EP2948427A2 - Élément de sécurité comportant un hologramme en volume et une caractéristique imprimée - Google Patents

Élément de sécurité comportant un hologramme en volume et une caractéristique imprimée

Info

Publication number
EP2948427A2
EP2948427A2 EP14701330.4A EP14701330A EP2948427A2 EP 2948427 A2 EP2948427 A2 EP 2948427A2 EP 14701330 A EP14701330 A EP 14701330A EP 2948427 A2 EP2948427 A2 EP 2948427A2
Authority
EP
European Patent Office
Prior art keywords
dyes
hologram
printing
dye
holographic
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Withdrawn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
EP14701330.4A
Other languages
German (de)
English (en)
Inventor
Rainer Hagen
Thomas Fäcke
Volker Marker
Horst Berneth
Friedrich-Karl Bruder
Thomas RÖLLE
Marc-Stephan Weiser
Dennis Hönel
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Priority to EP14701330.4A priority Critical patent/EP2948427A2/fr
Publication of EP2948427A2 publication Critical patent/EP2948427A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/328—Diffraction gratings; Holograms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/62—Quaternary ammonium compounds
    • C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/0005—Adaptation of holography to specific applications
    • G03H1/0011—Adaptation of holography to specific applications for security or authentication
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/18—Particular processing of hologram record carriers, e.g. for obtaining blazed holograms
    • B42D2033/20—
    • B42D2035/34—
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
    • G03H1/024—Hologram nature or properties
    • G03H1/0248—Volume holograms
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/18—Particular processing of hologram record carriers, e.g. for obtaining blazed holograms
    • G03H1/181—Pre-exposure processing, e.g. hypersensitisation
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/18—Particular processing of hologram record carriers, e.g. for obtaining blazed holograms
    • G03H1/182—Post-exposure processing, e.g. latensification
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/20—Copying holograms by holographic, i.e. optical means
    • G03H1/202—Contact copy when the reconstruction beam for the master H1 also serves as reference beam for the copy H2
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/04—Processes or apparatus for producing holograms
    • G03H1/18—Particular processing of hologram record carriers, e.g. for obtaining blazed holograms
    • G03H2001/186—Swelling or shrinking the holographic record or compensation thereof, e.g. for controlling the reconstructed wavelength
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
    • G03H1/22—Processes or apparatus for obtaining an optical image from holograms
    • G03H1/2249—Holobject properties
    • G03H2001/2263—Multicoloured holobject
    • G03H2001/2271—RGB holobject
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2250/00—Laminate comprising a hologram layer
    • G03H2250/12—Special arrangement of layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2250/00—Laminate comprising a hologram layer
    • G03H2250/34—Colour layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2250/00—Laminate comprising a hologram layer
    • G03H2250/40—Printed information overlapped with the hologram
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2250/00—Laminate comprising a hologram layer
    • G03H2250/44—Colour tuning layer
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
    • G03H2260/00—Recording materials or recording processes
    • G03H2260/12—Photopolymer

Definitions

  • Safety pressure today fulfills important functions in the authentication and identification of goods, goods and persons.
  • Security printing is used, for example, on the packaging of technical products and consumer goods for their labeling.
  • the print features protect against product piracy and help to secure production chains.
  • security printing plays an important role in protecting securities, banknotes, badges, passports and passports against tampering and total counterfeiting.
  • plastic films which are combined with security printing suitable and can be further processed as rolls or sheets to security labels, film strips, laminates and similar sheet products.
  • security printing suitable and can be further processed as rolls or sheets to security labels, film strips, laminates and similar sheet products.
  • the use of plastic films resulted in new reproduction processes and new products.
  • the present application relates to such products.
  • various reproduction methods are known which can be categorized in printing, decoration and conversion technologies. Relevant for this application are printing and decoration.
  • textual and graphic information is applied to or introduced into plastic bodies.
  • the known printing methods include e.g. Inkjet printing, flexographic printing, offset lithography, gravure printing, laser printing, laser marking and combinations of these methods.
  • decoration By means of decoration, color, texture or graphics are applied to or integrated into plastic bodies in order to increase the aesthetic value of the product.
  • known and used decorative decoration methods include galvanization, vacuum metallization, liquid coating, inkjet printing and various embossing techniques such as injection compression, foil stamping, color embossing, relief embossing, hot stamping, embossing hollow and combinations of these technologies.
  • volume holograms belong to the class of light-diffractive optically variable image features.
  • “Diffractive Optics! Variable Image Devices” (DOVI) An overview of the holographic technique in practice is given by F. Unterseher et al. [Hoiography Handbook, Ross Books, 1982, ISBN 0894960164] and G. Saxby [" Practical Hoiography “, Third Edition, iOP , 2003, ISBN 075030912].
  • Volume holograms are usually designed as reflection holograms, which become visible according to their designation by reflecting incident light within the defined holographic diffraction condition.
  • Multicolor volume reflection holograms appear colorfast over wide areas of the viewing angle in comparison with transmission holograms or, in particular, relief holograms, which is the prerequisite for simple and therefore secure authentication with the naked eye.
  • the possibility of giving the holographic image color, depth (so-called 3D or 2D / 3D effects) and animation can also be used be an open security feature and a decorative element.
  • Typical recording and reconstruction methods for multicolor volume reflection holograms have been known since at least 1970, and e.g. in U.S. Patent Nos. 3,532,406 and 4,959,284.
  • Typical recording materials for multicolor volume reflection holograms are photopolymers, see US Pat. No. 4,963,471.
  • Photopolymer holography is considered the most important security printing technology of the coming years. In this application, the term photopolymer hologram / photopolymer holography is always associated with Voium reflection holograms.
  • the solution described is a multi-layered structure that ensures that the photopolymer layer breaks apart in a defined manner under mechanical attack.
  • Serialization and individualization is also possible and known in the case of product protection labels based on volume and in particular photopolymer holograms.
  • application EP 1 755,007 describes a volume holographic medium, for example a label, which contains a machine-readable holographic barcode. This hoiographic series information improves security in authentication against holographic labels that have no serial information, as well as labels that are conventional. eg via offset technology printed and therefore easy to copy barcode have.
  • the object has been achieved by a method for producing a security element with a hoiogra fish layer, in which a hologram is arranged, characterized by at least the following steps: a) providing the hoiogra tical layer; b) at least sectionwise exposing the telegraphic layer via a master hologram to produce a hologram copy in the holographic layer; c) at least partially printing the holographic layer with an ink to form a printing feature, wherein the ink contains the melt of a dye or a colorless component or a solvent and a dye dissolved therein or a colorless component dissolved therein; d) fixing the exposed holographic layer to produce the hologram in the holographic layer, wherein the printing mercury and the hologram are arranged in the holographic layer so that the Druckmerkmai and the hologram overlap at least in sections.
  • the holographic layer and the hologram preferably have the following main features:
  • the holographic layer consists of a photopolymer material.
  • the holographic layer contains a volume reflection hologram type hologram.
  • the hologram is designed as a DOVID and thus the primary security feature.
  • the hologram is two or more colors, i. It reconstructs light of at least two different wavelengths in the visible spectral range.
  • the holographic layer serves as substrate (support) for the individualized printing feature.
  • Image information does not appear as an optically variable element, but only as a color haze or shadow on the photographic copy.
  • the printing feature has the following further main features and embodiments: "The printing feature is used to customize the security element.
  • the printing feature is a security feature in that the printing ink penetrates into the substrate (i.e., the holographic layer) and is thus more likely to be tamper-evident.
  • the security function results from the fact that the hologram can not easily be isolated from the individual printing feature and thus can be used directly as a master for illegal serial copies.
  • the printing feature is a security feature in that it alters the image hologram.
  • the migration of the ink into the substrate shows an interaction with the hologram such that the lattice structures of the hologram are swollen, with the effect that the hologram reconstruction color and / or its diffraction efficiency and / or its reconstruction angle (so-called image window or hologram)
  • Eyebox are irreversibly changed as a result of migrating the ink components. Contact copies of the hologram thus always carry an individual identification, even if it is possible to avoid copying the printing feature itself as an additional hologram. Product identification systems such as those offered by the security industry today could detect and track such illegally duplicated code.
  • inkjet printing processes such as ink jet printing, thermal transfer printing or thermal diffusion printing, are used to produce the printing feature. These procedures are established. They are for printing variable data, such as serial numbers and the like. up to large quantities predestined, because the lead time for a conversion of the printed image is minimal. Further advantages are the simple adaptation to existing production processes, the ease of use, the flexibility (inks and printing parameters can be adapted to the requirements of the printing substrate), the good to very good print quality, ease of maintenance and low noise development. • The inkjet printer provides a rational and process-safe way to label after the ideal printing conditions have been determined. The particular advantage of inkjet printing in this application is that the ink and substrate can be designed and matched to make the printing feature an integrated one Security feature with the above features will.
  • Component 1 is an active substance characterized by good solubility in the photopolymer film serving as a printing substrate.
  • Component 2 is a solvent for component I.
  • the components are selected in such a way that the following properties can be adapted to the requirements:
  • Component 1 can be a) a dye that absorbs in the UV, VIS and / or IR range, preferably in the visible spectral range. The effect is essentially, but not exclusively, based on direct visualization by absorption or scattering. The possible second effect is the change in the properties of the hologram. b) be a colorless substance whose effect is based solely on a change in the properties of the hologram. It is also possible to use several components of type (a), or of type (b), or of mixtures of (a) and (b).
  • Component 2 is preferably characterized in that it is compatible with ink jet printing in terms of volatility and viscosity. After printing, it evaporates, ie does not remain permanently in the substrate.
  • the hologram is full color.
  • a full-color hologram concept requires at least three primary colors. With other colors, a higher gamut can be achieved, i. span a larger color space, so that even higher demands on the color design are met.
  • the reconstruction wavelengths of the hologram are preferred as contributing to copy protection in areas not covered by industrially available holographic lasers, with the aim of avoiding the event of the counterfeiter gaining access to the full set of lasers or laser gaps required is to that
  • the hologram is spatial, ie it gives image information in real 3D or at least depth - resolved image planes, so - called 2 D 3 D sounds.
  • the hologram carries hidden features that can only be visualized with appropriate lighting or by using aids other than the naked eye.
  • the hologram has a restricted space-angle area in which it is reconstructed so that there are viewing directions from which the image information is not visible. So there is a Jardinwinkei Scheme before the security element, in which the hologram no light bends. A prerequisite for machine recognizability of the printing feature is thus given.
  • a register or register-accurate positioning of hologram and printing feature in the hologram layer is a register or register-accurate positioning of hologram and printing feature in the hologram layer.
  • Passer is used in the printer language to denote the matching of the individual colors in multicolor printing. In all printing processes, the Passer designates the stand-alone printing with melireren successive printing processes. Here we use the term for successive print runs, which combine the two different printing technologies in one printed image.
  • the individual features are positioned in register with each other and their graphic structures work together to form an overall graphical representation. The entire print image is neither blurred nor out of focus, or shows color shifts, which have a quality-reducing effect.
  • the two features may e.g. be complementary to each other.
  • the printing units are to be executed in accordance with associated positioning and pressing devices, so that the required positioning accuracy can be achieved.
  • an automatic registration control the so-called in-line color register measurement, is used. If the marks are no longer exactly one above the other, an automatic correction of the printing units takes place.
  • the registration control preferably takes place via two types of markers with corresponding measuring devices: 1.) Markers which are part of the inkjet printing image according to the invention. 2.) Markers that are transferred as part of the hologram master into the hologram copy. Corresponding measuring devices record the two different types of markers.
  • the marks are preferably within the printed image and are designed so that they are barely visible or under ambient lighting.
  • the problem is solved by preferring to lie very low behind the copy plane, especially preferably far ahead of the copy film plane lying hologram marker used, which is under point-like monochromatic light, as it must be used in the sensor, visible, but blurred so much under ambient light that it can no longer be recognized as an image.
  • This effect is intrinsically present in volume reflection holograms that are sufficiently far out of the film plane. This distance is 0.5 to 100 cm, preferably 1.0 to 20 cm, particularly preferably 1, 0 to 10 cm.
  • Inkjet printing solves the problem by making very small markers having a diameter of 0.1 to 2.0 mm, preferably about 1 mm, so that they are barely noticeable.
  • the markers can also be very close. but not be introduced into the predefined surface of the security feature, so that the cutting loss can remain low.
  • the print feature is a visible alphanumeric code.
  • the print feature is a 2D or 3D barcode.
  • the printing feature is a digital portrait of a person.
  • the printing feature is machine-readable.
  • the substrate consisting of or including a flat executed entity, which is referred to as holographic copy film, and based on photopolymer, is also the printing substrate.
  • the printing substrate is preferably between 1 and 65 ⁇ , preferably between 5 and 20 ⁇ , and particularly preferably between 10 and 17 ⁇ thick. ⁇
  • the printing substrate can itself be applied to a carrier foil.
  • the carrier film made of plastic or paper, preferably made of plastic, particularly preferably of transparent, non-scattering plastic.
  • the security element when applied to a surface, eg a product package or a housing, can serve as a decorative element.
  • the printed image or the color of the product packaging is not completely covered, but remains, at least partially, visible. It is particularly preferred if the overall graphics of the security element is matched to the graphics of the underlying surface, so that the design of the security element supports the packaging or housing design.
  • the security element may have a top coat or cover slip on the printed side of the hologram layer, which must be applied after printing.
  • the security element can contain several carrier foils and cover foils or lacquers.
  • the security element is being crafted in several steps:
  • conversion encompasses process steps that serve to refine the security element and thus prepare it for downstream process steps. Typical conversion steps are: application of a topcoat, delamination or lamination of laminations and substrates, stamping, embossing, lamination of a transfer film or application of an adhesive layer.
  • the depression (6) can take place before and / or after the exposure sequence (4).
  • the printing (6) can take place before and / or after the fixing step (5).
  • the depression can occur before or after the conversion steps (7), provided, of course, that the print side of the print substrate is not covered during printing.
  • the printing (6) takes place as the last process step or at least after the fixation (5).
  • This subsequent individualization of the prepared security element allows the decentralized marking, for example in the labeling or in the manufacture of a security document.
  • the tagging includes customization, personalization, serialization, and all forms of registration / signing, eg, by printing a digitized authenticating feature.
  • the security element according to the invention can be transferred or integrated, for example, into a product protection label or brand label.
  • the security element can be used for the purpose of certifying ID cards, passports, credit cards, etc.
  • the label is preferably transferred to the data page (data page) and then safely integrated into the transparent front side masking (front laminate or topcoat).
  • the security element can be integrated as a batch, thread or strip into a banknote.
  • the position in the banknote is free.
  • Conceivable are gluing, weaving, or integrating as an optical window or element of a window.
  • the formation of the printing feature takes place before and / or after the generation of the hologram copy and / or the fixing of the illuminated liologra tical layer, wherein the formation of the print feature is preferably carried out after the generation of the hologram copy, particularly preferably after fixing the exposed hoary layer.
  • the ink contains colored and / or colorless, especially salt-like components as well as a solvent. In particular, the ink contains no components which are insoluble in the solvent.
  • the colored component of the ink is a salt-like dye which is selected in particular from cationic dyes which preferably belong to the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes , Phenoxazine dyes, phenothiazine dyes, coumarin dyes, tri (het) arylmethane dyes, especially diamino and triamino (het) arylmethane dyes, mono-, di-, tri-.
  • cationic dyes which preferably belong to the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes , Phenoxazine dyes, phenothiazine dyes, coumarin dyes, tri (het) arylmethane dyes, especially diamino and triamino (het) arylmethane dyes, mono
  • Tetra- and pentamethine cyanine dyes Tetra- and pentamethine cyanine dyes, hemicyanine dyes, diazahemicyanine dyes, zero-methine dyes, especially naphtholactam dyes, streptocyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, externally cationic phthalo-cyanine dyes, externally cationic dyes
  • Anthraquinone dyes, externally cationic azo dyes, or anionic dyes which preferably belong to the following classes: oxonols, di- and trihydroxy-triarylmethane dyes, the group of merocyanine, neutrocyanine, coumarin, anthraquinone, anthrapyridone, dioxazine, mono- , Dis- and Tris-azo dyes having at least one sulfo group which (iruppe of acridine
  • the colorless component of the ink is a salt-like substance which is in particular selected from colorless salts such as ammonium, sulfonium or phosphonium.
  • colorless salts such as ammonium, sulfonium or phosphonium.
  • the ink contains a mixture of at least one salt-like dye and / or at least one colorless component which is a salt-like substance.
  • the dye and / or the colorless component migrate into the holographic layer, wherein in particular the lattice structure of the hologram copy and / or the hologram is swollen by the dye migrated into the holographic layer.
  • the reconstruction color of the hologram, its diffraction efficiency and / or its reconstruction angle are irreversibly changed by the dye migrated into the holographic layer.
  • the dye used is preferably chosen such that it reflects upon irradiation with white light in the visible wavelength range, in particular in the range of 400 to 800 nm.
  • the holographic layer comprises or consists of a photopolymer material and / or the holographic layer is applied to a support.
  • the hologram can be formed at least in sections by a volume hologram, in particular by a volume reflection hologram.
  • the hologram reconstructs light of at least two different wavelengths in the visible spectral range, wherein the different wavelengths are in particular at least 10 nm apart, preferably at least 20 nm or even 30 nm.
  • the holographic layer is printed at least in sections with an ink to form the printing feature.
  • the area of the holographic layer or the hologram overprinted by the printing feature preferably amounts to 5 to 95% of its area, in particular 10 to 90%.
  • the Druckmerkmai projects beyond the hologram on at least one side.
  • the Druckmerkmai is an image, a pattern, an alphanumeric code, a 2D or 3D barcode or other machine-readable code, such as a biometric feature, the resolution and content in particular sufficiently precisely defined information for the software-based machine image recognition, and / or contains information about a product or a person, which is designed as a hidden or only about aids to be recognized security feature.
  • the method according to the invention can in principle be carried out by means of any suitable printing method.
  • printing by means of inkjet printing is particularly preferred.
  • Another object of the present invention relates to a security element which can be produced or prepared by a method according to the invention.
  • the invention also relates to a document, certificate or other value document, a banknote, a passport, a high security access card, a tax stamp, an electronic ticket, an electronic card, credit card or debit card, a product packaging or product label for consumer goods, industrial goods and consumer goods, the with a erfmdungsdorfen
  • Another object of the invention relates to the use of an ink for improving the security against forgery of a hologram, wherein the ink contains the melt of a dye or a colorless component or a solvent and a dye dissolved therein or a colorless component dissolved therein. Any combinations are possible.
  • the chemical composition of the photopolymer-based printing substrate will be described.
  • polyisocyanate component a it is possible to use all compounds which are well known to the person skilled in the art or mixtures thereof which on average have two or more NCO functions per molecule. These may be aromatic, araliphatic, aliphatic or cycloaliphatic. In minor amounts, it is also possible to use monoisocyanates and / or polyisocyanates containing unsaturated groups.
  • the polyisocyanates of component a) are particularly preferably di- or oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates. Very particular preference is given to isocyanurates, uretdiones and / or iminooxadiazinediones based on HDI, 1,8-diisocyanato-4- (isocyanatomethyl) octane or mixtures thereof.
  • NCO-functional prepolymers with urethane, ailophanate, biuret and / or amide groups as component a).
  • Prepolymers of component a) are obtained in a manner well-known to the person skilled in the art by reacting monomeric, oligomeric or polyisocyanates a1) with isocyanate-reactive compounds a2) in suitable stoichiometry with the optional use of catalysts and solvents.
  • Suitable polyisocyanates a1) are all aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanates known to the person skilled in the art, it being immaterial whether these were obtained by phosgenation or by phosgene-free processes.
  • the higher molecular weight secondary product e of monomeric di- and / or triisocyanates with urethane, urea, carbodiimide, acylurea, isocyanurate, ailophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione structure can each also be used be used individually or in any mixtures with each other.
  • Suitable monomeric di- or triisocyanates which can be used as component al) are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (I PDI), trimethyl hexamethylene diisocyanate (TM DI), 1,8-diisocyanato -4- (isocyanatomethyl) octane, isocyanatomethyl-l, 8-octane diisocyanate (TIN), 2,4- and / or 2,6-toluene diisocyanate.
  • HDI hexamethylene diisocyanate
  • I PDI isophorone diisocyanate
  • TM DI trimethyl hexamethylene diisocyanate
  • 1,8-diisocyanato -4- (isocyanatomethyl) octane isocyanatomethyl-l, 8-octane diisocyanate (TIN), 2,4- and / or
  • OH-functional compounds are preferably used. These are analogous to the OH-functional compounds as described below for component b).
  • amines for prepolymer production.
  • ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine, diaminocyclohexane, diaminobenzene / ol are suitable.
  • isocyanate is reacted in excess with amine to form a biuret group.
  • Suitable amines in this case for the reaction with the di-, tri- and polyisocyanates mentioned are all oligomeric or polymeric, primary or secondary, difunctional amines of the abovementioned type.
  • Preferred prepolymers are urethanes, ailophanates or biurets of aliphatic isocyanate-functional compounds and oligomeric or polymeric isocyanate-reactive compounds having number-average molar masses of from 200 to 10,000 g of mol, particular preference being given to urethanes, Ailophanates or biurets of aliphatic isocyanate-functional compounds and oligomeric or polymeric polyols or polyamines having number average molecular weights of 500 to 8500 g / Moi and very particularly preferred are ailophanates of HD! or TM DI and difunctional Polyetherpoiyolen having number average molecular weights of 1000 to 8200 g / Moi.
  • the prepolymers described above preferably have residual contents of free monomeric
  • Isocyanate of less than 1 wt .-%, more preferably less than 0.5 wt .-% and most preferably less than 0.2 wt .-% to.
  • polyisocyanate component may contain proportionally in addition to the described prepolymers further isocyanate components. Suitable for this purpose are aromatic, aliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates.
  • Suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (H Di), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,2,4- and / or 2,4,4 - Trimethylhexa-methylene diisocyanate (TM DI), the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof any isomer content, isocyanatomethyl-l, 8-octane diisocyanate, 1, 4-cyclohexylene diisocyanate, the isomeric cyclohexanedi-methylene diisocyanates, 1, 4 - Phenylene diisocyanate, 2,4- and / or 2,6-Toluylendiisocya-nat, 1, 5-Naphthylendiis
  • the oligomeric isocyanurates, uretdiones and iminooxadiazinediones of HDI and mixtures thereof are particularly preferred.
  • the polyisocyanate component a) contains proportionate isocyanates which are partially reacted with isocyanate-reactive ethylenically unsaturated compounds.
  • isocyanate-reactive ethylenically unsaturated compounds ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleate, fumarates, maleimides, acrylamides, and vinyl ether, Propenyiether, allyl ether and dicyclopentadienyl units containing compounds containing at least one isocyanate-reactive group have used.
  • acrylates and methacrylates having at least one isocyanate-reactive group are particularly preferably acrylates and methacrylates having at least one isocyanate-reactive group.
  • Suitable hydroxy-functional acrylates or methacrylates are, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (8-caprolactone) mono (meth) acrylates , such as Tone® Ml 00 (Dow, USA), 2-hydroxypropyl (meth) acrylate, 4-hydroxy-butyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, the hydroxy-functional mono-, di- or tetra (meth) acrylates of polyhydric alcohols such as Trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, ethoxylated, propoxylated or aikoxyliertes trimethylolpropane, glycerol, pent
  • isocyanate-reactive oligomeric or polymeric unsaturated acrylate and / or methacrylate group-containing compounds are suitable alone or in combination with the aforementioned monomeric compounds.
  • the proportion of isocyanates in the isocyanate component a) which are partially reacted with isocyanate-reactive ethylenically unsaturated compounds is 0 to 99%, preferably 0 to 50%, more preferably 0 to 25% and most preferably 0 to 15%.
  • polyisocyanate component a) it is also possible for the abovementioned polyisocyanate component a) to comprise, completely or proportionally, isocyanates which are reacted in whole or in part with blocking agents known to the person skilled in the art from the scrubbing technology.
  • blocking agents which may be mentioned are: alcohols, lactams, oximes, malonic esters, alkyl acetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as e.g. Butanone oxime, diisopropylamine, 1, 2,4-triazoi, dimethyl-1, 2,4-tria / ol.
  • Imidazole diethyl malonate, acetoacetic ester, acetone oxime, 3,5-Dimethyipyrazol, ⁇ -caprolactam, N-tert-butyl benzylamine, cyclopentanone carboxyethyl or any mixtures of these blocking agents.
  • the polyisocyanate component is an aliphatic polyisocyanate or an aliphatic prepolymer and preferably an aliphatic polyisocyanate or prepolymer with primary NCO groups.
  • polyol component b) it is possible to use all polyfunctional, isocyanate-reactive compounds per se, which on average have at least 1 .5 isocyanate-reactive groups per molecule.
  • Isocyanate-reactive groups in the context of the present invention are preferably hydroxy, amino or thio groups, particularly preferred are hydroxy compounds.
  • Suitable polyfunctional, isocyanate-reactive compounds are, for example, polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.
  • Suitable polyester polyols are, for example, linear polyester diols or branched polyester polyols, as are obtained in a known manner from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides with polyhydric alcohols having an OH functionality> 2.
  • di- or polycarboxylic acids or anhydrides are succinic, glutaric, adipic.
  • suitable alcohols are ethanediol, di-. Tri-, tetraethylene glycol, 1, 2-propanediol.
  • Di-, tri- Tetrapropylenglykoi 1, 3-propanediol, butanediol-1, 4, butanediol-1, 3, butanediol-2,3, pentanediol-1,5, hexanediol-1, 6, 2,2-dimethyl-1, 3-propanediol.
  • 1, 4-di-hydroxycyclohexane 1, 4-dimethylol-cyclohexane, octanediol-1, 8, decanediol-1, 10, dodecane-1,12, trimethylolpropane, glycerol or any mixtures thereof.
  • the polyester polyols can also be based on natural raw materials such as castor oil. It is also possible that the polyester polyols are based on homo- or copolymers of lactones, as preferred by addition of lactones or lactone mixtures such as butyrolactone, ⁇ -caprolactone and / or methyl e-caproiactone to hydroxy-functional compounds such as polyhydric alcohols of an OH functionality > 2, for example, the above-mentioned type can be obtained.
  • Such polyester polyols preferably have number-average molar masses of from 400 to 4000 g / mol, particularly preferably from 500 to 2000 g / mol.
  • Their OH functionality is preferably 1.5 to 3.5, more preferably 1.8 to 3.0.
  • Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with dioxides or diol mixtures.
  • Suitable organic carbonates are dimethyl, diethyl and diphenyl carbonate.
  • Suitable dioxides or mixtures include the polyhydric alcohols of an OH functionality> 2, preferably 1,4-butanediol, 1,6-hexanediol and / or 3-methylpentanediol, which are per se in the context of the polyester segments, or else polyester polyols can be converted into polycarbonate polyols ,
  • Such polycarbonate polyols preferably have number-average molar masses of from 400 to 4000 g / mol, particularly preferably from 500 to 2000 g / mol.
  • the OH functionality of these polyols is preferably 1.8 to 3.2, particularly preferably 1.9 to 3.0.
  • Suitable polyether polyols are optionally block-formed polyaddition of cyclic ethers to OH or NH-functional starter molecules.
  • Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin. as well as their arbitrary mixtures.
  • the starter used may be the polyhydric alcohols of OH functionality> 2 mentioned in the context of the polyesterpolyols and also primary or secondary amines and amino alcohols.
  • Preferred polyether polyols are those of the aforementioned type based solely on propylene oxide or random or block copolymers based on propylene oxide with further 1-alkylene oxides, wherein the 1 - Alykenoxidanteil is not higher than 80 wt .-%.
  • Particular preference is given to propylene oxide homopolymers and random or block copolymers which contain oxyethylene, oxypropylene and / or oxybutylene units, the proportion of oxypropylene units based on the total amount of all oxyethylene, oxypropylene and oxybutylene units being at least 20% by weight. -%, preferably at least 45 wt .-% makes.
  • Oxypropylene and oxybutylene here include all respective linear and branched C3 and C4 isomers.
  • Such polyether polyols preferably have number-average molar masses of from 250 to 10,000 g / mol, more preferably from 500 to 8,500 g mol and most preferably from 600 to 4500 g mol.
  • the OH functionality is preferably from 1.5 to 4.0, particularly preferably from 1.8 to 3.1.
  • isocyanate-reactive compounds low molecular weight, i. with molecular weights less than 500 g mol, short chain, i. 2 to 20 carbon atoms containing aliphatic, araliphatic or cycloaliphatic di-, tri- or polyfunctional alcohols suitable.
  • These may be, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tri-propylene 1-enyl, and the like. 1, 2-propanediol. 1, 3-propanediol.
  • 1,4-butanediol neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, positionally isomeric diethyloctanediols, 1,3-butylglycol, cyclohexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 1, 2, and 1, 4- Cyclohexanediol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 2,2-dimethyl-3-hydroxypropionic acid (2,2-dimethyl-3-hydroxypropyl ester).
  • trioids examples include trimethylolethane, trimethylolpropane or glycerol.
  • Suitable higher-functionality alcohols are ditrimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol.
  • the polyol component is a difunctional polyether, polyester or a polyether-polyester-block copolyester or a polyether-polyester block copolymer having primary OH functions.
  • Particularly preferred is a combination of components a) and b) in the preparation of the matrix polymers consisting of addition products of butyrolactone, ⁇ -caprolactone and / or methyl-e-caprolactone to Polyetherpolyoien a functionality of 1, 8 to 3.1 with average molecular weights of 200 to 4000 g mol in combination with isocyanurates, uretdiones, Iminooxadiazinediones and / or other oligomers based on HDI.
  • the photoinitiators used are usually initiators which can be activated by actinic radiation and trigger polymerization of the corresponding polymerizable groups.
  • Photoinitiators are known per se, commercially sold compounds, wherein a distinction is made between unimolecular (type I) and bimolecular (type II) initiators.
  • the type I photoinitiators may in particular comprise a cationic dye and a coinitiator.
  • Ammonium arylborates as described by way of example in EP-A 0223587, can be used as co-initiators.
  • ammonium ammonium borate examples include T etrabuty lammonium triphenylhexyl borate, T etrabuty lammonium triphenylbutyl borate, T etrabutylammonium trinapihyl hexyl borate, T etrabutylammonium tris (4-tert-butyl) phenylbutyl borate, T etrabutylammonium tris (3-fluorophenyl) hexyl borate, Tetramethylammonium triphenylbenzyl borate, Tetra (n-hexyl) -ammonium (sec-butyl) triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate, and T etrabutylammonium tris (3-chloro-4-methylphenyl) -hexylborate (Cunningham et al., RadTech'98 North
  • Preferred photoinitiators are mixtures of tetrabutylammonium T etrahexylborate, T etrabutylammonium triphenylhexylborate, T etrabutylammonium tris (3-fluorophenyl) hexylborate
  • the photopolymer formulation additionally contains urethanes as plasticizer, wherein the urethanes may be substituted in particular with at least one fluorine atom.
  • the urethanes may preferably have the general formula (I) have in which n> l and n ⁇ 8 and R 'is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical and / or R 2 , R' are independently hydrogen, preferably at least one of Leftovers R ! R 2 , R 3 is substituted with at least one fluorine atom and more preferably R 'is an organic radical having at least one fluorine atom.
  • R 1 is particularly preferably a linear, branched, cyclic or heterocyclic organic radical which is unsubstituted or optionally also substituted by heteroatoms such as, for example, fluorine.
  • the writing monomer comprises at least one mono- and / or one multifunctional writing monomer, which may in particular be mono- and multi-functional acrylate writing monomers. More preferably, the writing monomer may comprise at least one monofunctional and one multifunctional urethane (meth) acrylate.
  • the acrylate writing monomers may in particular be compounds of the general formula (Ii)
  • R 5 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical and / or R 4 is hydrogen, a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical.
  • R 4 is particularly preferably hydrogen or methyl and / or R 5 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical.
  • unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleates, fumarates, maleimides, acrylamides, vinyl ethers, propenyl ethers, Ailylether and dicyclopentadienyl units containing Compounds and olefinically unsaturated compounds such as styrene, ⁇ -methylstyrene,
  • acrylates and methacrylates are preferred.
  • Acrylates or methacrylates are generally esters of acrylic acid or methacrylic acid.
  • acrylates and methacrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert. Butyl acrylate, tert.
  • urethane acrylates can be used.
  • urethane acrylates is meant compounds having at least one Acrylsäiireesteroli. which additionally have at least one urethane bond. It is known that such compounds can be obtained by reacting a hydroxy-functional acrylic ester with an isocyanate-functional compound.
  • Suitable isocyanate-functional compounds are aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates.
  • di-, tri-polyisocyanates examples include butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (I DI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate , the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof of any desired monomer content, such as cyanoethyl 1-1, 8-octanediisocyanate, 1,4-cyclohexylenediisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1, 4- phenylene diisocyanate, tolylene 2,4- and / or 2,6-diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,
  • Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates are, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (8-caproiactone) mono- (meth) acrylates, such as Tone® M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth) acrylate , Acrylic acid (2-hydroxy-3-phenoxy- propyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as Trimethyloipropan, glycerol, pentaerythritol, dipentaerythrito
  • isocyanate-reactive oligomeric or polymeric unsaturated acrylate and / or methacrylate groups containing compounds alone or in combination with the aforementioned monomeric compounds are suitable.
  • hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH Contents of 20 to 300 mg KOH / g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures hydroxyl phenomenonhaitiger unsaturated polyester with polyester (meth) acrylates.
  • Another object of the present invention relates to compounds of the formulas
  • R "and R! Independently represent methyl, ethyl, propyl. Butyl, hydroxyethyl or cyanoethyl, R 13 is Ci6- C22-alkyl or represents CIO to C22 alkyl when R 1 and R can not be
  • R 14 is optionally branched G - to C 12 alkyl
  • R 15 is C 12 - to C 2 2-alkyl
  • R 16 and R 17 independently of one another represent methyl, ethyl, propyl, butyl and R 17 additionally represents benzyi,
  • X is a (C ' H;) n term and n is an integer from 4 to 10.
  • These compounds are ammonium salts. These compounds are particularly suitable as an ink or component of an ink in the context of the method according to the invention, wherein the application of these compounds is explicitly not limited thereto.
  • R "and R 12 independently of one another represent methyl, ethyl or hydroxyethyl, in particular methyl,
  • R 13 is hexadecyl or octadecyl
  • R 14 is n-hexyl, n-octyl, 2-ethylhexyl or decyl, especially 2-ethylhexyl
  • R ! 5 for dodecyl, tetradecyl, hexadecyl or octadecyl, in particular for hexadecyl or octadecyl,
  • R 16 and R 17 independently of one another are methyl, ethyl, propyl or butyl, in particular propyl or butyl, X is a ⁇ (CH 2 ) n bridge and n is an integer from 4 to 8, in particular 6.
  • the active substances of component 1 are substances which absorb in the UV range, in the visible range and / or in the IR range of the electromagnetic spectrum.
  • Substances that absorb in the UV range are organic substances without an extended ⁇ system as well as UV absorbers and whiteners. Also included are rare earth complexes that exhibit visible fluorescence. Substances that absorb in the visible range are organic dyes.
  • Substances that absorb in the infrared (IR) region are organic I R dyes.
  • the substances may be nonionic or ionic compounds.
  • Non-ionic, UV-absorbing substances are, for example, UV absorbers or neutral whiteners.
  • ionic, UV-absorbing substances are alkali metal, ammonium, sulfonium, phosphonium or cycloimmonium salts of colorless anions, cationic or anionic whiteners.
  • Nonionic, visible absorbing substances are, for example, neutral dyes.
  • ionic, visible-absorbing substances examples include cationic or anionic dyes.
  • Nonionic substances which are absorbed in the laundry are, for example, neutral IR dyes.
  • Ionic IR-absorbing substances are, for example, cationic or anionic IR dyes.
  • Whiteners, dyes and IR dyes are known, for example, from H. Zollinger. Color Chemistry, Wiley-VCH, 3rd edition, 2003.
  • UV absorbers are known from .1. Bieleman, Lackadditive, Wiley-VCH, 1998, Chapter 8.2.
  • the molecular weight is above 200 but below 1000.
  • Alkali, ammonium, sulfonium, phosphonium, cycloammonium or cycloimmonium ions are to be understood as meaning lithium, sodium, potassium;
  • R 21 to R 25 are independently substituted for optionally substituted G to C - alkyl, C3 to Cs cycloalkyl, C? until Go-Aralkyi remains stand and
  • R 21 may additionally be optionally substituted phenyl.
  • colorless anions are meant: Cs to C25 alkanesulfonate, preferably CB to C25 alkanesulfonate, C3 to Cis perfluoroalkanesulfonate, preferably C4 to Cis perfluoroalkanesulfonate, C to C25 alkanoate, C to C25 Alkenoate, Cs to C25 alkylsulfate, preferably CB to C25 alkylsulfate, Cs to C25 alkenylsulfate, preferably CB to C25 alkenylsulfate, C3 to Gs perfluoroalkylsulfate, preferably C5 to Cis perfluoroalkylsulfate, polyethersulfates based at least 4 equivalents of ethylene oxide and / or equivalents 4 propylene oxide, bis-C 4 to C 25 -alkyl, C 5 to C 6 -cycloalkyl, C 3 to C 5 -alkenyl or
  • kyl or phenyl groups dodecahydro-dicarbadodecaborate (2-) or B-Cj - to C12-alkyl-C-phenyl dodecahydro-dicarbadodecaborate (I-), where in the case of polyvalent anions, such as naphthalenedisulfonate, An represents one equivalent of this anion, and where the alkane and alkyl groups may be branched and / or by halogen, cyano, methoxy, ethoxy, methoxycarbonyl or ethoxycarbonyl may be substituted. Particularly preferred are:
  • Preferred colorless salts are ionic liquids as are commercially available. Also preferred colorless salts are ammonium, sulfonium, phosphonium, cycloammonium or cycloimmonium salts of organic mono-, bis- or tris- sulfonic acids, wherein both the cation and the anion each carry at least one long-chain, optionally branched alkyl radical.
  • Long-chain alkyl radicals are to be understood as meaning at least 6, preferably at least 8, more preferably at least 10, very preferably at least 12, with outstanding preference at least 16 C atoms. It is also to be understood that the total number of carbon atoms is at least 12, preferably at least 18, particularly preferably at least 24, when the cation or anion carries at least two alkyl groups.
  • colorless salts are:
  • Preferred ionic dyes are cationic dyes, as described, for example, in H. Berne! in UUmann's Encyclopedia of Industrial Chemistry, Cationic Dyes, Wiley-VCH Verlag, 2008. They preferably belong to the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, coumarin dyes, tri (het) arylmethane dyes - especially diamino- and tri-methylene dyes.
  • amino (het) arylmethane dyes mono-, di- and trimethycyanine dyes, hemicyanine dyes, diazahemicyanine dyes, zero methine dyes - in particular naphtholactam dyes - substances, streptocyanine dyes, externally cationic merocyanine dyes , externally cationic neutrocyanine dyes, externally cationic phthalocyanine dyes, externally cationic anthraquinone dyes, externally cationic azo dyes.
  • Such dyes are described, for example, in I.I. Bemeth in UUmann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008, H.
  • Suitable anions are all colorless, but also colored anions, for example chloride, nitrate, phosphate, sulfate, acetate, PF ,, perchlorate, methosulfate, methanesulfonate, trifluoromethanesulfonate, toluenesulfonate, tetraphenylborate, anionic dyes, anions of organic mono-, bis- or tris-sulfonic acids, each carrying at least one long-chain, optionally branched alkyl radical.
  • Long-chain alkyl radicals are to be understood as meaning at least 8, preferably at least 10, more preferably at least 12, very preferably at least 14, most preferably at least 16 C atoms. It is also to be understood that the total number of C atoms is at least 12, preferably at least 18, more preferably at least 24, when the anion carries at least two alkyl groups.
  • Preferred anions are the latter.
  • cationic dyes are: -32-
  • ionic dyes are anionic dyes. They preferably belong to the following classes: oxonols, di- and trihydroxy-triarylmethane dyes, the group of merocyanine, neutrocyanine, coumarin, anthraquinone, anthrapyridone, dioxazine, mono-, dis- and tris-azo dyes having at least a suifo group, the group of acridine, xanthene, thioxanthene, phenazine, phenoxazine, phenothiazine, tri (het) arylmethane, in particular diamino and triamino (het) arylmethane dyes, having at least two sulfo groups.
  • Such dyes are for example in H. Berneth in Ulimann's Encyclopedia of Industrial Chemistry, Azine Dyes, Wiley-VCH Verlag, 2008, H. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Methine Dyes and Pigments, Wiley-VCH Verlag, 2008, T. Gessner, U. Mayer in Ullmann's Encyclopedia of Industrial Chemistry, Triarylmethanes and Diaryl mediane Dyes, Wiley-VCH Verlag, 2000, H.-S. Bien, J. Stawitz, K. Wunderlich in Ullmann's Encyclopedia of Industrial Chemistry, Anthraquinone Dyes and Intermediates, Wiley-VCH Verlag, 2008, K. Hunger, P. Mischke, W. Rieper, R.
  • phthalocyanines and Azometallkomplexe carrying at least one Suifooire are described, for example, in Gert Löbbert in Ullmann's Encyclopedia of Industrial Chemistry, Phthalocyanines, Wiley-VCH Verlag, 2000, and Klaus Grychtol, Winfried Mennicke in Ullmann's Encyclopedia of Industrial Trials Chemistry, Metal-Complex Dyes, Wiley-VCH Verlag, 2000.
  • Suitable cations in such anionic dyes are the alkali, ammonium, sulfonium, phosphonium or cycloimmonium ions described above. Tetralky lammonium and cycloimmonium ions are preferred.
  • anionic dyes are:
  • two or more of the abovementioned components for example two or more dyes, two or more colorless salts or one or more colorless salts and one or more dyes.
  • it is a mixture of a colorless salt and a dye, a colorless salt and a rare earth complex or a rare earth complex and a dye.
  • Component 2 is a solvent with a boiling point between 60 ° C and 240 ° C, preferably between 77 ° C and 220 ° C (each at 1013 mbar). It should be able to solve component 1. Also suitable as component 2 are mixtures of such solvents.
  • Suitable solvents include: 2-butanone, cyclohexanone, ethyl acetate, butyl acetate, methoxypropyl acetate or diethylene glycol monoethyl ether acetate.
  • the holographic exposure process will be described below.
  • To record a multi-color volume reflection hologram one takes a copy film, a master carrying the hologram to be copied, and several lasers of different wavelengths.
  • the copy film is based on the photopolymer whose photosensitivity matches the laser wavelengths so that the photopolymer forms the bulk phase grating during exposure to the laser (s).
  • the master is a multicolor volume reflection hologram that reconstructs the hologram at the laser wavelengths used.
  • the master is a digital element, e.g. a spatial light modulator (Spatial Light Modulator, SLM).
  • SLM spatial Light Modulator
  • the master may also be a combination of volume reflection hologram and digital element.
  • Industrial lasers that have sufficient coherence, frequency stability and performance for the hologram are known, e.g. frequency doubled neodymium: YAG lasers, krypton ion lasers, argon ion lasers, helium neon lasers and diode pumped solid state lasers.
  • frequency doubled neodymium YAG lasers, krypton ion lasers, argon ion lasers, helium neon lasers and diode pumped solid state lasers.
  • the common method for series production of holograms is replication, which is based on the principle of contact exposure.
  • This principle means that the photopolymer is in contact with or near the master hologram during the coating phase, eg at a distance of 0.2-2.0 cm, preferably 0.5-1.0 cm, more preferably about 1 cm.
  • the master is either designed as a plate or applied as a curved sheet on a roller.
  • the photopolymer is a film on a substrate that is laminated to the master. If the photopolymer has two substrates, for example a support and a lamination, the lamination is preferably removed before lamination onto the master. As already described, the number of lasers determines the color space.
  • a white laser beam is generated from the R (i laser beams by deflection, directed divergently and at a defined angle, eg close to 45 °, to an adapted reflection master hologram with a suitable reference angle
  • the diffraction efficiency is adjusted individually for each color, so that the beam proportion, which is ideal for the geometry and the copy film, results - the intensity ratio of the object beam to the reference beam -
  • the laser beam can be flat, or scanning as a line or as a scanning point beam.
  • a copy of the master hologram is now inserted in the copy film.
  • the copy must now be fixed.
  • Da / u is after a waiting time after the end of the laser exposure, the so-called Dunkeire counselingzeit, which is 1-60 s, preferably 8-12 s, more preferably 10 s, started a lamp exposure with actinic radiation to cure the copy film, to fix and to bleach.
  • a lamp is used in the spectral range of 100-1000 nm, particularly preferably 200-800 nm, particularly preferably 250-550 nm.
  • This overall process can be realized in a roll-to-roll process.
  • the master can be configured as a plate for "step-and-repeat" or applied to a roller for continuous replication.
  • the replication can use laser wave lengths and light output ranges that are not considered standard and thus present an additional hurdle to the counterfeiter, provided that the hologram follows the typical characteristic and can also be copied at its original exposure wavelength.
  • the contact copying from the master has a wavelength offset which is smaller than the spectral half-width of the hologram.
  • color tuning methods can be used to shift the reconstruction wavelength to a copy-safe area.
  • the individual print image is integrated into the security concept of the security element according to the invention in such a way that efficient protection against counterfeiting, serial copies and imitation is provided.
  • a printing ink, a da / u compatible printing substrate and suitable printing parameters are used, which are coordinated so that the ink penetrates sufficiently far into the substrate, and thus brings the required protection against tampering with it.
  • Possible manipulation attempts include, for example, wiping, erasing, scratching or comparable mechanical attacks, also in conjunction with chemical dissolution, attempted bleaching or, in particular, washing out of the printed image.
  • the ink penetrates the substrate in depth preferably by 20-100%, and more preferably by 50-100%. The penetration depth can be determined experimentally, for example, using a focal laser microscope.
  • the inventive ink was filled in a cartridge which is part of the print head.
  • the substrate to be printed has a temperature close to room temperature (16 ° C to 25 ° C), preferably 22 ° C.
  • the distance of the printing nozzles from the printing substrate, as well as other printing parameters such as scanning speed, nozzle spacing, nozzle diameter determine the resolution and quality of the printed image.
  • inkjet printer all popular models can be used. , In the following Dmcklag and primary security features of the inventive security element will be described.
  • the requirement for secure visual verification is that both the trained examiner, e.g. to enable the security printer or the retailer, but also the untrained user, to recognize the security element as an original document as quickly and as unambiguously as possible; this requires clear optical information that can only be copied or imitated with great effort.
  • the decorative claim derives from the claims that the label should be conspicuous, yet support the design of the product or its packaging.
  • the end product should be upgraded visually.
  • the integration of the label into the product design must be balanced in particular with regard to the color and the transparency of the label.
  • These claims are fulfilled by a colored 2D / 3D or 3D photopolymer hologram. Due to its color, but also its transparency outside the hologram image or outside of its reconstruction angle range, it can with printed motifs, such as. the Dmcksent a folding box, be combined.
  • the individual information should be visible information or at least contain visible elements. Depending on the application, it may, for example, be any series designation or reproduce a machine-readable (alpha-) numeric code, barcode, QR "Data Matrix” code or individual product information In the case of personalized products, this information may relate to the person to be expelled
  • Such features are known from other printing processes, for example from offset printing of barcodes on paper and plastic, or from laser engraving in polycarbonate or PVC-based security documents, see, for example, the application US 20090251749. Therefore, the claim to machine readability or machine authentication of the printing features according to the invention, which the reader manufacturers use according to the current state of the art, and which primarily concerns the characteristics of resolution, contrast and color.
  • Another security note is that the misprinted ink prevents illegal replication of the holographic security feature by contrac- tual copies. This can be done on the basis of three different mechanisms:
  • the ink partially absorbs the copy beam, which is to reach the recording medium as the object beam, and thus prevents the replication of the hologram with sufficient
  • the ink induces light scattering which reduces the diffraction efficiency of the copy.
  • the explanation is that the efficiently usable dynamic range of the photopolymer is reduced by the ink-induced intermodulation noise, which in turn writes competing sub-holograms ("ghost holograms").
  • the ink prevents copying by continuously color-shifting the reconstruction color of the hologram image spectrally from the respective original color (which is locally different in the case of the colored image hologram according to the invention) in the hologram image
  • the intensity of the spectral shift, measured in wavelengths [nm] is stronger in the middle of a pressure field (dot density) than at its edge A 1: 1 reproduction of the continuous color spectrum becomes very complex, as it would require many reproduction lasers with narrow
  • FIGS. 1 to 7 explained in more detail. It shows
  • FIG. 1 shows a schematic exposure structure
  • FIG. 2 shows a photograph of a volume hologram master in the direction perpendicular to the master plate
  • FIG. 1 shows a schematic exposure structure
  • FIG. 2 shows a photograph of a volume hologram master in the direction perpendicular to the master plate
  • FIG. 1 shows a schematic exposure structure
  • FIG. 2 shows a photograph of a volume hologram master in the direction perpendicular to the master plate
  • FIG. 2 shows a photograph of a volume hologram master in the direction perpendicular to the master plate
  • FIG. 3 shows measurement results in a representation of the intensity values (red) [w.E.] against the
  • Fig. 4 results in a representation of the intensity values (red) [w.E.] against the
  • FIG. 5 shows measurement results in a representation of the RGB intensity values [w.E.] against the
  • FIG. 6 shows measurement results in a representation of the RGB intensity values [wE] against the
  • Example 1 Contact exposures from the master, optimization of the exposure sequence
  • Fig. 1 shows the schematic exposure setup used to optimize the RGB laser exposure sequence.
  • Bayfol® HX 101 from Bayer MaterialScience AG (Leverkusen, Germany) is used as the photopolymer.
  • the photopolymer layer is 16 ⁇ thick and has a 36 ⁇ PET carrier film.
  • a liner was removed from the other side of the photopolymer layer and the photopolymer was laminated with the free side on the spacer glass to the master hologram.
  • the PET film faces the expanded laser beam (s).
  • the laser beam is white because it consists of overlapping laser beams of the colors red, green and blue. By hiding individual laser beams, mixed colors or monochromatic illumination can be realized.
  • the master on S i 1 is supercalibrated and reconstructs at the laser wavelengths used and generates the object beam in the photopolymer.
  • the master hologram used was a colored volume hologram which has two-dimensional, single-color, reflective, scattering image surfaces, as well as surfaces with additive colors, as can be seen in FIG. The overall structure is in the dark lab.
  • Example 1a Generating a monochrome red hologram copy
  • the red 633 nm laser is directed onto the photopolymer film at an intensity of 1.5 mW / cm 2 .
  • the exposure time was varied in the exposure series and was 2, 4, 8, 16, 32, 64, 84, 104, 124, and 144 s for the exposed samples, respectively.
  • visible, bright holograms from an irradiated energy density of about 12 mJ / cm 2 form.
  • the brightness reaches over 12 mJ / cm 2
  • Example 1 h Discontinuous exposure with red laser
  • the exposure process is slightly modified: The exposure with the red 633 nm laser is interrupted for 1 min. The total exposure time, respectively the irradiated absorbed dose, were kept constant.
  • the exposure sequences were as follows: a) 25 s; Break for 1 min; another 5 s b) 20 s; Break for 1 min; another 10 s c) 15 s; Break for 1 min; another 15 s
  • the contact exposures were made with overlapping laser beams of red (633 nm wavelength), green (561 nm) and blue (491 nm) at 2, 4, 8, 16, 32, 64 and 128 s
  • Figure 6 demonstrates how the point of equally intense single colors can be achieved and how the intensity curves depend on the exposure time.
  • a blue exposure of 32 s duration follows in each case a simultaneous RG exposure of 4 to 16 s duration.
  • the curves have an intersection at 13 s RG exposure time.
  • Fig. 7 prove that the white tone can be adjusted by the type of temporal grouping of the laser beams, if one chooses the exposure times as they follow from the intersection of Fig. 6.
  • the left-hand group corresponds to a three-color simultaneous printing
  • the middle group to an R-G exposure followed by B-exposure
  • the right-hand group to a sequential RGB exposure.
  • Example A1 Benzyl-dinetr , t-yl-hexadecylanioniuni-bis (2-ethylhexyl) sulfosuccinate 3.00 g of sodium bis (2-ethylhexyl) sulfosuccinate and 2.79 g of benzyldimethyl-hexadecylammonium chloride hydrate were dissolved in 30 ml of ethyl acetate stirred for 3 h at room temperature. It was about one Filt filter filtered and the filtrate was freed from the solvent. After drying at 50 ° C. in vacuo, 5.03 g (95.3% of theory) of a colorless honeylike substance of the formula ## STR16 ## were obtained
  • Step Example! A-2 N, N, N, N ', N', N'-hexabutyl, hexa-methanediammonium bis (bis (2-ethylhexyl) sulfosuccinate)
  • ammonium sulfosuccinate 75.6%
  • Step Example! Bl Tctrabutylaninionium salt of the europium complex with 4-thienyl-1,1-trifluoro-hutan-2,4-dione analogous to DE 69103448 in which tetra-methyl-1-hydroxime was replaced by tetrabutylammonium hydroxide the europium complex of the formula
  • Example C-1 Basic Blue 3- (bis (2-ethylhexy! Sulfosuccinate)
  • the RG B-capable photopolymer Bayfol® HX 101 (manufacturer: Bayer MaterialScience) was selected, which was previously exposed with a green 32 nm laser volume laser holographic in the contact printing method.
  • the image hologram as a result was a diffuse green reflecting mirror.
  • the hologram in the photopolymer was then fixed by the UV / VIS light of an iron-doped mercury lamp.
  • the printing inten, consisting of component 1 (dye) and component 2 (solvent butyiacetate) were added dropwise by Eppendorf pipette in amounts of 20 ⁇ (preliminary) or 2 ⁇ (final measurement series) on the photopolymer layer, so that a standing drop was formed. After application, the drop was wiped within a few seconds.
  • the prints were printed using an Inkjet LP50 series printer from PixDro B.V. Cartridge and ink supply system are not susceptible to many chemicals, so different solvents can be used for the print cartridge and refill the print cartridge (part of the "miniature ink supply system") Ink and for the cleaning procedure could be used.
  • the electrical print head voltages U 20 V, 40 V, 60 V were tested. The best results were given in the range of 40 to 60 V.
  • the gas pressure control system was set to provide enough negative pressure for the experiment (setting: 17 mbar) or overpressure to quickly replace the ink.
  • the digital image selected was the "PixDro" signature offered in the software, which was well suited for examining the color tuning effect with lines of different thicknesses (0.25 mm to 1 mm) and round printing dots (about 2 mm in diameter) ,
  • the printhead used has 128 nozzles. Trigger, drip rate, time-of-flight, and other quality-related parameters have been optimized for an ink, but not checked in the series. Also, the inks were not checked or selected for the maximum achievable resolution. There were no significant differences between the printed inks regarding the post-print edge sharpness and the shelf-life of the print image over the 3-month period: the print bins looked clean.
  • the substrates used were paper (only in preliminary experiments) and the holographic photopolymer from Ex. 4.
  • the prepared inks were partially diluted again by admixing more butyiacetate to vary the contrasts.
  • Angle Detuning refers to hologram areas with altered lighting and / or viewing angles.
  • the microscopic cause is probably spatial swelling of hoograflscher lattice structures, with the result that the lattice vectors, in particular at the Change border of printed edges strongly, ie that the lattices bend.
  • the holograms in the area of the image glow at different angles.
  • Exposed substrates of Ex. 5 were subjected to storage at elevated temperature.
  • One sample was laminated with the photopolymer side down on a 1 mm thick glass substrate and placed in this orientation between the hot plates of a FP82 HT Heating Stage (FP 90 controller, manufacturer Mettler Toledo). Only colored inks were examined.
  • inks tested C-1, C-2, C-3, C-4, C-5 and D-1. Result: No visible change in color strength, color value and resolution of the printed image. All combinations of ink and substrate have proven to be stable under these conditions.

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Abstract

L'invention concerne un procédé de fabrication d'un élément de sécurité comprenant une couche holographique dans laquelle un hologramme est disposé, caractérisé au moins par les étapes suivantes : a) préparation de la couche holographique; b) éclairage au moins par endroits de la couche holographique au moyen d'un hologramme maître pour produire une copie d'hologramme dans la couche holographique; c) impression au moins par endroits de la couche holographique au moyen d'une encre pour produire une caractéristique imprimée, l'encre contenant la matière fondue d'un colorant ou d'un constituant incolore ou d'un solvant et un colorant ou un constituant incolore dissout dans la matière fondue. d) fixation de la couche holographique éclairée pour produire l'hologramme dans la couche holographique, la caractéristique imprimée et l'hologramme étant disposés dans la couche holographique de telle manière que la caractéristique imprimée et l'hologramme se superposent au moins par endroits. L'invention concerne également une caractéristique de sécurité fabriquée ou pouvant être fabriquée selon ce procédé.
EP14701330.4A 2013-01-25 2014-01-20 Élément de sécurité comportant un hologramme en volume et une caractéristique imprimée Withdrawn EP2948427A2 (fr)

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