EP1200272A1 - Valuable document - Google Patents

Valuable document

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Publication number
EP1200272A1
EP1200272A1 EP00941978A EP00941978A EP1200272A1 EP 1200272 A1 EP1200272 A1 EP 1200272A1 EP 00941978 A EP00941978 A EP 00941978A EP 00941978 A EP00941978 A EP 00941978A EP 1200272 A1 EP1200272 A1 EP 1200272A1
Authority
EP
European Patent Office
Prior art keywords
dye
document
value
molecular sieve
luminescent substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00941978A
Other languages
German (de)
French (fr)
Other versions
EP1200272B1 (en
Inventor
Thomas Giering
Rainer Hoppe
Thomas Attenberger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Giesecke and Devrient GmbH
Original Assignee
Giesecke and Devrient GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Giesecke and Devrient GmbH filed Critical Giesecke and Devrient GmbH
Publication of EP1200272A1 publication Critical patent/EP1200272A1/en
Application granted granted Critical
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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.

Abstract

The invention relates to a document of value, such as a paper of value, ID card or the like, having at least one authenticity feature in the form of a luminescent substance. The luminescent substance has particles consisting of a dye-laden molecular sieve whose structure forms an optical resonator. In said resonator at least one dye can be excited to show stimulated emission, the dye being incorporated in the cavities of the molecular sieve or located in or on the internal and external surfaces of the molecular sieve, and the transition to stimulated emission being accompanied by a detectable change in the luminescent properties of the dye.

Description

Wertdokument Value document
Die Erfindung betrifft ein Wertdokument, wie Wertpapier, Ausweiskarte oder dergleichen, mit wenigstens einem Echtheitsmerkmal in Form einer lumineszierenden Substanz. Die Erfindung betrifft ferner ein Sicherheitselement mit wenigstens einem Echtheitsmerkmal in Form einer lumineszierenden Substanz sowie ein Verfahren zur Markierung von Produkten, wobei das Produkt mit einer lumineszierenden Substanz versehen wird.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.
Zur Markierung von Produkten werden insbesondere für Sicherheitsanwendungen seit langem lumineszierende Substanzen eingesetzt. Der Vorteil einer derartigen Markierung liegt darin, dass bei geeigneter Beleuchtung des markierten Objekts die lumineszierenden Substanzen mit hoher Intensität emittieren und damit detektierbar sind, während Bereiche ohne die lumi- neszierenden Substanzen im Wesentlichen dunkel erscheinen. Auf dieseLuminescent 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. To this
Weise lassen sich die Markierungen mit hoher Empfindlichkeit nachweisen. Zur Markierung w irden in der Vergangenheit zahlreiche Lumineszenzstoffe eingesetzt, die sehr breite Emissionsbanden besitzen. Typisch ist dies insbesondere für organische Farbstoffe, deren Lumineszenzlinienbreiten einige 50 nm und mehr betragen können. Ähnliche Linienbreiten besitzen auch viele klassische anorganische Lumineszenzstoffe.The markings can be detected with high sensitivity. In the past, 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 beschreibt die Herstellung lumineszenzfähiger Molekularsiebe und deren Verwendung als Lampenleuchtstoff. Per Diffusion in Lö- sung werden die Reaktanden (Komplexbildner und Seltenerdionen) in die Hohlräume von Zeolithen eingebracht, wo sie zu Chelatkomplexen abreagieren. Der Chelatkomplex ist im Inneren der Hohlräume fixiert.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) are introduced into the cavities of zeolites by diffusion in solution, where they react to form chelate complexes. The chelate complex is fixed inside the cavities.
Des Weiteren sind farbige Molekularsiebe, die Metallsalze als farbgebende Komponente enthalten, seit langem unter dem Namen „ Ultramar infarb- stoffe/ -pigmente bekannt (Deutsches Reichspatent Nr. 1, 1877). Diese rein anorganischen Systeme werden beispielsweise durch Erhitzen von Zeolith- Molekularsieben mit Alkalimetallsulfiden in nicht oxidierender Atmosphäre und anschließend in oxidierender Atmosphäre bei Temperaturen über 300°C hergestellt (JP-A-63-017 217; JP-A55-071 762).In addition, 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).
Organische Farbstoffe werden in der Regel durch Behandeln von farblosen Molekularsieben mit Farbstofflösungen auf die Molekularsiebe aufgebracht (siehe z.B. JP-A-63-0 17 217; JP-A-53-0 22 094 und JP-A-75-0 08 462). Dabei besteht insbesondere bei nur schwach an das Molekularsiebgerüst adsorbier- ten neutralen Farbstoffen die Gefahr, dass diese bei Zugabe von Lösungsmitteln wieder von dem Molekularsieb abgewaschen werden. Eine Verbesserung der Haftung wird mit stark basischen Farbstoffen erreicht.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) . In this case, in particular with 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.
Der Einsatz von Pigmenten, bestehend aus einem anorganischen Träger (oftmals Schichtmineralien, Zeolithe oder zeolithähnliche Materialien) und einem adsorbierten Färbemittel, in Lacken und Dispersionsfarben ist bekannt (JP-PS-75-0 08 452). Beim Einsatz dieser Pigmente ist es notwendig, die Zusammensetzung der Farbe so zu wählen, dass das Farbpigment nicht mit dem umgebenden Medium reagiert, in dem verwendeten Lösungsmittel unlöslich ist und einheitlich sedimentiert, was insbesondere bei Mischfarben von Bedeutung ist. Dadurch werden viele für die Farbherstellung interessante Löse- und Bindemittel ausgeschlossen und die Möglichkeiten der Mischfarbenherstellung unter Verwendung der beschriebenen Pigmente stark eingeschränkt.The use of 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). 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. As a result, many solvents and binders of interest for color production are excluded and the possibilities for producing mixed colors using the described pigments are severely restricted.
Die genannten Nachteile werden durch eine irreversible Fixierung von Farbstoffen in den Hohlräumen von geeigneten Molekularsieben umgangen. DE 41 26 461 beschreibt die Herstellung solcher Materialien sowie deren Einsatz als Pigment und optischen Datenspeicher. Farbstoffe, wie z.B. Phtha- locyanine, Phenoxazine, Azofarbstoffe usw. werden irreversibel fixiert, indem das Molekularsieb um den Farbstoff herum in-Situ gebildet wird. Diese Technik wird allgemein als „Crystallisation-Inclusion" bezeichnet (G. Schulz-Ekloff „Nonlinear optical effects of dye-loaded molecular sieves" in Advanced Zeolite Science and Application Studies in Surface Sciences Ca- talysis, Vol. 85 (1994), 145 - 175). Eine weitere Methode zur irreversiblen Fixierung von Farbstoffen in Molekularsieben, die „ship-in-the-bottle- Synthese", wurde z.B. von G. Meyer et al. beschrieben (Zeolites 4 (1984), 30). Hierzu werden Übergangsmetall-ausgetauschte Zeolithe mit o-Phthalo- dinitril umgesetzt, wobei der Farbstoff (Cobalt-, Nickel- oder Kupfer-The disadvantages mentioned are avoided by irreversible fixation of dyes in the cavities of suitable molecular sieves. DE 41 26 461 describes the production of such materials and their use as pigment and optical data storage. Dyes, such as phtha- Locyanins, phenoxazines, azo dyes, etc. are irreversibly fixed by forming the molecular sieve around the dye in situ. This technique is generally referred to as "crystallization inclusion" (G. Schulz-Ekloff "Nonlinear optical effects of dye-loaded molecular sieves" in Advanced Zeolite Science and Application Studies in Surface Sciences Catalysis, Vol. 85 (1994), 145 - 175). Another method for the irreversible fixation of dyes in molecular sieves, the "ship-in-the-bottle synthesis", has been described, for example, by G. Meyer et al. (Zeolites 4 (1984), 30). For this purpose, transition metal-exchanged zeolites reacted with o-phthalonitrile, the dye (cobalt, nickel or copper
Phthalocyanin) in den ca. 12 A großen Superkäfigen des Faujasits gebildet wird. Da diese Superkäfige nur durch ca. 7 A bis 8 A große Offnungen zugänglich sind, kann zwar das Phthalodinitril in die Hohlräume hineindiffundieren, ein Herausdiffundieren des gebildeten Farbstoffes ist jedoch aus sterischen Gründen nicht mehr möglich.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.
Basierend auf dieser sog. „ship-in-the-bottle" -Synthesetechnik beschreiben WO 93/17965, DE 42 07 339 AI und DE 41 31 447 AI die Herstellung von auf Molekularsieben basierenden Farbmitteln. Es werden indigoide Farbstoffe, Azofarbstoffe sowie Chinizarinfarbstoffe in Molekularsiebe aus den Klassen Zeolithe und zeolithähnliche Materialien eingebaut.Based on this so-called "ship-in-the-bottle" synthesis technique, 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.
Den beschriebenen Systemen und Verwendungszwecken gemein ist, dass die Lumineszenzstoffe ihre charakteristischen Eigenschaften behalten, die sie auch in Lösungen oder als Pulver besitzen. Durch den Einbau in den Zeoli- then werden insbesondere bei organischen Farbstoffen lediglich leichte Verschiebungen und Verbreiterungen der Spektralbanden beobachtet. Für die Anwendung als Markierung sind diese Effekte jedoch nicht von Vorteil. Da sie die Emissionsbanden zahlreicher verschiedener Lumineszenzstoffe über- läppen, wird die Selektivität des Nachweises der Substanzen stark eingeschränkt. Obwohl chemisch unterschiedliche Stoffe vorliegen, sind die Unterschiede ihrer Emissionsbanden oft so gering, dass ihre Lumineszenz über einen breiten Spektralbereich mit aufwändigen Mitteln untersucht werden muss, damit eine Identifizierung überhaupt möglich ist. Für viele Anwendungen ist der Aufwand einer eindeutigen Identifizierung deshalb so hoch, dass er nur in Ausnahmefällen durchgeführt werden kann.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.
Der Erfindung liegt daher die Aufgabe zugrunde, ein Wertdokument sowie ein Sicherheitselement zur Markierung von beliebigen Produkten mit wenigstens einem Lumineszenzstoff vorzuschlagen, der einfach nachweisbar und identifizierbar ist.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.
Diese Aufgabe wird durch die Merkmale der unabhängigen Ansprüche ge- löst. Weiterbildungen sind Gegenstand von UnteransprüchenThis task is solved by the features of the independent claims. Further training is the subject of subclaims
Gemäß der vorliegenden Erfindung wird als Echtheitsmerkmal für Wertdokumente ein lumineszierendes System verwendet, bei dem die Linienbreite von Farbstoffen durch den Effekt der stimulierten Emission stark verringert wird, um in einem ausgewählten Spektralbereich eine möglichst große Anzahl charakteristischer schmalbandiger Lumineszenzlinien verschiedener Farbstoff-Matrix -Systeme unterscheiden zu können. Die stimulierten Emissionsprozesse werden dadurch hervorgerufen, dass sich die Farbstoffe in einem Resonator befinden, der die Farbstoffe umschließt. Der Resonator wird von einem Molekularsieb-Kristallit gebildet, dessen Oberflächen die Lumineszenz der Farbstoffmoleküle einschließt. Die Lumineszenzstrahlung wird dabei über Mikrodefekte in diesen Oberflächen ausgekoppelt. Bei diesen Systemen handelt es sich um farbstoffbeladene Molekularsiebe, welche stimulierte Emission zeigen. Sie wurden erstmals auf der 10. Deutschen Zeolith-Tagung vorgestellt. Es handelte sich hierbei um mit Pyridin-2 beladene Molekularsiebe vom Typ AI PO-5. Der Effekt wurde ebenfalls an einem Molekularsieb AI PO-5 beobachtet, das mit Rhodamin dotiert und mittels „Crystallisation-Inclusion" hergestellt wurde.According to the present invention, 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".
Gemäß der Erfindung können jedoch auch beliebige andere farbstoffbeladene Molekularsiebe, die eine stimulierte Emission zeigen, verwendet werden. Als Farbstoffe können neben Vertretern aus den Klassen der Pyridine und Rhodamine auch Farbstoffe aus der Klasse der Cyanine oder Coumarine oder beliebige andere Farbstoffe aus der Klasse der Laserfarbstoffe eingesetzt werden. Die Spektraleigenschaften der Farbstoffe können dabei durch eine entsprechende chemische Modifikation des Chromophors eingestellt werden. Es können auch mehrere unterschiedliche Farbstoffe in einem Molekularsieb vorgesehen werden.However, any other dye-loaded molecular sieve that exhibits stimulated emission can also be used in accordance with the invention. In addition to representatives from the classes of pyridines and rhodamines, 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.
Bei dem verwendeten Molekularsieb handelt es sich vorzugsweise um ein Molekularsieb mit Kanalstruktur und geeigneter Morphologie, wie z.B. aus den Klassen AFI, LTL, MFI, M41S. Im Speziellen können beispielsweiseThe 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. In particular, for example
ALPO-5, SAPO-5 (AFI-Klasse) sowie weiterhin MAPO und MAPSO, ELAPO und ELAPSO verwendet werden. Hierbei steht M für ein beliebiges Metall, wie z.B. Mn, Mg, Co, Fe, Cr, Zn und EL für ein Element, wie z.B. Li, Be, B, Ti, As, Ga, Ge.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.
Um die Lichtechtheit des Materials zu erhöhen, kann zusätzlich zum Farbstoff in den Hohlräumen des Molekularsiebs ein UV- Absorber und/ oder ein UV-Stabilisator auf der Basis von sterisch gehinderten Aminen (HALS), vorzugsweise in einer Dosierung von 0,5 bis 3 Gew.% eingelagert werden. Auf diese Weise wird zusätzlich eine Photo-Stabilisierung außerhalb des UV- Bereichs, insbesondere bei der Wellenlänge des Farbstoffs erreicht. Als UV- Absorber kann beispielsweise Tinuvin-P, Tinuvin 928 (Ciba Geigy) verwendet werden. Bei den sterisch gehinderten Aminen handelt es sich beispiels- weise um Tinuvin 144 (Ciba Geigy), Tinuvin 123 (Ciba Geigy), HALS 3051 (Clariant) oder Derivate derselben.In order to increase the light fastness of the material, in addition to the dye in the cavities of the molecular sieve, a UV absorber and / or a UV stabilizer based on sterically hindered amines (HALS), preferably in a dosage of 0.5 to 3 wt .% are stored. On in this way, photo-stabilization outside the UV range, in particular at the wavelength of the dye, is additionally achieved. Tinuvin-P, Tinuvin 928 (Ciba Geigy), for example, 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.
Diese die Lichtechtheit erhöhenden Stoffe müssen nicht notwendigerweise in die Hohlräume des Molekularsiebes eingebracht werden, sondern können sich auch in oder an den inneren und äußeren Oberflächen des Molekularsiebes befinden.These substances which increase the light fastness do not necessarily have to be introduced into the cavities of the molecular sieve, but can also be located in or on the inner and outer surfaces of the molecular sieve.
Soll neben der Lichtechtheit auch die chemische Stabilität erhöht werden, so können statt der oder zusätzlich zu den UV-Stabilisatoren bzw. UV- Absorber auch Antioxidante mit in die Hohlräume eingebaut werden.If, in addition to light fastness, chemical stability is also to be increased, instead of or in addition to the UV stabilizers or UV absorbers, antioxidants can also be incorporated into the cavities.
Die Erfindung beruht nun auf der Erkenntnis, dass sich diese Systeme sehr vorteilhaft für Markierungsanwendungen eignen, da ein teilcheninterner Resonator dazu benutzt wird, die Lumineszenzlinienbreite des Systems bei geeigneter Anregung stark zu verringern. Es lässt sich deshalb eine großeThe 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
Anzahl verschiedener Farbstoffe über die spektrale Lage ihrer Lumineszenzspektren unterscheiden. D.h., mit Hilfe dieser Farbstoffe kann eine Vielzahl von Codierungen dargestellt werden. Die Zahl der unterschiedlichen Markierungen kann noch weiter erhöht werden, wenn zusätzlich die Intensität der emittierten Strahlung ausgewertet wird, die proportional zur Menge des vorhandenen Lumineszenz- bzw. Farbstoffes ist.Distinguish the number of different dyes by the spectral position of their luminescence spectra. This means that a multitude of codes can be represented with the help of these dyes. The number of different markings can be increased further if the intensity of the emitted radiation is also evaluated, which is proportional to the amount of luminescent or dye present.
Mit Hilfe der erfindungsgemäßen Idee können so unterschiedlichste Codierungssysteme gebildet werden. Beispielsweise kann ein Objekt mit verschie- denen der oben beschriebenen Farbstoffe markiert werden. Die Codierung entsteht dabei durch das Vorhandensein bzw. Fehlen eines oder mehrerer Partikel.With the help of the idea according to the invention, 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.
Es sind jedoch auch Codierungsysteme denkbar, bei welchen sowohl die Zahl als auch der Aufbau (Auswahl der Farbstoff-Molekularsieb-Kombination) variiert werden. Bei schwacher Anregung entsteht so ein undurchsichtiges und spektral nur schwer zu trennendes Mischspektrum. Erst bei starker Anregung offenbaren die oben beschriebenen Partikel ihre besondere Eigenschaft und treten aus dem breitbandigen Lumineszenzspektrum der Mischung hervor.However, coding systems are also conceivable in which both the number and the structure (selection of the dye-molecular sieve combination) are varied. With weak excitation, an opaque and spectrally difficult to separate mixed spectrum is created. The particles described above only reveal their special properties when strongly excited and emerge from the broadband luminescence spectrum of the mixture.
Die charakteristischen Eigenschaften der Farbstoff-Molekularsieb-Systeme zeigen sich erst bei intensiver optischer Anregung mit Licht geeigneter Wel- lenlänge. Aufgrund des Schwellenverhaltens der Systeme muss die optische Bestrahlungsstärke einen für die Systeme charakteristischen Schwellenwert überschreiten. Typische Schwellenwerte betragen 0,2 - 4 MW/ cm2. Als Anregungsquelle kommen Lichtquellen geeigneter Wellenlänge mit ausreichender Strahlungsleistung in Frage. Eine optische Vorrichtung kann ver- wendet werden, um das Licht der Anregungsquelle auf einen hinreichend kleinen Fleck zu konzentrieren und so die Bestrahlungsstärke der Systeme zu erhöhen.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.
Im Folgenden werden einige Beispiele der erfindungsgemäß verwendbaren Farbstoffe bzw. Echtheitsmerkmale angegeben. Beispiel 1Some examples of the dyes or authenticity features which can be used according to the invention are given below. example 1
Es werden Farbstoffe aus der Klasse der Pyridine in ein geeignetes Molekularsieb, wie z.B. ein SAPO-5 Molekularsieb eingeschlossen. Bei Anregung mit einem frequenzverdoppelten NdNAG-Laser absorbiert das farbstoffbelade- ne Molekularsieb im Bereich der Laserwellenlänge von 532 nm. Bei einer Laserleistungsdichte von 4 MW/ cm2 zeigt das farbstoffbeladene Molekularsieb im Bereich von ca. 680 nm ein sehr schmalbandiges laserartiges Fluoreszenzspektrum.Dyes from the class of pyridines are enclosed in a suitable molecular sieve, such as, for example, an SAPO-5 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.
Beispiel 2Example 2
Es wird ein Farbstoff aus der Klasse der Rhodamine in ein geeignetes Molekularsieb, welches z.B. zum Strukturtyp MFI, LTL, EMT, M41S, AFI, CHA gehört. Bei Anregung mit einem frequenzverdoppelten ΝdNAG-Laser und einer Laserleistungsdichte von 4 MW/ cm2 zeigt dieser Stoff im Bereich von 560 nm ein sehr schmalbandiges laserartiges Fluoreszenzspektrum.It 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. When excited with a frequency-doubled ΝdNAG 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.
Beispiel 3Example 3
Es wird ein Farbstoff aus der Klasse der Coumarine in ein geeignetes Molekularsieb, wie z.B. ein AI PO-5 Molekularsieb eingeschlossen. Bei Anregung mit einem Xe Cl-Excimer-Laser mit einer Wellenlänge von 308 nm und einer Laserleistungsdichte von 4 MW/ cm2 zeigt das Molekularsieb im Bereich von 530 nm ein sehr schmalbandiges laserartiges Fluoreszenzspektrum.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. 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.
Der Nachweis der Systeme muss den Nachweis mindestens einer der folgenden charakteristischen Eigenschaften der Systeme beinhalten, um eine Abgrenzung gegenüber herkömmlichen, nicht stimuliert emittierenden Lumineszenzstoffen zu ermöglichen.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.
Der charakteristische Intensitätsanstieg in einem schmalen Wellenlängenbe- reich bei überschwelliger Anregung kann bei Beobachtung durch das charakteristische Schwellenverhalten des Intensitätsanstiegs bei Erhöhung der Bestrahlungsstärke mittels eines geeigneten spektral einengenden Elements im Nachweiskanal nachgewiesen werden.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.
Die charakteristische Lumineszenzlinienverschmälerung kann durch den Vergleich der Intensitäten in dem für das Farbstoffsystem charakteristischen engen Wellenlängenbereich mit der Intensität in anderen Wellenlängenbereichen nachgewiesen werden. Dies geschieht z.B. mittels eines Spektrome- teraufbaus hinreichender spektraler Auflösung oder durch Messung in ver- schiedenen Nachweiskanälen, die durch geeignete spektral selektive Elemente die Intensität in dem benötigten Spektralbereich messen. Bei überschwelliger Anregung beobachtet man eine charakteristische Spektralverteilung mit einem Intensitätsmaximum bei der charakteristischen Wellenlänge bzw. charakterstische Intensitätsverhältnisse in den verschiedenen Kanälen, die mit herkömmlichen Lumineszenzfarbstoffen nicht auftreten.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.
Die charakteristische Verkürzung der Lumineszenzlebensdauer bei der charakteristischen Wellenlänge des Farbstoffsystems auf typischerweise < 300 ps ermöglicht ebenfalls die Unterscheidung der Systeme von her- kömmlichen Lumineszenzfarbstoffen (typische Lebensdauer > 3 ns). Hierfür werden Anregungsquellen benötigt, deren Abschaltzeiten deutlich kürzer sind als die Lebensdauer der herkömmlichen Lumineszenzfarbstoffe. Auch die Abklingzeiten von Detektor und Nachweiselektronik müssen vergleichbar schnell sein. Als weitere charakteristische Eigenschaft der Systeme tritt die Sättigung des optischen Übergangs erst bei sehr viel höheren Lumineszenzintensitäten auf, so dass mit diesen Systemen wesentlich höhere Lumineszenzintensitäten beobachtet werden können als bei herkömmlichen Lumineszenzstoffen.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.
Die beschriebenen Molekularsiebe bilden bei geeigneter Synthese Mikrokri- stalle oder kristallähnliche Strukturen, die im Folgenden als Partikel bezeichnet werden. Die Partikel können direkt zur Markierung beliebiger Ge- genstände, insbesondere von Wertpapieren, Pässen, Formularen, CDs oder sonstigen Produkten des täglichen Bedarfs benutzt werden. Die einfachste Möglichkeit besteht dabei darin, die Partikel einer Druckfarbe zuzusetzen. Die Partikel können jedoch auch direkt dem Material des Gegenstandes zugesetzt werden. Dies ist beispielsweise sinnvoll, wenn der zu sichernde Ge- genstand ein Wertdokument, wie eine Banknote oder eine Ausweiskarte ist. Im Fall der Banknote werden die Partikel vorzugsweise der Papiermasse während der Herstellung des Banknotenpapiers zugesetzt. Bei Ausweiskarten dagegegen kann eine der Deck- oder Inlettschichten im Volumen mit den Partikeln versetzt sein. Ebenso können die Partikel auch direkt in ein Poly- mer eingebettet werden.With a suitable synthesis, 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.
Gemäß einer weiteren Ausführungsform kann das erfindungsgemäße Echtheitsmerkmal bzw. der oder die farbstoffbeladenen Molekularsiebe auch mit einer Art Tarnstoff kombiniert werden. In diesem Fall werden für die Erzeu- gung einer Markierung zwei Lumineszenzstoffe verwendet, wobei einer der Stoffe ein herkömmlicher Lumineszenzstoff und der andere ein erfindungsgemäßes farbstoffbeladenes Molekularsieb ist. Bei unterschwelliger Anregung verhalten sich beide Stoffe gleich, während sich bei überschwelliger Anregung das Emissionsverhalten des farbstoffbeladenen Molekularsiebs, wie bereits erläutert, verändert. Wird nun beispielsweise ein Barcode mit den erfindungsgemäßen Partikeln gedruckt und die Zwischenräume des Barcodes mit dem herkömmlichen Lumineszenzstoff, so ist bei unterschwelliger Anregung lediglich ein einheitlich lumineszierendes Feld nachzuwei- sen. Bei überschwelliger Anregung der erfindungsgemäßen Partikel ergeben sich im Emissionsspektrum im Bereich der Balken des Barcodes schmale Lumineszenzpeaks und machen auf diese Weise den Code sichtbar. Mit Hilfe dieses Prinzips können selbstverständlich auch beliebige andere Codierungen oder Informationen dargestellt werden.According to a further embodiment, 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. In this case, 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. With 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. If, for example, 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. When the particles according to the invention are stimulated above threshold, 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. With the help of this principle, of course, any other coding or information can be displayed.
Die Stoffe, herkömmlicher Lumineszenzstoff und erfindungsgemäßes Molekularsieb, können auch gemeinsam in einer Druckfarbe oder einem anderen Trägermaterial enthalten sein. In diesem Fall dient die überschwellige Anregung des Molekularsiebes als zusätzliches Echtheitsmerkmal und erhöht somit die Fälschungssicherheit.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. In this case, the excitation of the molecular sieve serves as an additional authenticity feature and thus increases the security against forgery.
Weitere Ausführungsbeispiele sowie Vorteile der Erfindung werden anhand der Figuren erläutert. Es wird darauf hingewiesen, dass es sich hierbei lediglich um Prinzipskizzen handelt, die keinerlei Anspruch auf Vollständigkeit oder maßstabsgetreue Darstellung erheben.Further exemplary embodiments and advantages of the invention are explained on the basis of the figures. It is pointed out that these are only sketches that do not claim to be complete or true to scale.
Es zeigen:Show it:
Fig. 1 erfindungsgemäßes Wertdokument mit einem erfindungsge- mäßen Echtheitsmerkmal,1 document of value according to the invention with an authenticity feature according to the invention,
Fig. 2 Schnitt entlang A - A des Wertdokuments in Fig. 1,2 section along A - A of the value document in Fig. 1,
Fig. 3 Schnitt entlang A - A einer weiteren Ausführungsform des erfindungsgemäßen Wertdokuments,Fig. 3 section along A - A of another embodiment of the document of value according to the invention,
Fig. 4 Absorptionsspektrum eines erfindungsgemäßen Echtheitsmerkmals,4 absorption spectrum of an authenticity feature according to the invention,
Fig. 5 Emissionsspektrum eines erfindungsgemäßen Echtheitsmerkmals,5 emission spectrum of an authenticity feature according to the invention,
Fig. 6 Verhalten der Emissionsintensität in Abhängigkeit von der Anregungsintensität eines erfindungsgmäßen Echtheitsmerkmals.6 behavior of the emission intensity as a function of the excitation intensity of an authenticity feature according to the invention.
Fig. 1 zeigt ein erfindungsgemäßes Wertdokument 1 mit einem erfindungsgemäßen Sicherheitselement 2. Im gezeigten Beispiel besteht das Sicherheits- element 2 aus einem strichliert gezeichneten Bereich, in dem das eigentliche Echtheitsmerkmal, ein Aufdruck 3, angeordnet ist. Dieser Aufdruck 3 enthält die erfindungsgemäßen farbstoffbeladenen Molekularsiebpartikel.1 shows a document of value 1 according to the invention with a security element 2 according to the invention. In the example shown, the security element 2 consists of an area drawn in broken lines, in which the actual authenticity feature, an imprint 3, is arranged. This imprint 3 contains the dye-loaded molecular sieve particles according to the invention.
Alternativ könnte das Sicherheitselement 2 auch in Form eines Etiketts aus- gebildet sein, welches das Echtheitsmerkmal 3 in Form eines Aufdrucks trägt. Ebenso ist es denkbar, das Sicherheitselement 2 in Form eines Fadens oder Bandes auszubilden, wobei das Echtheitsmerkmal 3 auf einem Trägermaterial, vorzugsweise einer Kunststofffolie angeordnet wird. Dieses Band kann entweder vollflächig auf der Oberfläche des Wertdokuments 1 ange- ordnet werden oder zumindest teilweise in das Wertdokument eingebettet sein. Diese Art der Einbringung bietet sich insbesondere bei Banknoten an, die häufig mit sogenannten „Fenstersicherheitsfäden" versehen werden. Hier wird der Sicherheitsfaden quasi in das Papier während dessen Herstel- lung eingewebt, so dass er in bestimmten Bereichen direkt an die Oberfläche des Papiers tritt.Alternatively, 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". Here, 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 zeigt das in Fig. 1 dargestellte Wertdokument entlang der Linie A - A im Querschnitt. Der Aufdruck 3 auf dem Wertdokument 1, welcher im vorliegenden Fall das Echtheitsmerkmal bildet, enthält Partikel, die von einem farbstoffbeladenen Molekularsieb gebildet werden. Unter normaler Beleuchtung ist das Echtheitsmerkmal 3 üblicherweise nicht sichtbar, sondern wird erst nach Anregung mit entsprechender Strahlung erkennbar. Je nach ge- wünschtem Effekt kann das Echtheitsmerkmal 3 bzw. der das Echtheitsmerkmal 3 bildende Aufdruck auch weitere visuell durchaus sichtbare Farbstoffe enthalten. Hierbei ist allerdings darauf zu achten, dass diese zusätzlichen Farbstoffe im Emissionswellenlängenbereich der erfindungsgemäßen Partikel keine nennenswerte Absorption aufweisen.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. Depending on the desired effect, 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.
Fig. 3 zeigt eine weitere Ausführungsform des erfindungsgemäßen Wertdokuments 1 im Querschnitt entlang der Linie A - A. Hier besteht das Sicherheitsmerkmal 2 nicht nur aus dem Echtheitsmerkmal 3 in Form eines Aufdrucks, sondern es weist zusätzlich einen Tarnaufdruck 4 auf, der das Echt- heitsmerkmal 3 im gesamten Bereich des Sicherheitselements 2 umgibt. D.h., die in Fig. 1 strichliert dargestellte Fläche ist vollständig mit dem Tarnaufdruck 4 versehen, ausgenommen der Bereich des Echtheitsmerkmals 3. Dieser Tarnaufdruck 4 enthält einen gewöhnlichen Lumineszenzstoff, der ebenfalls vorzugsweise im visuellen Spektralbereich transparent ist. Zusätzlich zeigt dieser Lumineszenzstoff das gleiche Absorptions- und Emissionsverhalten wie die erfindungsgemäßen Partikel, so lange sie mit einer Laserleistungsdichte unterhalb des für diese Partikel charakteristischen Schwellwerts angeregt werden. Auf diese Weise kann ein entsprechender Detektor bei unterschwelliger Anregung das Sicherheitselement 2 lediglich als ein- heitiich lumineszierende Fläche wahrnehmen. Bei überschwelliger Anregung ändert sich das Emissionsverhalten des Echtheitsmerkmals 3 und die durch das Echtheitsmerkmal 3 dargestellte Markierung tritt in Form von schmalen, sehr intensitätsstarken Emissionslinien aus dem lumineszierenden Unter- grund, der durch den Tarnaufdruck 4 gebildet wird, hervor.3 shows a further embodiment of the document of value 1 according to the invention in cross section along the line A - A. Here, 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. In this way, a corresponding detector with subliminal excitation can only use the security element 2 as a perceive luminescent surface. With excitation above threshold, the emission behavior of the authenticity feature 3 changes and the marking represented by the authenticity feature 3 emerges in the form of narrow, very high-intensity emission lines from the luminescent background formed by the camouflage print 4.
Fig. 4 zeigt das Absorptionsspektrum eines erfindungsgemäßen farbstoffbeladenen Molekularsiebs im Bereich von 530 nm.4 shows the absorption spectrum of a dye-loaded molecular sieve according to the invention in the range of 530 nm.
Wird für die Bestrahlung des Echtheitsmerkmals 3 eine Lichtquelle mit einer geringen Strahlungsdichte verwendet, so zeigt das Echtheitsmerkmal eine relativ breitbandige Lumineszenzemission, die auf spontaner Emission beruht und in Figur 5 durch die Kurve A dargestellt wird. Liegt die Strahlungsdichte der Anregungslichtquelle allerdings oberhalb eines bestimmten Schwellwerts, so zeigen die in dem Molekularsieb eingeschlossenen Farbstoffe eine stimulierte Emission. Hier zeigt das Material eine sehr schmal- bandige Emission im Bereich von 680 nm, wie durch die Kurve B in Fig. 5 dargestellt.If a light source with a low radiation density is used for the irradiation of the authenticity feature 3, the authenticity feature shows a relatively broadband luminescence emission which is based on spontaneous emission and is represented by curve A in FIG. However, if 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. Here the material shows a very narrow-band emission in the range of 680 nm, as shown by curve B in FIG. 5.
Diesen Sachverhalt verdeutlicht Fig. 6. Die Emissionsintensität IE wächst unterhalb der Schwelle Is nur langsam mit der Anregungsintensität. Oberhalb des Schwellwerts Is setzt die stimulierte Emission des farbstoffbeladenen Molekularsiebs ein, so daß die Emissionsintensität sehr viel schneller mit der Anregungsintensität wächst. Hier wirkt das den Farbstoff umgebende Mole- kularsieb wie ein Laserresonator, der die vom Farbstoff emittierte Lumines- zenzstrahlung laserähnlich verstärkt.This situation is illustrated in FIG. 6. 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. Here, 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.
Gemäß der Erfindung können auch mehrere Partikel, die aus unterschiedlichen farbstoffbeladenen Molekularsieben bestehen, miteinander gemischt werden. Bei unterschwelliger Anregung entsteht hierbei ein praktisch nicht auflösbares Emissionsspektrum, da sich die relativ breiten Emissionsbande der einzelnen Lumineszenzfarbstoffe stark überlappen. Erst bei überschwelliger Anregung verengen sich die Emissionslinien der einzelnen Farbstoffe sehr stark und zeigen das oben beschriebene laserartige Verhalten. In diesem Zustand können die einzelnen Spektrallinien der Farbstoffe sehr gut voneinander unterschieden werden. According to the invention, several particles consisting of different dye-laden molecular sieves can also be mixed with one another become. With subliminal excitation, a practically non-resolvable emission spectrum arises, since the relatively broad emission band of the individual luminescent dyes overlap strongly. Only with excitation above threshold does the emission lines of the individual dyes narrow very sharply and show the laser-like behavior described above. In this state, the individual spectral lines of the dyes can be distinguished very well from one another.

Claims

P a t e n t a n s p r ü c h e Patent claims
1. Wertdokument (1), wie Wertpapier, Ausweiskarte oder dergleichen, mit wenigstens einem Echtheitsmerkmal (3) in Form einer lumineszierenden Substanz, wobei die lumineszierende Substanz (3) Partikel aufweist, die aus einem farbstoffbeladenen Molekularsieb bestehen, dessen Struktur einen optischen Resonator ausbildet, in dem zumindest ein Farbstoff zu stimulierter Emission angeregt werden kann, wobei der Farbstoff in den Hohlräumen des Molekularsiebs eingebaut ist bzw. sich in oder an den inneren und äuße- ren Oberflächen des Molekularsiebs befindet und der Übergang zur stimulierten Emission mit einer nachweisbaren Veränderung der Lumineszenzeigenschaften des Farbstoffs einhergeht.1. document of value (1), such as security, identity card or the like, with at least one authenticity feature (3) in the form of a luminescent substance, the luminescent substance (3) having particles which consist of a dye-laden molecular sieve, the structure of which forms an optical resonator , in which at least one dye can be stimulated to stimulated emission, the dye being built into the cavities of the molecular sieve or being located in or on the inner and outer surfaces of the molecular sieve, and the transition to stimulated emission with a detectable change in Luminescence properties of the dye goes hand in hand.
2. Wertdokument (1) nach Anspruch 1, dadurch gekennzeichnet, dass die lumineszierende Substanz (3) verschiedene Partikel aufweist, die aus unterschiedlichen farbstoffbeladenen Molekularsieben bestehen.2. document of value (1) according to claim 1, characterized in that the luminescent substance (3) has different particles consisting of different dye-loaded molecular sieves.
3. Wertdokument (1) nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass Molekularsiebe mit Kanalstruktur, wie z.B. aus den Klassen Aluminophos- phate eingesetzt werden.3. document of value (1) according to claim 1 or 2, characterized in that molecular sieves with channel structure, such as. from the classes of aluminophosphates.
4. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Farbstoffmoleküle aus der Klasse der Laserfarbstoffe eingesetzt werden.4. document of value (1) according to at least one of claims 1 to 3, characterized in that the dye molecules from the class of laser dyes are used.
5. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Spektraleigenschaften des Farbstoffs durch Wahl der Endgruppen eingestellt wird. 5. document of value (1) according to at least one of claims 1 to 4, characterized in that the spectral properties of the dye is adjusted by choice of the end groups.
6. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Molekularsieb verschiedene anregbare Farbstoffe aufweist.6. document of value (1) according to at least one of claims 1 to 5, characterized in that the molecular sieve has different excitable dyes.
7. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Wertdokument (1) ein weiteres Echtheitsmerkmal aufweist.7. document of value (1) according to at least one of claims 1 to 6, characterized in that the document of value (1) has a further authenticity feature.
8. Wertdokument (1) nach Anspruch 7, dadurch gekennzeichnet, dass das zweite Echtheitsmerkmal ein weiterer Lumineszenzstoff ist, der vorzugsweise die gleiche Körperfarbe aufweist wie die lumineszierende Substanz.8. document of value (1) according to claim 7, characterized in that the second authenticity feature is a further luminescent substance, which preferably has the same body color as the luminescent substance.
9. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die lumineszierende Substanz (3) im Volumen des Wertdokuments (1) vorliegt.9. document of value (1) according to at least one of claims 1 to 8, characterized in that the luminescent substance (3) is present in the volume of the document of value (1).
10. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die lumineszierende Substanz (3) einer Druckfarbe zugemischt ist.10. document of value (1) according to at least one of claims 1 to 8, characterized in that the luminescent substance (3) is mixed with a printing ink.
11. Wertdokument (1) nach Anspruch 10, dadurch gekennzeichnet, dass die Druckfarbe in Form einer Codierung, insbesondere eines Barcodes aufgebracht ist.11. document of value (1) according to claim 10, characterized in that the printing ink is applied in the form of a coding, in particular a barcode.
12. Wertdokument (1) nach Anspruch 10 oder 11, dadurch gekennzeichnet, dass die Druckfarbe mit der lumineszierenden Substanz von einer zweiten Druckfarbe mit einer weiteren lumineszierenden Substanz umgeben ist. 12. document of value (1) according to claim 10 or 11, characterized in that the printing ink with the luminescent substance is surrounded by a second printing ink with a further luminescent substance.
13. Wertdokument (1) nach wenigstens einem der Ansprüche 10 bis 12, dadurch gekennzeichnet, dass die Druckfarbe zumindest bereichsweise auf dem Wertdokument (1) oder einem Träger aufgebracht ist, der mit dem Wertdokument (1) verbunden ist.13. document of value (1) according to at least one of claims 10 to 12, characterized in that the printing ink is applied at least in regions to the document of value (1) or a carrier which is connected to the document of value (1).
14. Wertdokument (1) nach wenigstens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die lumineszierende Substanz (3) in oder auf einem Sicherheitselement (2) angeordnet ist, das mit dem Wertdokument verbunden ist.14. document of value (1) according to at least one of claims 1 to 8, characterized in that the luminescent substance (3) is arranged in or on a security element (2) which is connected to the document of value.
15. Sicherheitselement (2) mit wenigstens einem Echtheitsmerkmal (3) in Form einer lumineszierenden Substanz, wobei die lumineszierende Substanz (3) Partikel aufweist, die aus einem farbstoffbeladenen Molekularsieb bestehen, dessen Struktur einen optischen Resonator ausbildet, in dem zumindest ein Farbstoff zu stimulierter Emission angeregt werden kann, wobei der Farbstoff in den Hohlräumen des Molekularsiebs eingebaut ist bzw. sich in oder an den inneren und äußeren Oberflächen des Molekularsiebs befindet und der Übergang zur stimulierten Emission mit einer nachweisbaren Veränderung der Lumineszenzeigenschaften des Farbstoffs einhergeht.15. Security element (2) with at least one authenticity feature (3) in the form of a luminescent substance, the luminescent substance (3) having particles which consist of a dye-laden molecular sieve, the structure of which forms an optical resonator in which at least one dye is stimulated Emission can be excited, wherein the dye is built into the cavities of the molecular sieve or is located in or on the inner and outer surfaces of the molecular sieve and the transition to stimulated emission is accompanied by a detectable change in the luminescent properties of the dye.
16. Sicherheitselement (2) nach Anspruch 15, dadurch gekennzeichnet, dass das Sicherheitselement (2) wenigstens ein Trägermaterial aufweist, in dessen Volumen oder auf dessen Oberfläche die lumineszierende Substanz (3) angeordnet ist.16. Security element (2) according to claim 15, characterized in that the security element (2) has at least one carrier material, in the volume or on the surface of which the luminescent substance (3) is arranged.
17. Sicherheitselement (2) nach Anspruch 15 oder 16, dadurch gekennzeichnet, dass das Sicherheitselement (2) die Form eines Streifens, Bandes oder Etiketts aufweist. 17. Security element (2) according to claim 15 or 16, characterized in that the security element (2) has the shape of a strip, tape or label.
18. Verfahren zur Markierung von Produkten, wobei das Produkt mit einer lumineszierenden Substanz versehen wird, die Partikel aufweist, die aus einem farbstoffbeladenen Molekularsieb bestehen, dessen Struktur einen optischen Resonator ausbildet, in dem zumindest ein Farbstoff zu stimulierter Emission angeregt werden kann, wobei der Farbstoff in den Hohlräumen des Molekularsiebs eingebaut ist bzw. sich in oder an den inneren und äußeren Oberflächen des Molekularsiebs befindet und der Übergang zur stimulierten Emission mit einer nachweisbaren Veränderung der Lumineszenzeigenschaften des Farbstoffs einhergeht.18. A method for marking products, the product being provided with a luminescent substance which has particles which consist of a dye-loaded molecular sieve, the structure of which forms an optical resonator in which at least one dye can be excited to stimulate emission, the Dye is built into the cavities of the molecular sieve or is located in or on the inner and outer surfaces of the molecular sieve and the transition to stimulated emission is accompanied by a detectable change in the luminescent properties of the dye.
19. Verfahren zur Überprüfung einer lumineszierenden Substanz, die Partikel aufweist, die aus die aus einem farbstoffbeladenen Molekularsieb bestehen, dessen Struktur einen optischen Resonator ausbildet, in dem zumindest ein Farbstoff zu stimulierter Emission angeregt werden kann, wobei der Farbstoff in den Hohlräumen des Molekularsiebs eingebaut ist bzw. sich in oder an den inneren und äußeren Oberflächen des Molekularsiebs befindet und der Übergang zur stimulierten Emission mit einer nachweisbaren Veränderung der Lumineszenzeigenschaften des Farbstoffs einhergeht, wobei die Linienverschmälerung und -Verschiebung und/ oder das Schwellenver- halten und/ oder die Lebensdauerverkürzung als Echtheitsmerkmal verwendet werden.19. A method for checking a luminescent substance which has particles which consist of a dye-loaded molecular sieve, the structure of which forms an optical resonator in which at least one dye can be excited to stimulate emission, the dye being incorporated into the cavities of the molecular sieve is or is located in or on the inner and outer surfaces of the molecular sieve and the transition to the stimulated emission is accompanied by a detectable change in the luminescent properties of the dye, the line narrowing and shifting and / or the threshold behavior and / or the shortening of the lifespan as Authenticity feature can be used.
20. Verwendung von farbstoffbeladenen Molekularsieben, welche ohne äußeren Resonator eine stimulierte Lumineszenz zeigen, zur Markierung von Produkten. 20. Use of dye-loaded molecular sieves, which show stimulated luminescence without an external resonator, for labeling products.
EP00941978A 1999-05-25 2000-05-23 Valuable document Expired - Lifetime EP1200272B1 (en)

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