EP1370424B1 - Value document - Google Patents

Value document Download PDF

Info

Publication number
EP1370424B1
EP1370424B1 EP02748334A EP02748334A EP1370424B1 EP 1370424 B1 EP1370424 B1 EP 1370424B1 EP 02748334 A EP02748334 A EP 02748334A EP 02748334 A EP02748334 A EP 02748334A EP 1370424 B1 EP1370424 B1 EP 1370424B1
Authority
EP
European Patent Office
Prior art keywords
document
value according
host lattice
formula
range
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.)
Expired - Lifetime
Application number
EP02748334A
Other languages
German (de)
French (fr)
Other versions
EP1370424B2 (en
EP1370424A1 (en
Inventor
Thomas Giering
Rainer Hoppe
Fritz Stahr
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=7676708&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP1370424(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Giesecke and Devrient GmbH filed Critical Giesecke and Devrient GmbH
Publication of EP1370424A1 publication Critical patent/EP1370424A1/en
Publication of EP1370424B1 publication Critical patent/EP1370424B1/en
Application granted granted Critical
Publication of EP1370424B2 publication Critical patent/EP1370424B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • 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
    • 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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • 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
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light
    • 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
    • Y10T428/22—Nonparticulate element embedded or inlaid in substrate and visible
    • 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.]
    • 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.]
    • Y10T428/24934—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including paper layer

Definitions

  • the invention relates to a printed document of value with at least one authenticity feature in the form of a luminescent substance based on host gittons doped with chromophores of the electron configuration (3d) 2 .
  • the emissions are at wavelengths between approx. 400 nm and approx. 700 nm, so are the luminescent substances with suitable excitation detectable to the eye. This is desirable for some applications, e.g. in the authenticity check by lighting with UV light. For others On the other hand, it is advantageous for applications if the emission is outside the visible spectral range, because then special detectors for detection of substances are necessary.
  • Luminophores with characteristic properties that are used for hedging of value documents and in particular for automatic authenticity detection are suitable, but their number is limited. Most inorganic and organic luminophores have uncharacteristic, broad spectra and are also often commercially available. This makes their identification difficult and makes the simultaneous use of several of these substances impractical.
  • DE-A-198 04 021 describes a document of value with at least one authenticity feature in the form of a luminescent substance based on doped host lattices.
  • Interference pigments are not luminescent. These interference pigments are silicate flakes made with titanium dioxide are coated.
  • the object of the invention underlying, the number of luminophores that prove to be authenticity suitable for value documents, increase, and in particular value documents with authenticity features in the form of luminescent substances to create that different from value documents with previously known luminophores through a characteristically modified excitation and / or Distinguish emission spectrum.
  • the invention is based on the knowledge that with increasing Emission wavelength in the IR spectral range difficult to detect certain luminescences are very advantageous for increasing protection against counterfeiting can be used.
  • At least for securing security documents uses a luminescent substance whose emission spectrum is outside of the visible spectral range, preferably even outside the response sensitivity of silicon detectors.
  • the substances suitable for the authenticity assurance according to the invention are luminescent substances based on host lattices which are doped with chromophores of the electron configuration (3d) 2 . These can be chromophores of one type or a mixture of at least two different chromophores.
  • the chromophores according to the invention are preferably the transition metals titanium in the oxidation state Ti 2+ , hereinafter referred to as Ti (II), vanadium in the oxidation state V 3+ , hereinafter referred to as V (III), chromium in the oxidation state Cr 4+ , hereinafter Cr (IV), manganese in the oxidation state Mn 5+ , hereinafter Mn (V), and iron in the oxidation state Fe 6+ , hereinafter Fe (VI).
  • the host lattices are inorganic matrices or organic ones Chelates, e.g. Apatite, Spodiosite, Palmierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphites, garnets, perovskites, olivines and certain silicates, titanates, Vanadates, phosphates, sulfates, aluminates, zirconates.
  • Chelates e.g. Apatite, Spodiosite, Palmierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphites, garnets, perovskites, olivines and certain silicates, titanates, Vanadates, phosphates, sulfates, aluminates,
  • the host lattice Ba SO 4 is particularly preferred.
  • Y PO 4 , La PO 4 , Zr Si O 4 is particularly preferred.
  • K Ti 2 (PO 4 ) 3 , K Zr 2 (PO 4 ) 3 is particularly preferred.
  • Host lattices with a strong crystal field are particularly preferred.
  • the locations and forms of the excitation and / or emission bands are depending on the position of the chromophores in the host lattice.
  • the chromophores can both in the oxidic structural units of the host lattice exist in the tetrahedron as well as in the octahedron configuration.
  • the tetroxo configuration in the host lattice is preferred.
  • the locations and forms of the excitation and / or emission band on the strength of the crystal field in the host lattice.
  • 1a shows how the position and sequence of the electronic levels of the chromophore Cr 3+ depend on the strength of the crystal field, ie the interaction between the chromophore and the lattice (Tanabe-Sugano diagram).
  • the electronic state 4 T 2 is the first excited state above the ground state 4 A 2 , a broadband luminescence from the level 4 T 2 is observed.
  • the state 2 E which is only weakly dependent on the crystal field, is the first excited electronic state and a narrow-band emission from this level is observed.
  • Analog energy level schemes can be formulated for the (3d) 2 configuration according to the invention with the corresponding designations of the levels.
  • O h octahedral
  • T d tetrahedral
  • the excitation and emission spectra of the luminescent according to the invention Influencing substances and so a variety of security features to produce.
  • the excitation and / or emission spectra can also be the lciminescence lifetime be used to differentiate.
  • the number of distinguishable substances according to the invention can be increase further if mixed crystals of the host lattice are also permitted or the host lattice can be varied with additional doping.
  • mixed crystals of the host lattice can be Apatite and Spodiosite or grenade and Perovskite in certain Concentration ratios of the starting substances form mixed crystals, where the grids merge.
  • the crystal field, that acts on the chromophore can be changed.
  • Chromophores to introduce more chromophores into the host lattice and so on a combined luminescence of both systems or an energy transfer reach between systems and use for identification.
  • rare earth ions are suitable for this, because of their shielded Shells retain their typical luminescence even in the host lattice.
  • Nd neodymium
  • Ho holmium
  • Er erbium
  • Tm thulium
  • Yb ytterbium
  • the document of value instead of one with several of the invention luminescent substances marked, so the number of distinguishable Further increase combinations. Also become different Mixing ratios differ from each other, the number can Combinations can be increased again.
  • the marking can either at different points in the value document or at the same Place. If the luminescent substance is in different places of the A value code can be applied or introduced, so a spatial code in the simplest case e.g. a barcode.
  • the security against forgery of the value document can be increased, if the particular luminescent substance chosen e.g. in a value document is linked to other information in the value document, so that a check using a suitable algorithm is possible.
  • the document of value in addition to the invention luminescent substance still further additional authenticity features, such as classic fluorescence and / or magnetism.
  • the luminescent substances can according to the invention in various Way into the value document. So the luminescent substances can, for example, in a printing ink be introduced. But also an admixture of the luminescent substance to paper pulp or plastic pulp when producing a value document on the basis of paper or plastic is possible. As well can the luminescent substances on or in a plastic carrier material are provided, which, for example, at least in turn can be partially embedded in the pulp.
  • the carrier material on a suitable polymer, e.g. PMMA based and in that the luminescent substance according to the invention is embedded here the form of a security thread, a mottled fiber or a planchette to have.
  • the luminescent substance can also be used to secure the product e.g. directly into the material of the object to be secured, e.g. in Insert housings and plastic bottles.
  • the plastic or paper carrier material can also be on any other item, e.g. be secured for product safety.
  • carrier material is preferably in the form of a label. If the carrier material is part of the product to be secured, as it e.g. the case of tear threads is of course also any other Shape possible. It can be useful in certain applications be the luminescent substance as an invisible coating to provide the value document. It can cover the entire surface or in Shape of certain patterns, e.g. Stripes, lines, circles or else are in the form of alphanumeric characters.
  • the carrier material can already be suitably colored so that colored luminescent substances due to their Own color can not be perceived.
  • the luminescent substances according to the invention are usually used processed in the form of pigments.
  • the pigments can increase their stability especially as individual encapsulated pigment particles are present or with an inorganic or organic coating.
  • the individual For this purpose, pigment particles are surrounded with a silicate shell and can be so disperse more easily in media.
  • Different pigment particles can also be used a combination can be encapsulated together, e.g. in fibers, threads, Silicathüllen. So it is e.g. no longer possible the "code” of the combination to change later. Under “encapsulation” there is a complete Enveloping the pigment particles to understand while using "Coating" too the partial covering or coating of the pigment particles is meant.
  • LiCO 3 preferably 1 to 5%
  • additional LiOH preferably 1 to 20% by weight
  • Corresponding amounts of sulfates (for example K 2 SO 4 ) or chromates (for example K 2 CrO 4 ) and the amount of the dopant such as Na 2 FeO 4 are dissolved in an alkaline medium.
  • the doping with Na 2 FeO 4 can be up to 20%.
  • the product is obtained by evaporation of the solvent and is ground for further use.
  • K 2 SO 4 is ground with NaCl and intimately mixed with Fe 3 O 4 .
  • the mixture is then annealed at temperatures between 700 and 1800 ° C.
  • the product is ground for further use.
  • the alkaline medium can consist entirely or partially, for example of a silicate suspension (for example LUDOX® AS-40, Dupont).
  • a material coated with silicate is obtained during spray drying.
  • a subsequent annealing process preferably at temperatures of 200 ° C to 600 ° C, creates an SiO 2 protective layer and stabilizes the substance against solubility in water.
  • the material can be embedded in a polymer, for example PMMA, and processed into film material. This is then cut into planchettes.
  • the security element consists of a label 2 which consist of a paper or plastic layer 3, a transparent cover layer 4 and an adhesive layer 5.
  • This label is 2 connected to any substrate 1 via the adhesive layer 5.
  • Substrate 1 can be value documents, ID cards, passports, certificates or the like but also around other objects to be secured, such as Trade CDs, packaging or similar.
  • the luminescent substance In this exemplary embodiment, 6 is contained in the volume of layer 3.
  • the luminescent substance could also be in a not shown Ink may be included on one of the label layers, preferably is printed on the surface of layer 3.
  • the luminescent substance in or on a carrier material, which is then attached to an object as a security element is, it is also possible according to the invention; the luminescent substance directly into the document of value to be secured or on its surface to be provided in the form of a coating.

Landscapes

  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Luminescent Compositions (AREA)
  • Braking Elements And Transmission Devices (AREA)
  • Valve Device For Special Equipments (AREA)
  • Holo Graphy (AREA)
  • Printing Methods (AREA)
  • Credit Cards Or The Like (AREA)
  • Control Of Motors That Do Not Use Commutators (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

The invention relates to a printed document of value having at least one authenticity feature in the form of a luminescent substance based on doped host lattices. The host lattice has a strong crystal field and is doped with at least one chromophore with the electron configuration (3d)2.

Description

Die Erfindung betrifft ein bedrucktes Wertdokument mit zumindest einem Echtheitsmerkmal in Form einer lumineszierenden Substanz auf der Basis von Wirtsgittem, die mit Chromophoren der Elektronenkonfiguration (3d)2 dotiert sind.The invention relates to a printed document of value with at least one authenticity feature in the form of a luminescent substance based on host gittons doped with chromophores of the electron configuration (3d) 2 .

Unter der Bezeichnung "Wertdokument" sind im Rahmen der Erfindung Banknoten, Schecks, Aktien, Wertmarken, Ausweise, Kreditkarten, Pässe und auch andere Dokumente sowie Etiketten, Siegel, Verpackungen oder andere Elemente für die Produktsicherung zu verstehen.Under the name "document of value" are within the scope of the invention Banknotes, checks, shares, tokens, ID cards, credit cards, passports and also other documents as well as labels, seals, packaging or understand other elements for product assurance.

Die Absicherung von Wertdokumenten gegen Fälschung mittels lumineszierender Substanzen ist bereits seit langem bekannt. Auch die Verwendung von Seltenerdmetallen wurde in diesem Zusammenhang bereits diskutiert. Sie haben den Vorteil, dass sie schmalbandige charakteristische Spektrallinien aufweisen, die einen sicheren Nachweis und die Abgrenzung gegen andere Spektren erleichtern. Vorzugsweise werden Stoffe verwendet, bei denen entweder die Absorption oder die Emission außerhalb des sichtbaren Spektralbereichs liegen.Securing documents of value against forgery by means of luminescent Substances have been known for a long time. Use too rare earth metals have already been discussed in this context. They have the advantage that they have narrow-band characteristic spectral lines have reliable proof and differentiation from others Facilitate spectra. Substances are preferably used in which either absorption or emission outside the visible spectral range lie.

Liegen die Emissionen bei Wellenlängen zwischen ca. 400 nm und ca. 700 nm, so sind die lumineszierenden Substanzen bei geeigneter Anregung mit dem Auge nachweisbar. Für manche Anwendungen ist dies erwünscht, z.B. bei der Echtheitsüberprüfung durch Beleuchtung mit UV-Licht. Für andere Anwendungen ist es hingegen von Vorteil, wenn die Emission außerhalb des sichtbaren Spektralbereichs liegt, da dann spezielle Detektoren zum Nachweis der Stoffe notwendig sind.The emissions are at wavelengths between approx. 400 nm and approx. 700 nm, so are the luminescent substances with suitable excitation detectable to the eye. This is desirable for some applications, e.g. in the authenticity check by lighting with UV light. For others On the other hand, it is advantageous for applications if the emission is outside the visible spectral range, because then special detectors for detection of substances are necessary.

Luminophore mit charakteristischen Eigenschaften, die sich zur Absicherung von Wertdokumenten und insbesondere für eine automatische Echtheitserkennung eignen, sind jedoch in ihrer Zahl beschränkt. Die meisten anorganischen und organischen Luminophore haben uncharakteristische, breite Spektren und sind überdies oft handelsüblich. Dies erschwert ihre Identifizierung und macht die gleichzeitige Verwendung mehrerer dieser Stoffe unpraktikabel.Luminophores with characteristic properties that are used for hedging of value documents and in particular for automatic authenticity detection are suitable, but their number is limited. Most inorganic and organic luminophores have uncharacteristic, broad spectra and are also often commercially available. This makes their identification difficult and makes the simultaneous use of several of these substances impractical.

DE-A-198 04 021 beschreibt ein Wertdokument mit zumindest einem Echtheitsmerkmal in Form einer lumineszierenden Substanz auf der Basis von dotierten Wirtsgittern.DE-A-198 04 021 describes a document of value with at least one authenticity feature in the form of a luminescent substance based on doped host lattices.

DE-A-4 419 089 beschreibt die Verwendung von Interferenzpigmenten zur Herstellung von fälschungssicheren Wertschriften und Verpackungen; Interferenzpigmenten sind nicht lumineszierend. Diese Interferenzpigmente sind silicatische Plättchen, die mit Titandioxid beschichtet sind.DE-A-4 419 089 describes the use of interference pigments for the production counterfeit-proof securities and packaging; Interference pigments are not luminescent. These interference pigments are silicate flakes made with titanium dioxide are coated.

Ausgehend von diesem Stand der Technik liegt der Erfindung die Aufgabe zugrunde, die Anzahl von Luminophoren, die sich als Echtheitskennzeichnung für Wertdokumente eignen, zu erhöhen, und insbesondere Wertdokumente mit Echtheitsmerkmalen in Form von lumineszierenden Substanzen zu schaffen, die sich von Wertdokumenten mit bisher bekannten Luminophoren durch ein charakteristisch abgeändertes Anregungs- und/oder Emissionsspektrum unterscheiden.Based on this prior art, the object of the invention underlying, the number of luminophores that prove to be authenticity suitable for value documents, increase, and in particular value documents with authenticity features in the form of luminescent substances to create that different from value documents with previously known luminophores through a characteristically modified excitation and / or Distinguish emission spectrum.

Die Lösung dieser Aufgabe ergibt sich aus den unabhängigen Ansprüchen. Weiterbildungen sind Gegenstand der Unteransprüche.The solution to this problem results from the independent claims. Further training is the subject of the subclaims.

Die Erfindung beruht nun auf der Erkenntnis, dass die mit zunehmender Emissionswellenlänge im IR-Spektralbereich schwierige Nachweisbarkeit bestimmter Lumineszenzen sehr vorteilhaft zur Erhöhung des Fälschungsschutzes genutzt werden kann.The invention is based on the knowledge that with increasing Emission wavelength in the IR spectral range difficult to detect certain luminescences are very advantageous for increasing protection against counterfeiting can be used.

Erfindungsgemäß wird zur Absicherung von Wertdokumenten mindestens eine lumineszierende Substanz verwendet, deren Emissionsspektrum außerhalb des sichtbaren Spektralbereichs, vorzugsweise sogar außerhalb der Ansprechempfindlichkeit von Silicium-Detektoren liegt.According to the invention, at least for securing security documents uses a luminescent substance whose emission spectrum is outside of the visible spectral range, preferably even outside the response sensitivity of silicon detectors.

Die für die erfindungsgemäße Echtheitsabsicherung geeigneten Stoffe sind lumineszierende Substanzen auf der Basis von Wirtsgittern, die mit Chromophoren der Elektronenkonfiguration (3d)2 dotiert sind. Dabei kann es sich um Chromophore einer Sorte oder um ein Gemisch von wenigstens zwei verschiedenen Chromophoren handeln. Bei den erfindungsgemäßen Chromophoren handelt es sich vorzugsweise um die Übergangsmetalle Titan inder Oxidationsstufe Ti2+, im Folgenden Ti(II), Vanadium in der Oxidationsstufe V3+, im Folgenden V(III), Chrom in der Oxidationsstufe Cr4+, im Folgenden Cr(IV), Mangan in der Oxidationsstufe Mn5+, im Folgenden Mn(V), und Eisen in der Oxidationsstufe Fe6+, im Folgenden Fe(VI).The substances suitable for the authenticity assurance according to the invention are luminescent substances based on host lattices which are doped with chromophores of the electron configuration (3d) 2 . These can be chromophores of one type or a mixture of at least two different chromophores. The chromophores according to the invention are preferably the transition metals titanium in the oxidation state Ti 2+ , hereinafter referred to as Ti (II), vanadium in the oxidation state V 3+ , hereinafter referred to as V (III), chromium in the oxidation state Cr 4+ , hereinafter Cr (IV), manganese in the oxidation state Mn 5+ , hereinafter Mn (V), and iron in the oxidation state Fe 6+ , hereinafter Fe (VI).

Bei den Wirtsgittern handelt es sich um anorganische Matrizen oder organische Chelate, z.B. Apatite, Spodiosite, Palmierite, Forsterit, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphite, Granate, Perovskite, Olivine sowie bestimmte Silicate, Titanate, Vanadate, Phosphate, Sulfate, Aluminate, Zirkonate.The host lattices are inorganic matrices or organic ones Chelates, e.g. Apatite, Spodiosite, Palmierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphites, garnets, perovskites, olivines and certain silicates, titanates, Vanadates, phosphates, sulfates, aluminates, zirconates.

Bevorzugt handelt es sich bei dem Wirtsgitter um eine Verbindung der Formel: [Baa Cab Src Pbd Cde (Pf Vg Ash Sij Sk Crl O4)3 Fm Cln Brp (OH)q]x, wobei
a + b + c + d + e = 5;
f + g + h + j + k + l = 1;
m + n + p + q = 1;
x = 1 oder 2; und
a, b, c, d, e jeweils von 0 bis 5; und
f, g, h, j, k, l, m, n, p, q jeweils von 0 bis 1 reichen.The host lattice is preferably a compound of the formula: [Ba a Ca b Sr c Pb d Cd e (P f V g As h Si j S k Cr l O 4 ) 3 F m Cl n Br p (OH) q ] x , in which
a + b + c + d + e = 5;
f + g + h + j + k + l = 1;
m + n + p + q = 1;
x = 1 or 2; and
a, b, c, d, e each from 0 to 5; and
f, g, h, j, k, l, m, n, p, q each range from 0 to 1.

Ein weiter bevorzugtes Wirtsgitter ist eine Verbindung der Formel: [Mga Bab Cac Srd Pbe Cdf] [Pg Vh Asj Sik SI Crm] O4 [Fn Clp Brq (OH)r], wobei a + b + c + d + e + f =2;
g + h + j + k + l + m = 1;
n + p + q + r = 1; und
a, b, c, d, e , f jeweils von 0 bis 2; und
g, h, j, k, l, m, n, p, q, r jeweils von 0 bis 1 reichen.A further preferred host lattice is a compound of the formula: [Mg a Ba b Ca c Sr d Pb e Cd f ] [P g V h As j Si k S I Cr m ] O 4 [F n Cl p Br q (OH) r ], where a + b + c + d + e + f = 2;
g + h + j + k + l + m = 1;
n + p + q + r = 1; and
a, b, c, d, e, f each from 0 to 2; and
g, h, j, k, l, m, n, p, q, r each range from 0 to 1.

Weiter eignet sich als Wirtsgitter eine Verbindung der Formel: [Mga Bab Cac Srd Pbe Cdf] [Sig Tih Gej] O4, wobei a + b + c + d + e + f = 2;
g + h + j = 1; und
a, b, c, d, e, f jeweils von 0 bis 2 und
g, h, j jeweils von 0 bis 1 reichen.A compound of the formula is also suitable as a host lattice: [Mg a Ba b Ca c Sr d Pb e Cd f ] [Si g Ti h Ge j ] O 4 , where a + b + c + d + e + f = 2;
g + h + j = 1; and
a, b, c, d, e, f each from 0 to 2 and
g, h, j each range from 0 to 1.

Des Weiteren ist ein Wirtsgitter der Formel: [Lia Nab Kc Rbd] [Pe Asf Vg] O4 bevorzugt, wobei a + b + c + d = 3;
e + f + g =1; und
a, b, c, d jeweils von 0 bis 3 und
e, f, g jeweils von 0 bis 1 reichen.Furthermore, a host lattice is of the formula: [Li a Na b K c Rb d ] [P e As f V g ] O 4 preferred, where a + b + c + d = 3;
e + f + g = 1; and
a, b, c, d each from 0 to 3 and
e, f, g each range from 0 to 1.

Weiterhin eignet sich besonders ein Wirtsgitter der Formel: [Ya Lab] [Sic Tid] O5, wobei a + b = 2;
c + d = 1; und
a, b jeweils von 0 bis 2 und
c, d jeweils von 0 bis 1 reichen.A host lattice of the formula is also particularly suitable: [Y a La b ] [Si c Ti d ] O 5 , where a + b = 2;
c + d = 1; and
a, b each from 0 to 2 and
c, d each range from 0 to 1.

Bevorzugt handelt es sich weiterhin bei dem Wirtsgitter um eine Verbindung der Formel: [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Crl O4)2, wobei a + b + c + d + e = 3;
f + g + h + j + k + l = 1; und
a, b, c, d, e jeweils von 0 bis 3 und
f, g, h, j, k, l jeweils von 0 bis 1 reichen.Furthermore, the host lattice is preferably a compound of the formula: [Ba a Ca b Sr c Pb d Cd e ] (P f V g As h Si j S k Cr l O 4 ) 2 , where a + b + c + d + e = 3;
f + g + h + j + k + l = 1; and
a, b, c, d, e each from 0 to 3 and
f, g, h, j, k, l each range from 0 to 1.

Bevorzug ist auch ein Wirtsgitter der Formel: [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Crl O4)3Cl, wobei a + b + c + d + e = 5;
f + g + h + j + l = 1; und
a, b, c, d , e jeweils von 0 bis 5 und
f, g, h, j, k, l jeweils von 0 bis 1 reichen.A host lattice of the formula: [Ba a Ca b Sr c Pb d Cd e ] (P f V g As h Si j S k Cr l O 4 ) 3 Cl, where a + b + c + d + e = 5;
f + g + h + j + l = 1; and
a, b, c, d, e each from 0 to 5 and
f, g, h, j, k, l each range from 0 to 1.

Des Weiteren eignet sich besonders ein Wirtsgitter der Formel: [Naa Kb Rbc Csd] [Se Sef Crg Moh] O4, wobei a + b + c + d = 2;
e + f + g + h = 1; und
a, b, c, d jeweils von 0 bis 2 und
e, f, g, h jeweils von 0 bis 1 reichen.Furthermore, a host lattice of the formula is particularly suitable: [Na a K b Rb c Cs d ] [S e Se f Cr g Mo h ] O 4 , where a + b + c + d = 2;
e + f + g + h = 1; and
a, b, c, d each from 0 to 2 and
e, f, g, h each range from 0 to 1.

Des Weiteren eignet sich besonders ein Wirtsgitter der Formel: [Mga Cab Src Bad] [Se Sef Crg Moh Wi] O4, wobei a + b + c + d = 1; und
e + f + g + h + i = 1 und
a, b, c, d jeweils von 0 bis 1 und
e, f, g, h, i jeweils von 0 bis 1 reichen. Besonders bevorzugt ist das Wirtsgitter Ba SO4.Furthermore, a host lattice of the formula is particularly suitable: [Mg a Ca b Sr c Ba d ] [S e Se f Cr g Mo h W i ] O 4 , where a + b + c + d = 1; and
e + f + g + h + i = 1 and
a, b, c, d each from 0 to 1 and
e, f, g, h, i each range from 0 to 1. The host lattice Ba SO 4 is particularly preferred.

Ein weiter bevorzugtes Wirtsgitter ist eine Verbindung der Formel: [ScaYbLacCedPreNdfPmgSmhEujGdkTblDymHonErpTmqYbrLns][AluFevCrx]O3, wobei a + b + c + d + e + f + g + h + j + k + l + m + n + p + q + r + s = 1;
u + v + x = 1; und
a, b, c, d, e, f, g, h, j, k, l, m, n, p, q, r ,s, u, v, x jeweils von 0 bis 1 reichen.A further preferred host lattice is a compound of the formula: [Sc a Y b La c Ce d Pr e Nd f Pm g Sm h Eu j Gd k Tb l Dy m Ho n Er p Tm q Yb r Ln s ] [Al u Fe v Cr x ] O 3 , where a + b + c + d + e + f + g + h + j + k + l + m + n + p + q + r + s = 1;
u + v + x = 1; and
a, b, c, d, e, f, g, h, j, k, l, m, n, p, q, r, s, u, v, x each range from 0 to 1.

Des Weiteren ist ein Wirtsgitter der Formel: [Ya Gdb Scc Lad Lne] [Alf Feg Crh] O12 bevorzugt, wobei a + b + c + d + e = 3;
f + g + h = 5; und
a, b, c, d, e jeweils von 0 bis 3 und
f, g, h jeweils von 0 bis 5 reichen.Furthermore, a host lattice is of the formula: [Y a Gd b Sc c La d Ln e ] [Al f Fe g Cr h ] O 12 preferred, where a + b + c + d + e = 3;
f + g + h = 5; and
a, b, c, d, e each from 0 to 3 and
f, g, h each range from 0 to 5.

Ein weiter bevorzugtes Wirtsgitter ist eine Verbindung der Formel: [Mga Cab Src Bad] [Ale Crf Feg Gah] O4, wobei a + b + c + d = 1;
e + f + g + h = 2; und
a, b, c, d jeweils von 0 bis 1 und
e, f, g, h jeweils von 0 bis 2 reichen
oder eine Verbindung der Formel [Mga Cab Src Bad] [Ale Crf Feg Gah] O7, wobei a + b + c + d = 1;
e + f + g + h = 4; und
a, b, c, d jeweils von 0 bis 1 und
e, f, g, h jeweils von 0 bis 4 reichen.A further preferred host lattice is a compound of the formula: [Mg a Ca b Sr c Ba d ] [Al e Cr f Fe g Ga h ] O 4 , where a + b + c + d = 1;
e + f + g + h = 2; and
a, b, c, d each from 0 to 1 and
e, f, g, h each range from 0 to 2
or a compound of the formula [Mg a Ca b Sr c Ba d ] [Al e Cr f Fe g Ga h ] O 7 , where a + b + c + d = 1;
e + f + g + h = 4; and
a, b, c, d each from 0 to 1 and
e, f, g, h each range from 0 to 4.

Bevorzugt ist auch ein Wirtsgitter der Formel Y2[Sia Tib Zrc] O7 oder MgCa2[SiaTib Zrc] O7, wobei a + b + c = 2 und
a, b und c jeweils von 0 bis 2 reichen. A host lattice of the formula is also preferred Y 2 [Si a Ti b Zr c ] O 7 or MgCa 2 [Si a Ti b Zr c ] O 7 , where a + b + c = 2 and
a, b and c each range from 0 to 2.

Weiterhin eignet sich als Wirtsgitter eine Verbindung der Formel [Baa Cab Src] [Sid Tie Zrf] O5, wobei a + b + c = 3;
d + e + f = 1; und
a, b, c jeweils von 0 bis 3 und
d, e, f jeweils von 0 bis 1 reichen.A compound of the formula is also suitable as the host lattice [Ba a Ca b Sr c ] [Si d Ti e Zr f ] O 5 , where a + b + c = 3;
d + e + f = 1; and
a, b, c each from 0 to 3 and
d, e, f each range from 0 to 1.

Weiterhin ist ein Wirtsgitter der Formel [Ya Lab Zrc] [Pd Sie] O4 bevorzugt, wobei a + b + c = 1;
d + e = 1 und
a, b, c jeweils von 0 bis 1,
d, e jeweils von 0 bis 1 reichen.
Besonders bevorzugt ist Y PO4, La PO4, Zr Si O4.Furthermore, a host lattice is of the formula [Y a La b Zr c ] [P d Si e ] O 4 preferred, where a + b + c = 1;
d + e = 1 and
a, b, c each from 0 to 1,
d, e each range from 0 to 1.
Y PO 4 , La PO 4 , Zr Si O 4 is particularly preferred.

Weiterhin ist ein Wirtsgitter der Formel K [Ti2aZr2b] (P O4)3 bevorzugt, wobei a + b = 1 und
a, b jeweils von 0 bis 1 reichen.
Besonders bevorzugt ist K Ti2 (P O4)3, K Zr2 (P O4)3.Furthermore, a host lattice is of the formula K [Ti 2a Zr 2b ] (PO 4 ) 3 preferred, where a + b = 1 and
a, b each range from 0 to 1.
K Ti 2 (PO 4 ) 3 , K Zr 2 (PO 4 ) 3 is particularly preferred.

Wirtsgitter mit starkem Kristallfeld sind insbesondere bevorzugt.Host lattices with a strong crystal field are particularly preferred.

Die Lagen und Formen der Anregungs- und/oder Emissionsbanden sind abhängig von der Einbaulage der Chromophore im Wirtsgitter. Die Chromophore können in den oxidischen Struktureinheiten des Wirtsgitters sowohl in der Tetraeder- wie auch in der Oktaeder-Konfiguration vorliegen. Bevorzugt ist jedoch die Tetroxokonfiguration im Wirtsgitter. Des Weiteren hängen die Lagen und Formen der Anregungs- und/ oder Emissionsbande von der Stärke des Kristallfeldes im Wirtsgitter ab. Durch die auftretenden Wechselwirkungen zwischen Chromophor und Wirtsgitter werden die elektronischen Niveaus der Chromophore gegenüber ihren Werten und Anordnung in der Gasphase verändert, d.h. (z.T. gegeneinander) verschoben.The locations and forms of the excitation and / or emission bands are depending on the position of the chromophores in the host lattice. The chromophores can both in the oxidic structural units of the host lattice exist in the tetrahedron as well as in the octahedron configuration. However, the tetroxo configuration in the host lattice is preferred. Furthermore depend on the locations and forms of the excitation and / or emission band on the strength of the crystal field in the host lattice. By the occurring Interactions between the chromophore and the host lattice become electronic Chromophore levels versus their values and arrangement changed in the gas phase, i.e. (partly against each other) shifted.

Am Beispiel des Systems Cr3+ in oktaedrischer Umgebung [Imbusch, G.F.; Spectroscopy of Solid-State Laser-Type Materials, Ed: B. Di Bartolo; p 165; 1987] wird der Begriff des Kristallfeldes erklärt. Fig. 1a zeigt, wie die Lage und Aufeinanderfolge der elektronischen Niveaus des Chromophors Cr3+ von der Stärke des Kristallfeldes, d.h. der Wechselwirkung zwischen Chromophor und Gitter, abhängen (Tanabe-Sugano-Diagramm). Für schwache oktaedrische Kristallfelder ist der elektronische Zustand 4T2 der erste angeregte Zustand über dem Grundzustand 4A2, man beobachtet eine breitbandige Lumineszenz aus dem Niveau 4T2. Für starke Kristallfelder ist schließlich der nur schwach vom Kristallfeld abhängige Zustand 2E der erste angeregte elektronische Zustand und man beobachtet eine schmalbandige Emission aus diesem Niveau. Analoge Energieniveauschemata können für die erfindungsgemäße (3d)2 Konfiguration mit den entsprechenden Bezeichnungen der Niveaus formuliert werden. Für die wichtige oktaedrische (Oh) und tetraedrische (Td) Konfiguration ist die Niveauabfolge in Fig. 1b gezeigt.Using the example of the Cr 3+ system in an octahedral environment [Imbusch, GF; Spectroscopy of Solid-State Laser-Type Materials, Ed: B. Di Bartolo; p 165; 1987] the term crystal field is explained. 1a shows how the position and sequence of the electronic levels of the chromophore Cr 3+ depend on the strength of the crystal field, ie the interaction between the chromophore and the lattice (Tanabe-Sugano diagram). For weak octahedral crystal fields, the electronic state 4 T 2 is the first excited state above the ground state 4 A 2 , a broadband luminescence from the level 4 T 2 is observed. For strong crystal fields, the state 2 E, which is only weakly dependent on the crystal field, is the first excited electronic state and a narrow-band emission from this level is observed. Analog energy level schemes can be formulated for the (3d) 2 configuration according to the invention with the corresponding designations of the levels. For the important octahedral (O h ) and tetrahedral (T d ) configuration, the level sequence is shown in Fig. 1b.

Für die Absicherung von Wertdokumenten können sowohl die breitbandige als auch die schmalbandige Lumineszenz verwendet werden, aus Gründen der Selektivität wird jedoch die schmalbandige Lumineszenz bevorzugt. Diese werden insbesondere von den Chromophoren Mn(V) und Fe(VI) in Wirtsgittern mit starkem Kristallfeld beobachtet.Both the broadband as well as narrow band luminescence are used for reasons selectivity, narrow-band luminescence is preferred. These are characterized in particular by the chromophores Mn (V) and Fe (VI) Host lattices with a strong crystal field observed.

Von Schmalbandigkeit einer Emission spricht man üblicherweise dann, wenn im Emissionsspektrum die auftretenden Banden eine mittlere Halbwertsbreite von kleiner 50 nm zeigen. Dies bedeutet jedoch nicht, dass Banden, die eine Halbwertbreite außerhalb dieses Bereichs aufweisen, nicht auch die erfindungsgemäße Aufgabe lösen.One usually speaks of narrowband emission, if the bands occurring in the emission spectrum have a medium half-width of less than 50 nm. However, this does not mean that gangs, that have a full width at half maximum outside this range, not also solve the problem of the invention.

Durch Variation und Kombination der erfindungsgemäßen Chromophore wie auch durch Variation der Wirtsgitter eröffnen sich zahlreiche Möglichkeiten, die Anregungs- und Emissionsspektren der erfindungsgemäßen lumineszierenden Substanzen zu beeinflussen und so eine Vielzahl von Sicherheitsmerkmalen zu produzieren. Neben der Auswertung der Anregungs- und/oder Emissionsspektren kann ebenso die Lcimineszenzlebensdauer zur Unterscheidung herangezogen werden. Bei der Auswertung können neben den Wellenlängen der Anregungs- bzw. Emissionslinien auch deren Anzahl und/oder Form und/oder deren Intensitäten berücksichtigt werden, womit sich eine beliebige Codierung darstellen lässt.By varying and combining the chromophores according to the invention as well as by varying the host lattice, there are numerous possibilities the excitation and emission spectra of the luminescent according to the invention Influencing substances and so a variety of security features to produce. In addition to evaluating the excitation and / or emission spectra can also be the lciminescence lifetime be used to differentiate. When evaluating in addition to the wavelengths of the excitation and emission lines, and their Number and / or shape and / or their intensities are taken into account with which any coding can be represented.

Die Anzahl der unterscheidbaren erfindungsgemäßen Substanzen lässt sich weiter erhöhen, wenn auch Mischkristalle der Wirtsgitter zugelassen werden oder die Wirtsgitter mit zusätzlichen Dotierungen variiert werden. Z.B. können Apatite und Spodiosite oder Granate und Perovskite in bestimmten Konzentrationsverhältnissen der Ausgangssubstanzen Mischkristalle bilden, bei denen die Gitter ineinander übergehen. Damit verbunden kann das Kristallfeld, das auf den Chromophor wirkt, verändert werden.The number of distinguishable substances according to the invention can be increase further if mixed crystals of the host lattice are also permitted or the host lattice can be varied with additional doping. For example, can Apatite and Spodiosite or grenade and Perovskite in certain Concentration ratios of the starting substances form mixed crystals, where the grids merge. The crystal field, that acts on the chromophore can be changed.

Ebenso ist es möglich, über Dotierung zusätzlich zu den erfindungsgemäßen Chromophoren weitere Chromophore in die Wirtsgitter einzubringen und so eine kombinierte Lumineszenz beider Systeme oder einen Energieübertrag zwischen den Systemen zu erreichen und für die Identifizierung zu nutzen. Beispielsweise eignen sich Seltenerdionen hierfür, die aufgrund ihrer abgeschirmten Schalen ihre typische Lumineszenz auch im Wirtsgitter behalten. It is also possible to use doping in addition to those according to the invention Chromophores to introduce more chromophores into the host lattice and so on a combined luminescence of both systems or an energy transfer reach between systems and use for identification. For example, rare earth ions are suitable for this, because of their shielded Shells retain their typical luminescence even in the host lattice.

Bevorzugt handelt es sich hierbei um Neodym (Nd)-, Holmium (Ho)-, Erbium (Er)-, Thulium (Tm)- oder Ytterbium (Yb)-Kationen oder Gemische davon.These are preferably neodymium (Nd) -, holmium (Ho) -, erbium (Er), thulium (Tm) or ytterbium (Yb) cations or mixtures thereof.

Wird das Wertdokument statt mit einer mit mehreren der erfindungsgemäßen lumineszierenden Substanzen markiert, so lässt sich die Anzahl der unterscheidbaren Kombinationen weiter steigern. Werden zudem verschiedene Mischungsverhältnisse voneinander unterschieden, kann die Anzahl an Kombinationen nochmals gesteigert werden. Die Markierung kann dabei entweder an verschiedenen Stellen des Wertdokuments oder am gleichen Ort erfolgen. Wird die Lumineszenzsubstanz an verschiedenen Stellen des Wertdokumentes auf- bzw. eingebracht, kann so ein räumlicher Code, im einfachsten Fall z.B. ein Barcode, erzeugt werden.If the document of value instead of one with several of the invention luminescent substances marked, so the number of distinguishable Further increase combinations. Also become different Mixing ratios differ from each other, the number can Combinations can be increased again. The marking can either at different points in the value document or at the same Place. If the luminescent substance is in different places of the A value code can be applied or introduced, so a spatial code in the simplest case e.g. a barcode.

Weiterhin lässt sich die Fälschungssicherheit des Wertdokuments erhöhen, wenn die spezielle gewählte lumineszierende Substanz z.B. in einem Wertdokument mit anderen Informationen des Wertdokuments verknüpft wird, so dass eine Überprüfung mittels eines geeigneten Algorithmus möglich ist. Selbstverständlich kann das Wertdokument neben der erfindungsgemäßen lumineszierenden Substanz noch weitere zusätzliche Echtheitsmerkmale, wie klassische Fluoreszenz und/ oder Magnetismus aufweisen.Furthermore, the security against forgery of the value document can be increased, if the particular luminescent substance chosen e.g. in a value document is linked to other information in the value document, so that a check using a suitable algorithm is possible. Of course, the document of value in addition to the invention luminescent substance still further additional authenticity features, such as classic fluorescence and / or magnetism.

Die lumineszierenden Substanzen können gemäß der Erfindung auf verschiedenste Art und Weise in das Wertdokument eingebracht werden. So können die lumineszierenden Substanzen beispielsweise in eine Druckfarbe eingebracht werden. Aber auch ein Zumischen der lumineszierenden Substanz zur Papiermasse oder Kunststoffmasse bei der Herstellung eines Wertdokuments auf der Basis von Papier oder Kunststoff ist möglich. Ebenso können die lumineszierenden Substanzen auf oder in einem Kunststoffträgermaterial vorgesehen werden, welches beispielsweise wiederum zumindest teilweise in die Papiermasse eingebettet werden kann. Das Trägermaterial, das auf einem geeigneten Polymer, wie z.B. PMMA basiert und in das die erfindungsgemäße lumineszierende Substanz eingebettet ist, kann hierbei die Form eines Sicherheitsfadens, einer Melierfaser oder einer Planchette haben. Ebenso lässt sich zur Produktsicherung die lumineszierende Substanz z.B. direkt in das Material des abzusichernden Gegenstandes, z.B. in Gehäusen und Plastikflaschen einbringen.The luminescent substances can according to the invention in various Way into the value document. So the luminescent substances can, for example, in a printing ink be introduced. But also an admixture of the luminescent substance to paper pulp or plastic pulp when producing a value document on the basis of paper or plastic is possible. As well can the luminescent substances on or in a plastic carrier material are provided, which, for example, at least in turn can be partially embedded in the pulp. The carrier material, on a suitable polymer, e.g. PMMA based and in that the luminescent substance according to the invention is embedded here the form of a security thread, a mottled fiber or a planchette to have. The luminescent substance can also be used to secure the product e.g. directly into the material of the object to be secured, e.g. in Insert housings and plastic bottles.

Das Kunststoff- oder Papierträgermaterial kann jedoch auch an jedem beliebigen anderen Gegenstand, z.B. zur Produktsicherung befestigt werden. Das Trägermaterial ist in diesem Fall vorzugsweise in Form eines Etiketts ausgebildet. Wenn das Trägermaterial Bestandteil des zu sichernden Produkts ist, wie es z.B. bei Aufreißfäden der Fall ist, ist selbstverständlich auch jede andere Formgebung möglich. In bestimmten Anwendungsfällen kann es sinnvoll sein, die lumineszierende Substanz als unsichtbare Beschichtung auf dem Wertdokument vorzusehen. Sie kann dabei vollflächig oder auch in Form von bestimmten Mustern,wie z.B. Streifen, Linien, Kreisen oder auch in Form von alphanumerischen Zeichen vorliegen. Um die Unsichtbarkeit des Lumineszenzstoffes zu gewährleisten, muss erfindungsgemäß entweder ein farbloser Lumineszenzstoff in der Druckfarbe oder dem Beschichtungslack verwendet werden oder ein farbiger Lumineszenzstoff in einer so geringen Konzentration, dass die Transparenz der Beschichtung gerade noch gegeben ist. Alternativ oder zusätzlich kann auch das Trägermaterial bereits geeignet eingefärbt sein, so dass farbige Lumineszenzstoffe aufgrund ihrer Eigenfarbe nicht wahrgenommen werden.However, the plastic or paper carrier material can also be on any other item, e.g. be secured for product safety. The In this case, carrier material is preferably in the form of a label. If the carrier material is part of the product to be secured, as it e.g. the case of tear threads is of course also any other Shape possible. It can be useful in certain applications be the luminescent substance as an invisible coating to provide the value document. It can cover the entire surface or in Shape of certain patterns, e.g. Stripes, lines, circles or else are in the form of alphanumeric characters. About invisibility To ensure the luminescent substance must either a colorless luminescent substance in the printing ink or coating lacquer be used or a colored luminescent substance in such a low Concentration that just gives the transparency of the coating is. As an alternative or in addition, the carrier material can already be suitably colored so that colored luminescent substances due to their Own color can not be perceived.

Üblicherweise werden die erfindungsgemäßen lumineszierenden Substanzen in Form von Pigmenten verarbeitet. Zur besseren Verarbeitung oder zur Erhöhung ihrer Stabilität können die Pigmente insbesondere als individuell verkapselte Pigmentpartikel vorliegen oder mit einem anorganischen oder organischen Coating überzogen werden. Beispielsweise werden die einzelnen Pigmentteilchen hierzu mit einer Silicathülle umgeben und lassen sich so leichter in Medien dispergieren. Ebenso können verschiedene Pigmentpartikel einer Kombination gemeinsam verkapselt werden, z.B. in Fasern, Fäden, Silicathüllen. So ist es z.B. nicht mehr möglich, den "Code" der Kombination nachträglich zu verändern. Unter "Verkapselung" ist dabei ein vollständiges Umhüllen der Pigmentpartikel zu verstehen, während mit "Coating" auch das teilweise Umhüllen bzw. Beschichten der Pigmentpartikel gemeint ist.The luminescent substances according to the invention are usually used processed in the form of pigments. For better processing or The pigments can increase their stability especially as individual encapsulated pigment particles are present or with an inorganic or organic coating. For example, the individual For this purpose, pigment particles are surrounded with a silicate shell and can be so disperse more easily in media. Different pigment particles can also be used a combination can be encapsulated together, e.g. in fibers, threads, Silicathüllen. So it is e.g. no longer possible the "code" of the combination to change later. Under "encapsulation" there is a complete Enveloping the pigment particles to understand while using "Coating" too the partial covering or coating of the pigment particles is meant.

Im Folgenden werden einige Beispiele der erfindungsgemäßen lumineszierenden Substanz näher erläutert.The following are some examples of the luminescent invention Substance explained in more detail.

Beispiel 1:Example 1:

Für die Präparation werden die Ausgangsstoffe in oxidischer Form oder Stoffe, die in Oxide überführt werden können, in einem geeigneten Verhältnis, z.B. wie in Gleichung (1) gemischt, mit dem Chromophor versehen und dann geglüht, zerkleinert, gewaschen (z.B. mit Wasser), getrocknet und vermahlen. Als Chromophor können z.B. Mn2O3, MnO, MnO2, MnCO3, MnCl2, KMnO4 sowie organische Manganverbindungen eingesetzt werden. Ihr Gewichtsanteil, bezogen auf die Gesamtmischung, kann bis zu 20 % Gew. betragen. Die Glühung erfolgt im Temperaturbereich von 200 bis 1700 °C und einer Haltezeit von 0.2 bis 24 h, jedoch bevorzugt bei 300 bis 500 °C sowie einer Haltezeit von 0.5 bis 2h. (1)   6 LiOH + As2O5 +x MnCl2 → 2 Li3AsO4 : Mn + 3 H2O + x Cl2 For the preparation, the starting materials in oxidic form or substances which can be converted into oxides are mixed with the chromophore in a suitable ratio, for example as in equation (1), and then annealed, crushed, washed (for example with water), dried and ground. For example, Mn 2 O 3 , MnO, MnO 2 , MnCO 3 , MnCl 2 , KMnO 4 and organic manganese compounds can be used as chromophore. Their proportion by weight, based on the total mixture, can be up to 20% by weight. Annealing takes place in the temperature range from 200 to 1700 ° C. and a holding time of 0.2 to 24 hours, but preferably at 300 to 500 ° C. and a holding time of 0.5 to 2 hours. (1) 6 LiOH + As 2 O 5 + x MnCl 2 → 2 Li 3 AsO 4 : Mn + 3 H 2 O + x Cl 2

Um das Gleichgewicht in Richtung der Produktbildung zu verschieben, kann der Ansatz zusätzlich mit LiCO3, bevorzugt 1 bis 5 %, sowie zusätzlichem LiOH, bevorzugt 1 bis 20 % Gew. versetzt werden.In order to shift the equilibrium in the direction of product formation, LiCO 3 , preferably 1 to 5%, and additional LiOH, preferably 1 to 20% by weight can be added to the mixture.

Beispiel 2:Example 2:

In alkalischem Medium werden entsprechende Mengen an Sulfaten (z.B. K2SO4) oder Chromaten (z.B. K2CrO4) sowie die Menge des Dotierstoffes, wie z.B. Na2FeO4 gelöst. Die Dotierung mit Na2FeO4 kann bis zu 20 % betragen. Durch Verdampfung des Lösungsmittels wird das Produkt gewonnen, welches für die weitere Verwendung vermahlen wird.Corresponding amounts of sulfates (for example K 2 SO 4 ) or chromates (for example K 2 CrO 4 ) and the amount of the dopant such as Na 2 FeO 4 are dissolved in an alkaline medium. The doping with Na 2 FeO 4 can be up to 20%. The product is obtained by evaporation of the solvent and is ground for further use.

Alternativ kann auch eine Festkörperreaktion durchgeführt werden. Dazu wird K2SO4 mit NaCl vermahlen und innig mit Fe3O4 vermengt. Anschließend wird die Mischung bei Temperaturen zwischen 700 und 1800 °C geglüht. Das Produkt wird für die weitere Verwendung vermahlen.Alternatively, a solid-state reaction can also be carried out. For this purpose, K 2 SO 4 is ground with NaCl and intimately mixed with Fe 3 O 4 . The mixture is then annealed at temperatures between 700 and 1800 ° C. The product is ground for further use.

Beispiel: 3Example: 3

Das in Beispiel 2 beschriebene Verfahren, kann derart abgeändert werden, dass zum Verdampfen des Lösungsmittel ein Sprühtrockner eingesetzt wird. Ferner kann das alkalische Medium vollständig oder zum Teil, z.B. aus einer Silicatsuspension (z.B. LUDOX® AS-40, Dupont) bestehen. In diesem Fall wird beim Sprühtrocknen ein mit Silicat ummanteltes Material gewonnen. Durch einen anschließenden Glühprozess, vorzugsweise bei Temperaturen von 200 °C bis 600 °C, wird eine SiO2-Schutzschicht erzeugt und die Substanz gegenüber Löslichkeit in Wasser stabilisiert. Zusätzlich kann das Material in ein Polymer, z.B. PMMA eingebettet werden, und zu Folienmaterial verarbeitet werden. Dieses wird anschließend in Planchetten verschnitten. The method described in Example 2 can be modified such that a spray dryer is used to evaporate the solvent. Furthermore, the alkaline medium can consist entirely or partially, for example of a silicate suspension (for example LUDOX® AS-40, Dupont). In this case a material coated with silicate is obtained during spray drying. A subsequent annealing process, preferably at temperatures of 200 ° C to 600 ° C, creates an SiO 2 protective layer and stabilizes the substance against solubility in water. In addition, the material can be embedded in a polymer, for example PMMA, and processed into film material. This is then cut into planchettes.

Weitere Ausführungsformen und Vorteile der Erfindung werden im Folgenden anhand der Figur 2 erläutert:

Fig. 2
erfindungsgemäßes Sicherheitselement im Querschnitt.
Further embodiments and advantages of the invention are explained below with reference to FIG. 2:
Fig. 2
Security element according to the invention in cross section.

Fig. 2 zeigt eine Ausführungsform des erfindungsgemäßen Sicherheitselements. Das Sicherheitselement besteht in diesem Fall aus einem Etikett 2, das sich aus einer Papier- oder Kunststoffschicht 3, einer transparenten Abdeckschicht 4 sowie einer Klebstoffschicht 5 zusammensetzt. Dieses Etikett 2 ist über die Kleberschicht 5 mit einem beliebigen Substrat 1 verbunden. Bei diesem Substrat 1 kann es sich um Wertdokumente, Ausweise, Pässe, Urkunden oder dergleichen aber auch um andere zu sichernde Gegenstände, wie beispielsweise CDs, Verpackungen o. ä. handeln. Die lumineszierende Substanz 6 ist in diesem Ausführungsbeispiel im Volumen der Schicht 3 enthalten.2 shows an embodiment of the security element according to the invention. In this case, the security element consists of a label 2 which consist of a paper or plastic layer 3, a transparent cover layer 4 and an adhesive layer 5. This label is 2 connected to any substrate 1 via the adhesive layer 5. With this Substrate 1 can be value documents, ID cards, passports, certificates or the like but also around other objects to be secured, such as Trade CDs, packaging or similar. The luminescent substance In this exemplary embodiment, 6 is contained in the volume of layer 3.

Alternativ könnte die lumineszierende Substanz auch in einer nicht gezeigten Druckfarbe enthalten sein, die auf eine der Etikettenschichten, vorzugsweise auf die Oberfläche der Schicht 3 aufgedruckt wird.Alternatively, the luminescent substance could also be in a not shown Ink may be included on one of the label layers, preferably is printed on the surface of layer 3.

Statt den Lumineszenzstoff in oder auf einem Trägermaterial vorzusehen, das anschließend als Sicherheitselement auf einem Gegenstand befestigt wird, ist es gemäß der Erfindung auch möglich; die lumineszierende Substanz direkt in das zu sichernde Wertdokument bzw. auf dessen Oberfläche in Form einer Beschichtung vorzusehen.Instead of providing the luminescent substance in or on a carrier material, which is then attached to an object as a security element is, it is also possible according to the invention; the luminescent substance directly into the document of value to be secured or on its surface to be provided in the form of a coating.

Claims (43)

  1. A document of value having at least one authenticity feature in the form of a luminescent substance based on doped host lattices, characterized in that the host lattice is doped with at least one chromophore with the electron configuration (3d)2.
  2. A document of value according to claim 1, wherein the host lattice has a strong crystal field.
  3. A document of value according to claim 1 or 2, wherein the chromophore is titanium in oxidation state 2 or vanadium in oxidation state 3 or chromium in oxidation state 4 or manganese in oxidation state 5 or iron in oxidation state 6.
  4. A document of value according to at least one of claims 1 to 3, wherein the document of value consists of paper or plastic.
  5. A document of value according to at least one of claims 1 to 4, wherein the authenticity feature is incorporated into the volume of the document of value or present in a layer applied to the document of value.
  6. A document of value according to at least one of claims 1 to 5, wherein the luminescent substance is provided on the document of value as an invisible, at least partial coating.
  7. A document of value according to at least one of claims 1 to 6, wherein the luminescent substance is admixed to a printing ink.
  8. A document of value according to at least one of claims 1 to 7, wherein the coating has the form of one or more stripes.
  9. A document of value according to at least one of claims 1 to 8, wherein the host lattice is additionally codoped with at least one representative from the group of rare earth metal cations.
  10. A document of value according to claim 9, wherein the rare earth metal cation is selected from neodymium (Nd), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb).
  11. A document of value according to at least one of claims 1 to 10, wherein the host lattice is selected from the class of apatites, spodiosites, palmierites, forsterites, brushites, dahllites, ellestadites, francolites, monetites, morinites, whitlockites, wilkeites, voelckerites, pyromorphites, garnets, perovskites, silicates, titanates, vanadates, phosphates.
  12. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Baa Cab Src Pbd Cde (Pf Vg Ash Sij Sk Crl O4)3 Fm Cln Brp (OH)q]x, where
    a + b + c + d + e = 5;
    f + g + h + j + k + l = 1;
    m + n + p + q = 1;
    x = 1 or 2; and
    a, b, c, d, e each range from 0 to 5; and
    f, g, h, j, k, l, m, n, p, q from 0 to 1.
  13. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Mga Bab Cac Srd Pbe Cdf] [Pg Vh Asj Sik Sl Crm] O4 [Fn Clp Brq (OH)r], where a + b + c + d + e + f = 2;
    g + h + j + k + l + m = 1;
    n + p + q + r = 1; and
    a, b, c, d, e, f each range from 0 to 2; and
    g, h, j, k, l, m, n, p, q, r from 0 to 1.
  14. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Mga Bab Cac Srd Pbe Cdf] [Sig Tih Gej] O4, where a + b + c + d + e + f = 2;
    g + h + j = 1; and
    a, b, c, d, e, f each range from 0 to 2, and
    g, h, j from 0 to 1.
  15. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Lia Nab Kc Rbd] [Pe Asf Vg] O4, where a + b + c + d = 3;
    e + f + g = 1; and
    a, b, c, d each range from 0 to 3, and
    e, f, g from 0 to 1.
  16. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Ya Lab] [Sic Tid] O5, where a + b = 2;
    c + d = 1; and
    a, b each range from 0 to 2, and
    c, d from 0 to 1.
  17. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Crl O4)2, where a + b + c + d + e = 3;
    f + g + h + j + k + l = 1; and
    a, b, c, d, e each range from 0 to 3, and
    f, g, h, j, k, from 0 to 1.
  18. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Crl O4)3Cl, where a + b + c + d + e = 5;
    f + g + h + j + l = 1; and
    a, b, c, d, e each range from 0 to 5, and
    f, g, h, j, k, l from 0 to 1.
  19. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Naa Kb Rbc Csd] [Se Sef Crg Moh] O4, where a + b + c + d = 2;
    e + f + g + h = 1; and
    a, b, c, d each range from 0 to 2, and
    e, f, g, h from 0 to 1.
  20. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Mga Cab Src Bad] [Se Sef Crg Moh Wi] O4, where a + b + c + d = 1; and
    e + f + g + h + i = 1, and
    a, b, c, d each range from 0 to 1, and
    e, f, g, h, i from 0 to 1.
  21. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [ScaYbLacCedPreNdfPmgSmhEujGdkTblDymHonErpTmqYbrLns] [AluFevCrx]O3' where a+ b + c + d + e + f + g + h +j + k + l + m + n + p + q + r + s = 1;
    u + v + x = 1; and
    a, b, c, d, e, f, g, h, j, k, l, m, n, p, q, r, s, u, v, x each range from 0 to 1.
  22. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Ya Gdb Scc Lad Lne] [Alf Feg Crh] O12, where a + b + c + d + e = 3;
    f + g + h = 5; and
    a, b, c, d, e each range from 0 to 3, and
    f, g, h from 0 to 5.
  23. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: [Mga Cab Src Bad] [Ale Crf Feg Gah] O4, where a + b + c + d = 1;
    e + f + g + h = 2; and
    a, b, c, d each range from 0 to 1, and
    e, f, g, h from 0 to 2
    or a compound with the formula [Mga Cab Src Bad] [Ale Crf Feg Gah] O7, where a + b + c + d = 1;
    e + f + g + h = 4; and
    a, b, c, d each range from 0 to 1, and
    e, f, g, h from 0 to 4.
  24. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula Y2[Sia Tib Zrc] O7 or MgCa2[SiaTibZrc] O7, where a + b + c = 2, and
    a, b and c each range from 0 to 2.
  25. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula [Baa Cab Src] [Sid Tie Zrf] O5, where a + b + c = 3;
    d + e + f = 1; and
    a, b, c each range from 0 to 3 and
    d, e, f from 0 to 1.
  26. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula [Ya Lab Zrc] [Pd Sie] O4, where a + b + c = 1;
    d + e = 1, and
    a, b, c each range from 0 to 1,
    d, e from 0 to 1.
  27. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound with the formula: K [Ti2a Zr2b] (P O4)3, where a + b = 1, and
    a, b each range from 0 to 1.
  28. A document of value according to at least one of claims 1 to 27, wherein the chromophores are present in the host lattice in the tetroxo configuration.
  29. A document of value according to at least one of claims 1 to 28, wherein the luminescent substance is present as pigment particles.
  30. A security element having a carrier material and at least one luminescent substance based on doped host lattices, characterized in that the host lattice is doped with at least one chromophore with the electron configuration (3d)2.
  31. A security element according to claim 30, wherein the host lattice has a strong crystal field.
  32. A security element according to claim 30 or 31, wherein the security element has the form of a stripe or band.
  33. A security element according to at least one of claims 30 to 32, wherein the carrier material is formed as a security thread, planchet or mottling fiber.
  34. A security element according to at least one of claims 30 to 33, characterized in that the security element is formed as a label.
  35. A security element according to at least one of claims 30 to 34, characterized in that the at least one luminescent substance is embedded in the carrier material or applied to the carrier material.
  36. A method for producing a document of value according to at least one of claims 1 to 29, characterized in that the luminescent substance is added to a printing ink.
  37. A method for producing a document of value according to at least one of claims 1 to 29, characterized in that the luminescent substance is applied by a coating process.
  38. A method for producing a document of value according to at least one of claims 1 to 29, characterized in that the luminescent substance is incorporated into the volume of the document of value.
  39. A method for producing a document of value according to at least one of claims 1 to 29, characterized in that the luminescent substance is supplied to the document of value by accordingly prepared mottling fibers.
  40. A method for producing a document of value according to at least one of claims 1 to 29, characterized in that the luminescent substance is supplied to the document of value by an accordingly prepared security thread.
  41. A test method for authenticity testing of a document of value according to at least one of claims 1 to 29 or a security element according to at least one of claims 30 to 35, characterized in that the wavelengths and/or number and/or shape and/or intensities of the emission lines and/or excitation bands of the luminescent substances are evaluated.
  42. A test method for authenticity testing of a document of value or security element according to claim 41, characterized in that the emission lines and/or excitation bands represent a coding and/or a coding is represented by varying the host lattices.
  43. A test method for authenticity testing of a document of value according to at least one of claims 1 to 29 or a security element according to at least one of claims 30 to 35, characterized in that the lifetimes of luminescence of the luminescent substances are evaluated.
EP02748334.6A 2001-03-08 2002-03-05 Value document Expired - Lifetime EP1370424B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10111116A DE10111116A1 (en) 2001-03-08 2001-03-08 value document
DE10111116 2001-03-08
PCT/EP2002/002405 WO2002070279A1 (en) 2001-03-08 2002-03-05 Value document

Publications (3)

Publication Number Publication Date
EP1370424A1 EP1370424A1 (en) 2003-12-17
EP1370424B1 true EP1370424B1 (en) 2004-09-01
EP1370424B2 EP1370424B2 (en) 2013-07-31

Family

ID=7676708

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02748334.6A Expired - Lifetime EP1370424B2 (en) 2001-03-08 2002-03-05 Value document

Country Status (16)

Country Link
US (1) US8663820B2 (en)
EP (1) EP1370424B2 (en)
KR (1) KR100868176B1 (en)
CN (1) CN1282555C (en)
AT (1) ATE275046T1 (en)
AU (1) AU2002308237B2 (en)
CA (1) CA2440078C (en)
DE (2) DE10111116A1 (en)
ES (1) ES2224072T5 (en)
HK (1) HK1062664A1 (en)
PL (1) PL202501B1 (en)
PT (1) PT1370424E (en)
RU (1) RU2286885C2 (en)
TR (1) TR200402236T4 (en)
UA (1) UA74062C2 (en)
WO (1) WO2002070279A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006047852A1 (en) * 2006-10-10 2008-04-17 Giesecke & Devrient Gmbh Authenticity feature in the form of a luminescent substance
DE102006047851A1 (en) * 2006-10-10 2008-04-17 Giesecke & Devrient Gmbh Authenticity feature in the form of luminescent substances
DE102010034256A1 (en) 2010-08-13 2012-02-16 Giesecke & Devrient Gmbh Luminescent substance exhibiting a host lattice doped with a luminescent activator, useful in a diagnostic or therapeutic method or a tissue labeling method in vivo or in vitro, where the diagnostic method is graphical angiographic method

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10111116A1 (en) 2001-03-08 2002-09-19 Giesecke & Devrient Gmbh value document
DE10346685A1 (en) * 2003-10-08 2005-05-04 Giesecke & Devrient Gmbh Coding system for value documents
DE10346687A1 (en) 2003-10-08 2005-05-04 Giesecke & Devrient Gmbh Coding system for value documents
CN101076835B (en) * 2004-09-02 2012-12-12 德国捷德有限公司 Value document with luminescent properties
DE102004063217A1 (en) * 2004-12-29 2006-07-13 Giesecke & Devrient Gmbh Security feature for value documents
DE102005041054A1 (en) * 2005-08-30 2007-03-01 Giesecke & Devrient Gmbh Bank notes e.g. US-notes, originality verification method, involves providing material as authenticity feature activated for emission of luminance radiation, to bank notes, and detecting emitted radiation in specific wavelength range
AR053508A1 (en) 2006-05-31 2007-05-09 Agustin Jose Luis Perez SYSTEM FOR THE RECORDING AND READING OF DATA TO BE PRESSED FROM PRINTED CHROMATIC INFORMATION THAT MODIFIES PATTERNS ISSUED BY A SOURCE OF ELECTROMAGNETIC WAVES, GENERATING NEW PATTERNS AND ORIGINATING RECOGNIZABLE CATEGORIES AND ASSIGNABLE TO A CODE
US8550358B2 (en) 2006-05-31 2013-10-08 Agustin Jose Luis Perez Procedure for data encoding and reading starting from interference of wave patterns generated in a printed chromatic system
DE102008050768C5 (en) † 2008-10-09 2017-11-02 Bundesdruckerei Gmbh Security feature based on luminescence emitting materials, value and security document with such a security feature, a method and an apparatus for verification of such a security feature
DE102011122246A1 (en) 2011-12-23 2013-06-27 Giesecke & Devrient Gmbh Security feature with multiple components
DE102011122243A1 (en) 2011-12-23 2013-06-27 Giesecke & Devrient Gmbh Security feature with multiple components
DE102011122240A1 (en) 2011-12-23 2013-06-27 Giesecke & Devrient Gmbh Security feature with multiple components
RU2526211C2 (en) * 2012-10-03 2014-08-20 Федеральное Государственное Унитарное Предприятие "Гознак" (Фгуп "Гознак") Counterfeit-proof valuable document and method for determining its authenticity
DE102013007811A1 (en) 2013-05-07 2014-11-13 Giesecke & Devrient Gmbh Method for marking a feature substance, security feature, value document and method for testing the same
RU2614980C1 (en) * 2015-12-21 2017-03-31 Акционерное общество "Гознак" (АО "Гознак") Security marking and product containing this marking

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627692A (en) * 1968-05-28 1971-12-14 Westinghouse Electric Corp Fluoroapatite laser material doped with holmium or thulium and chromium
US3800142A (en) * 1972-01-05 1974-03-26 W Harshaw Method of verifying the authenticity of a document and identifiable document produced thereby
US4452843A (en) * 1980-05-30 1984-06-05 Gao Gesellschaft Fur Automation Und Organisation Mbh. Security paper
CH659145A5 (en) * 1980-05-30 1986-12-31 Gao Ges Automation Org METHOD FOR CHECKING THE VALIDITY OF SECURITIES SECURED WITH LUMINESCENT SUBSTANCES AND DEVICE FOR IMPLEMENTING THE METHOD.
DE3121484A1 (en) † 1980-05-30 1982-04-29 GAO Gesellschaft für Automation und Organisation mbH, 8000 München Securities with substances, method and device for testing the latter
FR2603051B1 (en) * 1986-12-05 1988-11-10 Commissariat Energie Atomique MIXED LANTHANE-MAGNESIUM ALUMINATES, LASERS USING MONOCRYSTALS OF SUCH ALUMINATES
US5507976A (en) * 1993-11-24 1996-04-16 Eastman Kodak Company Stabilized phosphor intermediates, storage phosphors, radiation image storage panels, and preparation methods
DE4419089A1 (en) * 1994-06-01 1995-12-07 Basf Ag Interference pigments used for security documents and packaging
FR2730332B1 (en) * 1995-02-08 1997-03-28 Plasto Sa SAFETY LABEL
EP0833605A1 (en) * 1995-06-22 1998-04-08 Minnesota Mining And Manufacturing Company Stable hydroalcoholic compositions
DE19803997B4 (en) * 1998-02-02 2018-01-25 Giesecke+Devrient Currency Technology Gmbh value document
DE19804024A1 (en) * 1998-02-02 1999-08-05 Giesecke & Devrient Gmbh Value document
DE19804021A1 (en) * 1998-02-02 1999-08-05 Giesecke & Devrient Gmbh Value document
DE19804012A1 (en) 1998-02-02 1999-08-05 Giesecke & Devrient Gmbh Value document
DE19804032A1 (en) 1998-02-02 1999-08-05 Giesecke & Devrient Gmbh Value document
US6211526B1 (en) * 1998-09-30 2001-04-03 The United States Of America As Represented By The Secretary Of The Navy Marking of materials using luminescent and optically stimulable glasses
GB9824246D0 (en) 1998-11-06 1998-12-30 Kelsill Limited Electronic circuit
US6203069B1 (en) * 1998-11-18 2001-03-20 Dna Technologies Inc. Label having an invisible bar code applied thereon
KR100319739B1 (en) * 1998-11-19 2002-02-19 오길록 Cr and Yb codoped optical material systems for enhanced infrared fluores cence emission and their application schemes
DE19905394A1 (en) * 1999-02-10 2000-08-17 Basf Ag Liquid crystalline mixture
US6514435B1 (en) * 1999-03-05 2003-02-04 The United States Of America As Represented By The Secretary Of The Navy High density and fast persistent spectral holeburning in II-VI compounds for optical data storage
US6149862A (en) * 1999-05-18 2000-11-21 The Atri Group Ltd. Iron-silicon alloy and alloy product, exhibiting improved resistance to hydrogen embrittlement and method of making the same
US6210605B1 (en) * 1999-07-26 2001-04-03 General Electric Company Mn2+ activated green emitting SrAL12O19 luminiscent material
KR100355456B1 (en) * 1999-07-30 2002-10-11 한국전자통신연구원 A red phosphor for fluorescent display and a preparation method thereof
US6402987B1 (en) * 1999-12-01 2002-06-11 General Electric Company YMO4:Eu,L phoshpor with improved lumen maintenance
US7152047B1 (en) * 2000-05-24 2006-12-19 Esecure.Biz, Inc. System and method for production and authentication of original documents
US6572784B1 (en) * 2000-11-17 2003-06-03 Flex Products, Inc. Luminescent pigments and foils with color-shifting properties
KR100393045B1 (en) * 2000-12-29 2003-07-31 삼성에스디아이 주식회사 Phosphors
KR100393046B1 (en) * 2000-12-29 2003-07-31 삼성에스디아이 주식회사 Phosphors
DE10111116A1 (en) 2001-03-08 2002-09-19 Giesecke & Devrient Gmbh value document
CN1462304A (en) * 2001-04-27 2003-12-17 化成光学仪器株式会社 Phosphor and production method therefor
US6690705B2 (en) * 2001-11-09 2004-02-10 Vector Enery Corporation Method and apparatus for excitation of chemical bonds
RU2322695C2 (en) * 2001-12-21 2008-04-20 Гизеке Унд Девриент Гмбх Sheet material, and also devices and methods for manufacturing and processing such sheet material
JP4263453B2 (en) * 2002-09-25 2009-05-13 パナソニック株式会社 Inorganic oxide and light emitting device using the same
DE10259246A1 (en) * 2002-12-17 2004-07-01 Merck Patent Gmbh Inorganic spherical absorption pigments

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006047852A1 (en) * 2006-10-10 2008-04-17 Giesecke & Devrient Gmbh Authenticity feature in the form of a luminescent substance
DE102006047851A1 (en) * 2006-10-10 2008-04-17 Giesecke & Devrient Gmbh Authenticity feature in the form of luminescent substances
DE102010034256A1 (en) 2010-08-13 2012-02-16 Giesecke & Devrient Gmbh Luminescent substance exhibiting a host lattice doped with a luminescent activator, useful in a diagnostic or therapeutic method or a tissue labeling method in vivo or in vitro, where the diagnostic method is graphical angiographic method

Also Published As

Publication number Publication date
US8663820B2 (en) 2014-03-04
CN1282555C (en) 2006-11-01
CA2440078C (en) 2007-08-07
HK1062664A1 (en) 2004-11-19
PT1370424E (en) 2005-01-31
US20040105962A1 (en) 2004-06-03
KR100868176B1 (en) 2008-11-12
RU2286885C2 (en) 2006-11-10
EP1370424B2 (en) 2013-07-31
RU2003129071A (en) 2005-03-27
TR200402236T4 (en) 2004-10-21
DE50200931D1 (en) 2004-10-07
DE10111116A1 (en) 2002-09-19
AU2002308237B2 (en) 2006-08-17
UA74062C2 (en) 2005-10-17
ES2224072T5 (en) 2013-11-15
ATE275046T1 (en) 2004-09-15
CA2440078A1 (en) 2002-09-12
PL363008A1 (en) 2004-11-15
EP1370424A1 (en) 2003-12-17
PL202501B1 (en) 2009-06-30
CN1501864A (en) 2004-06-02
KR20030087016A (en) 2003-11-12
ES2224072T3 (en) 2005-03-01
WO2002070279A1 (en) 2002-09-12

Similar Documents

Publication Publication Date Title
EP1370424B1 (en) Value document
EP1836273B1 (en) Valuable document
EP2089237B1 (en) Authenticity mark in the form of luminescent substances
EP0053183B1 (en) Paper security with authenticity mark of luminescent material only in an invisible area of the light spectrum and checking method thereof
EP0975469B1 (en) Printed document having a value and comprising a luminescent authenticity feature based on a host lattice
DE69823321T2 (en) Use of inorganic particles and methods of marking and identifying a substrate or article
DE3048734C2 (en)
DE19860093B4 (en) Authenticity feature combination for value documents
WO1999038703A1 (en) Printed document having a value and comprising a luminescent authenticity feature
EP2095342B1 (en) Authenticity mark in the form of a luminescent substance
EP2591067A1 (en) Security feature
DE102010055976A1 (en) safety feature
EP1673233A2 (en) Coding system for security documents
EP3850594A1 (en) Valuable document system
DE3121484C2 (en)
EP2794776A1 (en) Security feature having several components
EP3487712B1 (en) Security feature and document of value

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20031008

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040901

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: PATENTANWAELTE SCHAAD, BALASS, MENZL & PARTNER AG

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: GERMAN

REF Corresponds to:

Ref document number: 50200931

Country of ref document: DE

Date of ref document: 20041007

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040922

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20041201

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Effective date: 20041124

LTIE Lt: invalidation of european patent or patent extension

Effective date: 20040901

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2224072

Country of ref document: ES

Kind code of ref document: T3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20050305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050331

REG Reference to a national code

Ref country code: IE

Ref legal event code: FD4D

ET Fr: translation filed
PLAQ Examination of admissibility of opposition: information related to despatch of communication + time limit deleted

Free format text: ORIGINAL CODE: EPIDOSDOPE2

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLAQ Examination of admissibility of opposition: information related to despatch of communication + time limit deleted

Free format text: ORIGINAL CODE: EPIDOSDOPE2

PLAR Examination of admissibility of opposition: information related to receipt of reply deleted

Free format text: ORIGINAL CODE: EPIDOSDOPE4

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

26 Opposition filed

Opponent name: BUNDESDRUCKEREI GMBH

Effective date: 20050601

R26 Opposition filed (corrected)

Opponent name: BUNDESDRUCKEREI GMBH

Effective date: 20050601

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

NLR1 Nl: opposition has been filed with the epo

Opponent name: BUNDESDRUCKEREI GMBH

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

APBP Date of receipt of notice of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA2O

APAH Appeal reference modified

Free format text: ORIGINAL CODE: EPIDOSCREFNO

APBQ Date of receipt of statement of grounds of appeal recorded

Free format text: ORIGINAL CODE: EPIDOSNNOA3O

APBU Appeal procedure closed

Free format text: ORIGINAL CODE: EPIDOSNNOA9O

PUAH Patent maintained in amended form

Free format text: ORIGINAL CODE: 0009272

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT MAINTAINED AS AMENDED

27A Patent maintained in amended form

Effective date: 20130731

AK Designated contracting states

Kind code of ref document: B2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Extension state: AL LT LV MK RO SI

REG Reference to a national code

Ref country code: CH

Ref legal event code: AELC

REG Reference to a national code

Ref country code: DE

Ref legal event code: R102

Ref document number: 50200931

Country of ref document: DE

Effective date: 20130731

REG Reference to a national code

Ref country code: DK

Ref legal event code: T4

Effective date: 20131031

Ref country code: DK

Ref legal event code: T4

REG Reference to a national code

Ref country code: ES

Ref legal event code: DC2A

Ref document number: 2224072

Country of ref document: ES

Kind code of ref document: T5

Effective date: 20131115

REG Reference to a national code

Ref country code: SE

Ref legal event code: RPEO

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 50200931

Country of ref document: DE

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20160322

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20170323

Year of fee payment: 16

REG Reference to a national code

Ref country code: DE

Ref legal event code: R081

Ref document number: 50200931

Country of ref document: DE

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH, DE

Free format text: FORMER OWNER: GIESECKE & DEVRIENT GMBH, 81677 MUENCHEN, DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PUE

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH, DE

Free format text: FORMER OWNER: GIESECKE AND DEVRIENT GMBH, DE

REG Reference to a national code

Ref country code: ES

Ref legal event code: PC2A

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH

Effective date: 20180123

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170305

REG Reference to a national code

Ref country code: NL

Ref legal event code: PD

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), ASSIGNMENT; FORMER OWNER NAME: GIESECKE & DEVRIENT GMBH

Effective date: 20171205

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20180118 AND 20180124

REG Reference to a national code

Ref country code: BE

Ref legal event code: PD

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH; DE

Free format text: DETAILS ASSIGNMENT: CHANGE OF OWNER(S), CESSION; FORMER OWNER NAME: GIESECKE & DEVRIENT GMBH

Effective date: 20180125

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

REG Reference to a national code

Ref country code: AT

Ref legal event code: PC

Ref document number: 275046

Country of ref document: AT

Kind code of ref document: T

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH, DE

Effective date: 20180425

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: GIESECKE+DEVRIENT CURRENCY TECHNOLOGY GMBH, DE

Effective date: 20180530

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20180331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20180331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20210322

Year of fee payment: 20

Ref country code: CH

Payment date: 20210324

Year of fee payment: 20

Ref country code: FI

Payment date: 20210318

Year of fee payment: 20

Ref country code: PT

Payment date: 20210224

Year of fee payment: 20

Ref country code: NL

Payment date: 20210319

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20210323

Year of fee payment: 20

Ref country code: GB

Payment date: 20210324

Year of fee payment: 20

Ref country code: TR

Payment date: 20210225

Year of fee payment: 20

Ref country code: SE

Payment date: 20210323

Year of fee payment: 20

Ref country code: AT

Payment date: 20210318

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20210331

Year of fee payment: 20

Ref country code: IT

Payment date: 20210331

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20210421

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 50200931

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: EUP

Expiry date: 20220305

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20220304

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20220304

REG Reference to a national code

Ref country code: FI

Ref legal event code: MAE

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 275046

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220304

REG Reference to a national code

Ref country code: SE

Ref legal event code: EUG

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220316

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220305

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220306