EP2059397B1 - Security and/or valuable document having sers-active particles - Google Patents

Security and/or valuable document having sers-active particles Download PDF

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Publication number
EP2059397B1
EP2059397B1 EP07801330.7A EP07801330A EP2059397B1 EP 2059397 B1 EP2059397 B1 EP 2059397B1 EP 07801330 A EP07801330 A EP 07801330A EP 2059397 B1 EP2059397 B1 EP 2059397B1
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EP
European Patent Office
Prior art keywords
security
sers
particles
valuable document
active
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EP07801330.7A
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German (de)
French (fr)
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EP2059397A2 (en
Inventor
Malte Pflughoefft
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Bundesdruckerei GmbH
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Bundesdruckerei GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B42D25/373—Metallic materials
    • B42D2035/34—

Definitions

  • the invention relates to a security and / or value document containing at least one security feature which is mounted in a defined spatial position in the security and / or value document, a method for producing such a security and / or value document, a method for verifying such a security - And / or value document and an ink for producing such a security and / or value document.
  • the Raman effect is based on the scattering of electromagnetic radiation, in particular light, at a scattering center, wherein absorption of a portion of the incident radiation by excitation of rotations or vibrations of the scattering center takes place simultaneously with the scattered pulse change of the scattered radiation with respect to the incident radiation.
  • This energy transfer distinguishes the Raman effect from the Rayleigh scattering, in which no energy transfer takes place, but only a scattered pulse change.
  • Raman spectroscopy A further development of Raman spectroscopy is the so-called surface-enhanced Raman spectroscopy (SERS).
  • SERS surface-enhanced Raman spectroscopy
  • an amplification of the Raman signal by a factor of 10 6 to 10 12 achieved in that the scattering centers are brought into contact with certain rough metal surfaces, typically metallic nanoparticles, such as Ag, Au, or Cu nanoparticles.
  • metallic nanoparticles such as Ag, Au, or Cu nanoparticles.
  • This effect is associated with the resonant excitation of surface plasmons.
  • An overview of the electromagnetic theory of SERS and the various processes involved is, for example, the reference M. Moskovits, Journal of Raman Spectroscopy 36: 485-496 (2005 ) removable.
  • the SERS effect is used, for example, in particles that are in the reference US-2002/0104762 are described. These can be formed for example as nanobar codes, wherein the particles are formed as a few ⁇ m long rods, which are composed of layers of different materials and thereby form the barcode. When measuring with sufficient local resolution ( ⁇ 1 ⁇ m), the barcode can be read out.
  • the rods can be coated with a reporter substance to increase sensitivity and selectivity, resulting in an intense and environmentally independent signal or signal sequence. Such particles are discussed for use in product protection.
  • the document WO 91/11492 A discloses particles associated with resonant Raman scattering. A similar technology is in the document WO 91/11703 A described.
  • the document US 6,259,509 B1 discloses a security element utilizing the Raman effect.
  • the document EP 0786498 A describes pigments with different Raman spectra.
  • the invention is based on the technical problem of specifying a security and / or value document which can be examined and verified in a particularly simple manner by means of SERS and without changing the security and / or value document.
  • the invention is based on the further technical problem of specifying a security and / or value document whose analyzability with SERS is not limited to the surface.
  • the invention is based on the technical problem of providing a particularly simple and inexpensive security and / or valuable document which can be verified by means of SERS.
  • the invention teaches the subject matter of claim 1.
  • value and / or security document includes in the invention in particular identity cards, passports, ID cards, access control cards, visas, tax stamps, tickets, driver's licenses, motor vehicle papers, banknotes, checks, postage stamps, credit cards, any smart cards and adhesive labels (eg product assurance).
  • security and / or value documents typically have a substrate, a printing layer and optionally a transparent cover layer.
  • a substrate is a support structure to which the print layer is applied with information, images, patterns, and the like.
  • a substrate may be single-layered or multi-layered. Suitable materials for a substrate or a substrate layer are all customary materials based on paper and / or plastic in question.
  • a security feature is a subarea (area or volume) of the security and / or value document that can be used to verify the security and / or value document.
  • the subarea can be structureless, but it can also be a pattern.
  • Such a pattern may be a similar pattern for different security and / or value documents. Then, the pattern is suitable for verification of one type of security and / or valuable document. Examples of such document type-specific lateral patterns are: seals, coats of arms, regular or irregular surface patterns, such as line coats or guilloches, 1D and 2D barcodes.
  • the pattern may be visible or um Under normal light patterns that are not visible under normal light, whereby the invisible patterns differ from the visible patterns in that the non-visible patterns first become visible by means of technical aids, such as the UV source.
  • the pattern can also be an individual pattern for different security and / or value documents (of the same document type), which pattern is coded in particular for identification information of the security and / or value document.
  • the following (pattern coded) data may be considered: alphanumeric strings, such as personal records, parts of personal records, such as names, first names, address, date of birth, place of birth, and / or document data, pieces of document data, such as serial number, issuing office, Date of issue, expiry date, and other data, in particular digital data, public key (in the case of a document with readable chip or for access to centralized or decentralized databases) and / or checksums, and biometric data such as photographs, fingerprints, vein patterns, for example, by hand or a finger, iris and / or retina. It is preferably a character string that uniquely identifies the document and / or the document carrier.
  • this string can also be a string not otherwise shown in the document. It is also possible to provide a plurality of patterns which can overlap one another (laterally) and can nevertheless be read out separately on the basis of the detected Raman spectra. Of course, it is also possible to provide a plurality of patterns which do not overlap each other (laterally). In both cases, in particular combinations of document type-specific patterns and individual patterns are possible and preferred.
  • SERS-active particles are particles which, on contacting the particles with a substance to be examined by Raman spectroscopy, have an increased signal intensity of at least 10 3 , in particular by at least 10 5 , compared with a Raman signal on the substance without contact with SERS active particles. It is essential to understand that the intensity of an SERS signal is by no means a function of the concentration or density of the SERS active particles. If a SERS signal is obtained due to a SERS-active particle, the addition of further SERS-active particles does not result in a significant increase in the SERS signal. For this purpose, in addition to the reference M. Moskovits, Journal of Raman Spectroscopy 36: 485-496 (2005 ).
  • a Raman signal with high signal intensity which is specific for the security feature can be obtained, without having to previously prepare or otherwise modify the security and / or value document in any way.
  • the security and / or value document remains completely unchanged as a result of the examination of the security feature and can still be used.
  • a repeated examination of the security feature or of the security and / or value document can take place without any changes of the security and / or value document, in contrast to the known preparation of the security and / or value document with a colloidal solution.
  • Verification can be quick and easy.
  • the positioning of the security feature or its examination is not limited to the surface of the security and / or value document. Rather, the security feature can be arranged at any point of the security and / or value document, even in the volume.
  • the security feature can be set up in the substrate, in a printing layer or in a generally transparent cover layer of the security and / or value document.
  • the SERS-active particles are introduced at the desired location or layer for the security feature, which is easily possible in the course of the production process of the substrate or a print layer or cover layer.
  • the SERS signal then originates from the material matrix surrounding the SERS active particles, which typically contains organic polymers which are Raman active.
  • the SERS active particles contain metallic copper, silver, gold, alkali metal, and / or coin metal. It may also be alloys with one or more such metals. They may consist of this, but also in the context of composite particles, such as core-shell particles, be set up.
  • Non-exhaustive examples include: coated with said metals or alloys inorganic particles, such as oxide particles, for example of SiO 2 , or polymer particles.
  • the SERS-active particles typically have a volume in the range of 1 nm 3 to 10 9 nm 3 , preferably from 1 nm 3 to 10 5 nm 3 , most preferably from 1 nm 3 to 10 3 nm 3 . It should be noted that SERS-active particles are typically clusters of nanoparticles (with a volume of up to 10 9 nm 3 ) of the metals in question.
  • their number in the volume unit of the security feature is in the range of 10 -6 or 10 -3 particles / ⁇ m 3 to 10 9 particles / ⁇ m 3 , in particular in the range of 10 particles / ⁇ m 3 to 10 6 particles / ⁇ m 3 , preferably in the range of 10 2 particles / ⁇ m 3 to 10 4 particles / ⁇ m 3 , is located.
  • the particles do not have a cladding layer with a Raman active substance, but are directly contacted with a polymer of a polymer layer or ink, this polymer itself being Raman active. This allows a simple and cost-effective production of the security and / or value document.
  • information about the materials of the examined safety and / or value document is obtained on the basis of the Raman spectra or resonances so that verification (with materials that are true to the original) or detection of counterfeiting (with materials that are not true to the original) can be carried out easily.
  • Raman-active means that a Raman spectrum or specific resonance frequency specific to the polymer layer or color or ink is obtained.
  • a Raman active material may be a synthetic organic polymer having one or more functional groups (such as, but not limited to, carbonyl, carboxyl, hydroxy, thiol, ether, thioether, nitro, nitroso, sulfonyl, sulfo, Phospho, phosphonyl, amino, etc.).
  • the functional group (s) may also be, for example, aromatics, conjugated aromatics and heterocycles such as quinolinyl, dioxanyl, furanyl, imidazolyl, indolyl, morpholinyl, oxazolyl, oxiranyl (ethylene oxide), piperidinyl, porphyrinyl, purinyl, pyranyl , Pyrazolyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, thiazolyl, thiazolidinyl, thiazolinyl, thiophenyl, trizinyl, triazolyl, trioxanyl, or isoforms of such groups, substituted or unsubstituted.
  • aromatics conjugated aromatics and heterocycles
  • quinolinyl dioxanyl
  • furanyl imidazolyl
  • indolyl morpholinyl
  • a security feature there are various possibilities. It can be simple or multiple. With multiple devices, the security features may be the same or different with respect to the SERS signal. Various security features are obtained, for example, in that the SERS-active particles in different matrices of the security and / or value document are embedded.
  • An inventive security feature can be arranged at any position of the security and / or value document. Thus, it can be arranged in a substrate or any substrate layer in the case of multilayer substrates, a printing layer and / or a cover layer, ie at any depth.
  • the shape of the security feature which is determined by the distribution of the SERS-active particles, can be arbitrary.
  • the security feature can be a homogeneous security feature, ie the distribution of the SERS-active particles is homogeneous within the security feature.
  • the security feature can also form a pattern, ie the distribution of the SERS-active particles is inhomogeneous (typically in a lateral direction, ie in directions parallel to a main surface of the security and / or value document) and forms the pattern. Then by spatially resolved SERS not only a verification of the SERS signal per se, but also on the specific pattern and its evaluation and comparison with target patterns done.
  • Several security features may be implemented in different layers (including the substrate) of the security and / or value document, ie at different depths.
  • the invention further relates to a method for producing a security and / or value document according to the invention, wherein SERS-active particles during the production of the security and / or value document therein in a defined spatial position or at several different defined spatial positions, lateral or related on the depth or layer, are introduced.
  • SERS-active particles during the production of the security and / or value document therein in a defined spatial position or at several different defined spatial positions, lateral or related on the depth or layer, are introduced.
  • SERS-active particles during the production of the security and / or value document therein in a defined spatial position or at several different defined spatial positions, lateral or related on the depth or layer, are introduced.
  • SERS-active particles during the production of the security and / or value document therein in a defined spatial position or at several different defined spatial positions, lateral or related on the depth or layer, are introduced.
  • the security feature is made by pressure and it can also easily form any defined pattern of the security feature.
  • Suitable printing methods for producing such a security feature are
  • the invention further relates to a method for verifying a security and / or value document according to the invention, wherein the security feature is subjected to a SERS examination and the resulting SERS spectrum or SERS signal having a desired SERS spectrum or a desired SERS signal is compared.
  • the desired SERS spectrum or desired SERS signal can be stored in a database and retrievable. If there is a match, the examined security and / or value document is verified; if it does not match, it is recognized as a forgery and can be confiscated or rejected.
  • verification can also take place via the detected position of the security feature within the security and / or value document by performing a spatially resolved SERS measurement and aligning the security and / or value document in a defined manner. In the case of verification by means of spatial resolution, instead of the measurement of the spectrum, a spatially resolved measurement can take place at one (or more) fixed (resonance) frequency, as is familiar to the person skilled in the art.
  • the verification takes place via the material characterization of the substance surrounding the SERS-active particles.
  • the presence or absence of a Raman-active substance in the SERS-active particles is determined, which is recommended, for example, in the spatially resolved examination.
  • the SERS examination can also be performed spatially resolved, for example by means of confocal Raman microscopy. This also makes it possible to pattern capture or detect a security feature executed as a pattern and with a desired pattern, stored in a database or attached to or in the security and / or value document patterns or information calculated or taken, to compare. If the pattern also matches, the examined security and / or value document is verified; if it does not match, it is recognized as a forgery even with per se SERS spectra or signals and can be confiscated or rejected.
  • these can each be subjected to a SERS examination, and the SERS spectra or SERS signals obtained are then compared with desired SERS spectra or signals respectively assigned to the spatial positions.
  • the pattern recognition described above can additionally take place with one or more of the security features, provided that these are designed as a pattern.
  • the invention relates to an ink or ink according to claim 11.
  • the further constituents of inks of the invention are in accordance with the components of inks and inks known in the art and typically comprise the usual other components of paints or inks, such as binders , Penetrants, adjusters, biocides, surfactants, buffering agents, solvents (water and / or organic solvents), fillers, pigments, dyes, effect pigments, antifoaming agents, anti-settling agents, UV stabilizers, etc.
  • Suitable color and ink formulations for various printing processes are One of ordinary skill in the art is well aware of and uses SERS-active ones employed in the present invention In this respect, particles are mixed in place or in addition to conventional dyes or pigments.
  • the proportion of the SERS active particles in the ink may be, for example, in the range of 0.00001 to 50% by weight, preferably 0.001 to 10% by weight, most preferably 0.001 to 2% by weight, based on the total weight of the ink between color.
  • Example 1 Lamination of SERS-active particles in two plastic layers.
  • FIGS. 1a and 1b show the production of a security feature according to the invention between two layers (substrate layers or substrate layer and cover layer).
  • SERS-active particles 1 for example Au nanoparticles, without further components except, if appropriate, a solvent in which the SERS-active particles 1 are suspended are applied to a first Raman-active polymer layer 2, for example by means of a Printing technology ( FIG. 1a ).
  • a second, optionally also Raman-active, polymer layer 3 preferably of the same polymer as that of the first polymer layer 2, is placed.
  • first polymer layer 2 and the second polymer layer 3 laminated together for example by gluing or welding ( FIG. 1b ).
  • first polymer layer 2 and / or the second polymer layer 3 carries an adhesive layer not shown for the sake of clarity.
  • a security and / or value document containing the illustrated first polymer layer 2 and second polymer layer provides SERS spectra or signals due to the Raman activity of the polymer material contacted with the SERS active particles, which are therefore specific for this purpose.
  • SERS spectrum provides information about the polymer material. If the SERS spectrum does not correspond to a SERS nominal spectrum of the polymer material used for genuine documents, then the examined security and / or value document contains a polymer material that is different from genuine security and / or value documents, whereby the counterfeiting is recognized can.
  • the spatial arrangement, laterally (in directions of the main plane of the layers 2, 3) and / or with respect to the depth (in directions orthogonal to the Main plane of the layers 2, 3) of the security feature forming SERS-active particles are determined and compared with a desired arrangement.
  • Example 2 Lamination of a color or ink with SERS-active particles in two plastic layers.
  • This example is substantially similar to Example 1, except that the SERS active particles 1 is colored or inked with a synthetic organic polymer-based component different from the polymer material of the first polymer layer 2 and the second polymer layer 3 , are printed on the first polymer layer 2. As a result, a printing layer 4 is formed ( Fig. 2 ). On this print layer 4, the second polymer layer 3 is then laminated.
  • the security feature is arranged inside the security and / or value document thus formed and can not be worn or rubbed off. In addition, a manipulation is at least difficult.
  • the analog information according to Example 1 can be obtained for verification purposes.
  • the security and / or value document at another position contains an area with the same color or ink, but no SERS-active particles 1 are contained in the ink, or a color or ink with same-looking color.
  • it is not visually apparent at which position the security feature is set up, which makes forgery more difficult.
  • it can be determined by comparison of SERS signals or spectra, which are obtained on areas with ink or color without SERS-active particles 1 and on a security feature according to the invention, whether an adjustment and / or manipulation of the security and / or or value document was carried out.
  • Example 3 Security and / or value document with several security features
  • FIG. 3 shows a security and / or value document according to the invention, wherein a plurality of regions 6, 7, 8 are arranged at different positions, laterally and with respect to the depth, with SERS-active particles 1. It can further be seen that various layers 9, 10, 11, 12 are set up within the framework of the security and / or value document. Within the scope of the areas 6, 7, 8, the variants of examples 1 to 3 can be set up independently of one another and each other, which is not shown for the sake of clarity.
  • the areas 6, 7, 8 form a defined three-dimensional pattern.
  • Pattern recognition and thus verification can be performed two-dimensionally or three-dimensionally using, for example, confocal Raman microscopy.
  • the establishment of such a pattern, in particular three-dimensional makes a difficult
  • SERS spectra of a region 6, 7, 8 or multiple regions 6, 7, 8 can also be recorded, whereby a verification of the above-described characterization of the substance in contact with the SERS-active particles 1 takes place.
  • Such a combination provides extremely high protection against readjustment and manipulation.
  • Example 4 Ink according to the invention
  • the total content of water considering the water introduced with the cartasol is 30% by weight based on the total amount of ink.
  • the use of cartasol also contains 1% by weight of acetic acid, based on the total amount of ink.

Description

Gebiet der ErfindungField of the invention

Die Erfindung betrifft ein Sicherheits- und/oder Wertdokument enthaltend zumindest ein Sicherheitsmerkmal welches in definierter räumlicher Position in dem Sicherheits- und/oder Wertdokument angebracht ist, ein Verfahren zur Herstellung eines solchen Sicherheits- und/oder Wertdokumentes, ein Verfahren zur Verifizierung eines solchen Sicherheits- und/oder Wertdokumentes sowie eine Tinte zur Herstellung eines solchen Sicherheits- und/oder Wertdokumentes.The invention relates to a security and / or value document containing at least one security feature which is mounted in a defined spatial position in the security and / or value document, a method for producing such a security and / or value document, a method for verifying such a security - And / or value document and an ink for producing such a security and / or value document.

Stand der Technik und Hintergrund der ErfindungPrior art and background of the invention

Der Raman-Effekt beruht auf der Streuung von elektromagnetischer Strahlung, insbesondere Licht, an einem Streuzentrum, wobei zugleich mit der streubedingten Impulsänderung der gestreuten Strahlung gegenüber der eingestrahlten Strahlung eine Absorption eines Teiles der eingestrahlten Strahlung durch Anregung von Rotationen oder Schwingungen des Streuzentrums erfolgt. Dieser Energieübertrag unterscheidet den Raman-Effekt von der Rayleigh-Streuung, bei welcher kein Energieübertrag stattfindet, sondern ausschließlich eine streubedingte Impulsänderung. Die physikalischen Zusammenhänge sind beispielsweise der Literaturstelle P.W. Atkins, Physikalische Chemie, 2. Auflage, VCH, Weinheim, New York, Basel, Cambridge, Tokyo, 1996, Seiten 531 ff ., oder Hesse, Meier, Zeeh, Spektroskopische Methoden in der organischen Chemie, 5. Auflage, Thieme Verlag, Stuttgart, 1995, Seiten 66ff ., näher erläutert. Die Raman-Spektroskopie wird insbesondere zur Charakterisierung organischer Stoffe verwendet, wobei das erhaltene Spektrum spezifisch für den analysierten Stoff ist. Die Raman-Spektroskopie ist auch zur Charakterisierung der Stoffe einer Festkörperoberfläche gut geeignet.The Raman effect is based on the scattering of electromagnetic radiation, in particular light, at a scattering center, wherein absorption of a portion of the incident radiation by excitation of rotations or vibrations of the scattering center takes place simultaneously with the scattered pulse change of the scattered radiation with respect to the incident radiation. This energy transfer distinguishes the Raman effect from the Rayleigh scattering, in which no energy transfer takes place, but only a scattered pulse change. The physical relationships are, for example, the literature PW Atkins, Physical Chemistry, 2nd edition, VCH, Weinheim, New York, Basel, Cambridge, Tokyo, 1996, pages 531 et seq ., or Hesse, Meier, Zeeh, Spectroscopic Methods in Organic Chemistry, 5th Edition, Thieme Verlag, Stuttgart, 1995, pages 66ff ., explained in more detail. Raman spectroscopy is used in particular for the characterization of organic substances, the spectrum obtained being specific for the substance being analyzed. Raman spectroscopy is also well suited for characterizing the materials of a solid surface.

Eine Weiterbildung der Raman-Spektroskopie ist die sogenannte surface-enhanced Raman Spectroscopy (SERS). Hierbei wird eine Verstärkung des Raman-Signals um einen Faktor 106 bis 1012 dadurch erreicht, dass die Streuzentren in Kontakt mit bestimmten rauhen Metalloberflächen, typischerweise metallische Nanopartikel, wie Ag-, Au-, oder Cu-Nanopartikel gebracht werden. Dieser Effekt wird mit der resonanten Anregung von Oberflächen-Plasmonen in Verbindung gebracht. Eine Übersicht zur elektromagnetischen Theorie der SERS sowie der verschiedenen Prozesse, die involviert sind, ist beispielsweise der Literaturstelle M. Moskovits, Journal of Raman Spectroscopy 36:485-496 (2005 ) entnehmbar.A further development of Raman spectroscopy is the so-called surface-enhanced Raman spectroscopy (SERS). In this case, an amplification of the Raman signal by a factor of 10 6 to 10 12 achieved in that the scattering centers are brought into contact with certain rough metal surfaces, typically metallic nanoparticles, such as Ag, Au, or Cu nanoparticles. This effect is associated with the resonant excitation of surface plasmons. An overview of the electromagnetic theory of SERS and the various processes involved is, for example, the reference M. Moskovits, Journal of Raman Spectroscopy 36: 485-496 (2005 ) removable.

Aus den Literaturstellen WO2000/055586 , WO2001/038858 , US-6,275,285 und US-2002/0048013 ist ein Raman-Mikroskop zur automatischen Materialuntersuchung von Dokumenten und Banknoten bekannt. Hierbei wird das Raman-Signal eines Probenbereichs gemessen, welches aus Tinten oder Substratmaterialien herrührt, analysiert und mit einer Datenbank verglichen. Dabei werden die normalerweise in einem Dokument anwesenden Substanzen untersucht.From the literature WO2000 / 055586 . WO2001 / 038858 . US 6,275,285 and US-2002/0048013 is a Raman microscope for automatic material examination of documents and banknotes known. Here, the Raman signal of a sample area derived from inks or substrate materials is measured, analyzed and compared to a database. The substances normally present in a document are examined.

Aus der Literaturstelle US-6,995,839 ist ein Scanner-System zur Raman-Untersuchung von Dokumenten bekannt, wobei die normalerweise in dem Dokument verwendeten Materialien anhand des Raman-Signals identifiziert und so das Dokument verifiziert wird.From the literature US 6,995,839 is a scanner system for Raman examination of documents known, wherein the materials normally used in the document identified by the Raman signal and so the document is verified.

Aus den Literaturstellen WO2005/114152 und US-2005/0255599 ist ein Raman-aktives Markierungssystem auf Basis von Polymeren bekannt, wobei die Raman-aktive Markierung mittels eines Lesegerätes durch Einstrahlung von elektromagnetischen Wellen gelöscht werden kann. Aus der Literaturstelle US-5,935,755 ist ein Raman-Markierungssystem mit aromatischen Molekülen, beispielsweise konjugierten aromatischen Molekülen, bekannt, welche mittels Xerographie aufgebracht sind.From the literature WO2005 / 114152 and US-2005/0255599 discloses a Raman-active labeling system based on polymers, wherein the Raman-active label can be erased by means of a reader by irradiation of electromagnetic waves. From the literature US 5,935,755 For example, a Raman labeling system is known with aromatic molecules, such as conjugated aromatic molecules, which are deposited by xerography.

Der SERS Effekt wird beispielsweise bei Partikeln verwendet, die in der Literaturstelle US-2002/0104762 beschrieben sind. Diese sind beispielsweise als Nanobarcodes ausbildbar, wobei die Partikel als einige µm lange Stäbchen ausgebildet sind, die aus Schichten verschiedener Materialien aufgebaut sind und dadurch den Barcode bilden. Bei einer Messung mit hinreichender örtlicher Auflösung (< 1µm) kann der Barcode ausgelesen werden. Die Stäbchen können zur Erhöhung der Sensitivität und der Selektivität mit einem Reporterstoff beschichtet sein, wodurch sich ein intensives und von der Umgebung unabhängiges Signal bzw. Signalfolge ergibt. Solche Partikel werden für den Einsatz im Produktschutz diskutiert.The SERS effect is used, for example, in particles that are in the reference US-2002/0104762 are described. These can be formed for example as nanobar codes, wherein the particles are formed as a few μ m long rods, which are composed of layers of different materials and thereby form the barcode. When measuring with sufficient local resolution (<1 μ m), the barcode can be read out. The rods can be coated with a reporter substance to increase sensitivity and selectivity, resulting in an intense and environmentally independent signal or signal sequence. Such particles are discussed for use in product protection.

Im Bereich der forensischen Analytik ist es bekannt, einen mit SERS zu untersuchenden Stoff mit einer Metall-Kolloid-Lösung zu versetzen, wobei die Kolloidpartikel an dem Stoff angelagert werden und das SERS Signal induzieren. Es findet dann ein Vergleich des Signals nach und vor der Behandlung mit der Metall-Kolloid-Lösung statt. Nachteilig hierbei ist, dass dadurch die Oberfläche des untersuchten Gegenstandes irreversibel verändert wird, da die Kolloidpartikel praktisch nicht mehr ohne Veränderung des Gegenstandes entfernt werden können. Zudem wird mit dieser Methode ausschließlich die Oberfläche des Gegenstandes analysiert.In the field of forensic analysis, it is known to treat a substance to be investigated with SERS with a metal colloid solution, wherein the colloid particles are attached to the substance and induce the SERS signal. A comparison of the signal after and before treatment with the metal colloid solution then takes place. The disadvantage here is that thereby the surface of the examined article is irreversibly changed, since the colloid particles can not be practically removed without changing the object. In addition, this method only analyzes the surface of the object.

Aus der Literaturstelle US 5,853,464 ist eine Tinte mit SERRS-aktiven Partikeln bekannt. Hierbei sind die Partikel mit einer Hülle aus einer Reportersubstanz versehen und stehen nicht in direktem Kontakt mit der Tinte. Die Herstellung solcher umhüllter Partikel ist aufwändig und teuer. Eine ähnliche Technologie ist in dem Dokument EP 0806460 A beschrieben.From the literature US 5,853,464 is an ink with SERRS-active particles known. Here, the particles are provided with a shell of a reporter substance and are not in direct contact with the ink. The production of such coated particles is complicated and expensive. A similar technology is in the document EP 0806460 A described.

Aus den Literaturstellen WO 2004/007767 A2 und US 2006/073612 A1 sind Polymere bekannt, welche Raman-aktive funktionelle Gruppen tragen.From the literature WO 2004/007767 A2 and US 2006/073612 A1 Polymers are known which carry Raman-active functional groups.

Sicherheits- und/oder Wertdokumente sind oft aus mehreren Schichten aufgebaut. Dies gilt insbesondere für Dokumente, die als Karten ausgebildet sind. Eine Übersicht über solche Karten ist der Literaturstelle Haghiri, Tarantino, "Vom Plastik zur Chipkarte", Hanser Verlag, München, 1999 , entnehmbar.Security and / or value documents are often composed of several layers. This is especially true for documents that are designed as cards. An overview of such maps is the reference Haghiri, Tarantino, "From Plastic to Chip Card", Hanser Verlag, Munich, 1999 , removable.

Das Dokument WO 91/11492 A offenbart Partikel im Zusammenhang mit resonanter Raman-Streuung. Eine ähnliche Technologie ist in dem Dokument WO 91/11703 A beschrieben. Das Dokument US 6,259,509 B1 offenbart ein Sicherheitselement unter Nutzung des Raman-Effektes. Das Dokument EP 0786498 A beschreibt Pigmente mit unterschiedlichen Raman-Spektren.The document WO 91/11492 A discloses particles associated with resonant Raman scattering. A similar technology is in the document WO 91/11703 A described. The document US 6,259,509 B1 discloses a security element utilizing the Raman effect. The document EP 0786498 A describes pigments with different Raman spectra.

Technisches Problem der ErfindungTechnical problem of the invention

Der Erfindung liegt das technische Problem zu Grunde, ein Sicherheits- und/oder Wertdokument anzugeben, welches auf besonders einfache Weise mittels SERS und ohne Veränderung des Sicherheits- und/oder Wertdokumentes untersuch- und verifizierbar ist. Der Erfindung liegt das weitere technische Problem zu Grunde, ein Sicherheits- und/oder Wertdokument anzugeben, dessen Analysierbarkeit mit SERS nicht auf die Oberfläche beschränkt ist. Schließlich liegt der Erfindung das technische Problem zu Grunde, ein besonders einfach und kostengünstig herzustellendes Sicherheits- und/oder Wertdokument abzugeben, welches mittels SERS verifizierbar ist.The invention is based on the technical problem of specifying a security and / or value document which can be examined and verified in a particularly simple manner by means of SERS and without changing the security and / or value document. The invention is based on the further technical problem of specifying a security and / or value document whose analyzability with SERS is not limited to the surface. Finally, the invention is based on the technical problem of providing a particularly simple and inexpensive security and / or valuable document which can be verified by means of SERS.

Grundzüge der Erfindung und bevorzugte Ausführungsformen.Broad features of the invention and preferred embodiments.

Zur Lösung dieses technischen Problems lehrt die Erfindung den Gegenstand des Anspruchs 1.To solve this technical problem, the invention teaches the subject matter of claim 1.

Der Begriff des Wert- und/oder Sicherheitsdokumentes umfasst im Rahmen der Erfindung insbesondere Personalausweise, Reisepässe, ID-Karten, Zugangskontrollausweise, Visa, Steuerzeichen, Tickets, Führerscheine, Kraftfahrzeugpapiere, Banknoten, Schecks, Postwertzeichen, Kreditkarten, beliebige Chipkarten und Haftetiketten (z.B. zur Produktsicherung). Solche Sicherheits- und/oder Wertdokumente weisen typischerweise ein Substrat, eine Druckschicht und optional eine transparente Deckschicht auf. Ein Substrat ist eine Trägerstruktur, auf welche die Druckschicht mit Informationen, Bildern, Mustern und dergleichen aufgebracht wird. Ein Substrat kann einschichtig oder mehrschichtig aufgebaut sein. Als Materialien für ein Substrat bzw. eine Substratschicht kommen alle fachüblichen Werkstoffe auf Papier- und/oder Kunststoffbasis in Frage.The term value and / or security document includes in the invention in particular identity cards, passports, ID cards, access control cards, visas, tax stamps, tickets, driver's licenses, motor vehicle papers, banknotes, checks, postage stamps, credit cards, any smart cards and adhesive labels (eg product assurance). Such security and / or value documents typically have a substrate, a printing layer and optionally a transparent cover layer. A substrate is a support structure to which the print layer is applied with information, images, patterns, and the like. A substrate may be single-layered or multi-layered. Suitable materials for a substrate or a substrate layer are all customary materials based on paper and / or plastic in question.

Ein Sicherheitsmerkmal ist ein Teilbereich (Fläche oder Volumen) des Sicherheits- und/oder Wertdokumentes, welcher zur Verifizierung des Sicherheits- und/oder Wertdokumentes verwendet werden kann. Dabei kann der Teilbereich strukturlos sein, es kann sich aber auch um ein Muster handeln. Ein solches Muster kann ein für verschiedene Sicherheits- und/oder Wertdokumente gleiches Muster sein. Dann ist das Muster für eine Verifizierung eines Typs von Sicherheits- und/oder Wertdokument geeignet. Beispiele für solche Dokumententyp-spezifische laterale Muster sind: Siegel, Wappen, regelmäßige oder unregelmäßige Flächenmuster, wie Linienscharen oder Guillochen, 1D- und 2D-Barcodes. Hierbei kann es sich um sichtbare oder um unter normalem Licht nicht sichtbare Muster handeln, wobei die nicht sichtbaren Muster sich von den sichtbaren Mustern dadurch unterscheiden, dass die nicht sichtbaren Muster erst mittels technischer Hilfsmittel, wie UV-Quelle, sichtbar werden. Das Muster kann aber auch ein für verschiedene Sicherheits- und/oder Wertdokumente (des gleichen Dokumententyps) individuelles Muster sein, welches insbesondere für Identinformationen des Sicherheits- und/oder Wertdokumentes codiert ist. Für Individualmuster kommen beispielsweise die folgenden (mustermäßig codierten) Daten in Frage: alphanumerische Zeichenfolgen, wie beispielsweise Personendatensätze, Teile von Personendatensätze, wie Namen, Vornamen, Anschrift, Geburtsdatum, Geburtsort, und/oder Dokumentendaten, Teile von Dokumentendaten, wie Seriennummer, Ausgabestelle, Ausgabedatum, Ablaufdatum, sowie andere Daten, insbesondere digitale Daten, Public Key (im Falle eines Dokumentes mit auslesbarem Chip oder für Zugriff auf zentrale oder dezentrale Datenbanken) und/oder Prüfsummen, und biometrische Daten, wie Photo, Fingerabdruck, Venenmuster beispielsweise der Hand oder eines Fingers, Iris und/oder Retina. Es handelt sich vorzugsweise um eine das Dokument und/oder den Dokumententräger ein-eindeutig identifizierende Zeichenfolge. Diese Zeichenfolge kann aber auch eine in dem Dokument nicht anders dargestellte Zeichenfolge sein. Es können auch mehrere Muster vorgesehen sein, die einander (lateral) überlagern können und dennoch separat auslesbar sind anhand der detektierten Raman-Spektren. Es können selbstverständlich aber auch mehrere Muster, die einander nicht (lateral) überlagern, vorgesehen sein. In beiden Fällen sind insbesondere Kombinationen von Dokumententyp-spezifischen Mustern und Individualmuster möglich und bevorzugt.A security feature is a subarea (area or volume) of the security and / or value document that can be used to verify the security and / or value document. The subarea can be structureless, but it can also be a pattern. Such a pattern may be a similar pattern for different security and / or value documents. Then, the pattern is suitable for verification of one type of security and / or valuable document. Examples of such document type-specific lateral patterns are: seals, coats of arms, regular or irregular surface patterns, such as line coats or guilloches, 1D and 2D barcodes. This may be visible or um Under normal light patterns that are not visible under normal light, whereby the invisible patterns differ from the visible patterns in that the non-visible patterns first become visible by means of technical aids, such as the UV source. However, the pattern can also be an individual pattern for different security and / or value documents (of the same document type), which pattern is coded in particular for identification information of the security and / or value document. For individual patterns, for example, the following (pattern coded) data may be considered: alphanumeric strings, such as personal records, parts of personal records, such as names, first names, address, date of birth, place of birth, and / or document data, pieces of document data, such as serial number, issuing office, Date of issue, expiry date, and other data, in particular digital data, public key (in the case of a document with readable chip or for access to centralized or decentralized databases) and / or checksums, and biometric data such as photographs, fingerprints, vein patterns, for example, by hand or a finger, iris and / or retina. It is preferably a character string that uniquely identifies the document and / or the document carrier. However, this string can also be a string not otherwise shown in the document. It is also possible to provide a plurality of patterns which can overlap one another (laterally) and can nevertheless be read out separately on the basis of the detected Raman spectra. Of course, it is also possible to provide a plurality of patterns which do not overlap each other (laterally). In In both cases, in particular combinations of document type-specific patterns and individual patterns are possible and preferred.

SERS-aktive Partikel sind Partikel, die bei Kontaktierung der Partikel mit einer mit Raman-Spektroskopie zu untersuchenden Substanz eine um zumindest 103, insbesondere um zumindest 105, erhöhte Signalintensität aufweisen, verglichen mit einem Raman-Signal an der Substanz ohne Kontakt mit SERS-aktiven Partikeln. Hierbei ist wesentlich zu verstehen, dass die Intensität eines SERS Signals keineswegs eine Funktion der Konzentration oder Dichte der SERS-aktiven Partikel ist. Wenn auf Grund eines SERS-aktiven Partikels ein SERS Signal erhalten wird, so führt die Zugabe weiterer SERS-aktiver Partikel nicht zu einer nennenswerten Erhöhung des SERS-Signals. Hierzu wird ergänzend auf die Literaturstelle M. Moskovits, Journal of Raman Spectroscopy 36:485-496 (2005 ) verwiesen.SERS-active particles are particles which, on contacting the particles with a substance to be examined by Raman spectroscopy, have an increased signal intensity of at least 10 3 , in particular by at least 10 5 , compared with a Raman signal on the substance without contact with SERS active particles. It is essential to understand that the intensity of an SERS signal is by no means a function of the concentration or density of the SERS active particles. If a SERS signal is obtained due to a SERS-active particle, the addition of further SERS-active particles does not result in a significant increase in the SERS signal. For this purpose, in addition to the reference M. Moskovits, Journal of Raman Spectroscopy 36: 485-496 (2005 ).

Mit der Erfindung wird erreicht, dass ein für das Sicherheitsmerkmal spezifisches Raman-Signal mit hoher Signalintensität erhalten werden kann, und zwar ohne das Sicherheits- und/oder Wertdokument in irgendeiner Weise zuvor präparieren oder sonstwie verändern zu müssen. Insbesondere bleibt das Sicherheits- und/oder Wertdokument in Verfolg der Untersuchung des Sicherheitsmerkmales völlig unverändert und weiterhin benutzbar. Hierdurch kann auch eine wiederholte Untersuchung des Sicherheitsmerkmales bzw. des Sicherheits- und/oder Wertdokumentes erfolgen, ohne dass dadurch Veränderungen des Sicherheits- und/oder Wertdokumentes eintreten, im Gegensatz zur bekannten Präparation des Sicherheits- und/oder Wertdokumentes mit einer kolloidalen Lösung. Hierdurch wird auch der Aufwand einer Präparation mit der damit verbundenen Wartezeit durch die Erfindung vermieden. Eine Verifizierung kann schnell und einfach erfolgen. Hinzu kommt, dass die Positionierung des Sicherheitsmerkmals bzw. dessen Untersuchung nicht auf die Oberfläche des Sicherheits- und/oder Wertdokumentes beschränkt ist. Das Sicherheitsmerkmal kann vielmehr an beliebiger Stelle des Sicherheits- und/oder Wertdokumentes, auch im Volumen, angeordnet sein. So kann das Sicherheitsmerkmal im Substrat, in einer Druckschicht oder einer in der Regel transparenten Deckschicht des Sicherheits- und/oder Wertdokumentes eingerichtet sein. Hierzu sind die SERS-aktiven Partikel an der für das Sicherheitsmerkmal gewünschten Stelle bzw. Schicht eingebracht, was unschwer im Zuge des Herstellungsprozesses des Substrates bzw. einer Druckschicht oder Deckschicht möglich ist. Das SERS Signal rührt dann von dem die SERS-aktiven Partikel umgebenden Stoffmatrix, die typischerweise organische Polymere enthält, welche Raman-aktiv sind.With the invention it is achieved that a Raman signal with high signal intensity which is specific for the security feature can be obtained, without having to previously prepare or otherwise modify the security and / or value document in any way. In particular, the security and / or value document remains completely unchanged as a result of the examination of the security feature and can still be used. As a result, a repeated examination of the security feature or of the security and / or value document can take place without any changes of the security and / or value document, in contrast to the known preparation of the security and / or value document with a colloidal solution. As a result, the expense of a preparation with the associated waiting time is avoided by the invention. Verification can be quick and easy. In addition, the positioning of the security feature or its examination is not limited to the surface of the security and / or value document. Rather, the security feature can be arranged at any point of the security and / or value document, even in the volume. Thus, the security feature can be set up in the substrate, in a printing layer or in a generally transparent cover layer of the security and / or value document. For this purpose, the SERS-active particles are introduced at the desired location or layer for the security feature, which is easily possible in the course of the production process of the substrate or a print layer or cover layer. The SERS signal then originates from the material matrix surrounding the SERS active particles, which typically contains organic polymers which are Raman active.

Vorzugsweise enthalten die SERS-aktiven Partikel metallisches Kupfer, Silber, Gold, Alkalimetall, und/oder Münzmetall. Es kann sich auch um Legierungen mit einem oder mehrerer solcher Metalle handelt. Sie können hieraus bestehen, aber auch im Rahmen von Verbundpartikeln, beispielsweise Kern-Schale-Partikeln, eingerichtet sein. Nicht abschließende Beispiele hierfür sind: mit den besagten Metallen bzw. Legierungen beschichtete anorganische Partikel, wie Oxid-Partikel, z.B. aus SiO2, oder Polymerpartikel.Preferably, the SERS active particles contain metallic copper, silver, gold, alkali metal, and / or coin metal. It may also be alloys with one or more such metals. They may consist of this, but also in the context of composite particles, such as core-shell particles, be set up. Non-exhaustive examples include: coated with said metals or alloys inorganic particles, such as oxide particles, for example of SiO 2 , or polymer particles.

Die SERS-aktiven Partikel haben typischerweise ein Volumen im Bereich von 1 nm3 bis 109 nm3, vorzugsweise von 1 nm3 bis 105 nm3, höchstvorzugsweise von 1 nm3 bis 103 nm3, aufweisen. Dabei ist anzumerken, dass es sich bei SERS-aktiven Partikeln typischerweise um Cluster aus Nanopartikeln (mit einem Volumen bis zu 109 nm3) der betreffenden Metalle handelt.The SERS-active particles typically have a volume in the range of 1 nm 3 to 10 9 nm 3 , preferably from 1 nm 3 to 10 5 nm 3 , most preferably from 1 nm 3 to 10 3 nm 3 . It should be noted that SERS-active particles are typically clusters of nanoparticles (with a volume of up to 10 9 nm 3 ) of the metals in question.

Auch wenn die Anzahl der Partikel auf Grund der hiervon unabhängigen Signalintensität (s.o.) unkritisch ist, ist es bevorzugt, wenn deren Anzahl in der Volumeneinheit des Sicherheitsmerkmals im Bereich von 10-6 oder 10-3 Partikel/µm3 bis 109 Partikel/µm3, insbesondere im Bereich von 10 Partikel/µm3 bis 106 Partikel/µm3, vorzugsweise im Bereich von 102 Partikel/µm3 bis 104 Partikel/µm3, liegt.Even if the number of particles is uncritical due to the independent signal intensity ( see above), it is preferred if their number in the volume unit of the security feature is in the range of 10 -6 or 10 -3 particles / μ m 3 to 10 9 particles / μ m 3 , in particular in the range of 10 particles / μ m 3 to 10 6 particles / μ m 3 , preferably in the range of 10 2 particles / μ m 3 to 10 4 particles / μ m 3 , is located.

Die Partikel haben keine Hüllschicht mit einer Raman-aktiven Substanz, sondern werden direkt mit einem Polymer einer Polymerschicht oder einer Tinte bzw. Farbe kontaktiert, wobei dieses Polymer selbst Raman-aktiv ist. Dadurch wird eine einfache und kostengünstige Herstellung des Sicherheits- und/oder Wertdokuments ermöglicht. Zudem werden anhand der Raman-Spektren bzw. -Resonanzen Informationen über die Werkstoffe des untersuchten Sicherheits- und/oder Wertdokuments erhalten, so dass eine Verifizierung (bei orginalgetreuen Werkstoffen) oder eine Aufdeckung von Fälschungen (bei nicht originalgetreuen Werkstoffen) leicht erfolgen kann.The particles do not have a cladding layer with a Raman active substance, but are directly contacted with a polymer of a polymer layer or ink, this polymer itself being Raman active. This allows a simple and cost-effective production of the security and / or value document. In addition, information about the materials of the examined safety and / or value document is obtained on the basis of the Raman spectra or resonances so that verification (with materials that are true to the original) or detection of counterfeiting (with materials that are not true to the original) can be carried out easily.

Der Begriff "Raman-aktiv" bedeutet, daß ein für die Polymerschicht bzw. Farbe oder Tinte spezifisches Raman-Spektrum bzw. eine spezifische Resonanzfrequenz erhalten wird. Bei einem Raman-aktiven Werkstoff kann es sich beispielsweise um ein synthetisches organisches Polymer handeln, welches eine oder mehrere funktionelle Gruppen (wie beispielsweise, aber nicht abschließend Carbonyl, Carboxyl, Hydroxy, Thiol, Ether, Thioether, Nitro, Nitroso, Sulfonyl, Sulfo, Phospho, Phosphonyl, Amino, etc.) enthält. Es kann sich bei der funktionellen Gruppe bzw. den funktionellen Gruppen aber auch beispielsweise um Aromaten, konjugierte Aromaten und Heterozyklen, wie Chinolinyl, Dioxanyl, Furanyl, Imidazolyl, Indolyl, Morpholinyl, Oxazolyl, Oxiranyl (Ethylenoxid), Piperidinyl, Porphyrinyl, Purinyl, Pyranyl, Pyrazolyl, Pyridinyl, Pyrimidinyl, Pyrrolyl, Pyrrolidinyl, Tetrahydrofuranyl, Thiazolyl, Thiazolidinyl, Thiazolinyl, Thiophenyl, Traizinyl, Triazolyl, Trioxanyl, oder Isoformen solcher Gruppen, substituiert oder unsubstituiert, handeln.The term "Raman-active" means that a Raman spectrum or specific resonance frequency specific to the polymer layer or color or ink is obtained. For example, a Raman active material may be a synthetic organic polymer having one or more functional groups (such as, but not limited to, carbonyl, carboxyl, hydroxy, thiol, ether, thioether, nitro, nitroso, sulfonyl, sulfo, Phospho, phosphonyl, amino, etc.). However, the functional group (s) may also be, for example, aromatics, conjugated aromatics and heterocycles such as quinolinyl, dioxanyl, furanyl, imidazolyl, indolyl, morpholinyl, oxazolyl, oxiranyl (ethylene oxide), piperidinyl, porphyrinyl, purinyl, pyranyl , Pyrazolyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuranyl, thiazolyl, thiazolidinyl, thiazolinyl, thiophenyl, trizinyl, triazolyl, trioxanyl, or isoforms of such groups, substituted or unsubstituted.

In Hinblick auf die Anordnung und Ausbildung eines erfindungsgemäßen Sicherheitsmerkmales bestehen die verschiedensten Möglichkeiten. Es kann einfach oder mehrfach eingerichtet sein. Bei mehrfacher Einrichtung können die Sicherheitsmerkmale gleich oder verschieden, bezogen auf das SERS-Signal, sein. Verschiedene Sicherheitsmerkmale werden beispielsweise dadurch erhalten, dass die SERS-aktiven Partikel in verschiedenen Stoffmatrices des Sicherheits- und/oder Wertdokumentes eingebettet sind. Ein erfindungsgemäßes Sicherheitsmerkmal kann an beliebiger Position des Sicherheits- und/oder Wertdokumentes angeordnet sein. So kann es in einem Substrat bzw. einer beliebigen Substratschicht im Falle von mehrschichtigen Substraten, einer Druckschicht und/oder einer Deckschicht angeordnet sein, i.e. in beliebiger Tiefe. Die Form des Sicherheitsmerkmales, welche durch die Verteilung der SERS-aktiven Partikel bestimmt wird, kann beliebig sein. So kann es sich um ein homogenes Sicherheitsmerkmal handeln, i.e. die Verteilung der SERS-aktiven Partikel ist innerhalb des Sicherheitsmerkmales homogen. Das Sicherheitsmerkmal kann aber auch ein Muster bilden, i.e. die Verteilung der SERS-aktiven Partikel ist (typischerweise in lateraler Richtung, d.h. in Richtungen parallel zu einer Hauptfläche des Sicherheits- und/oder Wertdokumentes) inhomogen und bildet das Muster. Dann kann durch ortsaufgelöste SERS nicht nur eine Verifizierung über das SERS-Signal per se, sondern auch über das bestimmte Muster und dessen Auswertung und Vergleich mit Sollmustern erfolgen. Mehrere Sicherheitsmerkmale können in verschiedenen Schichten (einschließlich des Substrates) des Sicherheits- und/oder Wertdokumentes eingerichtet sein, i.e. in verschiedenen Tiefen. Mehrere verschiedene Sicherheitsmerkmale können einander überlappen und sind durch die unterschiedlichen SERS-Signale dennoch unterschiedbar. Bei Anordnung überlappender Sicherheitsmerkmale in verschiedenen Schichten ergeben sich verschiedene Spektren bzw. Signale, sofern die mit den SERS-aktiven Partikeln in Kontakt stehenden Werkstoffe verschiedene chemische Strukturen aufweisen. Mehrere Sicherheitsmerkmale können aber auch lateral gegeneinander verschoben angeordnet sein. Dann können die Sicherheitsmerkmale gleich oder verschieden sein.With regard to the arrangement and design of a security feature according to the invention there are various possibilities. It can be simple or multiple. With multiple devices, the security features may be the same or different with respect to the SERS signal. Various security features are obtained, for example, in that the SERS-active particles in different matrices of the security and / or value document are embedded. An inventive security feature can be arranged at any position of the security and / or value document. Thus, it can be arranged in a substrate or any substrate layer in the case of multilayer substrates, a printing layer and / or a cover layer, ie at any depth. The shape of the security feature, which is determined by the distribution of the SERS-active particles, can be arbitrary. Thus, it can be a homogeneous security feature, ie the distribution of the SERS-active particles is homogeneous within the security feature. However, the security feature can also form a pattern, ie the distribution of the SERS-active particles is inhomogeneous (typically in a lateral direction, ie in directions parallel to a main surface of the security and / or value document) and forms the pattern. Then by spatially resolved SERS not only a verification of the SERS signal per se, but also on the specific pattern and its evaluation and comparison with target patterns done. Several security features may be implemented in different layers (including the substrate) of the security and / or value document, ie at different depths. Several different security features may overlap each other and are still distinguishable by the different SERS signals. When overlapping security features are arranged in different layers, different spectra or signals result, provided that the materials in contact with the SERS-active particles have different chemical structures. But there are several security features as well be laterally offset from each other. Then the security features can be the same or different.

Die Erfindung betrifft des Weiteren ein Verfahren zur Herstellung eines erfindungsgemäßen Sicherheits- und/oder Wertdokumentes, wobei SERS-aktive Partikel während der Herstellung des Sicherheits- und/oder Wertdokumentes darin an einer definierten räumlichen Position oder an mehreren verschiedenen definierten räumlichen Positionen, lateral oder bezogen auf die Tiefe bzw. Schicht, eingebracht werden. Bei der Einbringung in eine Druckschicht ist dies herstellungstechnisch besonders einfach, da dann der verwendeten Tinte oder Farbe lediglich die SERS-aktiven Partikel beigemischt werden müssen. Dann wird das Sicherheitsmerkmal durch Druck hergestellt und es lassen sich auch unschwer beliebige definierte Muster des Sicherheitsmerkmales ausbilden. Als Druckverfahren zur Herstellung eines solchen Sicherheitsmerkmales kommen die dem Fachmann gut vertrauten Verfahren des Tief-, Hoch-, Flach-, und Durchdrucks in Frage. Hierzu gehören: Stichtiefdruck, Rastertiefdruck, Flexodruck, Letterset, Offset oder Siebdruck. Darüber hinaus sind, Digitaldruckverfahren, wie Thermotransferdruck, Tintenstrahldruck oder Thermosublimationsdruck geeignet.The invention further relates to a method for producing a security and / or value document according to the invention, wherein SERS-active particles during the production of the security and / or value document therein in a defined spatial position or at several different defined spatial positions, lateral or related on the depth or layer, are introduced. In the case of incorporation into a printing layer, this is particularly easy to produce, since then only the SERS-active particles have to be added to the ink or ink used. Then the security feature is made by pressure and it can also easily form any defined pattern of the security feature. Suitable printing methods for producing such a security feature are the methods of deep, high, flat, and through-pressure which are well known to the person skilled in the art. These include: gravure printing, gravure printing, flexographic printing, letter set, offset or screen printing. In addition, digital printing methods such as thermal transfer printing, ink jet printing or thermal sublimation printing are suitable.

Die Erfindung betrifft des Weiteren ein Verfahren zur Verifizierung eines erfindungsgemäßen Sicherheits- und/oder Wertdokumentes, wobei das Sicherheitsmerkmal einer SERS Untersuchung unterworfen wird und das erhaltene SERS-Spektrum bzw. SERS-Signal mit einem Soll-SERS-Spektrum bzw. einem Soll-SERS-Signal verglichen wird. Das Soll-SERS-Spektrum bzw. Soll-SERS-Signal kann hierfür in einer Datenbank hinterlegt und Abrufbar sein. Bei Übereinstimmung ist das untersuchte Sicherheits- und/oder Wertdokument verifiziert, bei Nichtübereinstimmung ist es als Fälschung erkannt und kann eingezogen bzw. verworfen werden. Zusätzlich kann eine Verifizierung auch über die detektierte Position des Sicherheitsmerkmales innerhalb des Sicherheits- und/oder Wertdokumentes erfolgen, indem eine ortsaufgelöst SERS Messung durchgeführt und das Sicherheits- und/oder Wertdokument hierbei definiert ausgerichtet wird. Bei Verifikation mittels örtlicher Auflösung kann an Stelle der Messung des Spektrums eine ortsaufgelöste Messung bei einer (oder mehreren) festen (Resonanz-) Frequenz erfolgen, wie dem Fachmann vertraut.The invention further relates to a method for verifying a security and / or value document according to the invention, wherein the security feature is subjected to a SERS examination and the resulting SERS spectrum or SERS signal having a desired SERS spectrum or a desired SERS signal is compared. The desired SERS spectrum or desired SERS signal can be stored in a database and retrievable. If there is a match, the examined security and / or value document is verified; if it does not match, it is recognized as a forgery and can be confiscated or rejected. In addition, verification can also take place via the detected position of the security feature within the security and / or value document by performing a spatially resolved SERS measurement and aligning the security and / or value document in a defined manner. In the case of verification by means of spatial resolution, instead of the measurement of the spectrum, a spatially resolved measurement can take place at one (or more) fixed (resonance) frequency, as is familiar to the person skilled in the art.

Im Falle der Messung eines SERS-Spektrums erfolgt die Verifizierung über die stoffliche Charakterisierung der die SERS-aktiven Partikel umgebenden Substanz. Im Falle der Messung eines SERS-Signals wird nur die Anwesenheit oder Abwesenheit einer Raman-aktiven Substanz bei den SERS-aktiven Partikeln bestimmt, was sich beispielsweise bei der ortsaufgelösten Untersuchung empfiehlt.In the case of the measurement of a SERS spectrum, the verification takes place via the material characterization of the substance surrounding the SERS-active particles. In the case of measurement of a SERS signal, only the presence or absence of a Raman-active substance in the SERS-active particles is determined, which is recommended, for example, in the spatially resolved examination.

Die SERS Untersuchung kann dabei auch ortsaufgelöst durchgeführt werden, beispielsweise mittels konfocaler Raman-Mikroskopie. Dies erlaubt es zudem, ein als Muster ausgeführtes Sicherheitsmerkmal mustermäßig zu erfassen bzw. zu erkennen und mit einem Soll-Muster, in einer Datenbank hinterlegt oder aus auf oder in dem Sicherheits- und/oder Wertdokument angebrachten Mustern oder Angaben berechnet oder entnommen, zu vergleichen. Bei Übereinstimmung auch des Musters ist das untersuchte Sicherheits- und/oder Wertdokument verifiziert, bei Nichtübereinstimmung ist es - selbst bei per se zutreffenden SERS-Spektren bzw. -Signalen - als Fälschung erkannt und kann eingezogen bzw. verworfen werden.The SERS examination can also be performed spatially resolved, for example by means of confocal Raman microscopy. This also makes it possible to pattern capture or detect a security feature executed as a pattern and with a desired pattern, stored in a database or attached to or in the security and / or value document patterns or information calculated or taken, to compare. If the pattern also matches, the examined security and / or value document is verified; if it does not match, it is recognized as a forgery even with per se SERS spectra or signals and can be confiscated or rejected.

Im Falle der Einrichtung mehrerer verschiedener Sicherheitsmerkmale können diese jeweils einer SERS Untersuchung unterworfen werden und die erhaltenen SERS-Spektren bzw. SERS-Signale werden dann mit jeweils den räumlichen Positionen zugeordneten Soll-SERS-Spektren bzw. -Signalen verglichen. Auch hier kann zusätzlich die vorstehend beschrieben Mustererkennung bei einem oder mehreren der Sicherheitsmerkmale erfolgen, sofern diese als Muster ausgebildet sind.In the case of the establishment of a plurality of different security features, these can each be subjected to a SERS examination, and the SERS spectra or SERS signals obtained are then compared with desired SERS spectra or signals respectively assigned to the spatial positions. In this case too, the pattern recognition described above can additionally take place with one or more of the security features, provided that these are designed as a pattern.

Die Erfindung betrifft schließlich eine Tinte oder Farbe nach Anspruch 11. Die weiteren Bestandteile erfindungsgemäßer Tinten bzw. Farben stimmen mit den Bestandteilen von aus dem Stand der Technik bekannten Tinten und Farben überein und umfassen typischerweise die fachüblichen weiteren Komponenten von Farben oder Tinten, wie etwa Binder, Penetrationsmittel, Stellmittel, Biozide, Tenside, Puffersubstanzen, Lösungsmittel (Wasser und/oder organische Lösungsmittel), Füllstoffe, Pigmente, Farbstoffe, Effektpigmente, Antischaummittel, Antiabsetzmittel, UV-Stabilisatoren, etc.. Geeignete Farb- und Tintenformulierungen für verschiedene Druckverfahren sind dem Durchschnittsfachmann aus dem Stand der Technik wohl bekannt und erfindungsgemäß eingesetzte SERS-aktiven Partikel werden insofern an Stelle oder zusätzlich zu konventionellen Farbstoffen bzw. Pigmenten beigemischt. Der Anteil der SERS-aktiven Partikel in der Tinte bzw. Farbe kann beispielsweise im Bereich von 0,00001 bis 50 Gew.-%, vorzugsweise von 0,001 bis 10 Gew.-%, höchstvorzugsweise von 0,001 bis 2 Gew.-%, bezogen auf das Gesamtgewicht der Tinte zw. Farbe, betragen.Finally, the invention relates to an ink or ink according to claim 11. The further constituents of inks of the invention are in accordance with the components of inks and inks known in the art and typically comprise the usual other components of paints or inks, such as binders , Penetrants, adjusters, biocides, surfactants, buffering agents, solvents (water and / or organic solvents), fillers, pigments, dyes, effect pigments, antifoaming agents, anti-settling agents, UV stabilizers, etc. Suitable color and ink formulations for various printing processes are One of ordinary skill in the art is well aware of and uses SERS-active ones employed in the present invention In this respect, particles are mixed in place or in addition to conventional dyes or pigments. The proportion of the SERS active particles in the ink may be, for example, in the range of 0.00001 to 50% by weight, preferably 0.001 to 10% by weight, most preferably 0.001 to 2% by weight, based on the total weight of the ink between color.

Im Folgenden wird die Erfindung anhand von lediglich Ausführungsformen darstellenden Beispielen näher erläutert.In the following, the invention will be explained in more detail by way of embodiments that merely represent embodiments.

Beispiel 1: Einlaminieren von SERS-aktiven Partikeln in zwei Kunststoffschichten.Example 1: Lamination of SERS-active particles in two plastic layers.

Die Figuren 1a und 1b zeigen die Herstellung eines erfindungsgemäßen Sicherheitsmerkmals zwischen zwei Schichten (Substratschichten oder Substratschicht und Deckschicht). In der hier beschriebenen Ausführungsform werden SERS-aktiven Partikel 1, beispielsweise Au-Nanopartikel, ohne weitere Komponenten ausser ggf. einem Lösemittel, in welchem die SERS-aktiven Partikel 1 suspendiert sind, auf eine erste Raman-aktive Polymerschicht 2 aufgebracht, beispielsweise mittels einer Drucktechnik (Figur 1a). Sodann wird auf die Seite der ersten Polymerschicht 2 mit den SERS-aktiven Partikeln 1 eine zweite, optional ebenfalls Raman-aktive, Polymerschicht 3, vorzugsweise aus dem gleichen Polymer, wie jenes der ersten Polymerschicht 2, aufgelegt. Schließlich werden die erste Polymerschicht 2 und die zweite Polymerschicht 3 miteinander laminiert, beispielsweise durch Verkleben oder Verschweissen (Figur 1b). Im Falle der Verklebung trägt die erste Polymerschicht 2 und/oder die zweite Polymerschicht 3 eine der Übersichtlichkeit halber nicht dargestellte Klebstoffschicht.The FIGS. 1a and 1b show the production of a security feature according to the invention between two layers (substrate layers or substrate layer and cover layer). In the embodiment described here, SERS-active particles 1, for example Au nanoparticles, without further components except, if appropriate, a solvent in which the SERS-active particles 1 are suspended are applied to a first Raman-active polymer layer 2, for example by means of a Printing technology ( FIG. 1a ). Then, on the side of the first polymer layer 2 with the SERS-active particles 1, a second, optionally also Raman-active, polymer layer 3, preferably of the same polymer as that of the first polymer layer 2, is placed. Finally, the first polymer layer 2 and the second polymer layer 3 laminated together, for example by gluing or welding ( FIG. 1b ). In the case of bonding, the first polymer layer 2 and / or the second polymer layer 3 carries an adhesive layer not shown for the sake of clarity.

Ein Sicherheits- und/oder Wertdokument, das die dargestellte erste Polymerschicht 2 und zweite Polymerschicht enthält, liefert SERS-Spektren bzw. - Signale auf Grund der Raman-Aktivität des mit den SERS-aktiven Partikeln kontaktierten Polymerwerkstoffs, welche also hierfür spezifisch sind. Hieraus sind zwei Informationen zum Zwecke der Verifizierung erhältlich. Ein SERS-Spektrum liefert zum einen Informationen über den Polymerwerkstoff. Stimmt das SERS-Spektrum nicht einem SERS-Soll-Spektrum des für echte Dokumente verwendeten Polymerwerkstoffs überein, so enthält das untersuchte Sicherheits- und/oder Wertdokument einen Polymerwerkstoff, der von echten Sicherheits- und/oder Wertdokumenten verschieden ist, wodurch die Fälschung erkannt werden kann. Zum anderen kann durch ortsaufgelöste Messung eines SERS-Signals nach vorheriger definierter Ausrichtung des Sicherheits- und/oder Wertdokumentes die räumliche Anordnung, und zwar lateral (in Richtungen der Hauptebene der Schichten 2, 3) und/oder bezüglich der Tiefe (in Richtungen orthogonal zur Hauptebene der Schichten 2, 3) der das Sicherheitsmerkmal bildenden SERS-aktiven Partikel bestimmt und mit einer Soll-Anordnung verglichen werden.A security and / or value document containing the illustrated first polymer layer 2 and second polymer layer provides SERS spectra or signals due to the Raman activity of the polymer material contacted with the SERS active particles, which are therefore specific for this purpose. There are two pieces of information available for verification purposes. On the one hand, a SERS spectrum provides information about the polymer material. If the SERS spectrum does not correspond to a SERS nominal spectrum of the polymer material used for genuine documents, then the examined security and / or value document contains a polymer material that is different from genuine security and / or value documents, whereby the counterfeiting is recognized can. On the other hand, by spatially resolved measurement of a SERS signal according to a previously defined orientation of the security and / or value document, the spatial arrangement, laterally (in directions of the main plane of the layers 2, 3) and / or with respect to the depth (in directions orthogonal to the Main plane of the layers 2, 3) of the security feature forming SERS-active particles are determined and compared with a desired arrangement.

Beispiel 2: Einlaminieren einer Farbe bzw. Tinte mit SERS-aktiven Partikeln in zwei Kunststoffschichten.Example 2: Lamination of a color or ink with SERS-active particles in two plastic layers.

Dieses Beispiel entspricht im wesentlichen dem Beispiel 1 mit dem Unterschied, dass die SERS-aktiven Partikel 1 im Rahmen einer Farbe oder Tinte mit einer Komponente auf Basis eines synthetischen organischen Polymers, welches unterschiedlich von dem Polymerwerkstoff der ersten Polymerschicht 2 und der zweiten Polymerschicht 3 ist, auf die erste Polymerschicht 2 aufgedruckt werden. Hierdurch ist eine Druckschicht 4 gebildet (Fig. 2). Auf diese Druckschicht 4 wird dann die zweite Polymerschicht 3 auflaminiert. Durch diesen Aufbau ist das Sicherheitsmerkmal im Inneren des damit gebildeten Sicherheits- und/oder Wertdokumentes angeordnet und kann sich nicht abnutzen bzw. abreiben. Zudem ist eine Manipulation zumindest erschwert.This example is substantially similar to Example 1, except that the SERS active particles 1 is colored or inked with a synthetic organic polymer-based component different from the polymer material of the first polymer layer 2 and the second polymer layer 3 , are printed on the first polymer layer 2. As a result, a printing layer 4 is formed ( Fig. 2 ). On this print layer 4, the second polymer layer 3 is then laminated. By virtue of this structure, the security feature is arranged inside the security and / or value document thus formed and can not be worn or rubbed off. In addition, a manipulation is at least difficult.

In dieser Variante wird ein SERS-Spektrum bzw. SERS-Signal erhalten, welches für das synthetische Polymer der Farbe bzw. Tinte spezifisch ist, da nur dieses Polymer mit den SERS-aktiven Partikeln 1 kontaktiert ist.In this variant, a SERS spectrum or SERS signal is obtained which is specific for the synthetic polymer of the ink or ink, since only this polymer is contacted with the SERS-active particles 1.

Es lassen sich die analogen Informationen gemäß Beispiel 1 erhalten zu Verifikationszwecken. In einer Weiterbildung dieser Variante enthält das Sicherheits- und/oder Wertdokument an anderer Position einen Bereich mit der gleichen Farbe bzw. Tinte, wobei jedoch keine SERS-aktiven Partikel 1 in der Farbe bzw. Tinte enthalten sind, oder eine Farbe bzw. Tinte mit gleich aussehender Farbe. Dadurch ist visuell nicht ersichtlich, an welcher Position das Sicherheitsmerkmal eingerichtet ist, was eine Fälschung erschwert. Zudem kann durch Vergleich von SERS-Signalen bzw. -Spektren, die an Bereichen mit Tinte bzw. Farbe ohne SERS-aktive Partikel 1 sowie an einem erfindungsgemäßen Sicherheitsmerkmal gewonnen werden, festgestellt werden, ob eine Nachstellung und/oder Manipulation des Sicherheits- und/oder Wertdokumentes durchgeführt wurde.The analog information according to Example 1 can be obtained for verification purposes. In a development of this variant, the security and / or value document at another position contains an area with the same color or ink, but no SERS-active particles 1 are contained in the ink, or a color or ink with same-looking color. As a result, it is not visually apparent at which position the security feature is set up, which makes forgery more difficult. In addition, it can be determined by comparison of SERS signals or spectra, which are obtained on areas with ink or color without SERS-active particles 1 and on a security feature according to the invention, whether an adjustment and / or manipulation of the security and / or or value document was carried out.

Beispiel 3: Sicherheits- und/oder Wertdokument mit mehreren SicherheitsmerkmalenExample 3: Security and / or value document with several security features

Die Figur 3 zeigt ein erfindungsgemäßes Sicherheits- und/oder Wertdokument, wobei mehrere Bereiche 6, 7, 8 an verschiedenen Positionen, lateral und bezüglich der Tiefe, mit SERS-aktiven Partikeln 1 eingerichtet sind. Man erkennt weiterhin, dass im Rahmen des Sicherheits- und/oder Wertdokumentes verschiedene Schichten 9, 10, 11, 12 eingerichtet sind. Im Rahmen der Bereiche 6, 7, 8 können jeweils und unabhängig voneinander die Varianten der Beispiel 1 bis 3 eingerichtet sein, was der Übersichtlichkeit halber nicht dargestellt ist.The FIG. 3 shows a security and / or value document according to the invention, wherein a plurality of regions 6, 7, 8 are arranged at different positions, laterally and with respect to the depth, with SERS-active particles 1. It can further be seen that various layers 9, 10, 11, 12 are set up within the framework of the security and / or value document. Within the scope of the areas 6, 7, 8, the variants of examples 1 to 3 can be set up independently of one another and each other, which is not shown for the sake of clarity.

Die Bereich 6, 7, 8 bilden dabei ein definiertes dreidimensionales Muster. Eine Mustererkennung und folglich Verifikation kann mittels beispielsweise konfocaler Raman-Mikroskopie zweidimensional oder dreidimensional erfolgen. Die Einrichtung eines solchen Musters, insbesondere dreidimensional erschwert eineThe areas 6, 7, 8 form a defined three-dimensional pattern. Pattern recognition and thus verification can be performed two-dimensionally or three-dimensionally using, for example, confocal Raman microscopy. The establishment of such a pattern, in particular three-dimensional makes a difficult

Nachstellung oder Manipulation des Sicherheits- und/oder Wertdokumentes ganz erheblich. Zusätzlich oder unabhängig hiervon können auch SERS-Spektren eines Bereiches 6, 7, 8 oder mehrerer Bereiche 6, 7, 8 aufgenommen werden, wodurch eine Verifikation über die vorstehend erläuterte Charakterisierung des mit den SERS-aktiven Partikeln 1 in Kontakt stehenden Stoffes erfolgt. Durch eine solche Kombination wird ein extrem hoher Schutz gegen Nachstellung und Manipulation erhalten.Reconstitution or manipulation of the security and / or value document quite considerably. In addition or independently thereof, SERS spectra of a region 6, 7, 8 or multiple regions 6, 7, 8 can also be recorded, whereby a verification of the above-described characterization of the substance in contact with the SERS-active particles 1 takes place. Such a combination provides extremely high protection against readjustment and manipulation.

Beispiel 4: erfindungsgemäße TinteExample 4: Ink according to the invention

Für den Tintenstrahldruck eines Sicherheitsmerkmales in roter Farbe in einen Pass werden die folgenden Komponenten miteinander gemischt und homogenisiert:

  • 20,0 Gew.-% Cartasol Rot K-3B flüssig,
  • 40,6 Gew.-% Milchsäure (80 %ig),
  • 19,6 Gew.-% Ethandiol (Ethylenglykol),
  • 1,6 Gew.-% Wasser,
  • 16,7 Gew.-% Ethylenglykol-Monobutylether,
  • 0,2 Gew.-% Parmetol A26,
  • 1,3 Gew.-% Natrium-Lactat Lösung (50%ig).
For the inkjet printing of a security feature in red color in a passport, the following components are mixed together and homogenized:
  • 20.0% by weight of Cartasol Red K-3B liquid,
  • 40.6% by weight of lactic acid (80%),
  • 19.6% by weight of ethanediol (ethylene glycol),
  • 1.6% by weight of water,
  • 16.7% by weight of ethylene glycol monobutyl ether,
  • 0.2% by weight of Parmetol A26,
  • 1.3% by weight sodium lactate solution (50%).

Der Gesamtgehalt an Wasser unter Berücksichtigung des mit dem Cartasol mit eingebrachten Wassers liegt bei 30 Gew.-%, bezogen auf die Gesamtmenge an Tinte. Durch den Einsatz von Cartasol ist zudem 1 Gew.-% Essigsäure, bezogen auf die Gesamtmenge an Tinte, enthalten.The total content of water considering the water introduced with the cartasol is 30% by weight based on the total amount of ink. The use of cartasol also contains 1% by weight of acetic acid, based on the total amount of ink.

Der so hergestellten konventionellen Tinte werden 0,001 Gew.-%, bezogen auf die Gesamtmenge an Tinte, an SERS-aktiven Au-Nanoartikel beigemischt und die Tinte wird homogenisiert.To the thus-prepared conventional ink, 0.001% by weight, based on the total amount of ink, of SERS-active Au nanoparticle is mixed and the ink becomes homogenized.

Claims (11)

  1. A security and/or valuable document comprising at least one security feature, which is disposed in a defined spatial position in the security and/or valuable document and contains SERS-active particles, wherein the SERS-active particles do not have an envelope layer and wherein the particles are in direct contact with a Raman-active polymer of a polymer layer or a printing layer of the security and/or valuable document.
  2. The security and/or valuable document according to claim 1, wherein the SERS-active particles contain metallic copper, silver, gold, alkali metal, coin metal, and/or alloys containing such metals or consist thereof.
  3. The security and/or valuable document according to one of claims 1 or 2, wherein the SERS-active particles have a volume in the range from 1 nm3 to 109 nm3, preferably from 1 nm3 to 105 nm3, most preferably from 1 nm3 to 103 nm3.
  4. The security and/or valuable document according to one of claims 1 to 3, wherein the number of the particles in the unit volume of the security feature is in the range from 10-6 or 10-3 particles/µm3 to 109 particles/µm3, in particular in the range from 102 particles/µm3 to 106 particles/µm3, preferably in the range from 102 particles/µm3 to 104 particles/µm3.
  5. The security and/or valuable document according to one of claims 1 to 4, wherein a plurality of identical or different security features are disposed at different spatial locations in the security and/or valuable document.
  6. The security and/or valuable document according to claim 5, wherein the different spatial positions are different lateral positions and/or different depths.
  7. A method for producing a security and/or valuable document according to one of claims 1 to 6, wherein SERS-active particles are introduced during production of the security and/or valuable document thereinto at a defined spatial location or at several different defined spatial positions.
  8. A method for verifying a security and/or valuable document according to one of claims 1 to 6, wherein the security feature is subjected to a SERS investigation and the resulting SERS spectrum or SERS signal is compared with a preselected nominal SERS spectrum.
  9. The method according to claim 8, wherein the SERS investigation is carried out in a spatially resolved manner.
  10. The method according to claim 9, wherein a plurality of different security features are subjected to a SERS investigation, and the resulting SERS spectra or SERS signals are compared to the preselected nominal SERS spectra or signals as-signed to the respective spatial positions.
  11. An ink or paint for producing a security feature of a security and/or valuable document according to one of claims 1 to 6 by a printing process containing SERS-active particles that do not have an envelope layer, and comprising a Raman-active polymer.
EP07801330.7A 2006-09-07 2007-09-05 Security and/or valuable document having sers-active particles Revoked EP2059397B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006043107A DE102006043107A1 (en) 2006-09-07 2006-09-07 Security and / or value document with SERS-active particles
PCT/DE2007/001595 WO2008028476A2 (en) 2006-09-07 2007-09-05 Security and/or valuable document having sers-active particles

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EP2059397A2 EP2059397A2 (en) 2009-05-20
EP2059397B1 true EP2059397B1 (en) 2015-11-11

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Families Citing this family (6)

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DE102006043107A1 (en) 2006-09-07 2008-03-20 Bundesdruckerei Gmbh Security and / or value document with SERS-active particles
DE102010060563A1 (en) * 2010-11-15 2012-05-16 Technische Universität Dresden Method for spectroscopic determination of concentration distribution of ingredients in papers or in foils over thickness, involves cutting rectangular strip-shaped sample from paper or foil to be examined
DE102013016134A1 (en) 2013-09-27 2015-04-02 Giesecke & Devrient Gmbh Value document and method for checking the existence of the same
DE102013016121A1 (en) 2013-09-27 2015-04-02 Giesecke & Devrient Gmbh Value document and method for checking the existence of the same
FR3018474B1 (en) 2014-03-13 2019-05-10 Oberthur Fiduciaire Sas SECURITY DOCUMENT AND SYNTHETIC PARTICLES
DE102016009260A1 (en) 2016-07-29 2018-02-01 Giesecke+Devrient Mobile Security Gmbh Fingerprint of a security document

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EP2059397A2 (en) 2009-05-20
WO2008028476A3 (en) 2008-09-04
WO2008028476A2 (en) 2008-03-13

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