EP1934889B1 - Securing the authenticity of value documents by means of characteristic substances - Google Patents

Securing the authenticity of value documents by means of characteristic substances Download PDF

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Publication number
EP1934889B1
EP1934889B1 EP06792361.5A EP06792361A EP1934889B1 EP 1934889 B1 EP1934889 B1 EP 1934889B1 EP 06792361 A EP06792361 A EP 06792361A EP 1934889 B1 EP1934889 B1 EP 1934889B1
Authority
EP
European Patent Office
Prior art keywords
substance
feature
luminescent
nanoparticles
feature substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Not-in-force
Application number
EP06792361.5A
Other languages
German (de)
French (fr)
Other versions
EP1934889A1 (en
Inventor
Ulrich Scholz
Gregor Grauvogl
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
Application filed by Giesecke and Devrient GmbH filed Critical Giesecke and Devrient GmbH
Publication of EP1934889A1 publication Critical patent/EP1934889A1/en
Application granted granted Critical
Publication of EP1934889B1 publication Critical patent/EP1934889B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • B42D25/20—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
    • 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
    • B42D25/369—Magnetised or magnetisable materials
    • 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
    • B42D25/382—Special inks absorbing or reflecting infrared light
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
    • D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
    • D21H21/48—Elements suited for physical verification, e.g. by irradiation
    • 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.]
    • Y10T428/24835—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including developable image or soluble portion in coating or impregnation [e.g., safety paper, 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated

Definitions

  • the invention relates to feature substances for authenticity assurance of value documents, methods for their production, security elements and value documents which contain the feature substance according to the invention, as well as methods for the authenticity assurance of security elements and value documents using the feature substance according to the invention.
  • the feature substances according to the invention contain both at least one luminescent substance and at least one further substance, which is preferably magnetically or electrically conductive.
  • Security elements in the sense of the present invention are elements with authenticity features which are applied to a value document for authenticity assurance or introduced into a value document.
  • Documents of value within the scope of the invention are items such as banknotes, checks, stocks, tokens, identity cards, passports, credit cards, documents and other documents, labels, seals, and items to be protected, such as CDs, packaging and the like.
  • the preferred application is banknotes.
  • the authenticity assurance of value documents by means of luminescent substances has long been known. Preference is given to using rare earth-doped host lattices, wherein the absorption and emission ranges can be varied within a wide range by suitable tuning of rare earth metal and host lattice.
  • the use of magnetic and electrically conductive materials for authenticity assurance is known per se. Magnetism, electrical conductivity and luminescence emission are mechanically detectable by commercially available measuring devices, and luminescence is also visual in sufficient intensity when emitted in the visible range.
  • the security against counterfeiting can be increased, for example, by using not only one feature substance but several feature substances in combination, for example a luminescent substance and a magnetic substance, or a luminescent substance and a substance influencing the luminescence properties.
  • feature substances are provided in the form of a specific pattern, for example form a luminescent coding
  • An immediate introduction into the volume of a value document or security element in the form of a defined arrangement, or the generation of a defined arrangement of the feature substances on the surface of a value document or security element by other methods than printing methods has not been possible.
  • an inhomogeneity of feature substance mixtures by partial segregation is a particularly serious problem because it can lead to a wrong or illegible coding.
  • a pigmented luminescent substance is known.
  • a layer of gelatin gum arabic is used as the adhesive to prevent segregation of pigment and luminescent material.
  • the feature substance combination should preferably also be able to be provided by methods other than printing in the form of a pattern on or in a value document or security element.
  • the feature substance combination according to the invention has at least one luminescent substance which can be excited by radiation in the infrared and / or visible and / or ultraviolet region for luminescence emission, preferably fluorescence emission.
  • the combination of feature substances according to the invention has nanoparticles which are bound by adhesive forces to the surfaces of the luminescent substance particles. The adhesion is sufficiently strong that during storage and processing no separation of luminescent substance and nanoparticles occurs, at least not in a disturbing for the production of security features extent. Even when stored as a dispersion no segregation is to be feared.
  • the combination of feature substances according to the invention is thus a "composite feature substance" which, although composed of at least two different substances, behaves like a single feature substance.
  • the properties of the composite feature substance combine the properties of the luminescent substance and the nanoparticles In this case, a "combination" can be a purely additive combination and / or an influence on the properties.
  • the invention utilizes a phenomenon which is used in a similar way for the stabilization of emulsions and in the suspension polymerization.
  • the prerequisite for solid particles to act as "Pickering emulsifiers" is that the particle size is at least a factor of 10 smaller than the desired droplet size, and that the solid is wetted by the oil and water phases, but to both phases has different affinity.
  • Pickering emulsifiers are used in suspension polymerization as stabilizers against the sticking of the growing suspension particles.
  • the Pickering emulsifiers arrange themselves at the interface between the suspension particles and the liquid phase, encase the suspension particles and thus prevent their coalescence.
  • the first prerequisite for the principle of action as a Pickering emulsifier is that the emulsifier is insoluble in the liquid phase and is substantially smaller than the suspension particle to be stabilized.
  • the prerequisite for the enrichment process in the phase interface is a suitable interaction force, ie adhesion between the stabilizing suspension particles and the Pickering emulsifier, but at the same time also a sufficiently good wettability of the Pickering emulsifier with the surrounding liquid.
  • luminescent substance particles are coated with nanoparticles, whereby a nanoparticle monolayer, in which the nanoparticles form a dense packing, typically arises. But even a partial, preferably extensive, envelope may be sufficient.
  • the luminescent substance particles have an average particle size of about 1 to 100 ⁇ m.
  • the volumes of the nanoparticles are at least one order of magnitude, preferably by 2 to 3 orders of magnitude, less than the volumes of the luminescent substance particles.
  • the feature substance according to the invention is therefore actually a system of feature substances whose properties result from the combination of the properties of the individual components.
  • the luminescent substances which can be used for producing the feature substances according to the invention are not restricted in any way. In principle, all substances, in particular luminescent substances, which can be excited by irradiation with light in the infrared and / or visible and / or ultraviolet range for emission, in particular luminescence emission, are suitable. The emission or luminescence emission takes place preferably also in the infrared and / or visible and / or ultraviolet region.
  • the luminescent substances are preferably fluorescent substances.
  • suitable luminescent rare earth-doped host lattice for example, with ytterbium, praseodymium, neodymium, etc. doped garnets or perovskites may be mentioned, and mineral phosphors such as sulfides, oxides, selenides with traces of heavy metals such. As silver, copper, manganese or europium are suitable. However, these examples are intended as a guide only and should not be construed as limiting. Furthermore, organic luminescent substances can also be used, for example rhodamines, perylenes, isoindolinones, quinophthalones and oxazinones.
  • Substances which modify the luminescence properties of the luminescent substance are, for example, those which absorb in certain wavelength ranges in which the luminescent substance emits and thus change the luminescence spectrum.
  • An example of such a combination is Example 9 of the above WO 81/03508 A1 as luminescent substance and nanoscale Fe 3 O 4 as nanoparticle substance.
  • luminescent substances can also be used as nanoparticles, ie in principle the same substances which are also suitable for forming the core of the feature substance according to the invention.
  • a combination of different luminescent substances results in a superordinate luminescence spectrum.
  • nanoparticle sheath it is preferred to use substances which have a machine-detectable property which differs from the detectable property of the core material, for example magnetic or magnetizable substances, electrically conductive substances and semiconductors. These substances must be stable in the application medium; For example, nanoscale iron is unstable in water, but after wetting with water, it transforms into an indefinable magnetic oxide (nanoscale metals are usually pyrophoric).
  • nanoscale iron is unstable in water, but after wetting with water, it transforms into an indefinable magnetic oxide (nanoscale metals are usually pyrophoric).
  • nanoscale metals are usually pyrophoric.
  • the materials it should be noted that they are not allowed to absorb strongly in areas which are essential for the identification of the luminescence spectrum.
  • the luminescence spectrum must not be affected by the nanoparticles to a disturbing extent. How strong a change may be so as not to be perceived as a disturbing impairment, depends essentially on the intended application. In some cases, a
  • CNTs carbon nanotubes
  • CNTs are microscopic tubular carbon structures. In the walls of the tubes, the carbon is sp 2 -hybridized and forms honeycombs as in the planes of graphite.
  • the diameter of the tubes is usually in the range of 1 to 50 nm, but smaller tubes can be made.
  • the lengths of each tube can be up to be several millimeters.
  • SWCNT single-walled carbon nanotubes
  • MWCNT multi-walled carbon nanotubes
  • the electrical conductivity within a tube may be metallic or semiconducting.
  • CNTs are commercially available (eg from MER Corporation or NanoLab Inc.) and can be sized to size by conventional crushing techniques such as milling.
  • nanoparticle materials which can be combined with luminescent substances to feature substances according to the invention are nano- ⁇ -iron, nano-Fe 3 O 4 and nano-NiFe 2 O 4 .
  • the feature substances with nano- ⁇ -iron, nano-Fe 3 O 4 and with nano-NiFe 2 O 4 are luminescent and magnetic.
  • Example 9 cited above WO 81/03508 A1 as a luminescent substance, with MWCNT (particle size 20-50 nm), MWCNT (particle size 20-30 nm), MWCNT (particle size 40-70 nm), nano- ⁇ -iron (APS 25 nm), nano-Fe 3 O 4 (APS 20-30 nm), or nano-NiFe 2 O 4 (APS 20-30 nm).
  • APS refers to the diameter of the carbon tubes.
  • the materials are available, for example, from MER Corporation.
  • the mean particle sizes of the nanopowders can range from about 1 to 1000 nm, the optimum particle sizes also depending on the size of the nanopowders
  • the luminescent substance particles typically have mean particle sizes in the range from about 1 to 100 ⁇ m, and the nanoparticles are smaller by at least 1, preferably 2 to 3, orders of magnitude. Preferred average particle sizes for the nanopowders are in the range from 1 to 500 nm, more preferably 10 to 100 nm.
  • the weight ratios of luminescent substance and nanoparticle material depend on the type and particle size of the materials. In addition, they depend on the exact nature of the desired feature substance, i. That is, whether a feature substance is desired whose luminescent substance particles are optimally surrounded by a nanoparticle coating, whether a partial coating is also considered sufficient, or whether, if appropriate, free (uncoated) luminescent substance particles or free nanoparticles should also be present. If a feature substance is desired that consists of luminescent particles enveloped as completely as possible by nanoparticles but contains no free luminescent substance particles and no free nanoparticles, the weight ratio of luminescent substance to nanopowder is typically approximately in the range of 1: 1.
  • the weight ratios can also vary within a substantially broader range, for example from 100: 1 to 1: 100, preferably from about 5: 1 to 1: 3, in particular when the feature substance according to the invention contains additional free luminescent substances and / or nanoparticles. For such additives, it must be tested by previous tests whether the system obtained is stable against segregation.
  • the feature substance according to the invention is not limited to combinations of one type of luminescent substance with one type of nanoparticle. Rather, 2 or more different luminescent substances and / or 2 or more different nanoparticles can be combined with one another. In this way, it is possible to obtain a luminescent substance which is also magnetically and electrically conductive.
  • the detection of the combined properties of the feature substance according to the invention is carried out in the same way as conventionally the luminescence properties, magnetic properties and electrical conductivity properties of the individual feature substances are detected.
  • the required spectrometers, luminescence or magnetism controllers, and conductivity meters are commercially available.
  • the preparation of a feature substance according to the invention is carried out in a very simple manner by adding the luminescent substance or substances and a material in the form of a nanopowder, or optionally several different nanopowder materials, to a dispersion medium and stirring them together until a dispersion is obtained.
  • the dispersion may be used as such, but preferably the feature substance is separated from the dispersion, usually by filtration, and dried.
  • the dispersant used is preferably water.
  • the starting materials, especially the nanopowder, are difficult to disperse therein, but over time more and more nanoparticles are bound to the surfaces of the luminescent particles by adhesion, and if there is no excess of nanoparticles, finally, a dispersion of the feature substance is obtained no nanoparticle "clumps" are left.
  • the association of the nanoparticles with the luminescent substance particles takes several hours. The association is preferably carried out at room temperature, but it can also be heated slightly, but heating rarely leads to an acceleration of the attachment of the nanoparticles to the Lumineszenzstoffpizate leads.
  • the drying of the feature substance filtered off from the dispersion preferably takes place at elevated temperature, the temperature being dependent on the chosen dispersant. In the case of water as the dispersant, drying is preferably carried out at about 110.degree.
  • the dispersed nanoparticles are not retained during filtration by conventional standard filters. Their retention is possible through special filters. So if you want to produce a feature substance that consists of luminescent particles whose surfaces are coated as completely as possible with nanoparticles, but no free nanoparticles should be present, the production can be done in a simple manner by using a significant excess amount of nanopowder, stirred for a sufficient time (about 10 hours) and then filtered. Nanoparticles that are not bound in the form of a coating of luminescent material particles pass through the filter or, depending on the density, float on the dispersion while the feature substance sinks and later remains on the filter.
  • the feature substances according to the invention are both in terms of their properties (luminescence, magnetism, electrical conductivity) as well as their appearance, such.
  • the feature substance according to the invention is used for authenticity assurance of value documents or security elements.
  • Value documents and security elements each consist of at least one layer of carrier material and optionally further layers. In addition, they have at least one authenticity feature which is formed by one or more feature substances. In contrast to a value document, a security element is not marketed as such but in connection with a value document to which it is applied or incorporated.
  • the security elements and value documents according to the invention have at least one authenticity feature which is formed by a feature substance according to the invention.
  • the feature substance according to the invention does not differ from conventional luminescent substances. It can be introduced, for example, in the volume or in subregions of the volume of a security element or value document, wherein the carrier material may consist of paper or plastic. Alternatively, the feature substance may be provided in the form of a coating on at least one surface or on portions of at least one surface of a security element or value document.
  • the feature substance may be contained in a printing ink which is printed on a security element or document of value.
  • the feature substance of the invention is used in each case in concentrations, as are customary in the respective field of application for luminescent substances, ie about 0.05 to 1 wt.%, When the feature substance in the volume of a Paper layer is contained, and about 10 to 40 wt.%. When the feature substance is contained in a printing ink.
  • Security elements with the feature substance according to the invention are preferably security threads, mottling fibers, planchettes and labels, which are introduced into the volume of a value-document carrier material or glued to a surface of the carrier material or another layer of a value document.
  • the feature substance according to the invention can be rubbed into a lacquer, for example, which is then drawn out to a lacquer film and cut to a size suitable for a security element.
  • a suitable varnish is a polyamide varnish and suitable concentrations are in the range of about 0.1 to 1 wt%.
  • a particular advantage of the feature substances according to the invention becomes apparent when a feature substance according to the invention is intended to be provided in a defined distribution, for example when the feature substance is to form a code.
  • regions of high concentration of feature substance alternate with regions of low concentration of feature substance or completely without feature substance in a predetermined manner.
  • the arrangement of the regions with a high concentration of feature substance and with a low concentration of feature substance (or without feature substance) can be read out by machine. So far, such codes could only be produced by printing luminescent substances in a specific pattern. They could not be formed directly in the volume of a value document.
  • the feature substances according to the invention have the peculiarity that they not only have luminescence properties, but are preferably also magnetic or magnetizable or electrically conductive.
  • the nanoparticles of the envelope of the luminescent substance particles align in the field, and the feature substance has a tendency to migrate in the field.
  • the prerequisite for such alignment and, if appropriate, migration is that the surrounding medium of the feature substance is sufficiently fluid to permit movement of the feature substance.
  • the feature substance according to the invention can be aligned or moved in a desired manner in a carrier material or a printing ink by applying a suitable magnetic or electric field as long as the carrier material is still sufficiently soft or moist, or the printing ink is still sufficiently liquid is.
  • a pattern of regions of high concentration of feature substance and regions of low concentration of feature substance in a paper layer can be produced, for example, by introducing a feature substance according to the invention having luminescent and magnetic properties in the paper machine into the moist paper, while an arrangement of Magnet is located in the desired code pattern.
  • the magnetic nanoparticles of the feature substance then align in the wet pulp, and the feature substance particles migrate to the magnets, reproducing the pattern of arrangement of the magnets, that is, the code.
  • the code can be z. B. be read spectrometrically.
  • Example 9 In a beaker with about 50 ml of water, 2 g of the above Example 9 from WO 81/03508 A1 , and weighed 1.5 g of MWCNT nanopowder and stirred for one day at room temperature. At the beginning of the mixing process, the nanopowder floats and sometimes forms large lumps. After the sparingly dispersible nanopowder is finely dispersed in the resulting dispersion, the material is filtered. There is no filter breakthrough of the nano-material through the filter pores. The filtered material is dried at 110 ° C, for example, overnight.
  • the material can be rubbed into a polyamide varnish and the varnish can be drawn off to a varnish film, wherein the concentration of feature substance is also, for example, 0.4% by weight.
  • the paint film is suitable for sticking on banknotes.
  • the authenticity of the banknote can now be verified both by measuring the infrared luminescence and by measuring the electrical conductivity that is caused by the nanopowder. Of course, the authenticity can also be determined by measuring both properties.

Description

Die Erfindung betrifft Merkmalsstoffe zur Echtheitssicherung von Wertdokumenten, Verfahren zu ihrer Herstellung, Sicherheitselemente und Wertdokumente, die den erfindungsgemäßen Merkmalsstoff enthalten, sowie Verfahren zur Echtheitssicherung von Sicherheitselementen und Wertdokumenten unter Verwendung des erfindungsgemäßen Merkmalsstoffs. Die erfindungsgemäßen Merkmalsstoffe enthalten sowohl mindestens einen Lumineszenzstoff als auch mindestens einen weiteren Stoff, der bevorzugt magnetisch oder elektrisch leitfähig ist.The invention relates to feature substances for authenticity assurance of value documents, methods for their production, security elements and value documents which contain the feature substance according to the invention, as well as methods for the authenticity assurance of security elements and value documents using the feature substance according to the invention. The feature substances according to the invention contain both at least one luminescent substance and at least one further substance, which is preferably magnetically or electrically conductive.

Sicherheitselemente im Sinne der vorliegenden Erfindung sind Elemente mit Echtheitsmerkmalen, die zur Echtheitssicherung auf ein Wertdokument aufgebracht oder in ein Wertdokument eingebracht werden. Wertdokumente im Rahmen der Erfindung sind Gegenstände wie Banknoten, Schecks, Aktien, Wertmarken, Ausweise, Pässe, Kreditkarten, Urkunden und andere Dokumente, Etiketten, Siegel, und zu sichernde Gegenstände wie beispielsweise CDs, Verpackungen und ähnliches. Das bevorzugte Anwendungsgebiet sind Banknoten.Security elements in the sense of the present invention are elements with authenticity features which are applied to a value document for authenticity assurance or introduced into a value document. Documents of value within the scope of the invention are items such as banknotes, checks, stocks, tokens, identity cards, passports, credit cards, documents and other documents, labels, seals, and items to be protected, such as CDs, packaging and the like. The preferred application is banknotes.

Die Echtheitssicherung von Wertdokumenten mittels lumineszierender Substanzen ist seit langem bekannt. Bevorzugt werden mit Seltenerdmetallen dotierte Wirtsgitter eingesetzt, wobei durch geeignete Abstimmung von Seltenerdmetall und Wirtsgitter die Absorptions- und Emissionsbereiche in einem breiten Bereich variiert werden können. Auch die Verwendung magnetischer und elektrisch leitfähiger Materialien zur Echtheitssicherung ist an sich bekannt. Magnetismus, elektrische Leitfähigkeit und Lumineszenzemission sind durch im Handel verfügbare Messgeräte maschinell nachweisbar, Lumineszenz bei Emission im sichtbaren Bereich in ausreichender Intensität auch visuell.The authenticity assurance of value documents by means of luminescent substances has long been known. Preference is given to using rare earth-doped host lattices, wherein the absorption and emission ranges can be varied within a wide range by suitable tuning of rare earth metal and host lattice. The use of magnetic and electrically conductive materials for authenticity assurance is known per se. Magnetism, electrical conductivity and luminescence emission are mechanically detectable by commercially available measuring devices, and luminescence is also visual in sufficient intensity when emitted in the visible range.

Praktisch ebenso alt wie die Echtheitssicherung von Wertdokumenten ist die Problematik der Fälschung der Echtheitsmerkmale der Wertdokumente. Die Fälschungssicherheit kann beispielsweise dadurch erhöht werden, dass nicht nur ein Merkmalsstoff, sondern mehrere Merkmalsstoffe in Kombination verwendet werden, beispielsweise ein lumineszierender Stoff und ein magnetischer Stoff, oder ein lumineszierender Stoff und ein die Lumineszenzeigenschaften beeinflussender Stoff.Practically as old as the authenticity assurance of value documents is the problem of forgery of the authenticity features of the value documents. The security against counterfeiting can be increased, for example, by using not only one feature substance but several feature substances in combination, for example a luminescent substance and a magnetic substance, or a luminescent substance and a substance influencing the luminescence properties.

Wenn mehrere Merkmalsstoffe in Kombination eingesetzt werden sollten, gab es bislang nur die Möglichkeit, entweder ein physikalisches Gemisch der Stoffe herzustellen und das Gemisch auf die Oberfläche des Wertdokuments aufzubringen oder in das Volumen des Wertdokuments einzubringen, oder die Merkmalsstoffe separat aufzubringen. Das getrennte Aufbringen der Merkmalsstoffe in zwei oder mehr Schritten ist zeitraubend und umständlich. Kombinationen von Merkmalsstoffen werden daher vorwiegend als Gemische eingesetzt. Zur Herstellung der Gemische werden zuerst die einzelrien Merkmalsstoffe separat hergestellt, dann die fertigen Merkmalsstoffe, in der Regel trocken, zusammengemischt. In dem entstehenden physikalischen Gemisch sind die Partikel der verschiedenen Merkmalsstoffe zwar in Berührung miteinander, gehen aber in der Regel keine spezifischen Wechselwirkungen miteinander ein, d. h. die Merkmalsstoffe können, gewollt oder ungewollt, wieder voneinander getrennt werden. Eine Assoziierung der verschiedenen Merkmalsstoffe in einer Weise, dass ein nicht mehr in die Einzelbestandteile trennbares Produkt entsteht, findet nicht statt.If several feature substances were to be used in combination, the only option to date was either to produce a physical mixture of the substances and to apply the mixture to the surface of the value document or to incorporate it into the volume of the value document, or to apply the feature substances separately. The separate application of the feature substances in two or more steps is time consuming and cumbersome. Combinations of feature substances are therefore used predominantly as mixtures. To prepare the mixtures, the individual feature substances are first prepared separately, then the finished feature substances, generally dry, mixed together. Although the particles of the various feature substances are in contact with each other in the resulting physical mixture, they usually do not interact with each other in specific terms; H. the feature substances can, intentionally or unintentionally, be separated from each other again. An association of the various feature substances in such a way that a product which can no longer be separated into the individual components does not take place.

Diese Gemische haben den Nachteil, dass bei ihren Verarbeitungs- und Anwendungsprozessen eine mehr oder weniger ausgeprägte Entmischung eintreten kann, was zu Sicherheitsmerkmalen führt, die unterschiedliche Eigenschaften haben, abhängig davon, ob sie zu Beginn oder am Ende einer Charge hergestellt wurden. Häufig finden auch Entmischungen während der Lagerung eines Merkmalsstoffgemisches statt, insbesondere wenn die Lagerung in Form einer Dispersion, wie etwa einer Druckfarbe, geschieht. Es muß daher regelmäßig durch Qualitätstests überprüft werden, ob nicht ungewollt Entmischungen oder teilweise Entmischungen zur Inhomogenität und Unbrauchbarkeit des Gemisches geführt haben.These mixtures have the disadvantage that in their processing and application processes a more or less pronounced segregation can occur, which leads to safety features having different properties, depending on whether they were produced at the beginning or at the end of a batch. Frequently find also segregation during the Storage of a feature substance mixture instead, in particular if the storage in the form of a dispersion, such as a printing ink happens. It must therefore be regularly checked by quality tests, whether not unintentional demixing or partial segregation have led to the inhomogeneity and uselessness of the mixture.

Sollten Merkmalsstoffe in Form eines bestimmten Musters vorgesehen werden, beispielsweise eine lumineszierende Codierung bilden, gab es bisher nur die Möglichkeit, den Merkmalsstoff bzw. das Merkmalsstoffgemisch auf die Oberfläche eines Sicherheitselements oder Wertdokuments in Form des gewünschten Musters, beispielsweise der Codierung, aufzudrucken. Eine unmittelbare Einbringung ins Volumen eines Wertdokuments oder Sicherheitselements in Form einer definierten Anordnung, oder die Erzeugung einer definierten Anordnung der Merkmalsstoffe auf der Oberfläche eines Wertdokuments oder Sicherheitselements durch andere Verfahren als Druckverfahren war bisher nicht möglich. Bei der Herstellung von Codierungen stellt eine Inhomogenität von Merkmalsstoffgemischen durch teilweise Entmischung ein besonders gravierendes Problem dar, da sie zu einer falschen oder unlesbaren Codierung führen kann.If feature substances are provided in the form of a specific pattern, for example form a luminescent coding, it has hitherto only been possible to print the feature substance or the feature substance mixture on the surface of a security element or value document in the form of the desired pattern, for example the coding. An immediate introduction into the volume of a value document or security element in the form of a defined arrangement, or the generation of a defined arrangement of the feature substances on the surface of a value document or security element by other methods than printing methods has not been possible. In the production of encodings an inhomogeneity of feature substance mixtures by partial segregation is a particularly serious problem because it can lead to a wrong or illegible coding.

Aus der US 4,152,483 ist ein mit Pigmenten überzogener Lumineszenzstoff bekannt. Damit die Pigmente auf dem Lumineszenzstoff anhaften, wird jedoch eine Schicht aus Gelatine-Gummiarabikum als Klebstoff verwendet, um eine Entmischung von Pigment und Lumineszenzstoff zu verhindern.From the US 4,152,483 For example, a pigmented luminescent substance is known. However, in order for the pigments to adhere to the luminescent substance, a layer of gelatin gum arabic is used as the adhesive to prevent segregation of pigment and luminescent material.

Aufgabe der vorliegenden Erfindung ist es daher, eine Merkmalsstoff-Kombination bereitzustellen, die mindestens zwei verschiedene Stoffe aufweist, die ein sich nicht entmischendes System bilden.It is therefore an object of the present invention to provide a combination of feature substances which has at least two different substances which form a non-segregating system.

Die Merkmalsstoff-Kombination soll bevorzugt auch durch andere Verfahren als Druckverfahren in Form eines Musters auf oder in einem Wertdokument oder Sicherheitselement vorgesehen werden können.The feature substance combination should preferably also be able to be provided by methods other than printing in the form of a pattern on or in a value document or security element.

Aufgabe der vorliegenden Erfindung ist es auch, ein Verfahren zur Herstellung einer derartigen Merkmalsstoff-Kombination bereitzustellen.It is also an object of the present invention to provide a method for producing such a feature substance combination.

Aufgabe der vorliegenden Erfindung ist es ferner, ein Verfahren zur Echtheitssicherung eines Wertdokuments oder Sicherheitselements mittels einer derartigen Merkmalsstoff-Kombination bereitzustellen.It is also an object of the present invention to provide a method for securing the authenticity of a value document or security element by means of such a feature substance combination.

Aufgabe der vorliegenden Erfindung ist es darüber hinaus, ein Sicherheitselement oder ein Wertdokument bereitzustellen, das mindestens ein Echtheitsmerkmal auf der Basis einer derartigen Merkmalsstoff-Kombination aufweist.It is also an object of the present invention to provide a security element or a value document which has at least one authenticity feature based on such a feature substance combination.

Die Lösungen der obigen Aufgaben ergeben sich aus den Merkmalen der unabhängigen Ansprüche. Ausführungsformen der Erfindung sind in den jeweiligen abhängigen Ansprüchen angegeben.The solutions of the above objects emerge from the features of the independent claims. Embodiments of the invention are set forth in the respective dependent claims.

Die erfindungsgemäße Merkmalsstoff-Kombination weist mindestens einen Lumineszenzstoff auf, der durch Strahlung im infraroten und/oder sichtbaren und/oder ultravioletten Bereich zur Lumineszenzemission, bevorzugt Fluoreszenzemission, anregbar ist. Außerdem weist die erfindungsgemäße Merkmalsstoff-Kombination Nanopartikel auf, die durch Adhäsionskräfte an die Oberflächen der Lumineszenzstoff-Partikel gebunden sind. Die Haftung ist ausreichend stark, dass bei Lagerung und Verarbeitung keine Trennung von Lumineszenzstoff und Nanopartikeln auftritt, zumindest nicht in einem für die Herstellung von Sicherheitsmerkmalen störendem Ausmaß. Auch bei einer Lagerung als Dispersion ist keine Entmischung zu befürchten.The feature substance combination according to the invention has at least one luminescent substance which can be excited by radiation in the infrared and / or visible and / or ultraviolet region for luminescence emission, preferably fluorescence emission. In addition, the combination of feature substances according to the invention has nanoparticles which are bound by adhesive forces to the surfaces of the luminescent substance particles. The adhesion is sufficiently strong that during storage and processing no separation of luminescent substance and nanoparticles occurs, at least not in a disturbing for the production of security features extent. Even when stored as a dispersion no segregation is to be feared.

Bei der erfindungsgemäßen Merkmalsstoff-Kombination handelt es sich somit um einen "Verbund-Merkmalsstoff", der zwar aus mindestens zwei verschiedenen Stoffen aufgebaut ist, sich aber wie ein einziger Merkmalsstoff verhält. Die Eigenschaften des Verbund-Merkmalsstoffs stellen eine Kombination der Eigenschaften des Lumineszenzstoffs und der Nanopartikel dar. Eine "Kombination" kann dabei eine rein additive Kombination und/oder eine Beeinflussung der Eigenschaften sein.The combination of feature substances according to the invention is thus a "composite feature substance" which, although composed of at least two different substances, behaves like a single feature substance. The properties of the composite feature substance combine the properties of the luminescent substance and the nanoparticles In this case, a "combination" can be a purely additive combination and / or an influence on the properties.

Die Erfindung macht sich ein Phänomen zunutze, das in ähnlicher Form zur Stabilisierung von Emulsionen und bei der Suspensionspolymerisation verwendet wird.The invention utilizes a phenomenon which is used in a similar way for the stabilization of emulsions and in the suspension polymerization.

1907 entdeckte Pickering, dass Öl-Wasser-Emulsionen durch Kolloide, die spontan an der Tröpfchengrenzfläche aggregieren, stabilisiert werden können. Bei den sogenannten "Pickering-Emulsionen" wirken winzige Feststoffpartikel als Emulgatoren, d. h., es lassen sich tensidfreie Emulsionssysteme herstellen. Die Feststoffpartikel ordnen sich an der Öl-Wasser-Grenzfläche an und bilden eine dichte Packung, die die Tröpfchen der Emulsion umgibt. Dieses Feststoffnetzwerk stellt eine mechanische Barriere dar, die die Koaleszenz der Tröpfchen verhindert und so die Emulsion stabilisiert.In 1907, Pickering discovered that oil-water emulsions can be stabilized by colloids that spontaneously aggregate at the droplet interface. In the so-called "Pickering emulsions" tiny solid particles act as emulsifiers, d. h., surfactant-free emulsion systems can be produced. The solid particles line up at the oil-water interface to form a dense packing surrounding the droplets of the emulsion. This solids network provides a mechanical barrier that prevents coalescence of the droplets and thus stabilizes the emulsion.

Voraussetzung dafür, dass Feststoffpartikel als "Pickering-Emulgatoren" wirken können, ist, dass die Partikelgröße mindestens um den Faktor 10 kleiner ist als die gewünschte Tröpfchengröße, und dass der Feststoff von der Öl- und der Wasserphase benetzt wird, jedoch zu beiden Phasen eine unterschiedliche Affinität aufweist. In der chemischen Verfahrenstechnik verwendet man Pickering-Emulgatoren in der Suspensionspolymerisation als Stabilisatoren gegen das Verkleben der wachsenden Suspensionspartikel. Die Pickering-Emulgatoren ordnen sich an der Grenzfläche zwischen Suspensionspartikel und flüssiger Phase an, umhüllen die Suspensionspartikel und verhindern so ihre Koaleszenz. Die erste Voraussetzung für das Wirkungsprinzip als Pickering-Emulgator besteht darin, dass der Emulgator in der flüssigen Phase unlöslich ist und wesentlich kleiner ist als das zu stabilisierende Suspensionspartikel. Die Voraussetzung für den Anreicherungsprozeß in der Phasengrenzfläche ist eine geeignete Wechselwirkungskraft, d. h. Adhäsion zwischen dem zu stabilisierenden Suspensionspartikel und dem Pickering-Emulgator, gleichzeitig aber auch eine ausreichend gute Benetzbarkeit des Pickering-Emulgators mit der umgebenden Flüssigkeit.The prerequisite for solid particles to act as "Pickering emulsifiers" is that the particle size is at least a factor of 10 smaller than the desired droplet size, and that the solid is wetted by the oil and water phases, but to both phases has different affinity. In chemical engineering, Pickering emulsifiers are used in suspension polymerization as stabilizers against the sticking of the growing suspension particles. The Pickering emulsifiers arrange themselves at the interface between the suspension particles and the liquid phase, encase the suspension particles and thus prevent their coalescence. The first prerequisite for the principle of action as a Pickering emulsifier is that the emulsifier is insoluble in the liquid phase and is substantially smaller than the suspension particle to be stabilized. The prerequisite for the enrichment process in the phase interface is a suitable interaction force, ie adhesion between the stabilizing suspension particles and the Pickering emulsifier, but at the same time also a sufficiently good wettability of the Pickering emulsifier with the surrounding liquid.

Überfaschenderweise wurde nun gefunden, dass sich Substanzen von der Art der Pickering-Emulgatoren unter bestimmten Voraussetzungen zur Herstellung von Merkmalsstoffen für die Echtheitssicherung von Wertdokumenten einsetzen lassen, wobei Merkmalsstoffe mit bisher nicht erzielbaren Eigenschaften erhalten werden können.Überfaschenderweise it has now been found that substances of the type of Pickering emulsifiers can be used under certain conditions for the production of feature substances for the authenticity of value documents, with feature substances can be obtained with previously unattainable properties.

Erfindungsgemäß werden Lumineszenzstoffpartikel mit Nanopartikeln umhüllt, wobei typischerweise eine Nanopartikel-Monoschicht, in der die Nanopartikel eine dichte Packung bilden, entsteht. Aber auch eine teilweise, bevorzugt weitgehende, Umhüllung kann ausreichend sein. Die Lumineszenzstoffpartikel weisen eine mittlere Teilchengröße von etwa 1 bis 100 µm auf. Die Volumina der Nanopartikel sind um mindestens eine Größenordnung, bevorzugt um 2 bis 3 Größenordnungen, geringer als die Volumina der Lumineszenzstoffpartikel.According to the invention, luminescent substance particles are coated with nanoparticles, whereby a nanoparticle monolayer, in which the nanoparticles form a dense packing, typically arises. But even a partial, preferably extensive, envelope may be sufficient. The luminescent substance particles have an average particle size of about 1 to 100 μm. The volumes of the nanoparticles are at least one order of magnitude, preferably by 2 to 3 orders of magnitude, less than the volumes of the luminescent substance particles.

Durch das Umhüllen eines Lumineszenzstoffpartikel-Kerns mit Nanopartikeln werden verschiedene Merkmalsstoffe zu einem einzigen Merkmalsstoff, bestehend aus Kern und Hülle, vereinigt. Der erfindungsgemäße Merkmalsstoff ist daher eigentlich ein System von Merkmalsstoffen, dessen Eigenschaften sich aus der Kombination der Eigenschaften der Einzelkomponenten ergeben.By enveloping a luminescent substance particle core with nanoparticles, various feature substances are combined to form a single feature substance consisting of core and shell. The feature substance according to the invention is therefore actually a system of feature substances whose properties result from the combination of the properties of the individual components.

Die zur Herstellung der erfindungsgemäßen Merkmalsstoffe verwendbaren Lumineszenzstoffe sind nicht in irgendeiner Weise eingeschränkt. Grundsätzlich sind alle Stoffe, insbesondere Lumineszenzstoffe, geeignet, die durch Bestrahlung mit Licht im infraroten und/oder sichtbaren und/oder ultravioletten Bereich zur Emission, insbesondere Lumineszenzemission, angeregt werden können. Die die Emission bzw. Lumineszenzemission erfolgt bevorzugt ebenfalls im infraroten und/oder sichtbaren und/oder ultravioletten Bereich. Die Lumineszenzstoffe sind bevorzugt Fluoreszenzstoffe.The luminescent substances which can be used for producing the feature substances according to the invention are not restricted in any way. In principle, all substances, in particular luminescent substances, which can be excited by irradiation with light in the infrared and / or visible and / or ultraviolet range for emission, in particular luminescence emission, are suitable. The emission or luminescence emission takes place preferably also in the infrared and / or visible and / or ultraviolet region. The luminescent substances are preferably fluorescent substances.

Als Beispiele für geeignete Lumineszenzstoffe können mit Seltenerdmetallen dotierte Wirtsgitter, beispielsweise mit Ytterbium, Praseodym, Neodym, etc. dotierte Granate oder Perovskite, genannt werden, auch Mineralphosphore wie Sulfide, Oxide, Selenide mit Spuren von Schwermetallen wie z. B. Silber, Kupfer, Mangan oder Europium sind geeignet. Diese Beispiele sollen jedoch nur Anhaltspunkte darstellen, und keinesfalls beschränkend verstanden werden. Ferner können auch organische Lumineszenzstoffe verwendet werden, zum Beispiel Rhodamine, Perylene, Isoindolinone, Quinophthalone und Oxazinone Verfahren zur Herstellung der Lumineszenzstoffe sind dem Fachmann bekannt. Herstellungsverfahren sind beispielsweise beschrieben in WO 81/03508 A1 Etliche Lumineszenzstoffe sind auch im Handel erhältlich, beispielsweise Paliosecure Gelb von BASF, und Cartax von Clariant.As examples of suitable luminescent rare earth-doped host lattice, for example, with ytterbium, praseodymium, neodymium, etc. doped garnets or perovskites may be mentioned, and mineral phosphors such as sulfides, oxides, selenides with traces of heavy metals such. As silver, copper, manganese or europium are suitable. However, these examples are intended as a guide only and should not be construed as limiting. Furthermore, organic luminescent substances can also be used, for example rhodamines, perylenes, isoindolinones, quinophthalones and oxazinones. Processes for the preparation of the luminescent substances are known to the person skilled in the art. Manufacturing methods are described, for example, in WO 81/03508 A1 Several luminescent substances are also commercially available, for example Paliosecure Yellow from BASF, and Cartax from Clariant.

Zur Bildung der Umhüllung um die Lumineszenzstoffpartikel sind grundsätzlich alle Feststoffe geeignet, die ausreichend fein zerkleinert werden können, sich im zerkleinerten Zustand, d. h. als Nanopartikel, an die Lumineszenzstoffpartikel anlagern, und die entweder selbst Merkmalsstoff-Eigenschaften haben oder zumindest die Lumineszenzeigenschaften des Lumineszenzstoffs modifizieren.To form the coating around the luminescent substance particles, in principle all solids are suitable which can be comminuted sufficiently finely, in the comminuted state, ie. H. as nanoparticles, to which luminescent substance particles attach, and which either themselves have feature substance properties or at least modify the luminescence properties of the luminescent substance.

Stoffe, die die Lumineszenzeigenschaften des Lumineszenzstoffs modifizieren, sind beispielsweise solche, die in bestimmten Wellenlängenbereichen, in denen der Lumineszenzstoff emittiert, absorbieren und so das Lumineszenzspektrum verändern. Ein Beispiel für eine solche Kombination ist das Beispiel 9 aus der oben genannten WO 81/03508 A1 als Lumineszenzstoff und nanoskaliges Fe3O4 als Nanopartikel-Stoff.Substances which modify the luminescence properties of the luminescent substance are, for example, those which absorb in certain wavelength ranges in which the luminescent substance emits and thus change the luminescence spectrum. An example of such a combination is Example 9 of the above WO 81/03508 A1 as luminescent substance and nanoscale Fe 3 O 4 as nanoparticle substance.

Ferner können als Nanopartikel auch Lumineszenzstoffe verwendet werden, also grundsätzlich dieselben Stoffe, die auch zur Bildung des Kerns des erfindungsgemäßen Merkmalsstoffs geeignet sind. Eine Kombination verschiedener Lumineszenzstoffe ergibt ein Überlagerurigs-Lumineszenzspektrum.Furthermore, luminescent substances can also be used as nanoparticles, ie in principle the same substances which are also suitable for forming the core of the feature substance according to the invention. A combination of different luminescent substances results in a superordinate luminescence spectrum.

Bevorzugt werden für die Umhüllung aus Nanopartikeln jedoch Stoffe verwendet, die über eine maschinell nachweisbare Eigenschaft verfügen, die von der nachweisbaren Eigenschaft des Kernmaterials verschieden ist, beispielsweise magnetische oder magnetisierbare Stoffe, elektrisch leitfähige Stoffe und Halbleiter. Diese Stoffe müssen im Anwendungsmedium stabil sein; so ist nanoskaliges Eisen in Wasser instabil, wandelt sich aber nach Benetzung mit Wasser in ein nicht näher definierbares magnetisches Oxid um (nanoskalige Metalle sind in der Regel pyrophor). Bei der Wahl der Materialien ist zu beachten, dass sie nicht in Bereichen, die für die Identifizierung des Lumineszenzspektrums wesentlich sind, stark absorbieren dürfen. Das Lumineszenzspektrum darf durch die Nanopartikel nicht in einem störenden Ausmaß beeinträchtigt werden. Wie stark eine Veränderung sein darf, um noch nicht als störende Beeinträchtigung empfunden zu werden, hängt im wesentlichen von der beabsichtigten Anwendung ab. In manchen Fällen kann eine Veränderung oder Schwächung des Lumineszenzspektrums und/oder Absorptionsspektrums durchaus erwünscht sein, um eine Identifizierung zu erschweren.However, for the nanoparticle sheath, it is preferred to use substances which have a machine-detectable property which differs from the detectable property of the core material, for example magnetic or magnetizable substances, electrically conductive substances and semiconductors. These substances must be stable in the application medium; For example, nanoscale iron is unstable in water, but after wetting with water, it transforms into an indefinable magnetic oxide (nanoscale metals are usually pyrophoric). When choosing the materials, it should be noted that they are not allowed to absorb strongly in areas which are essential for the identification of the luminescence spectrum. The luminescence spectrum must not be affected by the nanoparticles to a disturbing extent. How strong a change may be so as not to be perceived as a disturbing impairment, depends essentially on the intended application. In some cases, a change or weakening of the luminescence spectrum and / or absorption spectrum may well be desirable to make identification more difficult.

Ein Beispiel für ein Nanopartikelmaterial sind Kohlenstoffnanoröhren (CNTs, carbon nano tubes). CNTs sind mikroskopisch kleine röhrenförmige Strukturen aus Kohlenstoff. In den Wänden der Röhren ist der Kohlenstoff sp2-hybridisiert und bildet Waben wie bei den Ebenen des Graphits. Der Durchmesser der Röhren liegt meist im Bereich von 1 bis 50 nm, aber auch kleinere Röhren können hergestellt werden. Die Längen der einzelnen Röhren können bis zu mehrere Millimeter betragen. Mehrere einwandige Röhren (SWCNT, single walled carbon nano tubes) können konzentrisch ineinander liegen, so dass mehrwandige Röhren (MWCNT, multi walled carbon nano tubes) vorliegen. Abhängig von der genauen Struktur kann die elektrische Leitfähigkeit innerhalb einer Röhre metallisch oder halbleitend sein.An example of a nanoparticle material is carbon nanotubes (CNTs). CNTs are microscopic tubular carbon structures. In the walls of the tubes, the carbon is sp 2 -hybridized and forms honeycombs as in the planes of graphite. The diameter of the tubes is usually in the range of 1 to 50 nm, but smaller tubes can be made. The lengths of each tube can be up to be several millimeters. Several single-walled carbon nanotubes (SWCNT) can be concentric with each other to form multi-walled carbon nanotubes (MWCNT). Depending on the exact structure, the electrical conductivity within a tube may be metallic or semiconducting.

CNTs sind im Handel erhältlich (z. B. von MER Corporation oder NanoLab Inc.) und können durch konventionelle Zerkleinerungsverfahren wie Mahlen auf die erforderlichen Abmessungen gebracht werden.CNTs are commercially available (eg from MER Corporation or NanoLab Inc.) and can be sized to size by conventional crushing techniques such as milling.

Weitere Beispiele für Nanopartikel-Materialien, die mit Lumineszenzstoffen zu erfindungsgemässen Merkmalsstoffen kombiniert werden können, sind nano-α-Eisen, nano-Fe3O4 und nano-NiFe2O4. Die Merkmalsstoffe mit nano-α-Eisen, nano-Fe3O4 und mit nano-NiFe2O4 sind lumineszierend und magnetisch.Further examples of nanoparticle materials which can be combined with luminescent substances to feature substances according to the invention are nano-α-iron, nano-Fe 3 O 4 and nano-NiFe 2 O 4 . The feature substances with nano-α-iron, nano-Fe 3 O 4 and with nano-NiFe 2 O 4 are luminescent and magnetic.

Im folgenden werden einige nicht beschränkende Beispiele für Zwei-Komponenten-Kombinationen eines Lumineszenzstoffs mit Nanopulvern aufgeführt. Beispiel 9 oben zitierter WO 81/03508 A1 als Lumineszenzstoff, mit
MWCNT (Partikelgröße 20-50 nm),
MWCNT (Partikelgröße 20-30 nm),
MWCNT (Partikelgröße 40-70 nm),
nano-α-Eisen (APS 25 nm),
nano-Fe3O4 (APS 20-30 nm), oder
nano-NiFe2O4 (APS 20-30 nm).The following are some non-limiting examples of two-component combinations of a luminescent with nanopowders. Example 9 cited above WO 81/03508 A1 as a luminescent substance, with
MWCNT (particle size 20-50 nm),
MWCNT (particle size 20-30 nm),
MWCNT (particle size 40-70 nm),
nano-α-iron (APS 25 nm),
nano-Fe 3 O 4 (APS 20-30 nm), or
nano-NiFe 2 O 4 (APS 20-30 nm).

APS bezieht sich auf den Rörendurchmesser der Kohlenstoffröhren. Die Materialien sind beispielsweise erhältlich von MER Corporation.APS refers to the diameter of the carbon tubes. The materials are available, for example, from MER Corporation.

Die mittleren Partikelgrößen der Nanopulver können im Bereich von etwa 1 bis 1000 nm liegen, wobei die optimalen Partikelgrößen auch von der Größe derThe mean particle sizes of the nanopowders can range from about 1 to 1000 nm, the optimum particle sizes also depending on the size of the

Lumineszenzstoffpartikel abhängen. Die Lumineszenzstoffpartikel haben typischerweise mittlere Partikelgrößen im Bereich von etwa 1 bis 100 µm, und die Nanopartikel sind um mindestens 1, bevorzugt 2 bis 3, Größenordnungen kleiner. Bevorzugte mittlere Partikelgrößen für die Nanopulver liegen im Bereich von 1 bis 500 nm, besonders bevorzugt 10 bis 100 nm.Depend on luminescent substance particles. The luminescent substance particles typically have mean particle sizes in the range from about 1 to 100 μm, and the nanoparticles are smaller by at least 1, preferably 2 to 3, orders of magnitude. Preferred average particle sizes for the nanopowders are in the range from 1 to 500 nm, more preferably 10 to 100 nm.

Die Gewichtsverhältnisse von Lumineszenzstoff und Nanopartikelmaterial hängen ab von Art und Partikelgröße der Materialien. Außerdem hängen sie von der genauen Beschaffenheit des erwünschten Merkmalsstoffs ab, d. h., davon, ob ein Merkmalsstoff erwünscht ist, dessen Lumineszenzstoffpartikel möglichst optimal mit einer Nanopartikel-Umhüllung umgeben sind, ob auch eine teilweise Umhüllung als ausreichend erachtet wird, oder ob gegebenenfalls auch freie (nicht umhüllte) Lumineszenzstoffpartikel oder freie Nanopartikel vorliegen sollen. Wenn ein Merkmalsstoff erwünscht ist, der aus möglichst vollständig von Nanopartikeln umhüllten Lumineszenzstoffpartikeln besteht, aber keine freien Lumineszenzstoffpartikel und keine freien Nanopartikel enthält, liegt das Gewichtsverhältnis von Lumineszenzstoff zu Nanopulver typischerweise etwa im Bereich von 1:1.The weight ratios of luminescent substance and nanoparticle material depend on the type and particle size of the materials. In addition, they depend on the exact nature of the desired feature substance, i. That is, whether a feature substance is desired whose luminescent substance particles are optimally surrounded by a nanoparticle coating, whether a partial coating is also considered sufficient, or whether, if appropriate, free (uncoated) luminescent substance particles or free nanoparticles should also be present. If a feature substance is desired that consists of luminescent particles enveloped as completely as possible by nanoparticles but contains no free luminescent substance particles and no free nanoparticles, the weight ratio of luminescent substance to nanopowder is typically approximately in the range of 1: 1.

Die Gewichtsverhältnisse können aber auch in einem wesentlich breiteren Bereich variieren, etwa von 100:1 bis 1:100, bevorzugt etwa 5:1 bis 1:3, insbesondere dann, wenn der erfindungsgemäße Merkmalsstoff zusätzliche freie Lumineszenzstoffe und/oder Nanopartikel enthält. Bei derartigen Zusätzen ist durch vorangehende Versuche zu testen, ob das erhaltene System stabil gegen Entmischung ist.However, the weight ratios can also vary within a substantially broader range, for example from 100: 1 to 1: 100, preferably from about 5: 1 to 1: 3, in particular when the feature substance according to the invention contains additional free luminescent substances and / or nanoparticles. For such additives, it must be tested by previous tests whether the system obtained is stable against segregation.

Der erfindungsgemäße Merkmalsstoff ist nicht auf Kombinationen einer Art von Lumineszenzstoff mit einer Art von Nanopartikel beschränkt. Vielmehr können 2 oder mehr verschiedene Lumineszenzstoffe und/oder 2 oder mehr verschiedene Nanopartikel miteinander kombiniert werden. Auf diese Weise kann man beispielsweise einen Lumineszenzstoff erhalten, der auch magnetisch und elektrisch leitfähig ist.The feature substance according to the invention is not limited to combinations of one type of luminescent substance with one type of nanoparticle. Rather, 2 or more different luminescent substances and / or 2 or more different nanoparticles can be combined with one another. In this way For example, it is possible to obtain a luminescent substance which is also magnetically and electrically conductive.

Der Nachweis der kombinierten Eigenschaften des erfindungsgemäßen Merkmalsstoffs erfolgt in derselben Weise, wie konventionell die Lumineszenzeigenschaften, magnetischen Eigenschaften und elektrischen Leitfähigkeitseigenschaften der einzelnen Merkmalsstoffe nachgewiesen werden. Die erforderlichen Spektrometer, Kontrollgeräte für Lumineszenz oder Magnetismus, und Leitfähigkeitsmessgeräte sind im Handel erhältlich.The detection of the combined properties of the feature substance according to the invention is carried out in the same way as conventionally the luminescence properties, magnetic properties and electrical conductivity properties of the individual feature substances are detected. The required spectrometers, luminescence or magnetism controllers, and conductivity meters are commercially available.

Die Herstellung eines erfindungsgemäßen Merkmalsstoffs erfolgt in sehr einfacher Weise, indem der Lumineszenzstoff oder die Lumineszenzstoffe und ein Material in Form eines Nanopulvers, oder gegebenenfalls mehrere verschiedene Nanopulver-Materialien, in ein Dispersionsmittel gegeben und so lange miteinander verrührt werden, bis eine Dispersion erhalten wird. Die Dispersion kann als solche verwendet werden, aber bevorzugt wird der Merkmalsstoff aus der Dispersion abgetrennt, in der Regel durch Filtrieren, und getrocknet.The preparation of a feature substance according to the invention is carried out in a very simple manner by adding the luminescent substance or substances and a material in the form of a nanopowder, or optionally several different nanopowder materials, to a dispersion medium and stirring them together until a dispersion is obtained. The dispersion may be used as such, but preferably the feature substance is separated from the dispersion, usually by filtration, and dried.

Als Dispersionsmittel wird bevorzugt Wasser verwendet. Die Ausgangsmaterialien, insbesondere das Nanopulver, sind darin nur schwer dispergierbar, aber im Laufe der Zeit werden immer mehr Nanopartikel an den Oberflächen der Lumineszenzstoffpartikel durch Adhäsion gebunden, und wenn kein Überschuß an Nanopartikeln vorhanden ist, erhält man schließlich eine Dispersion des Merkmalsstoffs, in der keine Nanopartikel-"Klumpen" mehr vorhanden sind. Die Assoziierung der Nanopartikel an die Lumineszenzstoffpartikel nimmt mehrere Stunden in Anspruch. Die Assoziierung wird bevorzugt bei Raumtemperatur durchgeführt, es kann aber auch leicht erwärmt werden, wobei eine Erwärmung aber nur selten zu einer Beschleunigung der Anlagerung der Nanopartikel an die Lumineszenzstoffpartikel führt. Das Trocknen des aus der Dispersion abfiltrierten Merkmalsstoffs findet bevorzugt bei erhöhter Temperatur statt, wobei die Temperatur von dem gewählten Dispersionsmittel abhängig ist. Bei Wasser als Dispersionsmittel wird bevorzugt bei etwa 110° C getrocknet.The dispersant used is preferably water. The starting materials, especially the nanopowder, are difficult to disperse therein, but over time more and more nanoparticles are bound to the surfaces of the luminescent particles by adhesion, and if there is no excess of nanoparticles, finally, a dispersion of the feature substance is obtained no nanoparticle "clumps" are left. The association of the nanoparticles with the luminescent substance particles takes several hours. The association is preferably carried out at room temperature, but it can also be heated slightly, but heating rarely leads to an acceleration of the attachment of the nanoparticles to the Lumineszenzstoffpartikel leads. The drying of the feature substance filtered off from the dispersion preferably takes place at elevated temperature, the temperature being dependent on the chosen dispersant. In the case of water as the dispersant, drying is preferably carried out at about 110.degree.

Die dispergierten Nanopartikel werden bei einer Filtration durch übliche Standardfilter nicht zurückgehalten. Ihre Rückhaltung ist allenfalls durch Spezialfilter möglich. Wenn man also einen Merkmalsstoff herstellen will, der aus Lumineszenzstoffpartikeln besteht, deren Oberflächen möglichst vollständig mit Nanopartikeln überzogen sind, wobei aber keine freien Nanopartikel mehr vorliegen sollen, so kann die Herstellung in einfacher Weise dadurch erfolgen, dass man eine deutliche Überschussmenge an Nanopulver verwendet, ausreichend lange (etwa 10 Stunden) rührt und dann filtriert. Nanopartikel, die nicht in Form eines Überzugs an Lumineszenzstoffpartikel gebunden sind, gehen durch den Filter hindurch oder schwimmen je nach Dichte auf der Dispersion, während der Merkmalsstoff absinkt und später auf dem Filter verbleibt. Sollten noch Nanopartikel-Klumpen in der Dispersion vorhanden sein, die ebenfalls vom Filter zurückgehalten werden, schafft vorsichtiges Verreiben und Nachwaschen mit Dispersionsmittel oder vorheriges Abschöpfen (z.B. bei spezifisch leichteren MWCNTs oder großvolumige Lufteinschlüsse der nanoskaligen Oxide)Abhilfe.The dispersed nanoparticles are not retained during filtration by conventional standard filters. Their retention is possible through special filters. So if you want to produce a feature substance that consists of luminescent particles whose surfaces are coated as completely as possible with nanoparticles, but no free nanoparticles should be present, the production can be done in a simple manner by using a significant excess amount of nanopowder, stirred for a sufficient time (about 10 hours) and then filtered. Nanoparticles that are not bound in the form of a coating of luminescent material particles pass through the filter or, depending on the density, float on the dispersion while the feature substance sinks and later remains on the filter. If there are any nanoparticle lumps in the dispersion that are also retained by the filter, careful rubbing and rinsing with dispersant or prior skimming (e.g., for specifically lighter MWCNTs or large volume air pockets of nanoscale oxides) will provide relief.

Die erfindungsgemäßen Merkmalsstoffe sind sowohl hinsichtlich ihrer Eigenschaften (Lumineszenz, Magnetismus, elektrische Leitfähigkeit) als auch ihres Aussehens, wie z. B. ihrer Farbe, Mischprodukte aus den Ausgangskomponenten. Wird beispielsweise ein weißer oder farbloser Lumineszenzstoff mit einem schwarzen oder einem braunen Nanopulver überzogen, resultiert ein homogenes Merkmalsstoff-Pulver mit grauer bzw. hellbrauner Farbe.The feature substances according to the invention are both in terms of their properties (luminescence, magnetism, electrical conductivity) as well as their appearance, such. B. their color, mixed products from the starting components. If, for example, a white or colorless luminescent substance is coated with a black or a brown nanopowder, a homogeneous feature substance powder with a gray or light brown color results.

Der erfindungsgemäße Merkmalsstoff wird zur Echtheitssicherung von Wertdokumenten oder Sicherheitselementen verwendet.The feature substance according to the invention is used for authenticity assurance of value documents or security elements.

Wertdokumente und Sicherheitselemente bestehen jeweils mindestens aus einer Schicht Trägermaterial sowie gegebenenfalls weiteren Schichten. Außerdem weisen sie mindestens ein Echtheitsmerkmal auf, das von einem oder mehreren Merkmalsstoffen gebildet wird. Im Unterschied zu einem Wertdokument wird ein Sicherheitselement nicht als solches in den Verkehr gebracht, sondern in Verbindung mit einem Wertdokument, auf das es aufgebracht oder in das es eingebracht wird.Value documents and security elements each consist of at least one layer of carrier material and optionally further layers. In addition, they have at least one authenticity feature which is formed by one or more feature substances. In contrast to a value document, a security element is not marketed as such but in connection with a value document to which it is applied or incorporated.

Die erfindungsgemäßen Sicherheitselemente und Wertdokumente weisen mindestens ein Echtheitsmerkmal auf, das von einem erfindungsgemäßen Merkmalsstoff gebildet wird.The security elements and value documents according to the invention have at least one authenticity feature which is formed by a feature substance according to the invention.

Hinsichtlich seiner Anbringungsmöglichkeiten unterscheidet sich der erfindungsgemäße Merkmalsstoff nicht von konventionellen Lumineszenzstoffen. Er kann beispielsweise in das Volumen oder in Teilbereiche des Volumens eines Sicherheitselements oder Wertdokuments eingebracht werden, wobei das Trägermaterial aus Papier oder Kunststoff bestehen kann. Alternativ kann der Merkmalsstoff in Form einer Beschichtung auf mindestens einer Oberfläche oder auf Teilbereichen mindestens einer Oberfläche eines Sicherheitselements oder Wertdokuments vorgesehen werden.With regard to its mounting possibilities, the feature substance according to the invention does not differ from conventional luminescent substances. It can be introduced, for example, in the volume or in subregions of the volume of a security element or value document, wherein the carrier material may consist of paper or plastic. Alternatively, the feature substance may be provided in the form of a coating on at least one surface or on portions of at least one surface of a security element or value document.

Als weitere Alternative kann der Merkmalsstoff in einer Druckfarbe enthalten sein, die auf ein Sicherheitselement oder Wertdokument aufgedruckt wird. Der erfindungsgemäße Merkmalsstoff wird jeweils in Konzentrationen verwendet, wie sie in dem jeweiligen Anwendungsbereich für Lumineszenzstoffe üblich sind, d. h. etwa 0,05 bis 1 Gew.%, wenn der Merkmalsstoff im Volumen einer Papierschicht enthalten ist, und etwa 10 bis 40 Gew.%., wenn der Merkmalsstoff in einer Druckfarbe enthalten ist.As a further alternative, the feature substance may be contained in a printing ink which is printed on a security element or document of value. The feature substance of the invention is used in each case in concentrations, as are customary in the respective field of application for luminescent substances, ie about 0.05 to 1 wt.%, When the feature substance in the volume of a Paper layer is contained, and about 10 to 40 wt.%. When the feature substance is contained in a printing ink.

Sicherheitselemente mit dem erfindungsgemäßen Merkmalsstoff sind bevorzugt Sicherheitsfäden, Melierfasern, Planchetten und Etiketten, die in das Volumen eines Wertdokument-Trägermaterials eingebracht werden oder auf eine Oberfläche des Trägermaterials oder einer anderen Schicht eines Wertdokuments aufgeklebt werden.Security elements with the feature substance according to the invention are preferably security threads, mottling fibers, planchettes and labels, which are introduced into the volume of a value-document carrier material or glued to a surface of the carrier material or another layer of a value document.

Zur Herstellung eines Sicherheitselements kann der erfindungsgemäße Merkmalsstoff beispielsweise in einen Lack eingerieben werden, der dann zu einem Lackfilm ausgezogen und auf eine für ein Sicherheitselement geeignete Größe zugeschnitten wird. Ein geeigneter Lack ist ein Polyamid-Lack, und geeignete Konzentrationen liegen im Bereich von etwa 0,1 bis 1 Gew. %.To produce a security element, the feature substance according to the invention can be rubbed into a lacquer, for example, which is then drawn out to a lacquer film and cut to a size suitable for a security element. A suitable varnish is a polyamide varnish and suitable concentrations are in the range of about 0.1 to 1 wt%.

Ein besonderer Vorteil der erfindungsgemäßen Merkmalsstoffe wird erkennbar, wenn ein erfindungsgemäßer Merkmalsstoff in einer definierten Verteilung vorgesehen werden soll, wenn der Merkmalsstoff beispielsweise einen Code bilden soll. Bei einem derartigen Code wechseln Bereiche mit hoher Konzentration an Merkmalsstoff mit Bereichen geringer Konzentration an Merkmalsstoff bzw. ganz ohne Merkmalsstoff in einer vorbestimmten Weise ab. Die Anordnung der Bereiche mit hoher Konzentration an Merkmalsstoff und mit niedriger Konzentration an Merkmalsstoff (bzw. ohne Merkmalsstoff) ist maschinell auslesbar. Bisher konnten derartige Codes nur durch Aufdrucken von Lumineszenzstoffen in einem bestimmten Muster hergestellt werden. Im Volumen eines Wertdokuments konnten sie nicht unmittelbar gebildet werden.A particular advantage of the feature substances according to the invention becomes apparent when a feature substance according to the invention is intended to be provided in a defined distribution, for example when the feature substance is to form a code. In such a code, regions of high concentration of feature substance alternate with regions of low concentration of feature substance or completely without feature substance in a predetermined manner. The arrangement of the regions with a high concentration of feature substance and with a low concentration of feature substance (or without feature substance) can be read out by machine. So far, such codes could only be produced by printing luminescent substances in a specific pattern. They could not be formed directly in the volume of a value document.

Die erfindungsgemäßen Merkmalsstoffe jedoch weisen die Besonderheit auf, dass sie nicht nur Lumineszenzeigenschaften haben, sondern bevorzugt auch magnetisch oder magnetisierbar oder elektrisch leitfähig sind. In einem elektrischen oder magnetischen Feld richten sich die Nanopartikel der Umhüllung der Lumineszenzstoffpartikel in dem Feld aus, und der Merkmalsstoff hat die Tendenz, in dem Feld zu wandern. Voraussetzung für eine derartige Ausrichtung und gegebenenfalls Wanderung ist, dass das umgebende Medium des Merkmalsstoffs ausreichend flüssig ist, um eine Bewegung des Merkmalsstoffs zu erlauben. Das bedeutet in der Praxis, dass der erfindungsgemäße Merkmalsstoff in einem Trägermaterial oder einer Druckfarbe durch Anlegen eines geeigneten magnetischen oder elektrischen Feldes in einer gewünschten Weise ausgerichtet oder bewegt werden kann, solange das Trägermaterial noch ausreichend weich oder feucht, bzw. die Druckfarbe noch ausreichend flüssig ist. Ein Muster aus Bereichen hoher Konzentration an Merkmalsstoff und Bereichen niedriger Konzentration an Merkmalsstoff in einer Papierschicht kann beispielsweise dadurch erzeugt werden, dass ein erfindungsgemäßer Merkmalsstoff mit lumineszierenden und magnetischen Eigenschaften in der Papiermaschine in das feuchte Papier eingebracht wird, während sich an dem Papier eine Anordnung von Magneten in dem gewünschten Code-Muster befindet. Die magnetischen Nanopartikel des Merkmalsstoffs richten sich dann in der feuchten Papiermasse aus, und die Merkmalsstoffpartikel wandern zu den Magneten, wobei sie das Anordnungsmuster der Magneten, also den Code, reproduzieren. Der Code kann z. B. spektrometrisch ausgelesen werden.However, the feature substances according to the invention have the peculiarity that they not only have luminescence properties, but are preferably also magnetic or magnetizable or electrically conductive. In one electric or magnetic field, the nanoparticles of the envelope of the luminescent substance particles align in the field, and the feature substance has a tendency to migrate in the field. The prerequisite for such alignment and, if appropriate, migration is that the surrounding medium of the feature substance is sufficiently fluid to permit movement of the feature substance. This means in practice that the feature substance according to the invention can be aligned or moved in a desired manner in a carrier material or a printing ink by applying a suitable magnetic or electric field as long as the carrier material is still sufficiently soft or moist, or the printing ink is still sufficiently liquid is. A pattern of regions of high concentration of feature substance and regions of low concentration of feature substance in a paper layer can be produced, for example, by introducing a feature substance according to the invention having luminescent and magnetic properties in the paper machine into the moist paper, while an arrangement of Magnet is located in the desired code pattern. The magnetic nanoparticles of the feature substance then align in the wet pulp, and the feature substance particles migrate to the magnets, reproducing the pattern of arrangement of the magnets, that is, the code. The code can be z. B. be read spectrometrically.

Nachfolgend wird ein allgemeines Herstellungsverfahren für einen erfindungsgemäßen Merkmalsstoff angegeben.A general production method for a feature substance according to the invention is given below.

In ein Becherglas mit ca. 50 ml Wasser werden 2 g des oben genannten Beispiels 9 aus WO 81/03508 A1 , und 1,5 g MWCNT-Nanopulver eingewogen und einen Tag bei Zimmertemperatur gerührt. Zu Beginn des Mischvorgangs schwimmt das Nanopulver auf und bildet teilweise große Klumpen. Nachdem das schwer dispergierbare Nanopulver in der entstandenen Dispersion fein verteilt vorliegt, wird das Material filtriert. Es findet kein Filterdurchbruch des Nano-Materials durch die Filterporen statt. Das filtrierte Material wird bei 110° C beispielsweise über Nacht getrocknet.In a beaker with about 50 ml of water, 2 g of the above Example 9 from WO 81/03508 A1 , and weighed 1.5 g of MWCNT nanopowder and stirred for one day at room temperature. At the beginning of the mixing process, the nanopowder floats and sometimes forms large lumps. After the sparingly dispersible nanopowder is finely dispersed in the resulting dispersion, the material is filtered. There is no filter breakthrough of the nano-material through the filter pores. The filtered material is dried at 110 ° C, for example, overnight.

Anschließend kann das so gewonnene Material beispielsweise bei der Herstellung von Banknotenpapier, z. B. in einer Dosierung von 0,4 Gew. %, eingebracht werden.Subsequently, the material thus obtained, for example, in the production of banknote paper, z. B. in a dosage of 0.4 wt.%, Are introduced.

Ebenso kann das Material in einen Polyamidlack eingerieben und der Lack zu einem Lackfilm ausgezogen werden, wobei die Konzentration an Merkmalsstoff ebenfalls beispielsweise 0,4 Gew.% beträgt. Der Lackfilm ist zum Aufkleben auf Banknoten geeignet.Likewise, the material can be rubbed into a polyamide varnish and the varnish can be drawn off to a varnish film, wherein the concentration of feature substance is also, for example, 0.4% by weight. The paint film is suitable for sticking on banknotes.

Die Echtheit der Banknote kann nun sowohl durch Messung der Infrarot-Lumineszenz als auch durch Messung der elektrischen Leitfähigkeit, die durch das Nanopulver bedingt wird, verifiziert werden. Selbstverständlich kann die Echtheit auch durch eine Messung beider Eigenschaften festgestellt werden.The authenticity of the banknote can now be verified both by measuring the infrared luminescence and by measuring the electrical conductivity that is caused by the nanopowder. Of course, the authenticity can also be determined by measuring both properties.

Statt des angegebenen Beispiels können auch die oben im Zusammenhang mit WO 81/03508 A1 erwähnten Nanopulver verwendet werden. Ebenso können andere Lumineszenzstoffe verwendet werden.Instead of the given example can also be used in conjunction with WO 81/03508 A1 mentioned nanopowders are used. Likewise, other luminescent substances can be used.

Claims (30)

  1. A feature substance for securing the authenticity of value documents, comprising at least one luminescent substance that can be excited to luminescence emission by radiation in the infrared and/or visible and/or ultraviolet spectrum, in particle form, with nanoparticles enveloping the surfaces of the luminescent substance particles at least partially, wherein properties of the feature substance result from the interaction of the luminescence emission properties of the luminescent substance and properties of the nanoparticles, characterized in that the nanoparticles are chosen from the group consisting of carbon nano tubes, nano α iron, nano Fe3O4, nano NiFe2O4 and mixtures thereof.
  2. The feature substance according to claim 1, characterized in that the luminescent substance emits in the infrared and/or visible and/or ultraviolet spectrum.
  3. The feature substance according to claim 1 or 2, characterized in that the luminescent substance particles are enveloped substantially completely by substantially a monolayer of nanoparticles.
  4. The method according to any of the claims 1 to 3, characterized in that the luminescent substance is selected from luminescent substances on the basis of host lattices doped with at least one rare earth metal.
  5. The feature substance according to any of the claims 1 to 3, characterized in that the luminescent substance is selected from the mineral phosphors.
  6. The feature substance according to any of the claims 1 to 3, characterized in that the luminescent substance is chosen from organic luminescent substances.
  7. The feature substance according to any of the claims 1 to 6, characterized in that the luminescent substance is present in the form of particles with an average particle size in the range of 1 to 100 µm.
  8. The feature substance according to any of the claims 1 to 7, characterized in that the nanoparticles are chosen from magnetic materials, magnetizable materials, electroconductive materials, semiconductor materials and mixtures thereof.
  9. The feature substance according to any of the claims 1 to 8, characterized in that the nanoparticles have an average particle size in the range of 1 to 1000 nm, preferably 1 to 500 nm, particularly preferably 10 to 100 nm.
  10. The feature substance according to any of the claims 1 to 9, characterized in that the weight ratio of luminescent substance particles to nanoparticles is in the range of 10:1 to 1:10, preferably 5:1 to 1:3, particularly preferably 2:1 to 1:1.
  11. The feature substance according to any of the claims 1 to 10, characterized in that it additionally has luminescent substance particles that are not enveloped by nanoparticles, and/or free nanoparticles.
  12. The feature substance according to any of the claims 1 to 11, characterized in that it has at least two different luminescent substances and/or at least two different types of nanoparticles.
  13. A method for manufacturing a feature substance for securing the authenticity of value documents, comprising at least one luminescent substance that can be excited to luminescence emission by radiation in the infrared and/or visible and/or ultraviolet spectrum, with nanoparticles enveloping the surfaces of the luminescent substance at least partially, wherein the properties of the feature substance result from the interaction of the luminescent substance properties of the luminescent substance and properties of the nanoparticles, characterized in that the at least one luminescent substance in particle form and the nanoparticles in the form of a nano powder are added to a dispersant and mixed with each other until a dispersion is yielded, wherein the nanoparticles are bound to the surfaces of the luminescent substance particles by adhesive forces, and the association of the nanoparticles to the luminescent substance particles takes several hours.
  14. The method according to claim 13, characterized in that the dispersion is filtered to separate the feature substance.
  15. The method according to claim 14, characterized in that the separated feature substance is dried.
  16. The method according to any of the claims 13 to 15, characterized in that water is used as dispersant.
  17. The method according to any of the claims 13 to 16, characterized in that the feature substance is mixed with at least one further feature substance and/or at least one further type of nanoparticles.
  18. A method for securing the authenticity of a security element or value document, characterized by the step of:
    applying a feature substance as defined in any of the claims 1 to 12 to at least partial areas of at least one surface of the security element or value document, or
    integrating a feature substance as defined in any of the claims 1 to 12 in at least a partial area of the volume of the value document or security element.
  19. The method according to claim 18, characterized in that the security element or value document is subjected to electrical or magnetic fields during the application or integration of the feature substance in such a fashion that an orientation and, if desired, migration of the feature substance particles takes place within the electrical or magnetic field.
  20. The method according to claim 19, characterized in that the migration leads to a defined distribution of the feature substance particles that is machine-verifiable or visually verifiable.
  21. The method according to claim 20, characterized in that the defined distribution forms a code.
  22. A value document or security element comprising at least one carrier material and, on or in the carrier material, at least one authenticity feature on the basis of a feature substance, characterized in that the feature substance is such a substance as defined in any of the claims 1 to 12.
  23. The value document or security element according to claim 22, characterized in that the carrier material consists of paper or plastic.
  24. The value document or security element according to claim 22 or 23, characterized in that the feature substance is provided in the volume of the carrier material.
  25. The value document or security element according to claim 22 or 23, characterized in that the feature substance is present in a layer applied to at least partial areas of a surface of the carrier material.
  26. The value document or security element according to claim 22 or 23, characterized in that the feature substance is present in a printing ink applied to a surface of the value document or security element.
  27. The value document or security element according to any of the claims 22 to 26, characterized in that the feature substance is present in a defined distribution which is visually verifiable or machine-verifiable.
  28. The value document or security element according to claim 27, characterized in that the defined distribution forms a code.
  29. The security element according to any of the claims 22 to 28, characterized in that it is configured as a security thread or mottling fiber or planchet or label.
  30. The value document according to any of the claims 22 to 28, characterized in that it is equipped with a security element according to any of the claims 22 to 29.
EP06792361.5A 2005-10-05 2006-10-04 Securing the authenticity of value documents by means of characteristic substances Not-in-force EP1934889B1 (en)

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CA2624515C (en) 2016-01-19
US20090258200A1 (en) 2009-10-15
US20170036477A1 (en) 2017-02-09
WO2007039288A1 (en) 2007-04-12
CA2624515A1 (en) 2007-04-12
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AU2006299019B2 (en) 2011-03-24
US10836198B2 (en) 2020-11-17
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RU2449363C2 (en) 2012-04-27
EP1934889A1 (en) 2008-06-25

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