpiece or material with inert marker system |
DE102013020391A1 (en) * | 2013-12-10 | 2015-06-11 | Polysecure Gmbh | Marked layer structure, process for its preparation and use thereof |
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WO1997010307A1 (en) | 1995-09-15 | 1997-03-20 | Videojet Systems International, Inc. | A jet ink composition |
EP1116755A1 (en) | 2000-01-10 | 2001-07-18 | Sicpa Holding S.A. | Coating composition, preferably printing ink for security applications, method for producing a coating composition and use of glass ceramics |
US20030177941A1 (en) | 1998-11-10 | 2003-09-25 | Emilio Barbera-Guillem | Fluorescent ink compositions comprising functionalized fluorescent nanocrystals |
US20040262547A1 (en) | 2003-06-26 | 2004-12-30 | Ncr Corporation | Security labelling |
US20050143249A1 (en) | 2003-06-26 | 2005-06-30 | Ross Gary A. | Security labels which are difficult to counterfeit |
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DE60040595D1 (en) * | 2000-05-16 | 2008-12-04 | Sicpa Holding Sa | Method, device and system for authenticating a marker |
DE602004021945D1 (en) * | 2003-08-22 | 2009-08-20 | Du Pont | IDENTIFICATION VERIFICATION METHOD THROUGH THE USE OF TRANSPARENT LUMINESCENT POLYMERS |
-
2005
- 2005-12-13 US US11/301,990 patent/US7699230B2/en active Active
-
2006
- 2006-12-05 EP EP06820402A patent/EP1963446B1/en active Active
- 2006-12-05 WO PCT/GB2006/004516 patent/WO2007068886A1/en active Application Filing
- 2006-12-05 AT AT06820402T patent/ATE517955T1/en not_active IP Right Cessation
- 2006-12-05 ES ES06820402T patent/ES2366737T3/en active Active
Patent Citations (5)
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WO1997010307A1 (en) | 1995-09-15 | 1997-03-20 | Videojet Systems International, Inc. | A jet ink composition |
US20030177941A1 (en) | 1998-11-10 | 2003-09-25 | Emilio Barbera-Guillem | Fluorescent ink compositions comprising functionalized fluorescent nanocrystals |
EP1116755A1 (en) | 2000-01-10 | 2001-07-18 | Sicpa Holding S.A. | Coating composition, preferably printing ink for security applications, method for producing a coating composition and use of glass ceramics |
US20040262547A1 (en) | 2003-06-26 | 2004-12-30 | Ncr Corporation | Security labelling |
US20050143249A1 (en) | 2003-06-26 | 2005-06-30 | Ross Gary A. | Security labels which are difficult to counterfeit |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016015872A1 (en) | 2014-08-01 | 2016-02-04 | Giesecke & Devrient Gmbh | Security element, value document substrate, value document, method for producing said value document, and transfer belt |
DE102014011383A1 (en) | 2014-08-01 | 2016-02-04 | Giesecke & Devrient Gmbh | Security element, value document substrate, security paper, value document and method for producing the same and Trensferband |
Also Published As
Publication number | Publication date |
---|---|
US20070132984A1 (en) | 2007-06-14 |
EP1963446A1 (en) | 2008-09-03 |
ATE517955T1 (en) | 2011-08-15 |
EP1963446B1 (en) | 2011-07-27 |
US7699230B2 (en) | 2010-04-20 |
ES2366737T3 (en) | 2011-10-25 |
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