EP1826730A2 - Security feature for valuable documents - Google Patents

Security feature for valuable documents Download PDF

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Publication number
EP1826730A2
EP1826730A2 EP07003502A EP07003502A EP1826730A2 EP 1826730 A2 EP1826730 A2 EP 1826730A2 EP 07003502 A EP07003502 A EP 07003502A EP 07003502 A EP07003502 A EP 07003502A EP 1826730 A2 EP1826730 A2 EP 1826730A2
Authority
EP
European Patent Office
Prior art keywords
security feature
substance
luminescent substance
security
absorber
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.)
Withdrawn
Application number
EP07003502A
Other languages
German (de)
French (fr)
Other versions
EP1826730A3 (en
Inventor
Peter Schiffmann
Lars Dr. Karcher
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 EP1826730A2 publication Critical patent/EP1826730A2/en
Publication of EP1826730A3 publication Critical patent/EP1826730A3/en
Withdrawn legal-status Critical Current

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • B42D2033/20—
    • B42D2035/24—
    • 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

Definitions

  • the invention relates to a security feature for security papers, documents of value and the like with a UV-stimulable organic luminescent substance and a method for producing such a security feature.
  • Security documents such as banknotes, stocks, bonds, certificates, vouchers, checks, high-quality admission tickets, but also other papers that are prone to counterfeiting, such as passports or other identification documents, are usually provided with various security features to increase the security against counterfeiting.
  • a security feature may be embodied, for example, in the form of a security thread embedded in a banknote, an applied security strip or a self-supporting transfer element, such as a patch or a label, which is applied to a value document after its manufacture.
  • Such security features often contain luminescent substances that have a characteristic luminescence emission in the visible or infrared spectral range after excitation with UV radiation.
  • luminescence encompasses both fluorescence and phosphorescence.
  • the long-wave UV-excitable, inorganic luminescent materials available for security printing have a low photon yield and thus a low luminescence intensity. These are only partially applicable in the background or offset printing of the particle size.
  • Organic, long-wave UV-stimulable luminescent substances for security printing have only a low chemical, in some cases low thermal stability. When used in underground colors, they can be quenched by constituents of the overcoating paint. Out For this reason, currently used in security printing predominantly yellow or yellow-green luminescent substances.
  • the invention has the object to provide a security feature of the type mentioned, which avoids the disadvantages of the prior art.
  • the range of luminescent colors that can be used in security printing is to be expanded.
  • a generic security element contains core-shell particles in which the organic luminescent substance is coated as a core with a shell, which increases the chemical and / or physical resistance of the luminescent substance.
  • the shell is designed so that it increases the light fastness of the luminescent substance.
  • Light fastness is a measure of the color fastness of dyeings, dyes and prints against the bleaching effect of daylight, as defined by appropriate measuring methods in the European standard EN ISO 105 B01, as further detailed below.
  • the security feature preferably achieves a light fastness of 3 or more, preferably even a light fastness of 5 or more, by coating the luminescent substance core on the 8-stage wool scale.
  • the shell expediently contains a UV absorber which does not or does not have the UV excitability of the luminescent substance significantly impaired.
  • the shell contains as UV absorber TiO 2 , preferably nanoscale TiO 2 .
  • the shell contains as UV absorber a benzotriazole derivative or a polystyrene acrylate.
  • luminescent substance and UV absorber are preferably matched to one another such that the absorption maximum of the luminescent substance lies at longer wavelengths than the absorption maximum of the UV absorber. Although it is protected against fading by the UV absorber, the luminescent material core can then still be UV-excited in the long-term.
  • the security feature particularly advantageously has a luminescent substance which luminesces after UV excitation in the red or blue spectral range.
  • a luminescent substance which luminesces after UV excitation in the red or blue spectral range.
  • the range of luminescent colors available for security printing is thereby greatly expanded.
  • Benzoxazinone derivatives, oxinates, anthranilic acid derivatives or organic rare earth complexes are particularly suitable for use as a luminescent substance core.
  • the luminescent substance is coated in an advantageous variant of the invention with an organic shell, in particular polystyrene, SBS (styrene / butadiene / styrene triblock copolymers), polycarbonate, PVC (polyvinyl chloride), TPU (thermoplastic polyurethanes), ABS (acrylonitrile-butadiene-styrene copolymers) or PMMA (polymethyl methacrylate) contains.
  • an organic shell in particular polystyrene, SBS (styrene / butadiene / styrene triblock copolymers), polycarbonate, PVC (polyvinyl chloride), TPU (thermoplastic polyurethanes), ABS (acrylonitrile-butadiene-styrene copolymers) or PMMA (polymethyl methacrylate) contains.
  • the luminescent substance is coated with an inorganic shell.
  • the luminescent substance may also be coated with two or more different organic and / or inorganic shells.
  • the coating contains a feature substance.
  • the feature substance can be present in the coating in a concentration between 1 ppm and about 50% by weight.
  • the feature substance may be another luminescent substance that can be detected by its luminescence properties. This can be done, for example, by means of a luminescence spectrometer with determination of the excitation peaks, emission peaks or the decay behavior. It is understood that a luminescent substance is used as a feature substance, which differs in at least one of these parameters from the coated base material.
  • soluble substances can be incorporated as feature substances in the coating.
  • the detection can be carried out by means of thin-layer chromatography, visually or photometrically via the LF value (running value: distance traveled by a sample on the TLC plate for a defined solvent or mobile phase in a defined time), intensity and solvent quality used. Visually discernible dyes, luminescent substances, IR absorbers or activatable substances (reagents) are particularly suitable here.
  • detectable feature substances such as barium sulfate or chalk
  • detectable feature substances can also be used via a shape detection by means of a scanning electron microscope, or light-polarizing feature substances which are detected by means of a light microscope and polarization filter can.
  • liquid crystalline materials come into consideration, which can even serve alone as an organic shell.
  • IR absorbers - preferably having an absorption in the spectral range between 800 nm and 1100 nm - as feature substances in the shell can be detected by means of an optical microscope in the IR range, microscope spectrometer or spectroscopy.
  • feature substances with magnetically detectable properties such as soft iron (carbonyl iron, Fe 2 O 3 ) or hard iron (magnetite Fe 3 O 4 ), come into consideration, the proof succeeds here, for example by means of vibration sample magnetometer.
  • Electrically conductive feature substances in the shell such as carbon, silver, gold, copper or doped organic polymers, can be detected by measuring the surface resistance or conductivity of detached pigment material.
  • Other feature substances with special properties which can be detected by means of SEM, X-ray microanalysis or mass spectrometry, such as special oxides, metals or rare earths, come into consideration for the invention.
  • the invention also includes a method for producing a security feature for security papers, documents of value and the like, in which a UV-stimulable, organic luminescent substance is coated as a core with a shell, which increases the chemical and / or physical resistance of the luminescent substance.
  • the luminescent substance is coated with an organic shell.
  • an organic shell is coated with an organic shell.
  • the coating can be carried out, for example, by means of emulsion polymerization, water-insoluble Monomers are emulsified in water using emulsifiers and polymerized using water-soluble initiators.
  • the coating is carried out by a) dissolving or dispersing the polymers to be coated in solvent, b) mixing with the luminescent substance, c) evaporation of the solvent or solidification and d) dry grinding.
  • a) dissolving or dispersing the polymers to be coated in solvent b) mixing with the luminescent substance, c) evaporation of the solvent or solidification and d) dry grinding.
  • an annealing step may be carried out to close any capillaries.
  • Particularly suitable polymers for this process variant are the abovementioned polymers.
  • the coating can also be carried out by a) dissolving the polymers to be coated and a crosslinker, b) mixing in the luminescent substance, c) crosslinking, d) drying and milling.
  • resins from the group of diallyl phthalates, epoxide, urea-formaldehyde, melamine-formaldehyde, melamine-phenol-formaldehyde, phenol-formaldehyde or unsaturated polyester resins are suitable for this variant.
  • the coating is carried out by a) melting the polymers to be coated (for example so-called “hotmelts", polyamide, TPU) and optionally a crosslinker, such as isocyanate, b) mixing in the luminescent substance, c) crosslinking, d) drying and milling.
  • a) melting the polymers to be coated for example so-called “hotmelts", polyamide, TPU
  • a crosslinker such as isocyanate
  • the luminescent substance is provided with an inorganic shell by a sol-gel process.
  • a sol-gel process for example, partially organically functionalized silanes are hydrolyzed in an organic solvent by means of acid or base.
  • the Luminescent pigment is coated with SiO x , the aqueous components evaporated.
  • An annealing or sintering step is carried out with stirring or mixing in order to avoid an agglomerate.
  • Another variant is the coating of luminescent substances on an inorganic support (laking process).
  • the luminescent substance is solubilized, applied to a suitable inorganic support and then dried (e.g., acidic luminescent on basic support). Subsequently, an organic and / or inorganic shell is produced.
  • a UV absorber or a feature substance is to be incorporated into the shell, it is suitably added to the shell material in the preparation of the core-shell particles.
  • FIG. 1 shows a schematic representation of a banknote 10, which is provided in a region 12 with a security feature according to the invention.
  • the security feature according to the invention contains core-shell particles 20, in which a core 22 made of a long-wave UV-excitable, organic luminescent substance is coated with a shell 24 which has the chemical and / or physical resistance, in particular the light fastness of the luminescent increases.
  • the light fastness is a measure of the color fastness of dyeings, dyes and prints against the bleaching effect of daylight.
  • the European standard EN ISO 105 B01 describes the determination of color fastness according to the 8-step wool scale, which ranges from a very low light fastness (light fastness type 1) to an excellent light fastness (light fastness type 8).
  • An increase by one step corresponds to twice as good light stability, d. That is, when a light fastness type sample 4 undergoes a certain change under certain conditions in a given time, a light fastness type sample 3 will undergo this change under the same conditions already after half the time, a light fastness type sample 5 only after twice as long demonstrate.
  • the luminescent substance 22 used is the reddish orange fluorescent substance LUMILUX® CD 740 from Honeywell (composition: oxinate) after UV excitation. It is understood that other luminescent substances, such as, for example, the blue-fluorescent substance LUMILUX® CD 329, an antranilic acid derivative, or other desired luminescent substances, can also be used as core.
  • the luminescent substance 22 is encapsulated with an organic shell 24 containing a UV absorber 26.
  • the encapsulation on the one hand increases the resistance of the luminescent substance to acids and alkalis, and on the other hand significantly increases the light fastness of the security feature.
  • a polymer or prepolymer for example a melamine / formaldehyde resin
  • a 10% strength aqueous dispersion is produced.
  • the luminescent substance is added in portions in a round-bottomed flask with stirring, for example with a Teflon stirring fish and a magnetic stirrer. The dispersion is stirred until no longer visible large agglomerates of the luminescent.
  • the solvent is distilled off slowly under vacuum and constant stirring.
  • the solid is crushed and placed in a convection oven at 120 ° C for 2 hours to fully cure the polymer.
  • the drying of the encapsulated particles takes place at the same time.
  • the product can be further processed like a conventional pigment.
  • Suitable admixing UV absorbers 26 are inorganic UV absorbers, such as TiO 2, preferably nanoscale TiO 2 , or organic UV absorbers, such as benzotriazole derivatives or suitable polymers, such as polystyrene acrylates. If appropriate, an IR absorber, in particular with an absorption in the spectral range between 800 nm and 1100 nm, is added.
  • luminescent substance 22 and the UV absorber 26 are coordinated so that the luminescent substance 22 despite the Protective effect of the UV absorber 26 can still be stimulated.
  • luminescent substance 22 and absorber 26 can be chosen such that the absorption maximum of the luminescent substance 22 is at longer wavelengths than the absorption maximum of the UV absorber 26.
  • the luminescent substance 22 is provided with an inorganic shell 24 by a sol-gel process.
  • an inorganic shell 24 for example, partially organically functionalized silanes are hydrolyzed in an organic solvent by means of acid or base.
  • the luminescent substance pigment is coated with SiO x , the aqueous components evaporated.
  • An annealing or sintering step is carried out with stirring or mixing in order to avoid an agglomerate.
  • An inorganic shell 24 can also be produced by a laking process in which the luminescent substance 22 is solubilized, applied to a suitable inorganic support and then dried.
  • a feature substance 28 may be added to the coating 24 to increase the security of the imprint 12.
  • the above-described organic shell is compounded with an electrically conductive substance 28 such as carbon, silver, gold, copper or doped organic polymers, the presence of which can be detected by measurement of surface resistance or conductivity of detached pigment material.
  • Detectable feature substances such as barium sulfate or chalk, can also be used via a scanning electron microscope shape recognition, or IR absorbers, such as ADS1065A from American Dye Source (composition: C 62 H 92 N 6 F 12 Sb 2 ).
  • IR absorbers such as ADS1065A from American Dye Source (composition: C 62 H 92 N 6 F 12 Sb 2 ).
  • feature substances with magnetically detectable properties such as soft iron (carbonyl iron, Fe 2 O 3 ) or hard iron (magnetite Fe3O 4 ), come into consideration.
  • Other luminescent substances other than the luminescent substance core can also be admixed to the shell as a feature substance.
  • the concentration of such feature substances can range from a few ppm to about 50% by weight of the coating. For reasons of cost and to make detection difficult by potential counterfeiters, low concentrations are usually used.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Luminescent Compositions (AREA)
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Abstract

The security features for security papers and value documents with ultraviolet-stimulating organic luminescent materials, comprises a core-covering-particle (20), with which luminescence material as core (22) is coated with an organic covering (24). The covering contains a UV absorber (26), which does not substantially impair the UV-stimulating ability of the luminescence material, and IR (infrared)-absorber with an absorption in the spectral region of 800-1100 Nm. The absorption maximum of the luminescence material lies in larger wavelengths than the absorption maximum of the UV absorber. The security features for security papers and value documents with ultraviolet-stimulating organic luminescent materials, comprises a core-covering-particle (20), with which luminescence material as core (22) is coated with an organic covering (24). The covering contains a UV absorber (26), which does not substantially impair the UV-stimulating ability of the luminescence material, and IR (infrared)-absorber with an absorption in the spectral region of 800-1100 Nm. The absorption maximum of the luminescence material lies in larger wavelengths than the absorption maximum of the UV absorber. The luminescence material is luminized in the red or blue spectral region after UV-stimulation. The coating contains a characteristic material having concentration of 1 ppm-50wt.%. The characteristic material is a luminescent material, which shows another stimulation- and/or emission spectrum than the organic luminescent material in the core, and contains specific molded articles. The characteristic material is soluble, an infrared absorber, magnetic, light polarizing and electrically conductive. Independent claims are included for: (1) procedure for manufacturing a security feature for security papers and value documents or such a thing; (2) security papers for the production of safety- or value documents, like notes, cheque, badges or such a thing; and (3) branded article, value document or such a thing.

Description

Die Erfindung betrifft ein Sicherheitsmerkmal für Sicherheitspapiere, Wertdokumente und dergleichen mit einem UV-anregbaren organischen Lumineszenzstoff sowie ein Verfahren zum Herstellen eines derartigen Sicherheitsmerkmals.The invention relates to a security feature for security papers, documents of value and the like with a UV-stimulable organic luminescent substance and a method for producing such a security feature.

Wertdokumente, wie beispielsweise Banknoten, Aktien, Anleihen, Urkunden, Gutscheine, Schecks, hochwertige Eintrittskarten, aber auch andere fälschungsgefährdete Papiere, wie Pässe oder sonstige Ausweisdokumente, werden in der Regel mit verschiedenen Sicherheitsmerkmalen zur Erhöhung der Fälschungssicherheit versehen. Ein Sicherheitsmerkmal kann beispielsweise in Form eines in eine Banknote eingebetteten Sicherheitsfadens, eines aufgebrachten Sicherheitsstreifens oder eines selbsttragenden Transferelements, wie einem Patch oder einem Etikett, das nach seiner Herstellung auf ein Wertdokument aufgebracht wird, ausgebildet sein.Security documents, such as banknotes, stocks, bonds, certificates, vouchers, checks, high-quality admission tickets, but also other papers that are prone to counterfeiting, such as passports or other identification documents, are usually provided with various security features to increase the security against counterfeiting. A security feature may be embodied, for example, in the form of a security thread embedded in a banknote, an applied security strip or a self-supporting transfer element, such as a patch or a label, which is applied to a value document after its manufacture.

Derartige Sicherheitsmerkmale enthalten oft Lumineszenzstoffe, die nach Anregung mit UV-Strahlung eine charakteristische Lumineszenzemission im sichtbaren oder infraroten Spektralbereich aufweisen. Der Begriff Lumineszenz umfasst dabei sowohl Fluoreszenz als auch Phosphoreszenz. Die für den Sicherheitsdruck verfügbaren, langwellig UV-anregbaren, anorganischen Lumineszenzstoffe weisen jedoch eine geringe Photonenausbeute und damit eine geringe Lumineszenzintensität auf. Auch sind diese von der Partikelgröße her nur bedingt im Untergrund- bzw. Offsetdruck anwendbar.Such security features often contain luminescent substances that have a characteristic luminescence emission in the visible or infrared spectral range after excitation with UV radiation. The term luminescence encompasses both fluorescence and phosphorescence. However, the long-wave UV-excitable, inorganic luminescent materials available for security printing have a low photon yield and thus a low luminescence intensity. These are only partially applicable in the background or offset printing of the particle size.

Organische, langwellig UV-anregbare Lumineszenzstoffe für den Sicherheitsdruck weisen nur eine geringe chemische, teilweise auch geringe thermische Beständigkeit auf. Bei Verwendung in Untergrundfarben können sie durch Bestandteile des Lackes einer Überlackierung gequencht werden. Aus diesem Grund werden derzeit im Sicherheitsdruck überwiegend gelbe bzw. gelb-grünliche Lumineszenzstoffe eingesetzt.Organic, long-wave UV-stimulable luminescent substances for security printing have only a low chemical, in some cases low thermal stability. When used in underground colors, they can be quenched by constituents of the overcoating paint. Out For this reason, currently used in security printing predominantly yellow or yellow-green luminescent substances.

Ausgehend davon liegt der Erfindung die Aufgabe zugrunde, ein Sicherheitsmerkmal der eingangs genannten Art anzugeben, das die Nachteile des Standes der Technik vermeidet. Insbesondere soll die Palette der im Sicherheitsdruck einsetzbaren Lumineszenzfarben erweitert werden.Based on this, the invention has the object to provide a security feature of the type mentioned, which avoids the disadvantages of the prior art. In particular, the range of luminescent colors that can be used in security printing is to be expanded.

Diese Aufgabe wird durch das Sicherheitsmerkmal und das Herstellungsverfahren mit den Merkmalen der unabhängigen Ansprüche gelöst. Weiterbildungen der Erfindung sind Gegenstand der Unteransprüche.This object is achieved by the security feature and the manufacturing method having the features of the independent claims. Further developments of the invention are the subject of the dependent claims.

Gemäß der Erfindung enthält ein gattungsgemäßes Sicherheitselement Kern-Hülle-Teilchen, bei denen der organische Lumineszenzstoff als Kern mit einer Hülle beschichtet ist, die die chemische und/oder physikalische Beständigkeit des Lumineszenzstoffs erhöht.According to the invention, a generic security element contains core-shell particles in which the organic luminescent substance is coated as a core with a shell, which increases the chemical and / or physical resistance of the luminescent substance.

In einer bevorzugten Ausgestaltung ist die Hülle dabei so ausgebildet, dass sie die Lichtechtheit des Lumineszenzstoffs erhöht. Die Lichtechtheit ist ein Maß für die Farbechtheit von Färbungen, Farbstoffen und Drucken gegen die Bleichwirkung des Tageslichts, wie sie einschließlich geeigneter Messverfahren in der europäischen Norm EN ISO 105 B01 definiert ist, wie weiter unten näher dargestellt. Bevorzugt erreicht das Sicherheitsmerkmal durch die Umhüllung des Lumineszenzstoff-Kerns auf der 8-stufigen Wollskala eine Lichtechtheit von 3 oder mehr, vorzugsweise sogar eine Lichtechtheit von 5 oder mehr.In a preferred embodiment, the shell is designed so that it increases the light fastness of the luminescent substance. Light fastness is a measure of the color fastness of dyeings, dyes and prints against the bleaching effect of daylight, as defined by appropriate measuring methods in the European standard EN ISO 105 B01, as further detailed below. The security feature preferably achieves a light fastness of 3 or more, preferably even a light fastness of 5 or more, by coating the luminescent substance core on the 8-stage wool scale.

Um die Lichtechtheit zu erhöhen, enthält die Hülle zweckmäßig einen UV-Absorber, der die UV-Anregbarkeit des Lumineszenzstoffs nicht oder nicht wesentlich beeinträchtigt. In einer Erfindungsvariante enthält die Hülle als UV-Absorber TiO2, vorzugsweise nanoskalisches TiO2. In anderen Varianten enthält die Hülle als UV-Absorber ein Benzotriazol-Derivat oder ein Polystyrol-Acrylat.In order to increase the light fastness, the shell expediently contains a UV absorber which does not or does not have the UV excitability of the luminescent substance significantly impaired. In one variant of the invention, the shell contains as UV absorber TiO 2 , preferably nanoscale TiO 2 . In other variants, the shell contains as UV absorber a benzotriazole derivative or a polystyrene acrylate.

Um sicherzustellen, dass der UV-Absorber die Anregbarkeit des Lumineszenzstoff-Kerns nicht wesentlich beeinträchtigt, sind Lumineszenzstoff und UV-Absorber bevorzugt so aufeinander abgestimmt, dass das Absorptionsmaximum des Lumineszenzstoffs bei größeren Wellenlängen als das Absorptionsmaximum des UV-Absorbers liegt. Obwohl er durch den UV-Absorber gegen Ausbleichen geschützt ist, kann der Lumineszenzstoff-Kern dann nach wie vor langwellig UV-angeregt werden.In order to ensure that the UV absorber does not substantially impair the excitability of the luminescent substance core, luminescent substance and UV absorber are preferably matched to one another such that the absorption maximum of the luminescent substance lies at longer wavelengths than the absorption maximum of the UV absorber. Although it is protected against fading by the UV absorber, the luminescent material core can then still be UV-excited in the long-term.

Mit besonderem Vorteil weist das Sicherheitsmerkmal einen Lumineszenzstoff auf, der nach UV-Anregung im roten oder blauen Spektralbereich luminesziert. In Verbindung mit herkömmlichen Lumineszenzstoffen wird dadurch die für den Sicherheitsdruck zur Verfügung stehende Palette an Lumineszenzfarben stark erweitert.The security feature particularly advantageously has a luminescent substance which luminesces after UV excitation in the red or blue spectral range. In conjunction with conventional luminescent substances, the range of luminescent colors available for security printing is thereby greatly expanded.

Zur Verwendung als Lumineszenzstoff-Kern bieten sich insbesondere Benzoxazinonderivate, Oxinate, Anthranilsäurederivate oder organische Selten-Erden-Komplexe an.Benzoxazinone derivatives, oxinates, anthranilic acid derivatives or organic rare earth complexes are particularly suitable for use as a luminescent substance core.

Der Lumineszenzstoff ist in einer vorteilhaften Erfindungsvariante mit einer organischen Hülle beschichtet, die insbesondere Polystyrol, SBS (Styrol/Butadien/Styrol-Triblockcopolymere), Polycarbonat, PVC (Polyvinylchlorid), TPU (thermoplastische Polyurethane), ABS (Acrylnitril-Butadien-StyrolCopolymere) oder PMMA (Polymethylmethacrylat) enthält.The luminescent substance is coated in an advantageous variant of the invention with an organic shell, in particular polystyrene, SBS (styrene / butadiene / styrene triblock copolymers), polycarbonate, PVC (polyvinyl chloride), TPU (thermoplastic polyurethanes), ABS (acrylonitrile-butadiene-styrene copolymers) or PMMA (polymethyl methacrylate) contains.

In einer anderen ebenfalls vorteilhaften Erfindungsvariante ist der Lumineszenzstoff mit einer anorganischen Hülle beschichtet. Der Lumineszenzstoff kann auch mit zwei oder mehr unterschiedlichen organischen und/oder anorganischen Hüllen beschichtet sein.In another likewise advantageous variant of the invention, the luminescent substance is coated with an inorganic shell. The luminescent substance may also be coated with two or more different organic and / or inorganic shells.

Gemäß einer bevorzugten Weiterbildung der Erfindung enthält die Beschichtung einen Merkmalsstoff. Der Merkmalsstoff kann dabei in der Beschichtung in einer Konzentration zwischen 1 ppm und etwa 50 Gew-% vorliegen.According to a preferred embodiment of the invention, the coating contains a feature substance. The feature substance can be present in the coating in a concentration between 1 ppm and about 50% by weight.

Bei dem Merkmalsstoff kann es sich um einen weiteren Lumineszenzstoff handeln, der anhand seiner Lumineszenzeigenschaften nachgewiesen werden kann. Dies kann beispielsweise mittels Lumineszenzspektrometer unter Bestimmung der Anregungspeaks, Emissionspeaks oder des Abklingverhaltens erfolgen. Es versteht sich, dass ein Lumineszenzstoff als Merkmalsstoff eingesetzt wird, der sich in zumindest in einem dieser Parameter vom umhüllten Grundstoff unterscheidet.The feature substance may be another luminescent substance that can be detected by its luminescence properties. This can be done, for example, by means of a luminescence spectrometer with determination of the excitation peaks, emission peaks or the decay behavior. It is understood that a luminescent substance is used as a feature substance, which differs in at least one of these parameters from the coated base material.

Auch lösliche Stoffe können als Merkmalsstoffe in die Beschichtung eingebaut werden. Der Nachweis kann mittels Dünnschichtchromatographie, visuell oder photometrisch über den LF-Wert (Lauf-Wert: Strecke, die eine Probe auf der DC-Platte bei einem definierten Lösungs- bzw. Laufmittel in einer definierten Zeit zurücklegt), Intensität und verwendete Lösungsmittelqualität erfolgen. Infrage kommen hier insbesondere visuell sichtbare Farbstoffe, Lumineszenzstoffe, IR-Absorber oder aktivierbare Stoffe (Reagenzien).Also soluble substances can be incorporated as feature substances in the coating. The detection can be carried out by means of thin-layer chromatography, visually or photometrically via the LF value (running value: distance traveled by a sample on the TLC plate for a defined solvent or mobile phase in a defined time), intensity and solvent quality used. Visually discernible dyes, luminescent substances, IR absorbers or activatable substances (reagents) are particularly suitable here.

In weiteren Varianten können auch über eine Formerkennung mittels Rasterelektronenmikroskop nachweisbare Merkmalsstoffe, wie etwa Bariumsulfat oder Kreide, verwendet werden, oder lichtpolarisierende Merkmalsstoffe, die mittels Lichtmikroskop und Polarisationsfilter nachgewiesen werden können. Dabei kommen insbesondere flüssigkristalline Materialien in Betracht, die sogar alleine als organische Hülle dienen können.In further variants detectable feature substances, such as barium sulfate or chalk, can also be used via a shape detection by means of a scanning electron microscope, or light-polarizing feature substances which are detected by means of a light microscope and polarization filter can. In particular, liquid crystalline materials come into consideration, which can even serve alone as an organic shell.

IR-Absorber - vorzugsweise mit einer Absorption im Spektralbereich zwischen 800 nm und 1100 nm - als Merkmalsstoffe in der Hülle können mittels Lichtmikroskop im IR-Bereich, Mikroskopspektrometer oder Spektroskopie nachgewiesen werden. Auch Merkmalsstoffe mit magnetisch nachweisbaren Eigenschaften, beispielsweise Weicheisen (Carbonyleisen, Fe2O3) oder Harteisen (Magnetit Fe3O4), kommen in Betracht, der Nachweis gelingt hier beispielsweise mittels Vibration Sample Magnetometer.IR absorbers - preferably having an absorption in the spectral range between 800 nm and 1100 nm - as feature substances in the shell can be detected by means of an optical microscope in the IR range, microscope spectrometer or spectroscopy. Also feature substances with magnetically detectable properties, such as soft iron (carbonyl iron, Fe 2 O 3 ) or hard iron (magnetite Fe 3 O 4 ), come into consideration, the proof succeeds here, for example by means of vibration sample magnetometer.

Elektrisch leitfähige Merkmalsstoffe in der Hülle, wie etwa Kohlenstoff, Silber, Gold, Kupfer oder dotierte organische Polymere, können durch eine Messung des Oberflächenwiderstands oder der Leitfähigkeit abgelösten Pigmentmaterials nachgewiesen werden. Auch weitere Merkmalsstoffe mit speziellen Eigenschaften, die mittels REM, Röntgenmikroanalyse oder Massenspektrometrie nachgewiesen werden können, wie spezielle Oxide, Metalle oder seltene Erden, kommen für die Erfindung in Betracht.Electrically conductive feature substances in the shell, such as carbon, silver, gold, copper or doped organic polymers, can be detected by measuring the surface resistance or conductivity of detached pigment material. Other feature substances with special properties, which can be detected by means of SEM, X-ray microanalysis or mass spectrometry, such as special oxides, metals or rare earths, come into consideration for the invention.

Die Erfindung enthält auch ein Verfahren zum Herstellen eines Sicherheitsmerkmals für Sicherheitspapiere, Wertdokumente und dergleichen, bei dem ein UV-anregbarer, organischer Lumineszenzstoff als Kern mit einer Hülle beschichtet wird, die die chemische und/ oder physikalische Beständigkeit des Lumineszenzstoffs erhöht.The invention also includes a method for producing a security feature for security papers, documents of value and the like, in which a UV-stimulable, organic luminescent substance is coated as a core with a shell, which increases the chemical and / or physical resistance of the luminescent substance.

In einer vorteilhaften Verfahrensvariante wird der Lumineszenzstoff mit einer organischen Hülle beschichtet. Dabei kann eine aus einer Reihe möglicher Beschichtungsvarianten zum Einsatz kommen. Die Beschichtung kann beispielsweise mittels Emulsionspolymerisation erfolgen, wobei wasserunlösliche Monomere mithilfe von Emulgatoren in Wasser emulgiert und unter Verwendung wasserlöslicher Initiatoren polymerisiert werden.In an advantageous variant of the method, the luminescent substance is coated with an organic shell. One of a number of possible coating variants can be used. The coating can be carried out, for example, by means of emulsion polymerization, water-insoluble Monomers are emulsified in water using emulsifiers and polymerized using water-soluble initiators.

In einer anderen Beschichtungsvariante erfolgt die Beschichtung durch a) Lösen oder Dispergieren der zu beschichtenden Polymere in Lösungsmittel, b) Mischen mit dem Lumineszenzstoff, c) Abdampfen des Lösungsmittels bzw. Erstarren und d) trocken Vermahlen. Bei thermoplastischen oder aufschmelzbaren Polymeren kann nach dem Schritt d) ein Temperschritt zum Verschließen eventueller Kapillaren durchgeführt werden. Als Polymere kommen für diese Verfahrensvariante insbesondere die oben erwähnten Polymere in Betracht.In another coating variant, the coating is carried out by a) dissolving or dispersing the polymers to be coated in solvent, b) mixing with the luminescent substance, c) evaporation of the solvent or solidification and d) dry grinding. In the case of thermoplastic or meltable polymers, after step d) an annealing step may be carried out to close any capillaries. Particularly suitable polymers for this process variant are the abovementioned polymers.

Die Beschichtung kann auch erfolgen durch a) In-Lösung-Bringen der zu beschichtenden Polymere und einem Vernetzer, b) Einmischen des Lumineszenzstoffs, c) Vernetzen, d) Trocknen und Vermahlen. Für diese Variante kommen insbesondere Harze aus der Gruppe der Diallylphthalate, Epoxid-, Harnstoff-Formaldehyd-, Melamin-Formaldehyd-, Melamin-Phenol-Formaldehyd-, Phenol-Formaldehyd-, oder ungesättigter Polyester-Harze infrage.The coating can also be carried out by a) dissolving the polymers to be coated and a crosslinker, b) mixing in the luminescent substance, c) crosslinking, d) drying and milling. In particular, resins from the group of diallyl phthalates, epoxide, urea-formaldehyde, melamine-formaldehyde, melamine-phenol-formaldehyde, phenol-formaldehyde or unsaturated polyester resins are suitable for this variant.

Nach einer weiteren Beschichtungsvariante erfolgt die Beschichtung durch a) In-Schmelze-Bringen der zu beschichtenden Polymere (beispielsweise so genannte "Hotmelts", Polyamid, TPU) und gegebenenfalls eines Vernetzers, wie etwa Isocyanat, b) Einmischen des Lumineszenzstoffs, c) Vernetzen, d) Trocknen und Vermahlen.According to a further coating variant, the coating is carried out by a) melting the polymers to be coated (for example so-called "hotmelts", polyamide, TPU) and optionally a crosslinker, such as isocyanate, b) mixing in the luminescent substance, c) crosslinking, d) drying and milling.

In einer alternativen Ausgestaltung wird der Lumineszenzstoff über ein Sol-Gel-Verfahren mit einer anorganischen Hülle versehen. Dazu werden beispielsweise in einem organischen Lösungsmittel durch Katalyse teilweise organisch funktionalisierte Silane mittels Säure oder Base hydrolysiert. Das Lumineszenzstoff-Pigment wird mit SiOx umhüllt, die wässrigen Komponenten abgedampft. Ein Temper- bzw. Sinterschritt erfolgt unter Rühren bzw. Mischen um ein Agglomerat zu vermeiden.In an alternative embodiment, the luminescent substance is provided with an inorganic shell by a sol-gel process. For this purpose, for example, partially organically functionalized silanes are hydrolyzed in an organic solvent by means of acid or base. The Luminescent pigment is coated with SiO x , the aqueous components evaporated. An annealing or sintering step is carried out with stirring or mixing in order to avoid an agglomerate.

Eine weitere Variante ist das Aufziehen von Lumineszenzstoffen auf einen anorganischen Träger (Verlackungsprozess). Bei diesem Verfahren wird der Lumineszenzstoff in Lösung gebracht, auf einen geeigneten anorganischen Träger aufgebracht und anschließend getrocknet (z.B. saurer Lumineszenzstoff auf basischem Träger). Anschließend wird eine organische und/oder anorganische Hülle erzeugt.Another variant is the coating of luminescent substances on an inorganic support (laking process). In this process, the luminescent substance is solubilized, applied to a suitable inorganic support and then dried (e.g., acidic luminescent on basic support). Subsequently, an organic and / or inorganic shell is produced.

Soll ein UV-Absorber oder ein Merkmalsstoff in die Hülle eingebaut werden, wird dieser dem Hüllenmaterial bei der Herstellung der Kern-Hülle-Teilchen in geeigneter Weise zugesetzt.When a UV absorber or a feature substance is to be incorporated into the shell, it is suitably added to the shell material in the preparation of the core-shell particles.

Weitere Ausführungsbeispiele sowie Vorteile der Erfindung werden nachfolgend anhand der Figuren erläutert. Zur besseren Anschaulichkeit wird in den Figuren auf eine maßstabs- und proportionsgetreue Darstellung verzichtet.Further embodiments and advantages of the invention are explained below with reference to the figures. For better clarity, a scale and proportioned representation is omitted in the figures.

Es zeigen:

Fig. 1
eine schematische Darstellung einer Banknote mit einem erfindungsgemäßen Sicherheitsmerkmal, und
Fig. 2 und 3
schematisch Kern-Hülle-Teilchen nach Ausführungsbeispielen der Erfindung.
Show it:
Fig. 1
a schematic representation of a banknote with a security feature of the invention, and
FIGS. 2 and 3
schematically core-shell particles according to embodiments of the invention.

Die Erfindung wird nun am Beispiel einer Banknote erläutert. Fig.1 zeigt dazu eine schematische Darstellung einer Banknote 10, die in einem Bereich 12 mit einem erfindungsgemäßen Sicherheitsmerkmal versehen ist.The invention will now be explained using the example of a banknote. 1 shows a schematic representation of a banknote 10, which is provided in a region 12 with a security feature according to the invention.

Wie in Fig. 2 schematisch illustriert, enthält das erfindungsgemäße Sicherheitsmerkmal Kern-Hülle-Teilchen 20, bei denen ein Kern 22 aus einem langwellig UV-anregbaren, organischen Lumineszenzstöff mit einer Hülle 24 beschichtet ist, die die chemische und/ oder physikalische Beständigkeit, insbesondere die Lichtechtheit, des Lumineszenzstoffs erhöht.As schematically illustrated in FIG. 2, the security feature according to the invention contains core-shell particles 20, in which a core 22 made of a long-wave UV-excitable, organic luminescent substance is coated with a shell 24 which has the chemical and / or physical resistance, in particular the light fastness of the luminescent increases.

Die Lichtechtheit ist dabei ein Maß für die Farbechtheit von Färbungen, Farbstoffen und Drucken gegen die Bleichwirkung des Tageslichts. Die europäische Norm EN ISO 105 B01 beschreibt die Bestimmung der Farbechtheit nach der 8-stufigen Wollskala, die von einer sehr geringen Lichtechtheit (Lichtechtheitstyp 1) bis zu einer hervorragenden Lichtechtheit (Lichtechtheitstyp 8) reicht. Eine Erhöhung um eine Stufe entspricht dabei einer doppelt so guten Lichtbeständigkeit, d. h., wenn eine Probe des Lichtechtheitstyps 4 unter bestimmten Bedingungen in einer gegebenen Zeit eine bestimmte Änderung erfährt, wird eine Probe des Lichtechtheitstyps 3 diese Änderung unter gleichen Bedingungen bereits nach der halben Zeit, eine Probe des Lichtechtheitstyps 5 erst nach einer doppelt so langen Zeit zeigen.The light fastness is a measure of the color fastness of dyeings, dyes and prints against the bleaching effect of daylight. The European standard EN ISO 105 B01 describes the determination of color fastness according to the 8-step wool scale, which ranges from a very low light fastness (light fastness type 1) to an excellent light fastness (light fastness type 8). An increase by one step corresponds to twice as good light stability, d. That is, when a light fastness type sample 4 undergoes a certain change under certain conditions in a given time, a light fastness type sample 3 will undergo this change under the same conditions already after half the time, a light fastness type sample 5 only after twice as long demonstrate.

Im Ausführungsbeispiel der Fig. 2 ist als Lumineszenzstoff 22 der nach UV-Anregung rötlich orange fluoreszierende Stoff LUMILUX® CD 740 von Honeywell (Zusammensetzung: Oxinat) eingesetzt. Es versteht sich, dass auch andere Lumineszenzstoffe, wie beispielsweise der blau fluoreszierende Stoff LUMILUX® CD 329, ein Antranilsäurederivat, oder andere gewünschte Lumineszenzstoffe als Kern verwendet werden können.In the embodiment of FIG. 2, the luminescent substance 22 used is the reddish orange fluorescent substance LUMILUX® CD 740 from Honeywell (composition: oxinate) after UV excitation. It is understood that other luminescent substances, such as, for example, the blue-fluorescent substance LUMILUX® CD 329, an antranilic acid derivative, or other desired luminescent substances, can also be used as core.

Der Lumineszenzstoff 22 ist mit einer organischen Hülle 24 verkapselt, die einen UV-Absorber 26 enthält. Durch die Verkapselung wird zum einen die Beständigkeit des Lumineszenzstoffs gegen Säuren und Alkalien erhöht, und zum anderen die Lichtechtheit des Sicherheitsmerkmals deutlich gesteigert.The luminescent substance 22 is encapsulated with an organic shell 24 containing a UV absorber 26. The encapsulation on the one hand increases the resistance of the luminescent substance to acids and alkalis, and on the other hand significantly increases the light fastness of the security feature.

Zur Herstellung einer solchen organischen Hülle wird beispielsweise ein Polymer bzw. Prepolymer, etwa ein Melamin/Formaldehyd-Harz unter kräftigem Rühren in Wasser dispergiert und eine 10%-ige wässrige Dispersion erzeugt. Anschließend wird in einem Rundkolben unter Rühren, beispielsweise mit einem Teflonrührfisch und einem Magnetrührer portionsweise der Lumineszenzstoff zugegeben. Die Dispersion wird so lange gerührt, bis keine größeren Agglomerate des Lumineszenzstoffs mehr zu sehen sind.To produce such an organic shell, for example, a polymer or prepolymer, for example a melamine / formaldehyde resin, is dispersed with vigorous stirring in water and a 10% strength aqueous dispersion is produced. Subsequently, the luminescent substance is added in portions in a round-bottomed flask with stirring, for example with a Teflon stirring fish and a magnetic stirrer. The dispersion is stirred until no longer visible large agglomerates of the luminescent.

Anschließend wird unter Vakuum und ständigem Rühren langsam das Lösungsmittel Wasser abdestilliert. Der Feststoff wird zerkleinert und zum vollständigen Vernetzen des Polymers 2 Stunden bei 120 °C in einen Umluftheizofen gegeben. Durch das Erhitzen des Stoffes erfolgt gleichzeitig die Trocknung der verkapselten Teilchen. Anschließend kann das Produkt wie ein herkömmliches Pigment weiterverarbeitet werden.Subsequently, the solvent is distilled off slowly under vacuum and constant stirring. The solid is crushed and placed in a convection oven at 120 ° C for 2 hours to fully cure the polymer. By heating the substance, the drying of the encapsulated particles takes place at the same time. Subsequently, the product can be further processed like a conventional pigment.

Als beizumischende UV-Absorber 26 kommen anorganische UV-Absorber, wie etwa TiO2 vorzugsweise nanoskalisches TiO2, oder auch organische UV-Absorber, wie Benzotriazol-Derivate oder geeignete Polymere, wie etwa Polystyrol-Acrylate infrage. Gegebenenfalls wird ein IR-Absorber, insbesondere mit einer Absorption im Spektralbereich zwischen 800 nm und 1100 nm, zugesetzt.Suitable admixing UV absorbers 26 are inorganic UV absorbers, such as TiO 2, preferably nanoscale TiO 2 , or organic UV absorbers, such as benzotriazole derivatives or suitable polymers, such as polystyrene acrylates. If appropriate, an IR absorber, in particular with an absorption in the spectral range between 800 nm and 1100 nm, is added.

Es versteht sich, dass der Lumineszenzstoff 22 und der UV-Absorber 26 so aufeinander abgestimmt werden, dass der Lumineszenzstoff 22 trotz der Schutzwirkung des UV-Absorbers 26 noch angeregt werden kann. Beispielsweise können Lumineszenzstoff 22 und Absorber 26 so gewählt werden, dass das Absorptionsmaximum des Lumineszenzstoffs 22 bei größeren Wellenlängen als das Absorptionsmaximum des UV-Absorbers 26 liegt.It is understood that the luminescent substance 22 and the UV absorber 26 are coordinated so that the luminescent substance 22 despite the Protective effect of the UV absorber 26 can still be stimulated. For example, luminescent substance 22 and absorber 26 can be chosen such that the absorption maximum of the luminescent substance 22 is at longer wavelengths than the absorption maximum of the UV absorber 26.

In einer alternativen Ausgestaltung wird der Lumineszenzstoff 22 über ein Sol-Gel-Verfahren mit einer anorganischen Hülle 24 versehen. Dazu werden beispielsweise in einem organischen Lösungsmittel durch Katalyse teilweise organisch funktionalisierte Silane mittels Säure oder Base hydrolysiert. Das Lumineszenzstoff-Pigment wird mit SiOx umhüllt, die wässrigen Komponenten abgedampft. Ein Temper- bzw. Sinterschritt erfolgt unter Rühren bzw. Mischen um ein Agglomerat zu vermeiden. Eine anorganische Hülle 24 kann auch durch einen Verlackungsprozess erzeugt werden, bei dem der Lumineszenzstoff 22 in Lösung gebracht, auf einen geeigneten anorganischen Träger aufgebracht und anschließend getrocknet wird.In an alternative embodiment, the luminescent substance 22 is provided with an inorganic shell 24 by a sol-gel process. For this purpose, for example, partially organically functionalized silanes are hydrolyzed in an organic solvent by means of acid or base. The luminescent substance pigment is coated with SiO x , the aqueous components evaporated. An annealing or sintering step is carried out with stirring or mixing in order to avoid an agglomerate. An inorganic shell 24 can also be produced by a laking process in which the luminescent substance 22 is solubilized, applied to a suitable inorganic support and then dried.

Wie in Fig. 3 illustriert, kann der Beschichtung 24 weiter ein Merkmalsstoff 28 zugesetzt werden, um die Sicherheit des Aufdrucks 12 zu erhöhen. Im Ausführungsbeispiel der Fig. 3 ist der oben beschriebenen organischen Hülle ein elektrisch leitfähiger Stoff 28 beigemischt, wie etwa Kohlenstoff, Silber, Gold, Kupfer oder dotierte organische Polymere, deren Vorhandensein durch eine Messung des Oberflächenwiderstands oder der Leitfähigkeit abgelösten Pigmentmaterials nachgewiesen werden kann.As illustrated in FIG. 3, further, a feature substance 28 may be added to the coating 24 to increase the security of the imprint 12. In the embodiment of Fig. 3, the above-described organic shell is compounded with an electrically conductive substance 28 such as carbon, silver, gold, copper or doped organic polymers, the presence of which can be detected by measurement of surface resistance or conductivity of detached pigment material.

Es können auch über eine Formerkennung mittels Rasterelektronenmikroskop nachweisbare Merkmalsstoffe, wie etwa Bariumsulfat oder Kreide, verwendet werden, oder IR-Absorber, wie etwa ADS1065A von American Dye Source (Zusammensetzung: C62H92N6F12Sb2). Auch Merkmalsstoffe mit magnetisch nachweisbaren Eigenschaften, wie etwa Weicheisen (Carbonyleisen, Fe2O3) oder Harteisen (Magnetit Fe3O4), kommen in Betracht. Auch weitere, vom Lumineszenzstoff-Kern verschiedene Lumineszenzstoffe können der Hülle als Merkmalsstoff beigemischt werden.Detectable feature substances, such as barium sulfate or chalk, can also be used via a scanning electron microscope shape recognition, or IR absorbers, such as ADS1065A from American Dye Source (composition: C 62 H 92 N 6 F 12 Sb 2 ). Also feature substances with magnetically detectable properties, such as soft iron (carbonyl iron, Fe 2 O 3 ) or hard iron (magnetite Fe3O 4 ), come into consideration. Other luminescent substances other than the luminescent substance core can also be admixed to the shell as a feature substance.

Die Konzentration derartiger Merkmalsstoffe kann von wenigen ppm bis hin zu etwa 50 Gew-% der Beschichtung reichen. Aus Kostengründen und um die Erkennung durch potentielle Fälscher zu erschweren, werden meist geringe Konzentrationen eingesetzt.The concentration of such feature substances can range from a few ppm to about 50% by weight of the coating. For reasons of cost and to make detection difficult by potential counterfeiters, low concentrations are usually used.

Claims (33)

Sicherheitsmerkmal für Sicherheitspapiere, Wertdokumente und dergleichen, mit einem UV-anregbaren organischen Lumineszenzstoff, dadurch gekennzeichnet, dass das Sicherheitsmerkmal Kern-Hülle-Teilchen enthält, bei denen der organische Lumineszenzstoff als Kern mit einer Hülle beschichtet ist, die die chemische und/oder physikalische Beständigkeit des Lumineszenzstoffs erhöht.Security feature for security papers, documents of value and the like, with a UV-excitable organic luminescent material, characterized in that the security feature contains core-shell particles in which the organic luminescent material is coated as a core with a shell, the chemical and / or physical resistance of the luminescent substance increases. Sicherheitsmerkmal nach Anspruch 1, dadurch gekennzeichnet, dass die Hülle die Lichtechtheit des Lumineszenzstoffs erhöht.Security feature according to claim 1, characterized in that the shell increases the light fastness of the luminescent substance. Sicherheitsmerkmal nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Sicherheitsmerkmal auf der 8-stufigen Wollskala eine Lichtechtheit von 3 oder mehr, vorzugsweise eine Lichtechtheit von 5 oder mehr erreicht.Security feature according to claim 1 or 2, characterized in that the security feature on the 8-stage wool scale reaches a light fastness of 3 or more, preferably a light fastness of 5 or more. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Hülle einen UV-Absorber enthält, der die UV-Anregbarkeit des Lumineszenzstoffs nicht oder nicht wesentlich beeinträchtigt.Security feature according to at least one of claims 1 to 3, characterized in that the shell contains a UV absorber that does not or not significantly affect the UV excitability of the luminescent substance. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Hülle als UV-Absorber TiO2, vorzugsweise nanoskalisches TiO2, enthält.Security feature according to at least one of claims 1 to 4, characterized in that the shell contains as UV absorber TiO 2 , preferably nanoscale TiO 2 . Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Hülle als UV-Absorber ein Benzotriazol-Derivat oder ein Polystyrol-Acrylat enthält.Security feature according to at least one of claims 1 to 4, characterized in that the shell contains as UV absorber a benzotriazole derivative or a polystyrene acrylate. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 4 bis 6, dadurch gekennzeichnet, dass die Hülle weiter einen IR-Absorber, insbesondere mit einer Absorption im Spektralbereich zwischen 800 nm und 1100 nm, enthält.Security feature according to at least one of claims 4 to 6, characterized in that the shell further contains an IR absorber, in particular with an absorption in the spectral range between 800 nm and 1100 nm. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 4 bis 7, dadurch gekennzeichnet, dass das Absorptionsmaximum des Lumineszenzstoffs bei größeren Wellenlängen als das Absorptionsmaximum des UV-Absorbers liegt.Security feature according to at least one of claims 4 to 7, characterized in that the absorption maximum of the luminescent substance is at longer wavelengths than the absorption maximum of the UV absorber. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass der Lumineszenzstoff nach UV-Anregung im roten oder blauen Spektralbereich luminesziert.Security feature according to at least one of claims 1 to 8, characterized in that the luminescent substance luminesces after UV excitation in the red or blue spectral range. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass der Lumineszenzstoff ein Benzoxazinonderivat, ein Oxinat, ein Anthranilsäurederivat oder ein organischer Selten-Erden-Komplex ist.Security feature according to at least one of Claims 1 to 9, characterized in that the luminescent substance is a benzoxazinone derivative, an oxinate, an anthranilic acid derivative or an organic rare earth complex. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der Lumineszenzstoff mit einer organischen Hülle beschichtet ist, vorzugsweise dass die organische Hülle Polystyrol, SBS, Polycarbonat, PVC, TPU, ABS oder PMMA enthält.Security feature according to at least one of claims 1 to 10, characterized in that the luminescent substance is coated with an organic shell, preferably that the organic shell contains polystyrene, SBS, polycarbonate, PVC, TPU, ABS or PMMA. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass der Lumineszenzstoff mit einer anorganischen Hülle beschichtet ist.Security feature according to at least one of claims 1 to 10, characterized in that the luminescent substance is coated with an inorganic shell. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass der Lumineszenzstoff mit zwei oder mehr unterschiedlichen organischen und/ oder anorganischen Hüllen beschichtet ist.Security feature according to at least one of claims 1 to 12, characterized in that the luminescent substance is coated with two or more different organic and / or inorganic shells. Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass die Beschichtung einen Merkmalsstoff enthält.Security feature according to at least one of claims 1 to 13, characterized in that the coating contains a feature substance. Sicherheitsmerkmal nach Anspruch 14, dadurch gekennzeichnet, dass der Merkmalsstoff in der Beschichtung in einer Konzentration zwischen 1 ppm und 50 Gew-% vorliegt.Security feature according to claim 14, characterized in that the feature substance is present in the coating in a concentration between 1 ppm and 50% by weight. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff ein Lumineszenzstoff ist, insbesondere ein Lumineszenzstoff ist, der ein anderes Anregungs- und/ oder Emissionsspektrum aufweist als der organische Lumineszenzstoff im Kern.Security feature according to claim 14 or 15, characterized in that the feature substance is a luminescent substance, in particular a luminescent substance, which has a different excitation and / or emission spectrum than the organic luminescent substance in the core. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff ein löslicher Stoff ist.Security feature according to claim 14 or 15, characterized in that the feature substance is a soluble substance. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff spezifische Formkörper enthält.Security feature according to claim 14 or 15, characterized in that the feature substance contains specific shaped bodies. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff lichtpolarisierend ist.Security feature according to claim 14 or 15, characterized in that the feature substance is lichtpolarisierend. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff ein Infrarotabsorber ist.Security feature according to claim 14 or 15, characterized in that the feature substance is an infrared absorber. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff magnetisch ist.Security feature according to claim 14 or 15, characterized in that the feature substance is magnetic. Sicherheitsmerkmal nach Anspruch 14 oder 15, dadurch gekennzeichnet, dass der Merkmalsstoff elektrisch leitfähig ist.Security feature according to claim 14 or 15, characterized in that the feature substance is electrically conductive. Verfahren zum Herstellen eines Sicherheitsmerkmals für Sicherheitspapiere, Wertdokumente und dergleichen, bei dem ein UV-anregbarer, organischer Lumineszenzstoff als Kern mit einer Hülle beschichtet wird, die die chemische und/ oder physikalische Beständigkeit des Lumineszenzstoffs erhöht.A method for producing a security feature for security papers, documents of value and the like, in which a UV-stimulable, organic luminescent substance is coated as a core with a shell, which increases the chemical and / or physical resistance of the luminescent substance. Verfahren nach Anspruch 23, dadurch gekennzeichnet, dass der Lumineszenzstoff mit einer organischen Hülle beschichtet wird.A method according to claim 23, characterized in that the luminescent substance is coated with an organic shell. Verfahren nach Anspruch 24, dadurch gekennzeichnet, dass die Beschichtung mittels Emulsionspolymerisation erfolgt.A method according to claim 24, characterized in that the coating takes place by means of emulsion polymerization. Verfahren nach Anspruch 24, dadurch gekennzeichnet, dass die Beschichtung erfolgt durch a) Lösen oder Dispergieren der zu beschichtenden Polymere in Lösungsmittel, b) Mischen mit dem Lumineszenzstoff, c) Abdampfen des Lösungsmittels bzw. Erstarren und d) trocken Vermahlen.A method according to claim 24, characterized in that the coating is carried out by a) dissolving or dispersing the polymers to be coated in solvent, b) mixing with the luminescent substance, c) evaporation of the solvent or solidification and d) dry grinding. Verfahren nach Anspruch 26, dadurch gekennzeichnet, dass das zu beschichtende Polymer thermoplastisch ist oder aufgeschmolzen werden kann und dass nach dem Schritt d) ein Temperschritt zum Verschließen eventueller Kapillaren durchgeführt wird.A method according to claim 26, characterized in that the polymer to be coated is thermoplastic or can be melted and that after step d) an annealing step for closing any capillaries is performed. Verfahren nach Anspruch 24, dadurch gekennzeichnet, dass die Beschichtung erfolgt durch a) In-Lösung-Bringen der zu beschichtenden Polymere und einem Vernetzer, b) Einmischen des Lumineszenzstoffes, c) Vernetzen, d) Trocknen und Vermahlen.A method according to claim 24, characterized in that the coating is carried out by a) in-solution bringing the polymers to be coated and a crosslinker, b) mixing the luminescent substance, c) crosslinking, d) drying and milling. Verfahren nach Anspruch 24, dadurch gekennzeichnet, dass die Beschichtung erfolgt durch a) In-Schmelze-Bringen der zu beschichtenden Polymere und gegebenenfalls eines Vernetzers, b) Einmischen des Lumineszenzstoffes, c) Vernetzen, d) Trocknen und Vermahlen.A method according to claim 24, characterized in that the coating is carried out by a) in-melt bringing the polymers to be coated and optionally a crosslinker, b) mixing the luminescent substance, c) crosslinking, d) drying and milling. Verfahren nach Anspruch 23, dadurch gekennzeichnet, dass der Lumineszenzstoff in einem Sol-Gel-Verfahren mit einer anorganischen Hülle beschichtet wird.A method according to claim 23, characterized in that the luminescent substance is coated in a sol-gel process with an inorganic shell. Verfahren nach Anspruch 23, dadurch gekennzeichnet, dass zur Bildung des Kerns der Lumineszenzstoff in Lösung gebracht und auf einen anorganischen Träger aufgezogen wird.A method according to claim 23, characterized in that the luminescent substance is brought into solution to form the core and grown on an inorganic support. Sicherheitspapier für die Herstellung von Sicherheits- oder Wertdokumenten, wie Banknoten, Schecks, Ausweiskarten, Urkunden und dergleichen, dadurch gekennzeichnet, dass es mit einem Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 22 ausgestattet ist.Security paper for the production of security or value documents, such as banknotes, checks, identity cards, certificates and the like, characterized in that it is equipped with a security feature according to at least one of claims 1 to 22. Datenträger, insbesondere Markenartikel, Wertdokument oder dergleichen, der mit einem Sicherheitsmerkmal nach wenigstens einem der Ansprüche 1 bis 22 ausgestattet ist.Data carrier, in particular branded article, value document or the like, which is equipped with a security feature according to at least one of claims 1 to 22.
EP07003502A 2006-02-22 2007-02-20 Security feature for valuable documents Withdrawn EP1826730A3 (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2169650A1 (en) * 2008-09-29 2010-03-31 Giesecke & Devrient GmbH Safety marking for securing valuable objects
DE102012003601A1 (en) 2012-02-21 2013-08-22 Giesecke & Devrient Gmbh Printing process with Passer between print and watermark
WO2014005686A3 (en) * 2012-07-03 2014-04-03 Giesecke & Devrient Gmbh Value document, method for checking the presence of same and value document system
WO2015043761A3 (en) * 2013-09-27 2015-06-25 Giesecke & Devrient Gmbh Value document and method for verification of the presence thereof
WO2015043760A3 (en) * 2013-09-27 2015-06-25 Giesecke & Devrient Gmbh Document of value and method for verifying the presence thereof
WO2017080654A1 (en) * 2015-11-11 2017-05-18 Giesecke & Devrient Gmbh Pigment system, luminescent dye system, and value document

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013206130B4 (en) * 2013-04-08 2018-06-21 Bundesdruckerei Gmbh Multiluminescent security element and value or security document containing the same
DE102015014537A1 (en) 2015-11-11 2017-05-11 Giesecke & Devrient Gmbh Security pigment based on core-shell particles and manufacturing process
DE102015014539A1 (en) 2015-11-11 2017-05-11 Giesecke & Devrient Gmbh Security pigment based on core-shell particles and manufacturing process
DE102015014526A1 (en) 2015-11-11 2017-05-11 Giesecke & Devrient Gmbh A security pigment, a luminescent polymer resin and a process for producing the same
DE102015014525A1 (en) 2015-11-11 2017-05-11 Giesecke & Devrient Gmbh Security pigment based on core-shell particles and method of making same
DE102021003985A1 (en) 2021-08-03 2023-02-09 Giesecke+Devrient Currency Technology Gmbh Luminescent printing ink for security printing, object with a luminescent feature and manufacturing process

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005108110A1 (en) 2004-05-05 2005-11-17 Giesecke & Devrient Gmbh Layer-type value document comprising an ink mixture in one layer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3801782A (en) * 1968-10-01 1974-04-02 American Cyanamid Co Method of selectively generating fluorescence and its subsequent detection
FR2840094A1 (en) * 2002-05-23 2003-11-28 A S K Credit or identity card has layer between outer layers which under ultra violet light reveals distinctive pattern of fluorescent and non-fluorescent marks and may also support antenna

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005108110A1 (en) 2004-05-05 2005-11-17 Giesecke & Devrient Gmbh Layer-type value document comprising an ink mixture in one layer

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2169650A1 (en) * 2008-09-29 2010-03-31 Giesecke & Devrient GmbH Safety marking for securing valuable objects
DE102012003601A1 (en) 2012-02-21 2013-08-22 Giesecke & Devrient Gmbh Printing process with Passer between print and watermark
WO2013124059A1 (en) 2012-02-21 2013-08-29 Giesecke & Devrient Gmbh Method with register between print element and water mark
AU2013286338B2 (en) * 2012-07-03 2016-05-12 Giesecke+Devrient Currency Technology Gmbh Value document, method for checking the presence of same and value document system
CN104411505B (en) * 2012-07-03 2016-06-29 德国捷德有限公司 Value document, for checking the method and value document system that value document exists
RU2615262C2 (en) * 2012-07-03 2017-04-04 Гизеке Унд Девриент Гмбх Valuable document, verification method if any and system of valuable documents
CN104411505A (en) * 2012-07-03 2015-03-11 德国捷德有限公司 Value document, method for checking the presence of same and value document system
US9327542B2 (en) 2012-07-03 2016-05-03 Giesecke & Devrient Gmbh Value document, method for checking the presence of same and value document system
WO2014005686A3 (en) * 2012-07-03 2014-04-03 Giesecke & Devrient Gmbh Value document, method for checking the presence of same and value document system
US9542788B2 (en) 2013-09-27 2017-01-10 Giesecke & Devrient Gmbh Value document and method for checking the presence of the same
WO2015043760A3 (en) * 2013-09-27 2015-06-25 Giesecke & Devrient Gmbh Document of value and method for verifying the presence thereof
US9540772B2 (en) 2013-09-27 2017-01-10 Giesecke & Devrient Gmbh Value document and method for checking the presence of the same
WO2015043761A3 (en) * 2013-09-27 2015-06-25 Giesecke & Devrient Gmbh Value document and method for verification of the presence thereof
WO2017080654A1 (en) * 2015-11-11 2017-05-18 Giesecke & Devrient Gmbh Pigment system, luminescent dye system, and value document
CN108349281A (en) * 2015-11-11 2018-07-31 捷德货币技术有限责任公司 Pigments system, luminescent dye system and valuable document
US10953684B2 (en) 2015-11-11 2021-03-23 Giesecke+Devrient Currency Technology Gmbh Pigment system, luminescent dye system, and value document
CN108349281B (en) * 2015-11-11 2021-04-27 捷德货币技术有限责任公司 Pigment system, luminescent dye system and value document

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