EP1370424A1 - Value document - Google Patents

Value document

Info

Publication number
EP1370424A1
EP1370424A1 EP02748334A EP02748334A EP1370424A1 EP 1370424 A1 EP1370424 A1 EP 1370424A1 EP 02748334 A EP02748334 A EP 02748334A EP 02748334 A EP02748334 A EP 02748334A EP 1370424 A1 EP1370424 A1 EP 1370424A1
Authority
EP
European Patent Office
Prior art keywords
document
range
value
host lattice
value according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02748334A
Other languages
German (de)
French (fr)
Other versions
EP1370424B2 (en
EP1370424B1 (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
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Application filed by Giesecke and Devrient GmbH filed Critical Giesecke and Devrient GmbH
Publication of EP1370424A1 publication Critical patent/EP1370424A1/en
Application granted granted Critical
Publication of EP1370424B1 publication Critical patent/EP1370424B1/en
Publication of EP1370424B2 publication Critical patent/EP1370424B2/en
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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 value document with at least one authenticity feature in the form of a luminescent substance based on host lattices doped with chromophores of the electron configuration (3d) 2 .
  • value document means banknotes, checks, shares, tokens, ID cards, credit cards, passports and also other documents as well as labels, seals, packaging or other elements for product security.
  • the luminescent substances can be detected with the eye with suitable excitation. This is desirable for some applications, e.g. in the authenticity check by lighting with UV light. For other applications, however, it is advantageous if the emission lies outside the visible spectral range, since special detectors are then required to detect the substances.
  • Luminophores with characteristic properties that are used to secure documents of value and in particular for automatic authenticity 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.
  • the object of the invention is to increase the number of luminophores which are suitable as authenticity markings for documents of value, and in particular to create documents of value with authenticity features in the form of luminescent substances which differ from documents of value with hitherto distinguish known luminophores by a characteristically modified excitation and / or emission spectrum.
  • the invention is now based on the knowledge that the detection of certain luminescences, which is difficult to detect with increasing emission wavelength in the IR spectral range, can be used very advantageously to increase protection against counterfeiting.
  • At least one luminescent substance is used to secure documents of value, the emission spectrum of which lies outside 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 coated with chromium. mophores of the electron configuration (3d) 2 are doped. 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 e Ti 2+ , hereinafter referred to as Ti (II), vanadium in the oxidation state e V 3+ , hereinafter referred to as V (III), chromium in the oxidation state e Cr “ 1 ", 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 chelates, e.g. Apatite, Spodiosite, Pahnierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphite, Garnets, Perovskite, Olivine as well as certain silicates, Titanate, Vanadate, Phosphate, Sulfate, Aluminate, Zirkon ,
  • organic chelates e.g. Apatite, Spodiosite, Pahnierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphite, Garnets, Perovskite, Olivine as well as certain silicates, Titanate, Vanadate, Phosphate, Sulfate
  • the host lattice is preferably a compound of the formula:
  • the host lattice is preferably a compound of the formula:
  • a host lattice of the formula is particularly suitable:
  • a further preferred host lattice is a compound of the formula:
  • a host lattice is of the formula
  • Y PO4, La PO4 is particularly preferred .
  • a host lattice is of the formula
  • K Ti 2 (P 0 4 ) 3 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 position of the chromophores in the host lattice.
  • the chromophores can be present in the oxidic structural units of the host lattice both in the tetrahedron and in the octahedron configuration. However, preference is given to tetroxo configuration in the host lattice.
  • the locations and forms of the excitation and / or emission band also depend on the strength of the crystal field in the host lattice. Due to the interactions between the chromophore and the host lattice, the electronic levels of the chromophores are changed compared to their values and arrangement in the gas phase, ie they are shifted (at times).
  • Fig. La 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 A 1, 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.
  • the level sequence is shown in Fig. Lb.
  • the luminescence lifetime can also be used to differentiate.
  • their number and / or shape and / or their intensities can also be taken into account in the evaluation, so that any coding can be represented.
  • the number of distinguishable substances according to the invention can be increased further if mixed crystals of the host lattice are also permitted or the host lattice is varied with additional doping.
  • 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 that acts on the chromophore can be changed.
  • chromophores are suitable for this purpose, because their shielded shells also retain their typical luminescence in the host lattice.
  • Nd neodymium
  • Ho holmium
  • Er erbium
  • Tm thulium
  • Yb ytterbium
  • the number of distinguishable combinations can be further increased. If different mixing ratios are also distinguished from one another, the number of combinations can be increased again.
  • the marking can take place either at different points in the value document or at the same location. If the luminescent substance is applied or introduced at various points in the value document, a spatial code can be used, in the simplest case e.g. a barcode.
  • the security against forgery of the document of value can be increased if the specially selected luminescent substance e.g. in a value document is linked to other information of the value document, so that a check using a suitable algorithm is possible.
  • the document of value can also have further additional authenticity features, such as classic fluorescence and / or magnetism.
  • the luminescent substances can be introduced into the value document in a wide variety of ways.
  • the luminescent substances can be introduced into a printing ink.
  • admixing the luminescent substance to the paper pulp or plastic pulp is also possible when producing a value document based on paper or plastic.
  • the luminescent substances on or in a plastic carrier germ material are provided, which for example can be at least partially embedded in the paper pulp.
  • the carrier material which is based on a suitable polymer, such as PMMA and in which the luminescent substance according to the invention is embedded, can have the form of a security thread, a mottled fiber or a planchette.
  • the luminescent substance can also be introduced, for example, directly into the material of the object to be protected, for example into housings and plastic bottles, for product security.
  • the plastic or paper carrier material can also be attached to any other object, e.g. be secured for product safety.
  • the carrier material is preferably in the form of a label. If the carrier material is part of the product to be secured, e.g. any other shape is of course also possible with tear threads.
  • a colorless luminescent substance must be used in the printing ink or the coating varnish or a colored luminescent substance in such a low concentration that the transparency of the coating is just given.
  • the carrier material can also be suitably colored so that colored luminescent substances are not perceived due to their inherent color.
  • the luminescent substances according to the invention are usually processed in the form of pigments.
  • the pigments can be present in particular as individually encapsulated pigment particles or can be coated with an inorganic or organic coating.
  • the individual pigment particles are surrounded with a silicate shell and can thus be more easily dispersed in media.
  • different pigment particles of a combination can be encapsulated together, for example in fibers, threads, silicate casings. For example, it is no longer possible to subsequently change the "code” of the combination.
  • “Encapsulation” means complete encasing of the pigment particles, while “coating” also means the partial encasing or coating of the pigment particles.
  • 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.
  • a suitable ratio for example as in equation (1)
  • Mh 2 ⁇ 3, MnO, Mn ⁇ 2, MnC ⁇ 3, MhCl 2 , KMn0 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 h, but preferably at 300 to 500 ° C. and a holding time of 0.5 to 2 h.
  • the batch can additionally be mixed with LiCO 3, preferably 1 to 5%, and additional LiOH, preferably 1 to 20% by weight.
  • Corresponding amounts of sulfates (for example K2SO4) or chromates (for example K 2 Cr0 4 ) and the amount of the dopant such as Na2Fe0 4 are dissolved in an alkaline medium.
  • the doping with Na: _Fe04 can be up to 20%.
  • the product is obtained by evaporation of the solvent and is ground for further use.
  • K2SO4 is ground with NaCl and intimately mixed with Fe3 ⁇ 4 .
  • the mixture is then annealed at temperatures between 700 and 1800 ° C.
  • the product will be ground for further use.
  • Example 2 The method described in Example 2 can be modified such that a spray dryer is used to evaporate the solvent.
  • the alkaline medium can consist entirely or partially, for example of a silicate suspension (for example LUDOX ® AS-40, Dupont).
  • a silicate suspension for example LUDOX ® AS-40, Dupont.
  • spray-dried material is covered with silicate.
  • a subsequent annealing process preferably at temperatures from 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. Further embodiments and advantages of the invention are explained below with reference to FIG. 2:
  • the security element 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 to any substrate 1 via the adhesive layer 5.
  • This substrate 1 can be documents of value, ID cards, passports, certificates or the like, but also other objects to be secured, such as CDs, packaging or the like.
  • the luminescent substance 6 is contained in the volume of the layer 3.
  • 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 layer 3.
  • the luminescent substance in or on a carrier material, which is subsequently attached to an object as a security element, 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.

Landscapes

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

Wertdokument value document
Die Erfindung betrifft ein bedrucktes Wertdokument mit zurnindest einem Echtheitsmerkmal in Form einer lumineszierenden Substanz auf der Basis von Wirtsgittern, die mit Chromophoren der Elektronenkonfiguration (3d)2 dotiert sind.The invention relates to a printed value document with at least one authenticity feature in the form of a luminescent substance based on host lattices 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.In the context of the invention, the term “value document” means banknotes, checks, shares, tokens, ID cards, credit cards, passports and also other documents as well as labels, seals, packaging or other elements for product security.
Die Absicherung von Wertdokumenten gegen Fälschung mittels lumineszie- render Substanzen ist bereits seit langem bekannt. Auch die Verwendung von Seltenerdmetallen wurde in diesem Zusammenhang bereits diskutiert. Sie haben den Vorteil, dass sie sch albandige charakteristische Spektralli i- en 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 counterfeiting using 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. Substances are preferably used in which either the absorption or the emission lie 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 approx. 400 nm and approx. 700 nm, the luminescent substances can be detected with the eye with suitable excitation. This is desirable for some applications, e.g. in the authenticity check by lighting with UV light. For other applications, however, it is advantageous if the emission lies outside the visible spectral range, since special detectors are then required to detect the substances.
Luminophore mit charakteristischen Eigenschaften, die sich zur Absicherung von Wertdokumenten und insbesondere für eine automatische Echtheitser- kennung 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 unpraktika- bei.Luminophores with characteristic properties that are used to secure documents of value and in particular for automatic authenticity 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.
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 Wertdo- kumente 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.Proceeding from this prior art, the object of the invention is to increase the number of luminophores which are suitable as authenticity markings for documents of value, and in particular to create documents of value with authenticity features in the form of luminescent substances which differ from documents of value with hitherto distinguish known luminophores 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 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 now based on the knowledge that the detection of certain luminescences, which is difficult to detect 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 außer- halb des sichtbaren Spektralbereichs, vorzugsweise sogar außerhalb der Ansprechempfindlichkeit von Silicium-Detektoren liegt.According to the invention, at least one luminescent substance is used to secure documents of value, the emission spectrum of which lies outside 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 Chro- mophoren der Elektronenkonfiguration (3d)2 dotiert sind. Dabei kann es sich um Chromophore einer Sorte oder um ein Gemisch von w enigstens zwei verschiedenen Chromophoren handeln. Bei den erfindungsgemäßen Chro- mophoren handelt es sich vorzugsweise um die Übergangsmetalle Titan in- der Oxidationsstuf e Ti2+, im Folgenden Ti(II), Vanadium in der Oxidationsstuf e V3+, im Folgenden V(III), Chrom in der Oxidationsstuf e Cr "1", 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 coated with chromium. mophores of the electron configuration (3d) 2 are doped. 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 e Ti 2+ , hereinafter referred to as Ti (II), vanadium in the oxidation state e V 3+ , hereinafter referred to as V (III), chromium in the oxidation state e Cr " 1 ", 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, Pahnierite, Forsterit, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphite, Granate, Perovskite, Olivine sowie bestimmte Silicate, Titana- te, Vanadate, Phosphate, Sulfate, Aluminate, Zirkonate.The host lattices are inorganic matrices or organic chelates, e.g. Apatite, Spodiosite, Pahnierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Monetite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphite, Garnets, Perovskite, Olivine as well as certain silicates, Titanate, Vanadate, Phosphate, Sulfate, Aluminate, Zirkon ,
Bevorzugt handelt es sich bei dem Wirtsgitter um eine Verbindung der Formel:The host lattice is preferably a compound of the formula:
[Baa Cab Src Pbd Cde (Pf Vg Ash Sij Sk Cn 04)3 Fm Cln Brp (OH)q]x, wobei a + b + c + d + e = 5; f + g + h + j + k + l = l; m + n + p + q = l; x = 1 oder 2; und a, b, c, d, e jeweils von 0 bis 5; und f, g, h, j, k, 1, m, n, p, q jeweils von 0 bis 1 reichen.[Ba a Ca b Sr c Pb d Cd e (Pf V g As h Sij S k Cn 0 4 ) 3 Fm Cl n Br p (OH) q ] x , where a + b + c + d + e = 5; f + g + h + j + k + l = l; m + n + p + q = l; x = 1 or 2; and a, b, c, d, e each from 0 to 5; and f, g, h, j, k, 1, m, n, p, q each range from 0 to 1.
Ein weiter bevorzugtes Wirtsgitter ist eine Verbindung der Formel: [Mga Bab Cac Sra Pbe Cdf] \PS Vh ASj Sik Si Crm] 04 [Fn C1P Brq (OH)r], wobei a + b + c + d + e + f =2; g + h + j + k + l + m = l; n + p + q + r = l; und a, b, c, d, e , f jeweils von 0 bis 2; und g, h, j, k, 1, m, n, p, q, r jeweils von 0 bis 1 reichen.A further preferred host lattice is a compound of the formula: [Mga Ba b Cac Sra Pb e Cd f ] \ P S V h A Sj Si k Si Cr m ] 0 4 [F n C1 P Br q (OH) r ], where a + b + c + d + e + f = 2; g + h + j + k + l + m = l; n + p + q + r = l; and a, b, c, d, e, f each from 0 to 2; and g, h, j, k, 1, m, n, p, q, r each range from 0 to 1.
Weiter eignet sich als Wirtsgitter eine Verbindung der Formel: [Mga Ba Cac Srd Pbe Cdf] [Sig Tih Ge,] 04, 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.Also suitable as a host lattice is a compound of the formula: [Mg a Ba Cac Sr d Pb e Cd f ] [Si g Ti h Ge,] 0 4 , 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 each range from 0 to 1.
Des Weiteren ist ein Wirtsgitter der Formel: [Lia Na Kc Rbd] [Pe Asf Vg] 04 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 of the formula: [Li a Na Kc Rbd] [P e As f V g ] 0 4 is preferred, 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 each range from 0 to 1.
Weiterhin eignet sich besonders ein Wirtsgitter der Formel: wobei a + b = 2; c + d = 1; und a, b jeweils von 0 bis 2 und c, d jew eils von 0 bis 1 reichen.A host grid of the formula is also particularly suitable: where a + b = 2; c + d = 1; and a, b each range 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:Furthermore, the host lattice is preferably a compound of the formula:
[Baa Gab Src Pbd Cde] (Pf Vg Ash Sij S Cn 04)2. wobei a + b + c + d + e = 3; f + g + h + j + k + l = l; und a, b, c, d, e jeweils von 0 bis 3 und f, g, h, j, k, 1 jeweils von 0 bis 1 reichen.[Ba a Gab Sr c Pb d Cd e ] (Pf V g As h Sij S Cn 0 4 ) 2 . where a + b + c + d + e = 3; f + g + h + j + k + l = l; and a, b, c, d, e each range from 0 to 3 and f, g, h, j, k, 1 each range from 0 to 1.
Bevorzug ist auch ein Wirtsgitter der Formel: [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij S Cn O^O, wobei a + b + c + d + e = 5; f + g + h + j + l = l; und a, b, c, d , e jeweils von 0 bis 5 und f, g, h, j, k, 1 jeweils von 0 bis 1 reichen.Also preferred is a host lattice of the formula: [Ba a Ca b Sr c Pb d Cd e ] (Pf V g As h Sij S Cn O ^ O, 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, 1 each range from 0 to 1.
Des Weiteren eignet sich besonders ein Wirtsgitter der Formel: [Naa Kb Rbc Csd] [Se Set Crg Moh] 04/ wobei a + b + c + d = 2; e + f + g + h = l; 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 Kb Rb c Cs d ] [S e Set Cr g Moh] 0 4 / where a + b + c + d = 2; e + f + g + h = l; and a, b, c, d each range from 0 to 2 and e, f, g, h each range from 0 to 1.
Des Weiteren eignet sich besonders ein Wirtsgitter der Formel:Furthermore, a host lattice of the formula is particularly suitable:
[Mga Cab Src Bad] [Se Sef Crg Moh WJ 04, wobei a + b + c + d = l; und e + f + g + h + i = l 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[Mg a Ca b Sr c Ba d ] [S e Se f Cr g Mo h WJ 0 4 , where a + b + c + d = l; and e + f + g + h + i = l and a, b, c, d each range from 0 to 1 and e, f, g, h, i each range from 0 to 1. The host lattice is particularly preferred
Ba S04.Ba S0 4 .
Ein weiter bevorzugtes Wirtsgitter ist eine Verbindung der Formel: [ScaY LacCedPreNdfPmgSmhEujGdkTbiDymHonErpTmqYbrLnsItAluFevCrxjOs, wobei a + b + c + d + e + f + g + h + j + k + l + m + n + p + q + r + s = l; u + v + x = 1; und a, b, c, d, e , f, g, h, j, k, 1, 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: [ScaY LacCedPreNdfPmgSmhEujGdkTbiDymHonErpTmqYbrLnsItAluFevCrxjOs, where a + b + c + d + e + f + g + h + j + k + l + m + n + p + q + r + s = l; u + v + x = 1; and a, b, c, d, e, f, g, h, j, k, 1, 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 Li e] [Alf Feg Crπ] Oι2 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 of the formula: [Y a Gdb Sc c La d Li e] [Alf Fe g Crπ] Oι 2 is preferred, 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 each range from 0 to 5.
Ein weiter bevorzugtes Wirtsgitter ist eine Verbindung der Formel:A further preferred host lattice is a compound of the formula:
[Mga Cab Src Bad] [Ale Crf Feg Gah] 04, wobei a + b + c + d = l; 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[Mg a Cab Sr c Ba d ] [Al e Cr f Fe g Ga h ] 0 4 , where a + b + c + d = l; e + f + g + h = 2; and a, b, c, d each range from 0 to 1 and e, f, g, h each range from 0 to 2 or a compound of the formula
[Mga Cab Src Bad] [Ale Crf Feg Gah] 07. wobei a + b + c + d = l; 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.[Mg a Ca b Sr c Ba d ] [Ale Cr f Fe g Ga h ] 0 7. where a + b + c + d = l; e + f + g + h = 4; and a, b, c, d each range from 0 to 1 and e, f, g, h each range from 0 to 4.
Bevorzugt ist auch ein Wirtsgitter der Formel Y2[Sia Ti ZrJ 07 oder MgCa2[SiaTib Zrc] Oz. wobei a + b + c = 2 und a, b und c jeweils von 0 bis 2 reichen. Weiterhin eignet sich als Wirtsgitter eine Verbindung der Formel [BaaCabSrJ [SidTieZr ] Os, 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.Also preferred is a host lattice of the formula Y2 [Si a Ti ZrJ 0 7 or MgCa 2 [Si a Ti b Zr c ] Oz. Where a + b + c = 2 and a, b and c each range from 0 to 2. Also suitable as a host lattice is a compound of the formula [BaaCabSrJ [Si d Ti e Zr] Os, where a + b + c = 3; d + e + f = 1; and a, b, c each range from 0 to 3 and d, e, f each range from 0 to 1.
Weiterhin ist ein Wirtsgitter der FormelFurthermore, a host lattice is of the formula
[Ya Lab Zrc] JPd Sie] O 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.[Y a Lab Zr c ] JPd Sie] O preferred, where a + b + c = 1; d + e = 1 and a, b, c each range from 0 to 1, d, e each range from 0 to 1.
Besonders bevorzugt ist Y PO4, La PO4. Zr Si O4.Y PO4, La PO4 is particularly preferred . Zr Si O4.
Weiterhin ist ein Wirtsgitter der FormelFurthermore, a host lattice is of the formula
K [Ti2aZr2b] (P 04)3 bevorzugt, wobei a + b = 1 und a, b jeweils von 0 bis 1 reichen. Besonders bevorzugt ist K Ti2 (P 04)3. K Zr2 (P 04)3.K [Ti 2a Zr 2 b] (P 04) 3 is preferred, where a + b = 1 and a, b each range from 0 to 1. K Ti 2 (P 0 4 ) 3 is particularly preferred . K Zr 2 (P 0 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 Sttuktureinheiten des Wirtsgitters sowohl in der Tetraeder- wie auch in der Oktaeder-Konfiguration vorliegen. Bevorzugt ist jedoch die Tetroxokonftguration 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 position of the chromophores in the host lattice. The chromophores can be present in the oxidic structural units of the host lattice both in the tetrahedron and in the octahedron configuration. However, preference is given to tetroxo configuration in the host lattice. The locations and forms of the excitation and / or emission band also depend on the strength of the crystal field in the host lattice. Due to the interactions between the chromophore and the host lattice, the electronic levels of the chromophores are changed compared to their values and arrangement in the gas phase, ie they are shifted (at times).
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. la 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 Aι, man beobachtet eine breitbandi- ge 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 te- traedrische (Td) Konfiguration ist die Niveauabfolge in Fig. lb 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. Fig. La 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 A 1, 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 (Oh) and tetrahedral (T d ) configuration, the level sequence is shown in Fig. Lb.
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 VT) in Wirtsgittern mit starkem Kristallfeld beobachtet.Both broadband and narrowband luminescence can be used to secure documents of value, but narrowband luminescence is preferred for reasons of selectivity. These are observed in particular by the chromophores Mn (V) and Fe VT) in host lattices with a strong crystal field.
Von Schmalbandigkeit einer Emission spricht man üblicherweise dann, wenn im Emissionsspektrum die auftretenden Banden eine mittlere Halb- wertsbreite 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 when the bands occurring in the emission spectrum have a medium half Show value width of less than 50 nm. However, this does not mean that bands which have a full width at half maximum outside this range do not also achieve the object according to 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 Anre- gungs- und/oder Emissionsspektren kann ebenso die Lumineszenzlebensdauer 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 and also by varying the host lattice, numerous possibilities open up to influence the excitation and emission spectra of the luminescent substances according to the invention and thus to produce a large number of security features. In addition to evaluating the excitation and / or emission spectra, the luminescence lifetime can also be used to differentiate. 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 in the evaluation, so that 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 increased further if mixed crystals of the host lattice are also permitted or the host lattice is varied with additional doping. 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 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. Bevorzugt handelt es sich hierbei um Neodym (Nd)~, Holmium (Ho)-, Erbium (Er)-, Thulium (Tm)- oder Ytterbium (Yb)-Kationen oder Gemische davon.It is also possible to introduce additional chromophores into the host lattice in addition to the chromophores according to the invention and thus achieve a combined luminescence of both systems or an energy transfer between the systems and use them for identification. For example, rare earth ions are suitable for this purpose, because their shielded shells also retain their typical luminescence in the host lattice. 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 is marked instead of with one of several of the luminescent substances according to the invention, the number of distinguishable combinations can be further increased. If different mixing ratios are also distinguished from one another, the number of combinations can be increased again. The marking can take place either at different points in the value document or at the same location. If the luminescent substance is applied or introduced at various points in the value document, a spatial code can be used, 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 document of value can be increased if the specially selected luminescent substance e.g. in a value document is linked to other information of the value document, so that a check using a suitable algorithm is possible. Of course, in addition to the luminescent substance according to the invention, the document of value can also have 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 Kunststoffträ- germaterial 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 hier- bei 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.According to the invention, the luminescent substances can be introduced into the value document in a wide variety of ways. For example, the luminescent substances can be introduced into a printing ink. However, admixing the luminescent substance to the paper pulp or plastic pulp is also possible when producing a value document based on paper or plastic. Likewise, the luminescent substances on or in a plastic carrier germ material are provided, which for example can be at least partially embedded in the paper pulp. The carrier material, which is based on a suitable polymer, such as PMMA and in which the luminescent substance according to the invention is embedded, can have the form of a security thread, a mottled fiber or a planchette. The luminescent substance can also be introduced, for example, directly into the material of the object to be protected, for example into housings and plastic bottles, for product security.
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 an- dere 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 Beschichtungs- lack 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 attached to any other object, e.g. be secured for product safety. In this case, the carrier material is preferably in the form of a label. If the carrier material is part of the product to be secured, e.g. any other shape is of course also possible with tear threads. In certain applications, it may be useful to provide the luminescent substance as an invisible coating on the value document. It can be full-surface or in the form of certain patterns, such as Stripes, lines, circles or even 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 must be used in the printing ink or the coating varnish or a colored luminescent substance in such a low concentration that the transparency of the coating is just given. Alternatively or additionally, the carrier material can also 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.The luminescent substances according to the invention are usually 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 can be coated with an inorganic or organic coating. For example, the individual pigment particles are surrounded with a silicate shell and can thus be more easily dispersed in media. Likewise, different pigment particles of a combination can be encapsulated together, for example in fibers, threads, silicate casings. For example, it is no longer possible to subsequently change the "code" of the combination. "Encapsulation" means complete encasing of the pigment particles, while "coating" also means the partial encasing or coating of the pigment particles.
Im Folgenden werden einige Beispiele der erfindungsgemäßen lumineszierenden Substanz näher erläutert.Some examples of the luminescent substance according to the invention are explained in more detail below.
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 ver- mahlen. Als Chromophor können z.B. Mh2θ3, MnO, Mnθ2, MnCθ3, MhCl2, KMn04 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.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, Mh 2 θ3, MnO, Mnθ2, MnCθ3, MhCl 2 , KMn0 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 h, but preferably at 300 to 500 ° C. and a holding time of 0.5 to 2 h.
(1) 6 LiOH + AS2O5 +x MnCl2 ■» 2 Lis As04 : Mn + 3 H2O + x Cl2 Um das Gleichgewicht in Richtung der Produktbildung zu verschieben, kann der Ansatz zusätzlich mit LiCθ3, bevorzugt 1 bis 5 %, sowie zusätzlichem LiOH, bevorzugt 1 bis 20 % Gew. versetzt werden.(1) 6 LiOH + AS2O5 + x MnCl 2 ■ »2 Lis As0 4 : Mn + 3 H2O + x Cl 2 In order to shift the equilibrium in the direction of product formation, the batch can additionally be mixed with LiCO 3, preferably 1 to 5%, and additional LiOH, preferably 1 to 20% by weight.
Beispiel 2:Example 2:
In alkalischem Medium werden entsprechende Mengen an Sulfaten (z.B. K2SO4) oder Chromaten (z.B. K2Cr04) sowie die Menge des Dotierstoffes, wie z.B. Na2Fe04 gelöst. Die Dotierung mit Na:_Fe04 kann bis zu 20 % betragen. Durch Verdampfung des Lösungsmittels wird das Produkt gewonnen, welches für die weitere Verwendung vermählen wird.Corresponding amounts of sulfates (for example K2SO4) or chromates (for example K 2 Cr0 4 ) and the amount of the dopant such as Na2Fe0 4 are dissolved in an alkaline medium. The doping with Na: _Fe04 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 vermählen und innig mit Fe3θ4 vermengt. Anschließend wird die Mischung bei Temperaturen zwischen 700 und 1800 °C ge- glüht. Das Produkt wird für die weitere Verwendung vermählen.Alternatively, a solid-state reaction can also be carried out. For this purpose, K2SO4 is ground with NaCl and intimately mixed with Fe3θ 4 . The mixture is then annealed at temperatures between 700 and 1800 ° C. The product will be 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 Siθ2-Schutzschicht erzeugt und die Sub- stanz 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. Weitere Ausführungsformen und Vorteile der Erfindung werden im Folgenden anhand der Figur 2 erläutert: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, spray-dried material is covered with silicate. A subsequent annealing process, preferably at temperatures from 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. Further embodiments and advantages of the invention are explained below with reference to FIG. 2:
Fig. 2 erfindungsgemäßes Sicherheitselement im Querschnitt.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 Kunststoff Schicht 3, einer transparenten Abdeck- schicht 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 is composed of a paper or plastic layer 3, a transparent cover layer 4 and an adhesive layer 5. This label 2 is connected to any substrate 1 via the adhesive layer 5. This substrate 1 can be documents of value, ID cards, passports, certificates or the like, but also other objects to be secured, such as CDs, packaging or the like. In this exemplary embodiment, the luminescent substance 6 is contained in the volume of the 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 contained in a printing ink, not shown, which is printed on one of the label layers, preferably 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 subsequently attached to an object as a security element, 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

P a t e n t a n s p r ü c h e Patent claims
1. Wertdokument mit zumindest einem Echtheitsmerkmal in Form einer lumineszierenden Substanz auf der Basis von dotierten Wirtsgittern, dadurch gekennzeichnet, dass das Wirtsgitter mit wenigstens einem1. document of value with at least one authenticity feature in the form of a luminescent substance based on doped host lattices, characterized in that the host lattice with at least one
Chromophor der Elektronenkonfiguration (3d)2 dotiert ist.Chromophore of the electron configuration (3d) 2 is doped.
2. Wertdokument nach Anspruch 1, wobei das Wirtsgitter ein starkes Kristallfeld aufweist.2. A document of value according to claim 1, wherein the host lattice has a strong crystal field.
3. Wertdokument nach Anspruch 1 oder 2, wobei es sich bei dem Chromophor um Titan in der Oxidationsstufe 2 oder Vanadium in der Oxidationsstufe 3 oder Chrom in der Oxidationsstufe 4 oder Mangan in der Oxidationsstufe 5 oder Eisen in der Oxidationsstufe 6 handelt.3. Document of value according to claim 1 or 2, wherein the chromophore is titanium in the oxidation state 2 or vanadium in the oxidation state 3 or chromium in the oxidation state 4 or manganese in the oxidation state 5 or iron in the oxidation state 6.
4. Wertdokument nach wenigstens einem der Ansprüche 1 bis 3, wobei das Wertdokument aus Papier oder Kunststoff besteht.4. document of value according to at least one of claims 1 to 3, wherein the document of value consists of paper or plastic.
5. Wertdokument nach wenigstens einem der Ansprüche 1 bis 4, wobei das Echtheitsmerkmal in das Volumen des Wertdokumentes eingebracht oder in einer auf dem Wertdokument aufgebrachten Schicht vorliegt.5. Value document according to at least one of claims 1 to 4, wherein the authenticity feature is introduced into the volume of the value document or is present in a layer applied to the value document.
6. Wertdokument nach wenigstens einem der Ansprüche 1 bis 5, wobei die lumineszierende Substanz als unsichtbare zumindest teilweise Beschichtung auf dem Wertdokument vorgesehen ist.6. document of value according to at least one of claims 1 to 5, wherein the luminescent substance is provided as an invisible at least partial coating on the document of value.
7. Wertdokument nach wenigstens einem der Ansprüche 1 bis 6, wobei die lumineszierende Substanz einer Druckfarbe zugemischt ist. 7. document of value according to at least one of claims 1 to 6, wherein the luminescent substance is admixed with a printing ink.
8. Wertdokument nach wenigstens einem der Ansprüche 1 bis 7, wobei die Beschichtung die Form eines oder mehrerer Streifen aufweist.8. document of value according to at least one of claims 1 to 7, wherein the coating has the shape of one or more strips.
9. Wertdokument nach wenigstens einem der Ansprüche 1 bis 8, wobei das Wirtsgitter zusätzlich mit wenigsten einem Vertreter aus der9. document of value according to at least one of claims 1 to 8, wherein the host lattice additionally with at least one representative from the
Gruppe der Seltenerdmetallkationen codotiert ist.Group of rare earth metal cations is codoped.
10. Wertdokument nach Anspruch 9, wobei das SeltenerdmetaUkation ausgewählt ist aus Neodym (Nd), Holmium (Ho), Erbium (Er), Thuli- um (Tm) und Ytterbium (Yb).10. The 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. Wertdokument nach wenigstens einem der Ansprüche 1 bis 10, wobei das Wirtsgitter ausgewählt ist aus der Klasse der Apatite, Spodiosite, Palmierite, Forsterite, Brushite, Dahllite, Ellestadite, Francolite, Mone- tite, Morinite, Whitlockite, Wilkeite, Voelckerite, Pyromorphite, Granate, Perovskite, Silicate, Titanate, Vanadate, Phosphate.11. Value document according to at least one of claims 1 to 10, wherein the host lattice is selected from the class of apatite, spodiosite, palmierite, forsterite, brushite, dahllite, ellestadite, francolite, montite, morinite, whitlockite, Wilkeite, Voelckerite, pyromorphite , Garnets, perovskites, silicates, titanates, vanadates, phosphates.
12. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel: [Baa Cab Src Pbd Cde (Pf Vg Ash Sij Sk Cn 04)s Fm Cln BrP (OH)q]x handelt, wobei a + b + c + d + e = 5; f + g + h + j + k + l = l; m + n + p + q = l; x = 1 oder 2; und a, b, c, d, e jeweils von 0 bis 5; f, g, h, j, k, 1, m, n, p, q jeweils von 0 bis 1 reichen. 12. The document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula: [Ba a Ca b Sr c Pb d Cd e (Pf V g As h Sij S k Cn 0 4 ) s F m Cl n Br P (OH) q ] x , where a + b + c + d + e = 5; f + g + h + j + k + l = l; m + n + p + q = l; x = 1 or 2; and a, b, c, d, e each from 0 to 5; f, g, h, j, k, 1, m, n, p, q each range from 0 to 1.
13. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um ein Verbindung der Formel: [Mga Bab Cac Srd Pbe Cdf] Pg Vh ASJ Sik Si Crm] 04 [Fn C1P Brq (OH)r] handelt, wobei a + b + c + d + e + f =2; g + h + j + k + l + m = l; n + p + q + r = l; und a, b, c, d, e , f jeweils von 0 bis 2; g, h, j, k, 1, m, n, p, q, r jeweils von 0 bis 1 reichen.13. The document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula: [Mg a Ba b Ca c Sr d Pb e Cd f ] P g V h ASJ Si k Si Cr m ] 0 4 [F n C1 P Br q (OH) r ], where a + b + c + d + e + f = 2; g + h + j + k + l + m = l; n + p + q + r = l; and a, b, c, d, e, f each from 0 to 2; g, h, j, k, 1, m, n, p, q, r each range from 0 to 1.
14. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel:14. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
[Mga Bab Cac Srd Pbe Cdf] [Sig Tih Gej] 04 handelt, 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.[Mg a Ba b Ca c Sr d Pb e Cdf] [Si g Tih Gej] 0 4 , 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 each range from 0 to 1.
15. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel: [Lia Nab Kc Rbd] [Pe Asf Vg] 0 handelt, 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.15. Document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula: [Li a Na b Kc Rb d ] [P e As f V g ] 0, 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 each range from 0 to 1.
16. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel: [Ya Lab] [Sic Tid] 05 handelt, wobei a + b = 2; c + d = 1; und a, b, jeweils von 0 bis 2 und c, d jeweils von 0 bis 1 reichen.16. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula: [Ya Lab] [Si c Tid] 0 5 , where a + b = 2; c + d = 1; and a, b each range from 0 to 2 and c, d each range from 0 to 1.
17. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11 wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel: [Baa Cab Src Pbd CdJ (Pf Vg Ash Sij Sk Cri 04)2 handelt, wobei a + b + c + d + e = 3; f + g + h + j + k + l = l; a, b, c, d, e jeweils von 0 bis 3 und f, g, h, j, k, 1 jeweils von 0 bis 1 reichen.17. The document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula: [Ba a Ca b Sr c Pbd CdJ (Pf V g Ash Sij S k Cri 0 4 ) 2 , where a + b + c + d + e = 3; f + g + h + j + k + l = l; a, b, c, d, e each range from 0 to 3 and f, g, h, j, k, 1 each range from 0 to 1.
18. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel: [Baa Cab Src Pbd Cde] (Pf Vg Ash Sij Sk Cn 04)s Cl handelt, wobei a + b + c + d + e = 5; f + g + h + j + l = l; a, b, c, d , e jeweils von 0 bis 5 und f, g, h, j, k, 1 jeweils von 0 bis 1 reichen.18. The document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula: [Ba a Ca b Sr c Pb d Cd e ] (Pf V g As h Sij S k Cn 0 4 ) s Cl is where a + b + c + d + e = 5; f + g + h + j + l = l; a, b, c, d, e each range from 0 to 5 and f, g, h, j, k, 1 each range from 0 to 1.
19. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel:19. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
[Naa Kb Rbc Csd] [Se Set Crg Moh] 0 handelt, wobei a + b + c + d = 2; e + f + g + h = l; a, b, c, d jeweils von 0 bis 2 und e, f, g, h jeweils von 0 bis 1 reichen. [Na a Kb Rb c Cs d ] [S e Set Cr g Moh] 0, where a + b + c + d = 2; e + f + g + h = l; a, b, c, d each range from 0 to 2 and e, f, g, h each range from 0 to 1.
20. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel:20. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
[Mga Cab Src Bad] [Se Sef Crg Moh W] 04 handelt, wobei a + b + c + d = l; e + f + g + h + i = l und a, b, c, d jeweils von 0 bis 1 und e, f, g, h, i jeweils von 0 bis 1 reichen.[Mg a Ca b Sr c Ba d ] [S e Se f Cr g Mo h W] 0 4 , where a + b + c + d = l; e + f + g + h + i = l and a, b, c, d each range from 0 to 1 and e, f, g, h, i each range from 0 to 1.
21. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel:21. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
[ScäYbLacCedPreNdfPmgSmhEujGdfcTbiDy HonErpTr qYbrLnsJfAluFevCrx] 03 handelt, wobei 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, 1, m, n, p, q, r ,s, u, v, x jeweils von 0 bis 1 reichen.[ScäYbLacCedPreNdfPmgSmhEu j GdfcTbiDy HonErpTr qYbrLnsJfAluFevCrx] 0 3 , 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, 1, m, n, p, q, r, s, u, v, x each range from 0 to 1.
22. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um ei e Verbindung der Formel:22. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
[Ya Gdb Scc Lad Lne] [Alf Feg Crh] Oι2 handelt, wobei a + b + c + d + e = 3; f + g + h = 5; a, b, c, d, e jeweils von 0 bis 3 und f , g, h jeweils von 0 bis 5 reichen.[Y a Gdb Sc c La d Ln e ] [Alf Fe g Crh] Oι 2 , 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 each range from 0 to 5.
23. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel:23. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
[Mga Cab Src Bad] [Ale Crf Feg Gah] 04 handelt, wobei a + b + c + d = l; e + f + g + h = 2; 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[Mg a Cab Sr c Ba d ] [Al e Cr f Fe g Ga h ] 0 4 where a + b + c + d = l; e + f + g + h = 2; a, b, c, d each range from 0 to 1 and e, f, g, h each range from 0 to 2 or a compound of the formula
[Mga Ca Src Bad] [Ale Crf Feg Gah] O/ handelt, wobei a + b + c + d = l; e + f + g + h = 4; a, b, c, d jeweils von 0 bis 1 und e, f, g, h jeweils von 0 bis 4 reichen.[Mg a Ca Sr c Ba d ] [Ale Crf Fe g Ga h ] O /, where a + b + c + d = l; e + f + g + h = 4; a, b, c, d each range from 0 to 1 and e, f, g, h each range from 0 to 4.
24. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel Y2 [SiaTibZRc] O/ oder MgCa2 [SiaTibZrc] O/ handelt, wobei a + b + c = 2 und a, b und c jeweils von 0 bis 2 reichen.24. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula Y 2 [SiaTibZR c ] O / or MgCa 2 [Si a TibZr c ] O /, where a + b + c = 2 and a, b and c each range from 0 to 2.
25. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel25. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula
[BaaCabSrc] [SidTieZrf] Os handelt, 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. [Ba a CabSr c ] [Si d Ti e Zr f ] O s , where a + b + c = 3; d + e + f = 1; and a, b, c each range from 0 to 3 and d, e, f each range from 0 to 1.
26. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel26. The document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula
[Ya Lab Zrc] [Pd Sie] 0 handelt, wobei a + b + c = 1; d + e = 1; und a. b, c jeweils von 0 bis 1 und d, e jeweils von 0 bis 1 reichen.[Y a Lab Zr c ] [P d Si e ] 0, where a + b + c = 1; d + e = 1; and a . b, c each range from 0 to 1 and d, e each range from 0 to 1.
27. Wertdokument nach wenigstens einem der Ansprüche 1 bis 11, wobei es sich bei dem Wirtsgitter um eine Verbindung der Formel:27. A document of value according to at least one of claims 1 to 11, wherein the host lattice is a compound of the formula:
K [Ti2a Zr2b] (P 04)3 handelt, wobei a + b = 1; und a, b jeweils von 0 bis 1 reichen.K [Ti 2a Zr 2 b] (P 0 4 ) 3, where a + b = 1; and a, b each range from 0 to 1.
28. Wertdokument nach wenigstens einem der Ansprüche 1 bis 27, wobei die Chromophoren im Wirtsgitter in der Tetroxokonfiguration vorliegen.28. A document of value according to at least one of claims 1 to 27, wherein the chromophores in the host lattice are in the tetroxo configuration.
29. Wertdokument nach wenigstens einem der Ansprüche 1 bis 28, wobei die lumineszierende Substanz als Pigmentpartikel vorliegt.29. Document of value according to at least one of claims 1 to 28, wherein the luminescent substance is present as pigment particles.
30. Sicherheitselement, welches ein Trägermaterial und zumindest eine lumineszierende Substanz auf der Basis von dotierten Wirtsgittern aufweist, dadurch gekennzeichnet, dass das Wirtsgitter mit wenig- stens einem Chromophor der Elektronenkonfiguration (3d)2 dotiert ist.30. Security element, which has 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 of the electron configuration (3d) 2 .
31. Sicherheitselement nach Anspruch 30, wobei das Wirtsgitter ein starkes Kristallfeld aufweist. 31. The security element according to claim 30, wherein the host lattice has a strong crystal field.
32. Sicherheitselement nach Anspruch 30 oder 31, wobei das Sicherheitselement die Form eines Streifens oder Bandes aufweist.32. Security element according to claim 30 or 31, wherein the security element has the form of a strip or tape.
33. Sicherheitselement nach wenigstens einem der Ansprüche 30 bis 32, wobei das Trägermaferial als Sicherheitsfaden, Planchette oder Melierfaser ausgebildet ist.33. Security element according to at least one of claims 30 to 32, wherein the carrier material is designed as a security thread, planchette or mottled fiber.
34. Sicherheitselement nach wenigsten einem der Ansprüche 30 bis 33, dadurch gekennzeichnet, dass das Sicherheitselement als Etikett aus- gebildet ist.34. Security element according to at least one of claims 30 to 33, characterized in that the security element is designed as a label.
35. Sicherheitselement nach wenigstens einem der Ansprüche 30 bis 34, dadurch gekennzeichnet, dass die wenigstens eine lumineszierende Substanz in dem Trägermaterial eingebettet oder auf das Trägermate- rial aufgebracht ist.35. 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. Verfahren zur Herstellung eines Wertdokumentes nach wenigstens einem der Ansprüche 1 bis 29, dadurch gekennzeichnet, dass die lumineszierende Substanz einer Druckfarbe zugesetzt wird.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. Verfahren zur Herstellung eines Wertdokuments nach wenigstens einem der Ansprüche 1 bis 29, dadurch gekennzeichnet, dass die lumineszierende Substanz durch einen Beschichtungsprozess aufgetragen wird.37. A method for producing a value document according to at least one of claims 1 to 29, characterized in that the luminescent substance is applied by a coating process.
38. Verfahren zur Herstellung eines Wertdokuments nach wenigstens einem der Ansprüche 1 bis 29, dadurch gekennzeichnet, dass die lumineszierende Substanz in das Volumen des Wertdokumentes eingearbeitet wird. 38. A method for producing a value document according to at least one of claims 1 to 29, characterized in that the luminescent substance is incorporated into the volume of the value document.
39. Verfahren zur Herstellung eines Wertdokuments nach wenigstens einem der Ansprüche 1 bis 29, dadurch gekennzeichnet, dass die lumineszierende Substanz durch entsprechend präparierte Melierfasern dem Wertdokument zugeführt wird.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 appropriately prepared mottled fibers.
40. Verfahren zur Herstellung eines Wertdokuments nach wenigstens einem der Ansprüche 1 bis 29, dadurch gekennzeichnet, dass die lumineszierende Substanz durch einen entsprechend präparierten Sicherheitsfaden dem Wertdokument zugeführt wird.40. A method for producing a value document according to at least one of claims 1 to 29, characterized in that the luminescent substance is supplied to the value document by a correspondingly prepared security thread.
41. Prüfverfahren zur Echtheitsprüfung eines Wertdokumentes nach wenigstens einem der Ansprüche 1 bis 29 oder eines Sicherheitselementes nach wenigstens einem der Ansprüche 30 bis 35, dadurch gekennzeichnet, dass die Wellenlängen und/oder Anzahl und/ oder die Form und/ oder die Intensitäten der Emissionslinien und/ oder der41. Test method for the authenticity check of a value document 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 the shape and / or the intensities of the emission lines and / or the
Anregungsbanden der lumineszierenden Substanzen ausgewertet werden.Excitation bands of the luminescent substances are evaluated.
42. Prüfverfahren zur Echtheitsprüfung eines Wertdokumentes oder Si- cherheitselementes nach Anspruch 41, dadurch gekennzeichnet, dass die Emissionslinien und/ oder Anregungsbanden eine Codierung darstellen.42. Test method for verifying the authenticity of a value document or security element according to claim 41, characterized in that the emission lines and / or excitation bands represent a coding.
43. Prüfverfahren zur Echtheitsprüfung eines Wertdokumentes nach we- nigstens einem der Ansprüche 1 bis 29 oder eines Sicherheitselementes nach wenigstens einem der Ansprüche 30 bis 35, dadurch gekennzeichnet, dass die Lumineszenzlebensdauern der lumineszierenden Substanzen ausgewertet werden. 43. Test method for checking the authenticity 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 luminescence lifetimes 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
DE10111116 2001-03-08
DE10111116A DE10111116A1 (en) 2001-03-08 2001-03-08 value document
PCT/EP2002/002405 WO2002070279A1 (en) 2001-03-08 2002-03-05 Value document

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

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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)

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EP1370424B2 (en) 2013-07-31
AU2002308237B2 (en) 2006-08-17
PL363008A1 (en) 2004-11-15
WO2002070279A1 (en) 2002-09-12
US20040105962A1 (en) 2004-06-03
CA2440078C (en) 2007-08-07
US8663820B2 (en) 2014-03-04
ES2224072T3 (en) 2005-03-01
EP1370424B1 (en) 2004-09-01
KR20030087016A (en) 2003-11-12
RU2003129071A (en) 2005-03-27
PT1370424E (en) 2005-01-31
KR100868176B1 (en) 2008-11-12
UA74062C2 (en) 2005-10-17
DE50200931D1 (en) 2004-10-07
RU2286885C2 (en) 2006-11-10
CN1501864A (en) 2004-06-02
ES2224072T5 (en) 2013-11-15
PL202501B1 (en) 2009-06-30
CN1282555C (en) 2006-11-01
CA2440078A1 (en) 2002-09-12
TR200402236T4 (en) 2004-10-21
HK1062664A1 (en) 2004-11-19
ATE275046T1 (en) 2004-09-15
DE10111116A1 (en) 2002-09-19

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