Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
  • B41M3/14—Security printing
  • B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
  • B42D25/29—Securities; Bank notes
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
  • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
  • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
• • 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

Definitions

• the invention relates to a document of value, such as a security, identity card or the like, with at least one authenticity feature in the form of a luminescent substance.
• the invention further relates to a security element with at least one authenticity feature in the form of a luminescent substance and to a method for marking products, the product being provided with a luminescent substance.
• Luminescent substances have long been used for marking products, in particular for security applications.
• the advantage of such a marking is that with suitable illumination of the marked object, the luminescent substances emit with high intensity and can thus be detected, whereas areas without the luminescent substances appear essentially dark.
• the markings can be detected with high sensitivity.
• numerous luminescent substances with very broad emission bands have been used for marking. This is typical, in particular, for organic dyes whose luminescence line widths can be a few 50 nm and more. Similar line widths also have many classic inorganic luminescent substances.
• EP 0 522 627 AI describes the production of luminescent molecular sieves and their use as a lamp phosphor.
• the reactants complexing agents and rare earth ions
• the chelate complex is fixed inside the cavities.
• colored molecular sieves which contain metal salts as color-imparting components, have long been known under the name “Ultramar dye and pigment (German Reich Patent No. 1, 1877).
• This pure Inorganic systems are produced, for example, by heating zeolite molecular sieves with alkali metal sulfides in a non-oxidizing atmosphere and then in an oxidizing atmosphere at temperatures above 300 ° C. (JP-A-63-017 217; JP-A55-071 762).
• Organic dyes are generally applied to the molecular sieves by treating colorless molecular sieves with dye solutions (see, for example, JP-A-63-0 17 217; JP-A-53-0 22 094 and JP-A-75-0 08 462) .
• dye solutions see, for example, JP-A-63-0 17 217; JP-A-53-0 22 094 and JP-A-75-0 08 462 .
• neutral dyes which are only weakly adsorbed on the molecular sieve framework, there is a risk that they will be washed off the molecular sieve again when solvents are added. Adhesion is improved with strongly basic dyes.
• pigments consisting of an inorganic carrier (often layered minerals, zeolites or zeolite-like materials) and an adsorbed colorant in paints and emulsion paints is known (JP-PS-75-0 08 452).
• JP-PS-75-0 08 452 When using these pigments, it is necessary to choose the composition of the color so that the color pigment does not react with the surrounding medium, is insoluble in the solvent used and sediments uniformly, which is particularly important in the case of mixed colors.
• solvents and binders of interest for color production are excluded and the possibilities for producing mixed colors using the described pigments are severely restricted.
• Phthalocyanine is formed in the approximately 12 A supercages of faujasite. Since these supercages are only accessible through openings of approx. 7 A to 8 A, the phthalonitrile can diffuse into the cavities, but diffusing out of the dye formed is no longer possible for steric reasons.
• WO 93/17965, DE 42 07 339 AI and DE 41 31 447 AI describe the production of colorants based on molecular sieves.
• Indigoide dyes, azo dyes and quinizarin dyes are described in Molecular sieves from the classes zeolites and zeolite-like materials installed.
• the systems and uses described have in common that the luminescent substances retain their characteristic properties which they also have in solutions or as a powder. Due to the incorporation in the zeolites, only slight shifts and broadening of the spectral bands are observed, especially with organic dyes. However, these effects are not advantageous for use as a marker. Since they cover the emission bands of numerous different luminescent substances lapping, the selectivity of the detection of the substances is severely restricted. Although there are chemically different substances, the differences in their emission bands are often so small that their luminescence must be investigated over a wide spectral range using complex means so that identification is possible at all. For many applications, the effort involved in clear identification is so high that it can only be carried out in exceptional cases.
• the invention is therefore based on the object of proposing a document of value and a security element for marking any product with at least one luminescent substance which is easily detectable and identifiable.
• a luminescent system is used as the authenticity feature for value documents, in which the line width of dyes is greatly reduced by the effect of the stimulated emission in order to distinguish as large as possible a number of characteristic narrow-band luminescent lines of different dye matrix systems in a selected spectral range can.
• the stimulated emission processes are caused by the fact that the dyes are in a resonator that encloses the dyes.
• the resonator is formed by a molecular sieve crystallite, the surfaces of which include the luminescence of the dye molecules.
• the luminescence radiation is coupled out via microdefects in these surfaces.
• These systems are dye-loaded molecular sieves that show stimulated emission. They were first presented at the 10th German Zeolite Conference. These were molecular sieves of the AI PO-5 type loaded with pyridine-2. The effect was also observed on a molecular sieve AI PO-5, which was doped with rhodamine and was produced by means of "crystallization inclusion".
• any other dye-loaded molecular sieve that exhibits stimulated emission can also be used in accordance with the invention.
• dyes from the class of cyanines or coumarins or any other dyes from the class of laser dyes can be used as dyes.
• the spectral properties of the dyes can be adjusted by appropriate chemical modification of the chromophore.
• Several different dyes can also be provided in a molecular sieve.
• the molecular sieve used is preferably a molecular sieve with a channel structure and suitable morphology, such as e.g. from the classes AFI, LTL, MFI, M41S.
• suitable morphology such as e.g. from the classes AFI, LTL, MFI, M41S.
• ALPO-5, SAPO-5 (AFI class) and also MAPO and MAPSO, ELAPO and ELAPSO can be used.
• M stands for any metal, e.g. Mn, Mg, Co, Fe, Cr, Zn and EL for an element such as Li, Be, B, Ti, As, Ga, Ge.
• a UV absorber and / or a UV stabilizer based on sterically hindered amines preferably in a dosage of 0.5 to 3 wt .% are stored.
• HALS sterically hindered amines
• photo-stabilization outside the UV range, in particular at the wavelength of the dye is additionally achieved.
• Tinuvin-P, Tinuvin 928 (Ciba Geigy) can be used as the UV absorber.
• the sterically hindered amines are, for example, Tinuvin 144 (Ciba Geigy), Tinuvin 123 (Ciba Geigy), HALS 3051 (Clariant) or derivatives thereof.
• antioxidants can also be incorporated into the cavities.
• the invention is now based on the knowledge that these systems are very advantageously suitable for marking applications, since a particle-internal resonator is used to greatly reduce the luminescence line width of the system with suitable excitation. It can therefore be a big one
• the most varied of coding systems can be formed. For example, an object with different those of the dyes described above are marked.
• the coding arises from the presence or absence of one or more particles.
• the characteristic properties of the dye-molecular sieve systems only become apparent when there is intensive optical excitation with light of a suitable wavelength. Due to the threshold behavior of the systems, the optical irradiance must exceed a threshold value that is characteristic of the systems. Typical threshold values are 0.2 - 4 MW / cm 2 .
• Light sources of suitable wavelength with sufficient radiation power can be used as excitation sources.
• An optical device can be used to concentrate the light from the excitation source on a sufficiently small spot and thus to increase the irradiance of the systems.
• Dyes from the class of pyridines are enclosed in a suitable molecular sieve, such as, for example, an SAPO-5 molecular sieve.
• a suitable molecular sieve such as, for example, an SAPO-5 molecular sieve.
• the dye-loaded molecular sieve When excited with a frequency-doubled NdNAG laser, the dye-loaded molecular sieve absorbs in the range of the laser wavelength of 532 nm. With a laser power density of 4 MW / cm 2 , the dye-loaded molecular sieve shows a very narrow-band laser-like fluorescence spectrum in the range of approx. 680 nm.
• Rhodamine is a dye from the class of Rhodamine in a suitable molecular sieve, which belongs for example to the structure type MFI, LTL, EMT, M41S, AFI, CHA.
• a frequency-doubled ⁇ dNAG laser and a laser power density of 4 MW / cm 2 this substance shows a very narrow-band laser-like fluorescence spectrum in the range of 560 nm.
• a dye from the class of the coumarins is enclosed in a suitable molecular sieve, such as, for example, an AI PO-5 molecular sieve.
• a suitable molecular sieve such as, for example, an AI PO-5 molecular sieve.
• the molecular sieve When excited with a Xe Cl excimer laser with a wavelength of 308 nm and a laser power density of 4 MW / cm 2 , the molecular sieve shows a very narrow-band laser-like fluorescence spectrum in the range of 530 nm.
• the verification of the systems must include the verification of at least one of the following characteristic properties of the systems in order to achieve a To allow differentiation from conventional, non-stimulated emitting luminescent substances.
• the characteristic increase in intensity in a narrow wavelength range with above-threshold excitation can be detected by observation through the characteristic threshold behavior of the increase in intensity when the irradiance is increased by means of a suitable spectrally constricting element in the detection channel.
• the characteristic luminescence line narrowing can be demonstrated by comparing the intensities in the narrow wavelength range characteristic of the dye system with the intensity in other wavelength ranges. This happens e.g. by means of a spectrometer structure with adequate spectral resolution or by measurement in different detection channels which measure the intensity in the required spectral range by means of suitable spectrally selective elements. In the case of excitation above the threshold, a characteristic spectral distribution with an intensity maximum at the characteristic wavelength or characteristic intensity relationships in the different channels that do not occur with conventional luminescent dyes are observed.
• the characteristic shortening of the luminescence lifetime at the characteristic wavelength of the dye system to typically ⁇ 300 ps also enables the systems to be distinguished from conventional luminescent dyes (typical lifetime> 3 ns). This requires excitation sources whose switch-off times are significantly shorter than the lifespan of conventional luminescent dyes. The decay times of the detector and detection electronics must also be comparatively fast. As a further characteristic property of the systems, the saturation of the optical transition only occurs at much higher luminescence intensities, so that much higher luminescence intensities can be observed with these systems than with conventional luminescent substances.
• the molecular sieves described form microcrystals or crystal-like structures, which are referred to below as particles.
• the particles can be used directly to mark any objects, in particular securities, passports, forms, CDs or other everyday products. The easiest way is to add the particles to a printing ink. However, the particles can also be added directly to the material of the article. This is useful, for example, if the object to be secured is a document of value, such as a banknote or an identification card. In the case of the banknote, the particles are preferably added to the paper pulp during the production of the banknote paper. On the other hand, with ID cards, one of the cover or inlet layers in the volume can be mixed with the particles. The particles can also be embedded directly in a polymer.
• the authenticity feature according to the invention or the molecular sieve (s) loaded with dye can also be combined with a type of camouflage material.
• two luminescent substances are used to produce a label, one of the substances being a conventional luminescent substance and the other being a molecular sieve loaded with dye according to the invention.
• subliminal excitation both substances behave in the same way, while with subliminal excitation, the emission behavior of the dye-laden molecular sieve, as already explained, changed.
• a barcode is now printed with the particles according to the invention and the spaces between the barcodes are printed with the conventional luminescent substance, only a uniformly luminescent field can be detected with subliminal excitation.
• narrow luminescence peaks result in the emission spectrum in the area of the bars of the barcode and in this way make the code visible.
• any other coding or information can be displayed.
• the substances, conventional luminescent substance and molecular sieve according to the invention can also be contained together in a printing ink or another carrier material.
• the excitation of the molecular sieve serves as an additional authenticity feature and thus increases the security against forgery.
• the security element 2 could also be designed in the form of a label which bears the authenticity feature 3 in the form of an imprint. It is also conceivable to design the security element 2 in the form of a thread or tape, the authenticity feature 3 being arranged on a carrier material, preferably a plastic film. This band can either be arranged over the entire surface of the surface of the value document 1 or at least partially embedded in the value document. This type of insertion is particularly suitable for banknotes that are often provided with so-called "window security threads".
• the security thread is quasi in the paper during its manufacture. woven in so that it comes directly to the surface of the paper in certain areas.
• FIG. 2 shows the document of value shown in FIG. 1 along the line AA in cross section.
• the print 3 on the value document 1, which in the present case forms the authenticity feature, contains particles which are formed by a dye-laden molecular sieve.
• the authenticity feature 3 is usually not visible under normal lighting, but is only recognizable after excitation with appropriate radiation.
• the authenticity feature 3 or the print forming the authenticity feature 3 can also contain other visually quite visible dyes. However, it should be ensured here that these additional dyes do not have any significant absorption in the emission wavelength range of the particles according to the invention.
• the security feature 2 does not only consist of the authenticity feature 3 in the form of an imprint, but also has a camouflage imprint 4, which represents the authenticity feature 3 surrounds in the entire area of the security element 2. That is, the area shown in dashed lines in FIG. 1 is completely provided with the camouflage print 4, except for the area of the authenticity feature 3.
• This camouflage print 4 contains an ordinary luminescent substance, which is likewise preferably transparent in the visual spectral range. In addition, this luminescent substance exhibits the same absorption and emission behavior as the particles according to the invention, as long as they are excited with a laser power density below the threshold value characteristic for these particles.
• the authenticity feature shows a relatively broadband luminescence emission which is based on spontaneous emission and is represented by curve A in FIG.
• the radiation density of the excitation light source is above a certain threshold value, the dyes enclosed in the molecular sieve show a stimulated emission.
• the material shows a very narrow-band emission in the range of 680 nm, as shown by curve B in FIG. 5.
• the emission intensity IE grows slowly below the threshold Is with the excitation intensity. Above the threshold value Is the stimulated emission of the dye-loaded molecular sieve sets in, so that the emission intensity grows much faster with the excitation intensity.
• the molecular sieve surrounding the dye acts like a laser resonator, which amplifies the luminescent radiation emitted by the dye in a laser-like manner.

Landscapes

• Business, Economics & Management (AREA)
• Accounting & Taxation (AREA)
• Finance (AREA)
• Credit Cards Or The Like (AREA)
• Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
• Luminescent Compositions (AREA)
• Valve Device For Special Equipments (AREA)
• Holo Graphy (AREA)
• Braking Elements And Transmission Devices (AREA)
• Compounds Of Unknown Constitution (AREA)
• Saccharide Compounds (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Polarising Elements (AREA)

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Publications (2)

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• 1999
  • 1999-05-25 DE DE19923959A patent/DE19923959A1/de not_active Ceased
• 2000
  • 2000-05-23 RU RU2001133359/09A patent/RU2232422C2/ru not_active IP Right Cessation
  • 2000-05-23 CN CN00810135A patent/CN1119250C/zh not_active Expired - Fee Related
  • 2000-05-23 CA CA002374814A patent/CA2374814C/fr not_active Expired - Fee Related
  • 2000-05-23 EP EP00941978A patent/EP1200272B1/fr not_active Expired - Lifetime
  • 2000-05-23 MX MXPA01012084A patent/MXPA01012084A/es active IP Right Grant
  • 2000-05-23 DE DE50001811T patent/DE50001811D1/de not_active Expired - Lifetime
  • 2000-05-23 US US09/926,579 patent/US6858323B1/en not_active Expired - Lifetime
  • 2000-05-23 WO PCT/EP2000/004694 patent/WO2000071363A1/fr active IP Right Grant
  • 2000-05-23 AU AU56756/00A patent/AU5675600A/en not_active Abandoned
  • 2000-05-23 AT AT00941978T patent/ATE237479T1/de not_active IP Right Cessation

Non-Patent Citations (1)

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