EP1370424B2 - Value document - Google Patents

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Publication number
EP1370424B2
EP1370424B2 EP02748334.6A EP02748334A EP1370424B2 EP 1370424 B2 EP1370424 B2 EP 1370424B2 EP 02748334 A EP02748334 A EP 02748334A EP 1370424 B2 EP1370424 B2 EP 1370424B2
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EP
European Patent Office
Prior art keywords
document
range
value
value according
luminescent substance
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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.)
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EP02748334.6A
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German (de)
French (fr)
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EP1370424A1 (en
EP1370424B1 (en
Inventor
Thomas Giering
Rainer Hoppe
Fritz Stahr
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Giesecke and Devrient GmbH
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Giesecke and Devrient GmbH
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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 having at least one authenticity feature in the form of a luminescent substance on the basis of specific host lattices which interact with certain chromophores of the electron configuration (3d) 2 . are doped.
  • value document in the context of the invention banknotes, checks, shares, tokens, identity cards, credit cards, passports and other documents as well as labels, seals, packaging or other elements for product assurance to understand.
  • the luminescent substances can be detected by appropriate eye excitation. For some applications this is desirable, e.g. in the authenticity check by illumination with UV light. For other applications, however, it is advantageous if the emission is outside the visible spectral range, since then special detectors for detecting the substances are necessary.
  • luminophores with characteristic properties which are suitable for securing value documents and, in particular, for automatic authenticity recognition are limited in their number.
  • Most inorganic and organic luminophores have uncharacteristic, broad spectra and, moreover, are 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 value document having 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 silicatic platelets coated with titanium dioxide.
  • the object of the invention is to increase the number of luminophores which are suitable as authenticity markings for value documents, and in particular to provide value documents with authenticity features in the form of luminescent substances, which differ from value documents with hitherto known luminophores distinguished by a characteristically modified excitation and / or emission spectrum.
  • the invention is based on the finding that the detectability of certain luminescences, which is difficult with increasing emission wavelength in the IR spectral range, can be used very advantageously to increase protection against counterfeiting.
  • At least one luminescent substance whose emission spectrum lies outside the visible spectral range, preferably even outside the sensitivity of silicon detectors, is used to secure value documents.
  • 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 may be chromophores of one variety or a mixture of at least two different chromophores.
  • the chromophores according to the invention are the transition metals titanium in the oxidation state Ti 2+ , hereinafter Ti (II), vanadium in the oxidation state V 3+ , in the following V (III), chromium in the oxidation state Cr 4+ , hereinafter Cr (IV), manganese in the oxidation state Mn 5+ , in the following Mn (V), and iron in the oxidation state Fe 6+ , in the following Fe (VI).
  • the host lattices are inorganic templates, e.g. Apatites, Spodiosites, Palmierites, Forsterites, Brushites, Dahlites, Ellestadites, Francolites, Monetites, Morinites, Whitlockites, Wilkeites, Voelkkerites, Pyromorphites, Garnets, Perovskites, Olivines as well as certain silicates, titanates, vanadates, phosphates, sulfates, aluminates, zirconates.
  • the host lattices used according to the invention have one of the following formulas:
  • 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 .
  • the host lattice is particularly preferably BaSO 4 .
  • a host lattice of the formula 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.
  • Y PO 4 , La PO 4 , Zr Si O 4 is particularly preferred.
  • Host lattices with a strong crystal field are particularly preferred.
  • the positions and shapes of the excitation and / or emission bands depend on the mounting position of the chromophores in the host lattice.
  • the chromophores can be present in the oxidic structural units of the host lattice in both tetrahedral and octahedral configurations. However, the tetroxo configuration in the host lattice is preferred.
  • the positions and shapes of the excitation and / or emission bands depend on the strength of the crystal field in the host lattice. The interaction between chromophore and host lattice alters the electronic levels of the chromophores from their values and arrangement in the gas phase, i. (partly against each other) shifted.
  • Fig. 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 , one observes a broadband luminescence from the level 4 T 2 .
  • Narrow-band emission is usually termed when the bands appearing in the emission spectrum show a mean half width of less than 50 nm. However, this does not mean that bands having a half width outside this range do not solve the object of the invention.
  • the number of distinguishable substances according to the invention can be further increased if mixed crystals of the host lattice are also permitted or the host lattices are varied with additional dopants: For example, apatites and spodiosites or garnets and perovskites can form mixed crystals in certain concentration ratios of the starting substances, in which the lattices merge into one another , Associated with this, the crystal field, which acts on the chromophore, can be changed.
  • Ne neodymium
  • Ho holmium
  • Er erbium
  • Tm thulium
  • Yb ytterbium
  • the value document is marked instead of one with a plurality of the luminescent substances according to the invention, the number of distinguishable combinations can be further increased. In addition, if different mixing ratios are distinguished from each other, the number of combinations can be further increased.
  • the marking can be done either at different points of the value document or at the same place. If the luminescent substance is introduced or introduced at different points in the value document, a spatial code, in the simplest case e.g. a barcode to be generated.
  • the forgery security of the value document can be increased if the particular luminescent substance chosen is e.g. is linked in a value document with other information of the value document, so that a check by means of a suitable algorithm is possible.
  • the value document may have, in addition to the luminescent substance according to the invention, further additional authenticity features, such as classical fluorescence and / or magnetism.
  • the luminescent substances can be introduced according to the invention in a variety of ways in the value document.
  • the luminescent substances can be introduced into an ink. But also an admixing of the luminescent substance to the pulp or plastic mass in the production of a value document based on paper or plastic is possible.
  • the luminescent substances can be provided on or in a plastic carrier material which, for example, in turn, can be at least partially embedded in the paper pulp.
  • the luminescent substance can be used e.g. directly into the material of the object to be secured, z. B. in housings and plastic bottles.
  • the plastic or paper base material may also be attached to any other article, e.g. be attached to the product fuse.
  • the carrier material is preferably formed in this case in the form of a label. If the carrier material is part of the product to be protected, e.g. in the case of tearing threads, of course, any other shape is possible. In certain applications, it may be useful to provide the luminescent substance as an invisible coating on the document of value. It may be over the entire surface or in the form of certain patterns, such. Stripes, lines, circles or in the form of alphanumeric characters.
  • either a colorless luminescent substance in the printing ink or the coating lacquer must be used or a colored luminescent substance in such a low concentration that the transparency of the coating is just barely given.
  • the support material may already be suitably colored, so that colored luminescent substances are not perceived due to their inherent color.
  • the luminescent substances according to the invention are processed in the form of pigments.
  • the pigments can be present in particular as individually encapsulated pigment particles or coated with an inorganic or organic coating.
  • the individual pigment particles are surrounded for this purpose with a silicate shell and can thus be more easily dispersed in media.
  • various pigment particles of a combination may be co-encapsulated, e.g. in fibers, filaments, silicate wraps. So it is e.g. no longer possible to subsequently change the "code” of the combination.
  • encapsulation is meant a complete encasing of the pigment particles, while “coating” also means the partial encapsulation or coating of the pigment particles.
  • the starting materials in oxidic form or substances that can be converted into oxides in a suitable ratio, for example, as mixed in equation (1), provided with the chromophore and then calcined, crushed, washed (eg with water), dried and ground.
  • a chromophore for example: Mn 2 O 3 , MnO, MnO 2 , MnCO 3 , MnCl 2 , KMnO 4 and organic manganese compounds can be used.
  • Their proportion by weight, based on the total mixture can be up to 20% by weight.
  • the annealing is carried out in the temperature range of 200 to 1700 ° C and a holding time of 0.2 to 24 h, but preferably at 300 to 500 ° C and a holding time of 0.5 to 2h.
  • 6 LiOH + As 2 O 5 + x MnCl 2 ⁇ 2 Li 3 AsO 4 : Mn + 3H 2 O + xCl 2 (1)
  • the batch may additionally be admixed with LiCO 3 , preferably 1 to 5%, as well as additional LiOH, preferably 1 to 20% by weight.
  • sulfates eg K 2 SO 4
  • chromates eg K 2 CrO 4
  • the dopant such as Na 2 FeO 4
  • the doping with Na 2 FeO 4 can be up to 20%. Evaporation of the solvent yields the product which is ground for further use.
  • K 2 SO 4 is ground with NaCl and intimately mixed with Fe 3 O 4 . Subsequently, the mixture is annealed at temperatures between 700 and 1800 ° C. The product is ground for further use.
  • Example 2 The process described in Example 2 can be modified such that a spray dryer is used to evaporate the solvent.
  • the alkaline medium may consist entirely or in part, for example of a silicate suspension (eg LUDOX®AS-40, Dupont).
  • a silicate-jacketed material is obtained during spray-drying.
  • an SiO 2 protective layer is produced and the substance is stabilized against solubility in water.
  • the material can be embedded in a polymer, eg PMMA, and processed into film material. This is then blended into planchettes.
  • FIG. 2 explains: Fig. 2 Security element according to the invention in cross section.
  • Fig. 2 shows an embodiment of the security element according to the invention.
  • the security element in this case consists of a label 2, which is composed of a paper or plastic layer 3, a transparent cover layer 4 and an adhesive layer 5.
  • This label 2 is connected via the adhesive layer 5 with any substrate 1.
  • This substrate 1 can be documents of value, identity cards, passports, documents or the like, but also other objects to be protected, such as CDs, packaging or the like.
  • the luminescent substance 6 is contained in the volume of the layer 3 in this embodiment.
  • the luminescent substance could also be contained in a printing ink, not shown, which is printed on one of the label layers, preferably on the surface of the layer 3.

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  • 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)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Control Of Motors That Do Not Use Commutators (AREA)
  • Diaphragms For Electromechanical Transducers (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 bestimmter Wirtsgitter, die mit bestimmten Chromophoren der Elektronenkonfiguration (3d)2. dotiert sind.The invention relates to a printed document of value having at least one authenticity feature in the form of a luminescent substance on the basis of specific host lattices which interact with certain chromophores of the electron configuration (3d) 2 . are doped.

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.The term "value document" in the context of the invention banknotes, checks, shares, tokens, identity cards, credit cards, passports and other documents as well as labels, seals, packaging or other elements for product assurance to understand.

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 value documents against forgery by means of luminescent substances has been known for a long time. The use of rare earth metals has also been discussed in this context. They have the advantage that they have narrow-band characteristic spectral lines which facilitate reliable detection and differentiation from other spectra. Preferably, substances are used in which either the absorption or the emission are outside the visible spectral range.

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.If the emissions are at wavelengths between approximately 400 nm and approximately 700 nm, the luminescent substances can be detected by appropriate eye excitation. For some applications this is desirable, e.g. in the authenticity check by illumination with UV light. For other applications, however, it is advantageous if the emission is outside the visible spectral range, since then special detectors for detecting the 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.However, luminophores with characteristic properties which are suitable for securing value documents and, in particular, for automatic authenticity recognition are limited in their number. Most inorganic and organic luminophores have uncharacteristic, broad spectra and, moreover, are 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 value document having 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 of counterfeit-proof securities and packaging; Interference pigments are not luminescent. These interference pigments are silicatic platelets coated with titanium dioxide.

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.On the basis of this prior art, the object of the invention is to increase the number of luminophores which are suitable as authenticity markings for value documents, and in particular to provide value documents with authenticity features in the form of luminescent substances, which differ from value documents with hitherto known luminophores distinguished by a characteristically modified excitation and / or emission spectrum.

Die Lösung dieser Aufgabe ergibt sich aus den unabhängigen Ansprüchen. Weiterbildungen sind Gegenstand der Unteransprüche.The solution to this problem arises from the independent claims. Further developments are the subject of the dependent claims.

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 finding that the detectability of certain luminescences, which is difficult with increasing emission wavelength in the IR spectral range, can be used very advantageously to increase protection against counterfeiting.

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 one luminescent substance whose emission spectrum lies outside the visible spectral range, preferably even outside the sensitivity of silicon detectors, is used to secure value documents.

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 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 may be chromophores of one variety or a mixture of at least two different chromophores. The chromophores according to the invention are the transition metals titanium in the oxidation state Ti 2+ , hereinafter Ti (II), vanadium in the oxidation state V 3+ , in the following V (III), chromium in the oxidation state Cr 4+ , hereinafter Cr (IV), manganese in the oxidation state Mn 5+ , in the following Mn (V), and iron in the oxidation state Fe 6+ , in the following Fe (VI).

Bei den Wirtsgittern handelt es sich um anorganische Matrizen, z.B. Apatite, Spodiosite, Palmierite, Forsterit, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelkkerite, Pyromorphite, Granate, Perovskite, Olivine sowie bestimmte Silicate, Titanate, Vanadate, Phosphate, Sulfate, Aluminate, Zirkonate. Die erfindungsgemäß verwendeten Wirtsgitter haben eine der folgenden Formeln:.The host lattices are inorganic templates, e.g. Apatites, Spodiosites, Palmierites, Forsterites, Brushites, Dahlites, Ellestadites, Francolites, Monetites, Morinites, Whitlockites, Wilkeites, Voelkkerites, Pyromorphites, Garnets, Perovskites, Olivines as well as certain silicates, titanates, vanadates, phosphates, sulfates, aluminates, zirconates. The host lattices used according to the invention have one of the following formulas:

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 are 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 Sl 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 l 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 are 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.Further suitable as a host lattice is a compound of the formula:

[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 are each from 0 to 2 and
g, h, j range from 0 to 1, respectively.

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.Furthermore, a host lattice of the formula is particularly suitable:

[Y a La b ] [Si c Ti d ] O 5 ,

where a + b = 2;
c + d = 1; and
a, b are each from 0 to 2 and
c, d range from 0 to 1, respectively.

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.Preferably, the host lattice is furthermore 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 are 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.Favor is also 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 are 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 Cs c Rb d] [S Se e f g Cr Mo h] O 4,

where a + b + c + d = 2;
e + f + g + h = 1; and
a, b, c, d are each from 0 to 2 and
e, f, g, h range from 0 to 1, respectively.

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 are each from 0 to 1 and
e, f, g, h, i each range from 0 to 1. The host lattice is particularly preferably BaSO 4 .

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 + 1 + 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

preferably, where a + b + c + d + e = 3;
f + g + h = 5; and
a, b, c, d, e are each from 0 to 3 and
f, g, h range from 0 to 5, respectively.

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 are 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 are each from 0 to 1 and
e, f, g, h range from 0 to 4, respectively.

Bevorzugt ist auch ein Wirtsgitter der Formel

        Y2[Sia Tib Zrc] O7 oder MgCa2[Sia Tib Zrc] O7,

wobei a + b + c = 2 und
a, b und c jeweils von 0 bis 2 reichen.Also preferred is a host lattice of the formula

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.Furthermore, a compound of the formula is suitable as a 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 are 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 of the formula

[Y a La b Zr c ] [P d Si e ] O 4 is preferred

where a + b + c = 1;
d + e = 1 and
a, b, c are each from 0 to 1,
d, e range from 0 to 1, respectively.
Particularly preferred is Y PO 4 , La PO 4 , Zr Si O 4 .

Weiterhin ist ein Wirtsgitter der Formel

        K [Ti2a Zr2b] (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 of the formula

K [Ti 2a Zr 2b ] (PO 4 ) 3 is preferred,

where a + b = 1 and
a, b range from 0 to 1, respectively.
Particularly preferred is K Ti 2 (PO 4 ) 3 , K Zr 2 (PO 4 ) 3 .

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 positions and shapes of the excitation and / or emission bands depend on the mounting position of the chromophores in the host lattice. The chromophores can be present in the oxidic structural units of the host lattice in both tetrahedral and octahedral configurations. However, the tetroxo configuration in the host lattice is preferred. Furthermore, the positions and shapes of the excitation and / or emission bands depend on the strength of the crystal field in the host lattice. The interaction between chromophore and host lattice alters the electronic levels of the chromophores from their values and arrangement in the gas phase, i. (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 system Cr 3+ in an octahedral environment [Imbusch, GF; Spectroscopy of Solid-State Laser-Type Materials, Ed: B. Di Bartolo; p 165; 1987] the concept of the crystal field is explained. Fig. 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 , one observes a broadband luminescence from the level 4 T 2 . Finally, for strong crystal fields, state 2 E, which is only weakly dependent on the crystal field, is the first excited electronic state and a narrowband emission from this level is observed. Analog energy level schemes can be formulated for the inventive (3d) 2 configuration with the corresponding designations of levels. For the important octahedral (O h ) and tetrahedral (T d ) configuration, the level sequence in Fig. 1b shown.

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 broadband and narrowband luminescence can be used to secure value documents, but for reasons of selectivity, narrowband luminescence is preferred. These are observed in particular by the chromophores Mn (V) and Fe (VI) in host lattices with a strong crystal field.

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.Narrow-band emission is usually termed when the bands appearing in the emission spectrum show a mean half width of less than 50 nm. However, this does not mean that bands having a half width outside this range do not solve the object 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 Leimineszenziebensdauer 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 variation and combination of the chromophores according to the invention as well as by variation of the host lattice opens up numerous possibilities to influence the excitation and emission spectra of the luminescent substances according to the invention and thus to produce a variety of security features. In addition to the evaluation of the excitation and / or emission spectra, it is likewise possible to make use of the luminescent episode duration for differentiation. In the evaluation, in addition to the wavelengths of the excitation or emission lines, their number and / or shape and / or their intensities can also be taken into account, with which any desired 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 further increased if mixed crystals of the host lattice are also permitted or the host lattices are varied with additional dopants: For example, apatites and spodiosites or garnets and perovskites can form mixed crystals in certain concentration ratios of the starting substances, in which the lattices merge into one another , Associated with this, the crystal field, which 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 Energie-übertrag 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 likewise possible to introduce further chromophores into the host lattice via doping in addition to the chromophores according to the invention and thus to achieve a combined luminescence of both systems or an energy transfer between the systems and to use them for the identification. For example, rare earth ions are suitable for this, which retain their typical luminescence in the host lattice due to their shielded shells.

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 value document is marked instead of one with a plurality of the luminescent substances according to the invention, the number of distinguishable combinations can be further increased. In addition, if different mixing ratios are distinguished from each other, the number of combinations can be further increased. The marking can be done either at different points of the value document or at the same place. If the luminescent substance is introduced or introduced at different points in the value document, a spatial code, in the simplest case e.g. a barcode to be generated.

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 forgery security of the value document can be increased if the particular luminescent substance chosen is e.g. is linked in a value document with other information of the value document, so that a check by means of a suitable algorithm is possible. Of course, the value document may have, in addition to the luminescent substance according to the invention, further additional authenticity features, such as classical 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 be introduced according to the invention in a variety of ways in the value document. For example, the luminescent substances can be introduced into an ink. But also an admixing of the luminescent substance to the pulp or plastic mass in the production of a value document based on paper or plastic is possible. Likewise, the luminescent substances can be provided on or in a plastic carrier material which, for example, in turn, can be at least partially embedded in the paper pulp. The carrier material coated on a suitable polymer, e.g. PMMA based and in which the luminescent substance according to the invention is embedded, in this case may have the form of a security thread, a mottled fiber or a planchette. Likewise, for the purpose of securing the product, the luminescent substance can be used e.g. directly into the material of the object to be secured, z. B. in 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 base material may also be attached to any other article, e.g. be attached to the product fuse. The carrier material is preferably formed in this case in the form of a label. If the carrier material is part of the product to be protected, e.g. in the case of tearing threads, of course, any other shape is possible. In certain applications, it may be useful to provide the luminescent substance as an invisible coating on the document of value. It may be over the entire surface or in the form of certain patterns, such. Stripes, lines, circles or in the form of alphanumeric characters. In order to ensure the invisibility of the luminescent substance, according to the invention, either a colorless luminescent substance in the printing ink or the coating lacquer must be used or a colored luminescent substance in such a low concentration that the transparency of the coating is just barely given. Alternatively or additionally, the support material may already be suitably colored, so that colored luminescent substances are not perceived due to their inherent color.

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.Usually, the luminescent substances according to the invention are processed in the form of pigments. For better processing or to increase their stability, the pigments can be present in particular as individually encapsulated pigment particles or coated with an inorganic or organic coating. For example, the individual pigment particles are surrounded for this purpose with a silicate shell and can thus be more easily dispersed in media. Likewise, various pigment particles of a combination may be co-encapsulated, e.g. in fibers, filaments, silicate wraps. So it is e.g. no longer possible to subsequently change the "code" of the combination. By "encapsulation" is meant a complete encasing of the pigment particles, while "coating" also means the partial encapsulation or coating of the pigment particles.

Im Folgenden werden einige Beispiele der erfindungsgemäßen lumineszierenden Substanz näher erläutert.In the following, some examples of the luminescent substance according to the invention are 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: Mn2 O3, 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.

        6 LiOH + As2 O5 +x MnCl2 → 2 Li3 AsO4 : Mn + 3H2O + xCl2     (1)

For the preparation, the starting materials in oxidic form or substances that can be converted into oxides, in a suitable ratio, for example, as mixed in equation (1), provided with the chromophore and then calcined, crushed, washed (eg with water), dried and ground. As a chromophore, for example: Mn 2 O 3 , MnO, MnO 2 , MnCO 3 , MnCl 2 , KMnO 4 and organic manganese compounds can be used. Their proportion by weight, based on the total mixture, can be up to 20% by weight. The annealing is carried out in the temperature range of 200 to 1700 ° C and a holding time of 0.2 to 24 h, but preferably at 300 to 500 ° C and a holding time of 0.5 to 2h.

6 LiOH + As 2 O 5 + x MnCl 2 → 2 Li 3 AsO 4 : Mn + 3H 2 O + xCl 2 (1)

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, the batch may additionally be admixed with LiCO 3 , preferably 1 to 5%, as well as additional LiOH, preferably 1 to 20% by weight.

Beispiel 2:Example 2:

In alkalischem Medium werden entsprechende Mengen an Sulfaten (z.B. K2 SO4) oder Chromaten (z.B. K2 CrO4) sowie die Menge des Dotierstoffes, wie z.B. Na2 FeO4 gelöst. Die Dotierung mit Na2 FeO4 kann bis zu 20 % betragen. Durch Verdampfung des Lösungsmittels wird das Produkt gewonnen, welches für die weitere Verwendung vermahlen wird.In alkaline medium, appropriate amounts of sulfates (eg K 2 SO 4 ) or chromates (eg K 2 CrO 4 ) and the amount of the dopant, such as Na 2 FeO 4 are dissolved. The doping with Na 2 FeO 4 can be up to 20%. Evaporation of the solvent yields the product which is ground for further use.

Alternativ kann auch eine Festkörperreaktion durchgeführt werden. Dazu wird K2 SO4 mit NaCl vermahlen und innig mit Fe3 O4 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 . Subsequently, the mixture is 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 process described in Example 2 can be modified such that a spray dryer is used to evaporate the solvent. Furthermore, the alkaline medium may consist entirely or in part, for example of a silicate suspension (eg LUDOX®AS-40, Dupont). In this case, a silicate-jacketed material is obtained during spray-drying. By a subsequent annealing process, preferably at temperatures of 200 ° C to 600 ° C, an SiO 2 protective layer is produced and the substance is stabilized against solubility in water. In addition, the material can be embedded in a polymer, eg PMMA, and processed into film material. This is then blended 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 described below with reference to FIG FIG. 2 explains:

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. Fig. 2 shows an embodiment of the security element according to the invention. The security element in this case consists of a label 2, which is composed of a paper or plastic layer 3, a transparent cover layer 4 and an adhesive layer 5. This label 2 is connected via the adhesive layer 5 with any substrate 1. This substrate 1 can be documents of value, identity cards, passports, documents or the like, but also other objects to be protected, such as CDs, packaging or the like. The luminescent substance 6 is contained in the volume of the layer 3 in this embodiment.

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 contained in a printing ink, not shown, which is printed on one of the label layers, preferably on the surface of the 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 as a security element on an object, it is also possible according to the invention; to provide the luminescent substance directly in the document of value to be secured or on its surface in the form of a coating.

Claims (26)

  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, 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, and wherein the host lattice is a compound having one of formulae (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16) or (17):

            [Baa Cab Src Pbd Cde (Pf Vg Ash Sij Sk Crl O4)3 Fm Cln Brp (OH)q]x     (1)

    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;
    f, g, h, j, k, l, m, n, p, q from 0 to 1,

            [Mga Bab Cac Srd Pbe Cdf] [Pg Vh Asj Sik Sl Crm] O4 [Fn Clp Brq (OH)r]     (2)

    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;
    g, h, j, k, l, m, n, p, q, r from 0 to 1,

            [Mga Bab Cac Srd Pbe Cdf] [Sig Tih Gej] O4     (3)

    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,

            [Lia Nab Kc Rbd] [Pe Asf Vg] O4     (4)

    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,

            [Ya Lab] [Sic Tid] O5     (5)

    where a + b = 2;
    c + d = 1; and
    a, b each range from 0 to 2, and
    c, d from 0 to 1,

            [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Crl O4)2     (6)

    where a + b + c + d + e = 3;
    f + g + h + j + k + l = 1;
    a, b, c, d, e each range from 0 to 3, and
    f, g, h, j, k, l from 0 to 1,

            [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Crl O4)3 Cl     (7)

    where a + b + c + d + e = 5;
    f + g + h + j + l = 1;
    a, b, c, d, e each range from 0 to 5, and
    f, g, h, j, k, l from 0 to 1,

            [Naa Kb Rbc Csd] [Se Sef Crg Moh] O4     (8)

    where a + b + c + d = 2;
    e + f + g + h = 1;
    a, b, c, d each range from 0 to 2, and
    e, f, g, h from 0 to 1,

            [Mga Cab Src Bad] [Se Sef Crg Moh Wi] O4     (9)

    where a + b + c + d = 1;
    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,

            [Sca YbLacCedPreNdfPmgSmhEujGdkTblDymHonErpTmqYbrLns] [Al4FevCrx]O3     (10)

    where a + b + c + d + e + f + g + h + j + k + l + m + n + p + q + r + s = 1;
    u + v + x = 1;
    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,

            [Ya Gdb Scc Lad Lne] [Alf Feg Crh] O12     (11)

    where a + b + c + d + e = 3;
    f + g + h = 5;
    a, b, c, d, e each range from 0 to 3, and
    f, g, h from 0 to 5,

            [Mga Cab Src Bad] [Ale Crf Feg Gah] O4     (12)

    where a + b + c + d = 1;
    e + f + g + h = 2;
    a, b, c, d each range from 0 to 1, and
    e, f, g, h from 0 to 2,

            [Mga Cab Src Bad] [Ale Crf Feg Gah] O7     (13)

    where a + b + c + d = 1;
    e + f + g + h = 4;
    a, b, c, d each range from 0 to 1, and
    e, f, g, h from 0 to 4,

            Y2[Sia Tib Zrc] O7 or MgCa2[SiaTibZrc] O7     (14)

    where
    a + b + c = 2, and
    a, b and c each range from 0 to 2,

            [Baa Cab Src] [Sid Tie Zrf] O5     (15)

    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,

            [Ya Lab Zrc] [Pd Sie] O4     (16)

    where
    a + b + c = 1;
    d + e = 1, and
    a, b, c each range from 0 to 1, and
    d, e from 0 to 1,

            K [Ti2a Zr2b] (P O4)3     (17)

    where
    a + b = 1, and
    a, b each range from 0 to 1.
  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 document of value consists of paper or plastic.
  4. A document of value according to at least one of claims 1 to 3, 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.
  5. A document of value according to at least one of claims 1 to 4, wherein the luminescent substance is provided on the document of value as an invisible, at least partial coating.
  6. A document of value according to at least one of claims 1 to 5, wherein the luminescent substance is admixed to a printing ink.
  7. A document of value according to at least one of claims 1 to 6, wherein the coating has the form of one or more stripes.
  8. A document of value according to at least one of claims 1 to 7, wherein the host lattice is additionally co-doped with at least one representative from the group of rare earth metal cations.
  9. A document of value according to claim 8, wherein the rare earth metal cation is selected from neodymium (Nd), holmium (Ho), erbium (Er), thulium (Tm) and ytterbium (Yb).
  10. A document of value according to at least one of claims 1 to 9, 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.
  11. A document of value according to at least one of claims 1 to 10, wherein the chromophores are present in the host lattice in the tetroxo configuration.
  12. A document of value according to at least one of claims 1 to 11, wherein the luminescent substance is present as pigment particles.
  13. A security element having a carrier material and at least one luminescent substance as is defined in claim 1.
  14. A security element according to claim 13, wherein the host lattice has a strong crystal field.
  15. A security element according to claim 13 or 14, wherein the security element has the form of a stripe or band.
  16. A security element according to at least one of claims 13 to 15, wherein the carrier material is formed as a security thread, planchet or mottling fiber.
  17. A security element according to at least one of claims 13 to 16, characterized in that the security element is formed as a label.
  18. A security element according to at least one of claims 13 to 17, characterized in that the at least one luminescent substance is embedded in the carrier material or applied to the carrier material.
  19. A method for producing a document of value according to at least one of claims 1 to 12, characterized in that the luminescent substance is added to a printing ink.
  20. A method for producing a document of value according to at least one of claims 1 to 12, characterized in that the luminescent substance is applied by a coating process.
  21. A method for producing a document of value according to at least one of claims 1 to 12, characterized in that the luminescent substance is incorporated into the volume of the document of value.
  22. A method for producing a document of value according to at least one of claims 1 to 12, characterized in that the luminescent substance is supplied to the document of value by accordingly prepared mottling fibers.
  23. A method for producing a document of value according to at least one of claims 1 to 12, characterized in that the luminescent substance is supplied to the document of value by an accordingly prepared security thread.
  24. A test method for authenticity testing of a document of value according to at least one of claims 1 to 12 or a security element according to at least one of claims 13 to 18, 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.
  25. A test method for authenticity testing of a document of value or security element according to claim 24, characterized in that the emission lines and/or excitation bands represent a coding and/or a coding is represented by varying the host lattices.
  26. A test method for authenticity testing of a document of value according to at least one of claims 1 to 12 or a security element according to at least one of claims 13 to 18, characterized in that the lifetimes of luminescence of the luminescent substances are evaluated.
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