EP2118855B1 - Document de sécurité et/ou de valeur à cristal photonique - Google Patents

Document de sécurité et/ou de valeur à cristal photonique Download PDF

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Publication number
EP2118855B1
EP2118855B1 EP08715461.3A EP08715461A EP2118855B1 EP 2118855 B1 EP2118855 B1 EP 2118855B1 EP 08715461 A EP08715461 A EP 08715461A EP 2118855 B1 EP2118855 B1 EP 2118855B1
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Prior art keywords
security
photonic crystal
luminescent substance
particles
valuable document
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EP08715461.3A
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German (de)
English (en)
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EP2118855A2 (fr
Inventor
Malte Pflughoefft
Oliver Muth
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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
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/003—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using security elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • B42D25/387—Special inks absorbing or reflecting ultraviolet light

Definitions

  • the invention relates to a security and / or value document with a security element, the security element containing a photonic crystal and a luminescent substance arranged on a substrate with an orientation defined in relation to a surface of the substrate.
  • the invention also relates to a method for its production and a method for its verification.
  • optically variable colors have established themselves as a good security feature because they can be easily checked without technical aids.
  • Such optically variable colors are known from practice, for example from bank notes and documents. These are difficult to reproduce, a check at a cash register, for example, is often only fleeting, so that only the presence of a color change is observed. Due to the large number of colors and pigments, for example liquid crystals or platelets or flakes, which have such effects and are commercially available, falsified impressions are known which are clearly different from the original color change colors differ, but are not necessarily recognizable for an inexperienced layman.
  • a security and / or value document of the structure mentioned above is known.
  • a layer is used as the photonic crystal, which is made up of spheres or spheres with a narrow monomodal diameter distribution, the spheres forming a dense packing of spheres, that is, a crystal structure.
  • the diameter of the spheres is in a range of 50-500 nm, so that different reflection conditions according to Bragg's law are present at different network planes of the crystal for different components of visible light. This makes a visually more variable Obtain color effect, namely when pivoting the security and / or value document or viewing at changing viewing angles.
  • Document of value additionally contain a luminescent substance.
  • the diameter of the spheres is chosen so that the desired optically variable effects are achieved, completely independently of any possible luminescence.
  • Structures suitable for the production of photonic crystals are for example in the literature references WHERE. 03/025035 A2 , U.S. 4,391,928 , EP 0 441 559 B1 and EP 0 955 323 B1 described.
  • Luminescence radiation typically does not have a directional characteristic, since the emitter centers are oriented statistically within a coating, color or the like. From other technical fields, for example laser diode technology, it is known to generate directional luminescence radiation by using layer structures whose layers have a thickness that leads to the reflection or forward amplification of the luminescence radiation in a defined spatial direction. Such structures are less suitable for value and security printing due to the complex production.
  • the invention is therefore based on the technical problem of providing a security element which can easily be checked with minimal resources, but with increased reliability, even with a cursory inspection.
  • the particles with which the photonic crystal is formed in terms of diameter and arrangement with the proviso on the Emission wavelength adjusted so that the intensity of the luminescence radiation is different at different viewing angles.
  • the invention makes a considerable improvement in the safe and simple checking of luminescent security elements reached. Because a checking person only needs to expose the security and / or valuable document to radiation that stimulates luminescence, for example UV, and to check i) whether luminescence is observed, and ii) if so, whether its intensity when the security and / or or value document varies. The security and / or value document is only accepted as genuine if both criteria are met. A luminescence security element according to the invention can no longer be reproduced with simple means.
  • the invention uses the knowledge that a photonic crystal can also be used to equip the non-directional luminescence radiation with an anisotropic distribution of the intensity in the solid angle by refraction.
  • Security documents and / or documents of value are only mentioned as examples: ID cards, passports, ID cards, access control cards, visas, tax codes, tickets, driving licenses, vehicle documents, banknotes, checks, postage stamps, credit cards, any chip cards and adhesive labels (e.g. for product security).
  • 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 on which the printing layer is attached Information, images, patterns and the like is applied. All conventional materials based on paper and / or plastic can be used as materials for a substrate.
  • a security element is a structural unit that includes at least one security feature.
  • a security element can be an independent structural unit that can be connected to a security and / or value document, for example glued, but it can also be an integral part of a security and / or value document.
  • An example of the former is a visa that can be stuck onto a security and / or valuable document.
  • An example of the latter is a flat construct that is integrated, for example, laminated into a bank note or an identity card. The latter also includes layers or coatings that are applied to a substrate.
  • a security feature is a structure that can only be produced, reproduced, manipulated or changed with increased effort (compared to simple copying) or not at all in an unauthorized manner.
  • the security feature is formed by the composite of photonic crystal and luminescent substance.
  • the term “network” refers to the optical coupling with coordination of network level spacing and emission wavelength.
  • luminescence refers to the emission of electromagnetic radiation, especially in the IR, visible or UV range, in the course of a relaxation of an atomic or molecular electronic system from an excited state to an energetically lower state, generally the electronic ground state.
  • the previous excitation can take place through electrical energy or an electrical potential (electroluminescence), bombardment with electrons (cathodoluminescence), bombardment with photons (photoluminescence), the action of heat (thermoluminescence) or friction (triboluminescence).
  • photoluminescence is preferred.
  • Luminescence includes in particular phosphorescence and (photo) fluorescence.
  • Fluorescence is a radiant deactivation of excited electronic states, the transition from the excited state to the lower energetic state, for example the ground state, being spin-allowed.
  • the dwell time in the excited state is typically approx. 10 -8 s, ie the emission of fluorescent radiation ends immediately after the end of the energy input for excitation.
  • phosphorescence is a spin-forbidden deactivation of excited states via intercombination processes. Therefore the relaxation is weak and slow.
  • the dwell time in an excited state is a few milliseconds up to hours and the emission of the phosphorescent radiation can be observed for a correspondingly long time.
  • the emission wavelength of a luminescent substance is characteristic of the substance used and is determined by the energy difference between the excited state and the energetically lower electronic state, for example the ground state.
  • the maximum emission intensity in an emission spectrum is referred to as the emission wavelength.
  • a luminescent substance contains atoms, molecules or particles that are capable of luminescence.
  • a luminescent substance can be used to create a luminescent paint or ink that contains the other components of paints or inks customary in the art, such as binders, penetrants, adjusting agents, biocides, surfactants, buffer substances, solvents (water and / or organic solvents), fillers, pigments , Effect pigments, antifoam agents, anti-settling agents, UV stabilizers, etc ..
  • Suitable ink formulations for various printing processes are well known to those skilled in the art from the prior art and luminescent substances used according to the invention are in this respect added instead of or in addition to conventional dyes or pigments.
  • Radiation is typically functional to excite luminescence when the wavelength of the radiation is smaller than the wavelength of the luminescence radiation. However, radiation with a higher wavelength can be functional if the luminescent substance in question is capable of so-called up-conversion processes.
  • a network plane is defined in space by the Miller indices h, k, and 1.
  • the distance d is defined as the smallest distance between parallel network planes, i.e. of lattice planes with the same Miller indices.
  • a close packing of spheres corresponds to an fcc (face centered cubic, cubic close packing) or hcc or hcp (hexagonal close packed, hexagonal close packing) lattice.
  • diameter D denotes the mean diameter of the spheres (or mean distance between the closest spheres adjacent to one another), which is defined as the maximum of the number-related (monomodal) linear normalized density distribution.
  • the density distribution should be as narrow as possible so that clearly visible and reproducible angle dependencies arise when viewed. It is preferred if the (mostly Gaussian-like) density distribution at half the maximum value of the density has a width of less than 10% of the (mean) diameter D, preferably less than 5% of the diameter D, ideally less than 2% of the diameter D.
  • photonic crystals with a complete band gap have so far only been postulated theoretically and are characterized by the fact that light cannot propagate in any spatial direction.
  • photonic crystals with an incomplete band gap as used in particular in the context of the invention, the propagation of the light is only possible in certain spatial directions.
  • the luminescent substance can in principle emit in the IR, visible, or UV. It is preferred if the emission takes place in the visible, since then the Security and / or value documents can be done by simple inspection.
  • the luminescent substance can comprise a luminescent dye and / or a luminescent pigment.
  • the luminescent dye can be selected from the group consisting of "organic fluorescent dyes, naphthalimides, coumarins, xanthenes, thioxanthenes, naphtholactams, azlactones, methines, oxazines, thiazines, and mixtures of two or more different such substances".
  • the luminescent pigment can be selected from the group consisting of "ZnS: Ag, Zn-Silicate, SiC, ZnS, CdS (activated with Cu or Mn), ZnS / CdS: Ag, ZnS: Cu, Al, Y 2 O 2 S: Eu, Y 2 O 3 : Eu, YVO 4 : Eu, Zn 2 SiO 4 : Mn, CaVVO 4 , (Zn, Mg) F 2 : Mn, MgSiO 3 : Mn, ZnO: Zn, Gd 2 O 2 S: Tb , Y 2 O 2 S: Tb, La 2 O 2 S: Tb, BaFCl: Eu, LaOBr: Tb, Mg tungstate, (Zn, Be) silicate: Mn, Cd borate: Mn, Ca 10 (PO 4 ) 6 F, Cl: Sb, Mn, (SrMg) 2 P 2 O 7 : Eu, Sr 2 P 2 O 7 : Sn
  • the luminescent substance is a fluorescent dye which is selected from the group consisting of "organic fluorescent dyes, naphthalimides, coumarins, xanthenes, thioxanthenes, naphtholactams, azlactones, methines, oxazines, thiazines, and mixtures of two or more different such substances ".
  • organic fluorescent dyes naphthalimides, coumarins, xanthenes, thioxanthenes, naphtholactams, azlactones, methines, oxazines, thiazines, and mixtures of two or more different such substances ".
  • fluorescent dyes which is selected from the group consisting of "organic fluorescent dyes, naphthalimides, coumarins, xanthenes, thioxanthenes, naphtholactams, azlactones, methines, oxazines, thiazines, and mixture
  • two or more different luminescent substances can advantageously also be used, the different luminescent substances having different emission wavelengths.
  • the term of the different emission wavelengths denotes a wavelength difference of at least 3 nm, 5 nm, 10 nm, 20 nm, or 30 nm, in the visible.
  • the different emission wavelengths then result in different angles at which the different colors of the luminescence can be observed with particularly high or low intensity.
  • the term high intensity denotes the maximum intensity that can be observed with respect to an emission wavelength.
  • a low intensity then denotes an intensity that is reduced compared to the high intensity, for example reduced by at least 5%, 10%, 20%, 30%, 50%, or 80%.
  • a luminescence color change is generated when the security and / or value document is tilted.
  • the grid points or particles of the photonic crystal can in principle have any shape, for example as small discs or rods. However, it is preferred if the lattice points or particles are designed as spheres (spheres).
  • the spheres are core-shell particles which are arranged in a tight packing of spheres.
  • the mean diameter of the spheres to be set depends on the emission wavelength of the luminescent substance used.
  • the mean diameter of the spheres can thus be in the range from 270-5000 nm, in particular from 270-2500 nm, if the luminescent substance emits in the IR (780-3000 nm).
  • the mean diameter of the spheres can be in the range from 135 to 1200 nm, in particular from 135 to 600 nm, if the luminescent substance emits in the visible (380 to 780 nm).
  • the mean diameter of the spheres can be in the range of 35-600 nm, in particular 35-300 nm, if the luminescent substance emits in the UV (100-380 nm).
  • the photonic crystal can be produced by deposition from the liquid phase by means of self-assembly, for example under pressure, as in the inkjet printing process.
  • self-assembly for example under pressure
  • the production of artificial opals from SiO 2 from solutions is well known.
  • the core / shell particles have a core made of an organic or inorganic core material and a shell made of a polymer have organic shell material, wherein the shell material is flowable at an elevated temperature, while the core material is not flowable at the elevated temperature.
  • the periodic remote structure required for this for example the close packing of spheres, must be produced in a defined orientation in order to form a photonic crystal. If a bed or emulsion or suspension with such core-shell particles is exposed to a compressive force at an elevated temperature, the shear forces that arise between the particles cause the particles to arrange themselves to form a dense packing of spheres on a surface of a substrate and align themselves when the particles move can move against each other.
  • a jacket that is flowable under the pressure and temperature conditions facilitates such movements of the particles in relation to one another and the result is a photonic crystal with excellent long-range order and clear orientation on the substrate.
  • the inorganic core material can be selected from the group consisting of "metals, semimetals, metal chalcogenides, especially metal oxides, metal pnictides, especially metal nitrides or metal phosphides, and mixtures of two or more different such substances, the metal being an element of the first three main groups of the periodic table or a metallic element of the subgroups and wherein the semimetal can comprise Si, Ge, As, Sb, and Bi ", in particular is selected from the group consisting of "SiO 2 , TiO 2 , ZrO 2 , SnO 2 , and Al 2 O 3 ".
  • the organic core material is preferably selected from the group consisting of "aliphatic, aliphatic / aromatic or fully aromatic polyesters, polyamides, polycarbonates, polyurea, polyurethanes, aminoplast resins, phenoplast resins such as formaldehyde condensates of melamine, urea or phenol, epoxy resins, acrylic esters such as methyl ( meth) acrylate, butyl (meth) acrylate, isopropyl (meth) acrylate, polystyrene, PVC, polyacrylonitrile, random or block copolymers of one or more such homopolymers, and mixtures of two or more different such homo- or copolymers ".
  • the jacket material can be selected from the group consisting of "aliphatic, aliphatic / aromatic or fully aromatic polyesters, polyamides, polycarbonates, polyurea, polyurethanes, aminoplast resins, phenoplast resins such as formaldehyde condensates of melamine, urea or phenol, epoxy resins, polyepoxides, poly (meth) acrylates, such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, polyisopropyl (meth) acrylate, polystyrene, PVC, polyacrylonitrile, polyethylene, polypropylene, polyethylene oxide, polybutadiene, polytetrafluoroethylene, polyoxymethylene, rubber, polyisoprene, random or block copolymers a or more such homopolymers, and mixtures of two or more different such homo- or copolymers ".
  • the core material has a higher glass transition temperature than the cladding material, since then at a temperature between the glass transition temperatures of the materials only the cladding material and not the core material flows.
  • the core material can, for example, have a glass transition temperature in the range of more than 60 ° C, preferably more than 80 ° C, most preferably more than 90 ° C, while the jacket material, for example, has a glass transition temperature in the range of 40 - 90 ° C, in particular 60 - 80 ° C.
  • Such a range of glass transition temperatures is recommended as core material for organic polymers, for example.
  • the glass transition temperature of the core material can be above 300 ° C, and then the glass transition temperature of the cladding area, for example in the case of polycarbonates, can also be high, for example in the range of 80 - 250 ° C, in particular 120 - 200 ° C.
  • the cladding material which can form a matrix in the course of the production of the photonic crystal, in which the spheres or cores are embedded (and fixed), should have a refractive index (also called refractive index) different from the refractive index of the core material.
  • refractive index also called refractive index
  • the expression of the different refractive index denotes a difference of at least 0.001, better at least 0.01, advantageously at least 0.1.
  • the person skilled in the art can easily select suitable material pairings from the above materials for the core material and the cladding material with regard to the difference in the refractive index.
  • the core material, but also the cladding material have the higher refractive index in each case.
  • the weight ratio of core material to cladding material can be in the range from 2: 1 to 1: 5, in particular in the range from 3: 2 to 1: 3. In the case of polymeric materials, this ratio is preferably no greater than 2: 3 for both materials.
  • a coupling layer can be set up between the core and the shell of a core-shell particle.
  • crosslinked or partially crosslinked organic polymers come into consideration.
  • the surface of the core can be functionalized in a manner customary in the art for binding or adhesion of the jacket material.
  • core-shell particles suitable for the production of photonic crystals is described, for example, in the prior art mentioned at the beginning, as well as further variants and details for core materials, shell materials, coupling layers, etc. This prior art is hereby expressly described in Referenced.
  • Photonic crystals which can be used according to the invention can be formed as a film, layer or foil. Accordingly, they can be applied to a substrate using conventional coating processes or adhesion promoters. In doing so, they can be an integral part of a. Form document, for example in the case of card structures.
  • Photonic crystals according to the invention can form a visible pattern, for example the outline of an object or a person, or a sequence of characters made up of letters and / or numbers. Barcodes can also be used as samples. Then the coating takes place with the appropriate printing process or a film is cut out accordingly. It goes without saying that a photonic crystal is also macroscopically isotropic, i.e. without pattern, can be formed.
  • the luminescent substance can be arranged in the particles of the photonic crystal.
  • core-shell particles an arrangement in the core material and / or in the shell material of the core-shell particles is possible.
  • the material in question is preferably mixed homogeneously with the luminescent substance prior to solidification or polymerization in the course of producing the particles.
  • the luminescence-generating doping for example with rare earth elements, which are built into the host lattice of the core material, can take place.
  • the photonic crystal can then be produced without admixing luminescent particles, as a result of which disturbances in the formation of the photonic crystal due to the presence of interstitial luminescent particles are reliably avoided.
  • the respective polymer can contain luminescent monomer units, namely regularly, statically, in blocks or as side chains (graft copolymers).
  • the crosslinking agent can also be luminescent.
  • luminescent substances can be covalently, ionically or complexed bound to the polymer chain.
  • the luminescent substance can, however, also be arranged between the particles of the photonic grating.
  • the ratio of the diameter D p of the pigment particles to the diameter D (or D ⁇ ) of the particles of the photonic grating D p / D (or D p / D ⁇ ) is less than 0.5 , preferably less than 0.1, most preferably less than 0.02.
  • the pigment particles can then be arranged between the particles or spheres of the photonic crystal and damage to the particles or spheres as a result of the action of pressure is practically impossible.
  • the luminescent substance is a luminescent dye, it can in any case be freely distributed between the particles of the photonic grating without disturbing them or their arrangement.
  • the photonic crystal is produced by mixing particles of the photonic crystal with the luminescent substance and then forming the long-range order to form the crystal, as described above.
  • a variant of this is when the luminescent substance is deposited on the surface of the particles of the photonic crystal, for example by layer by layer Absorption. This results in a uniform growth on the particles of the photonic crystal, with the result that the narrow density distribution is maintained.
  • the advantage here is that the particles of the photonic crystal and the luminescent substance can be selected and modified independently of one another, which enables easier adaptation to different products of the value and security printing.
  • the photonic crystal can also be underlaid with the luminescent substance.
  • the substrate can be coated, for example printed, with a paint or ink which contains the luminescent substance.
  • the photonic crystal is then applied to the coating, for example in the simplest case as a film.
  • This variant is the simplest in terms of process engineering and also allows modifications of the luminescent substance / photonic crystal system in a simple manner, for example for different types or values of security and / or value documents.
  • non-luminescent colorants such as dyes or pigments
  • all colorants customary in the field of security and / or value documents that are known to the average person skilled in the art can be used.
  • Usual forensic feature substances can also be used in the photonic Crystal or another layer of the security and / or value document can be provided.
  • the invention further relates to a method for producing a security and / or value document according to the invention or a security element therefor, wherein a substrate is provided on a surface or partial surface with a coating containing the particles of the photonic crystal to be formed and this coating is provided with the simultaneous action of Heat and pressure is compressed, optionally with a luminescent layer containing the luminescent substance being applied to the substrate prior to coating with the particles, and / or wherein the particles contain the luminescent substance or are mixed with it.
  • the compression is used to form the photonic crystal.
  • the action of heat preferably takes place at a temperature in the range of 60-260 ° C, in particular 70-190 ° C, and for a duration of 0.5-7200 s, preferably 0.5-3600 s, most preferably 1 - 10 s.
  • the compression can take place at a pressure of 1-100 bar, preferably 1-20 bar.
  • the compaction takes place by means of a press, in particular a laminating press.
  • the action of heat is at correspondingly higher temperature, for example at 140-250 ° C.
  • a separating and / or protective layer can be arranged on the coating with particles of the photonic crystal.
  • the protective layer can be welded to the substrate, possibly the luminescent layer, and the coating with particles or laminated to form a layer composite.
  • the protective layer should be transparent in relation to the emission wavelength lambda.
  • a security and / or value document according to the invention can also be produced by applying a finished photonic crystal, in particular in the form of a film (thickness, for example 0.1-500 ⁇ m ), to the substrate and connecting it to it, be it by gluing, be it by lamination.
  • a finished photonic crystal in particular in the form of a film (thickness, for example 0.1-500 ⁇ m )
  • the luminescent substance can already be present in the photonic crystal.
  • the substrate it is also possible here for the substrate to be provided beforehand with a separate coating, for example a printing layer containing the luminescent substance.
  • the invention further relates to a security and / or value document which can be obtained using a method according to the invention mentioned above.
  • the invention relates to a method for verifying a security system according to the invention and / or value document or security element, the luminescent substance being stimulated to emit luminescent radiation, for example by exposure to UV radiation, the intensity of the luminescent radiation being determined as a function of the angle with respect to the surface of the security and / or value document, and wherein the specific angle dependence of the luminescence radiation is compared with a predetermined angle dependency. If no angle dependency is determined, or if the determined angle dependency does not match the predefined angle dependency, then this is not a security and / or valuable document according to the invention and consequently a replica. If the determined angle dependency corresponds to the predetermined angle dependency, the security and / or value document is verified as being according to the invention and consequently genuine.
  • the determination can be carried out by means of visual inspection. But it is also possible to determine the angle dependency by machine. In the case of different luminescent substances, the determination is carried out in each case for the relevant emission wavelengths for which different angle dependencies are specified.
  • a substrate 1 which can be single-layer or multi-layer.
  • a printing layer 2 is applied directly to this substrate, the printing layer 2 containing two different fluorescent substances in a uniform distribution.
  • a first fluorescent substance has an emission wavelength of 500 nm and a second fluorescent substance has an emission wavelength of 707 nm.
  • a photonic crystal 3 in the form of a film follows in the layer sequence.
  • This photonic crystal 3 is made of core-shell particles according to the literature reference WO 2003/025035 A2 educated.
  • the core / shell particles have a mean particle diameter of 354 nm.
  • the photonic crystal 3 is followed by a protective layer 4 which is transparent to visible light and which in turn can be single-layer or multilayer.
  • a single-layer or multi-layer intermediate layer is arranged between the printing layer 2 and the photonic crystal 3, which is not shown for the sake of clarity.
  • the substrate 1 with the printing layer 2, the photonic crystal 3 and the protective layer 4 are connected to one another by lamination and form a monolithic layer block.
  • red (707 nm) with maximum intensity at around 45 ° relative to the surface normal of the security and / or value document is emitted, but at 0 ° and 90 ° the intensity is greatly reduced, more typically below 90% of the maximum intensity.
  • green (500 nm) can be observed at 45 ° with only 10% or less of the maximum intensity, but at 0 ° and 90 ° with maximum intensity.

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  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Security & Cryptography (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Luminescent Compositions (AREA)
  • Credit Cards Or The Like (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Optical Filters (AREA)

Claims (15)

  1. Document de sécurité et/ou de valeur comportant un élément de sécurité, ledit élément de sécurité contenant un cristal photonique disposé sur un substrat ainsi qu'une substance luminescente, caractérisé en ce que
    les particules constituant le cristal photonique sont ajustées à une longueur d'onde d'émission lambda de la substance luminescente de telle manière qu'une longueur d'onde d'émission lambda de la substance luminescente de formule lambda = m * 2 * d
    Figure imgb0011
     suffise, d représentant la distance entre deux plans du réseau du cristal photonique et d s'exprimant de la manière suivante avec la constante de réseau a : d = a/(h2 + k2 + 12)0,5, et m étant un nombre entier positif, ce qui permet une intensité variable du rayonnement luminescent sous divers angles d'observation.
  2. Document de sécurité et/ou de valeur selon la revendication 1, dans lequel la substance luminescente émet dans l'IR, le visible ou l'UV, et/ou dans lequel la substance luminescente comprend un colorant luminescent et/ou un pigment luminescent, et/ou
    dans lequel le colorant luminescent est choisi dans le groupe constitué par les colorants fluorescents organiques, les naphtalimides, les coumarines, les xanthènes, les thioxanthènes, les naphtolactames, les azolactones, les méthines, les oxazines, les thiazines et les mélanges d'au moins deux de ces substances différentes, et/ou dans lequel le pigment luminescent est choisi dans le groupe constitué par ZnS:Ag, silicate de Zn, SiC, ZnS, CdS (activé au Cu ou Mn), ZnS/CdS:Ag, ZnS:Cu,Al, Y2O2S:Eu, Y2O3:Eu, YV04:Eu, Zn2SiO4:Mn, CaVVO4, (Zn,Mg)F2:Mn, MgSiO3:Mn, ZnO:Zn, Gd2O2S:Tb, Y2O2S:Tb, La2O2S:Tb, BaFCl:Eu, LaOBr:Tb, tungstate de Mg, silicate de (Zn, Be):Mn, borate de Cd:Mn, CalO (PO4) 6F, Cl:Sb, Mn, (SrMg) 2P2O7:Eu, Sr2P2O7:Sn, Sr4A114O25:Eu, Y2SiO5:Ce, Tb, Y (P, V) O4:Eu, BaMg2Al10O27:Eu, MaAl11O19:Ce, Tb et les mélanges d'au moins deux de ces substances différentes, et/ou
    dans lequel la substance luminescente consiste en un colorant fluorescent choisi dans le groupe constitué par les colorants fluorescents organiques, les naphtalimides, les coumarines, les xanthènes, les thioxanthènes, les naphtolactames, les azolactones, les méthines, les oxazines, les thiazines et les mélanges d'au moins deux de ces substances différentes.
  3. Document de sécurité et/ou de valeur selon l'une des revendications 1 et 2,
    dans lequel le cristal photonique est constitué par une structure fcc ou hcc présentant une constante de réseau a, et dans lequel d = a/n0,5 où n = 1 à 20, notamment 1 à 5, et dans lequel n représente (h2 + k2 + l2) où h, k, et l sont des indices de Miller, et/ou
    dans lequel les nœuds du cristal photonique sont constitués par des sphères ou leur centre.
  4. Document de sécurité et/ou de valeur selon la revendication 3, eu égard au deuxième cas de figure, dans lequel les sphères consistent en des particules noyau-enveloppe disposées selon un empilement dense de sphères et dans lequel le diamètre moyen des sphères est éventuellement compris dans la plage allant de 270 à 5000 nm, notamment de 270 à 2500 nm, lorsque la substance luminescente émet dans l'IR (780 à 3000 nm), ou
    le diamètre moyen des sphères est compris dans la plage allant de 135 à 1200 nm, notamment de 135 à 600 nm, lorsque la substance luminescente émet dans le visible (380 à 780 nm), ou
    le diamètre moyen des sphères est compris dans la plage allant de 35 à 600 nm, notamment de 35 à 300 nm, lorsque la substance luminescente émet dans l'UV (100 à 380 nm).
  5. Document de sécurité et/ou de valeur selon la revendication 4, dans lequel les particules noyau-enveloppe présentent un noyau en une matière organique ou inorganique et une enveloppe en une matière organique polymère, ladite matière de l'enveloppe étant fluide à température accrue tandis que la matière du noyau est non fluide à température accrue.
  6. Document de sécurité et/ou de valeur selon la revendication 5, dans lequel la matière organique du noyau est choisie dans le groupe constitué par des matières aliphatiques, aliphatico-aromatiques ou totalement aromatiques telles que polyesters, polyamides, polycarbonates, polyurée, polyuréthanes, résines aminoplastiques, résines phénoplastiques, telles que par exemple les condensats de formaldéhyde et de mélamine, d'urée ou de phénol, résines époxydes, esters acryliques tels que le (méth)acrylate de méthyle, le (méth)acrylate de butyle, le (méth)acrylate d'isopropyle, polystyrène, PVC, polyacrylonitrile, copolymères aléatoires ou séquencés d'un ou plusieurs de ces homopolymères et les mélanges d'au moins deux de ces homopolymères ou copolymères différents, ou
    dans lequel la matière inorganique du noyau est choisie dans le groupe constitué par les métaux, métalloïdes, chalcogénures de métaux, notamment les oxydes de métaux, les pnictures de métaux, notamment nitrures de métaux ou phosphures de métaux et les mélanges d'au moins deux de ces substances différentes, ledit métal pouvant consister en un élément des trois premiers groupes principaux du tableau périodique des éléments ou en un élément métallique des groupes voisins et dans lequel le métalloïde peut comprendre Si, Ge, As, Sb et Bi, ladite matière étant notamment choisie dans le groupe constitué par SiO2, TiO2, ZrO2, SnO2 et Al2O3.
  7. Document de sécurité et/ou de valeur selon l'une des revendications 5 et 6, dans lequel la matière du noyau présente une température de transition vitreuse supérieure à 60 °C, de préférence supérieure à 80 °C, de manière la plus préférable supérieure à 90 °C, ou dans lequel la matière du noyau présente une température de transition vitreuse supérieure à 300 °C, et/ou dans lequel la matière de l'enveloppe est choisie dans le groupe constitué par des matières aliphatiques, aliphatico-aromatiques ou totalement aromatiques telles que polyesters, polyamides, polycarbonates, polyurée, polyuréthanes, résines aminoplastiques, résines phénoplastiques, telles que par exemple les condensats de formaldéhyde et de mélamine, d'urée ou de phénol, résines époxydes, polyépoxydes, poly(méth)acrylates tels que le (méth)acrylate de polyméthyle, le (méth)acrylate de polybutyle, le (méth)acrylate de polyisopropyle, polystyrène, PVC, polyacrylonitrile, polyéthylène, polypropylène, oxyde de polyéthylène, polybutadiène, polytétrafluoroéthylène, polyoxyméthylène, caoutchouc, polyisoprène, copolymères aléatoires ou séquencés d'un ou plusieurs de ces homopolymères et les mélanges d'au moins deux de ces homopolymères ou copolymères différents, et dans lequel la matière de l'enveloppe présente de préférence une température de transition vitreuse située dans la plage de 40 à 90 °C, notamment de 60 à 80 °C, ou dans la plage de 80 à 250 °C.
  8. Document de sécurité et/ou de valeur selon l'une des revendications 1 à 7, dans lequel la substance luminescente est disposée dans le cristal photonique.
  9. Document de sécurité et/ou de valeur selon la revendication 8, dans lequel la substance luminescente est disposée dans les particules du cristal photonique, notamment dans la matière du noyau et/ou dans la matière de l'enveloppe des particules noyau-enveloppe, et/ou
    dans lequel la substance luminescente est disposée entre les particules du cristal photonique.
  10. Document de sécurité et/ou de valeur selon l'une des revendications 1 à 9, dans lequel le cristal photonique repose sur la substance luminescente.
  11. Procédé de production d'un document de sécurité et/ou de valeur ou d'un élément de sécurité selon l'une des revendications 1 à 10, dans lequel le substrat, sur une surface ou une surface partielle, est doté d'un revêtement contenant les particules du cristal photonique et ce revêtement est comprimé sous l'application simultanée de chaleur et de pression, dans lequel, facultativement, avant ledit revêtement de particules de cristal photonique, une couche luminescente contenant la substance luminescente est appliquée sur le substrat, et/ou dans lequel les particules de cristal photonique contiennent la substance luminescente ou y sont mélangées.
  12. Procédé selon la revendication 11, dans lequel l'application de la chaleur s'effectue au moyen d'une température située dans la plage de 60 à 180 °C, notamment de 70 à 130 °C, et pour une durée de 0,5 à 7200 s, de préférence de 0,5 à 3600 s, de manière la plus préférable de 1 à 10 s, et/ou dans lequel la compression s'effectue sous une pression de 1 à 100 bar, de préférence de 1 à 20 bar, et/ou dans lequel la compression s'effectue au moyen d'une presse, notamment une presse à stratifier, et/ou dans lequel une couche de séparation et/ou de protection est disposée sur le revêtement de particules de cristal photonique, et/ou dans lequel, au cours de l'application de chaleur et de pression, la couche de protection est soudée au substrat, éventuellement à la couche luminescente, et au revêtement de particules de cristal photonique ou est stratifiée avec ceux-ci pour produire un composite stratifié, ladite couche de protection étant éventuellement transparente à la longueur d'onde d'émission lambda.
  13. Document de sécurité et/ou de valeur ou élément de sécurité susceptible d'être obtenu à l'aide d'un procédé selon l'une des revendications 11 et 12.
  14. Document de sécurité et/ou de valeur selon l'une des revendications 1 à 10 ou 13 sous un mode de réalisation consistant en une pièce d'identité personnelle, un passeport, une carte d'identité, une carte de contrôle d'accès, un visa, un timbre fiscal, un ticket, un permis de conduire, un papier de véhicule, un billet de banque, un chèque, un timbre-poste, une carte de crédit, une carte à puce ou une vignette autocollante.
  15. Procédé de vérification d'un document de sécurité et/ou de valeur ou d'un élément de sécurité selon l'une des revendications 1 à 10 ou 13 et 14, dans lequel la substance luminescente est excitée pour émettre un rayonnement luminescent, dans lequel l'intensité du rayonnement luminescent est observée ou déterminée dans une dépendance angulaire par rapport à la surface du document de sécurité et/ou de valeur, et dans lequel la dépendance angulaire du rayonnement luminescent observée ou déterminée est comparée à une dépendance angulaire prédéfinie.
EP08715461.3A 2007-02-08 2008-02-06 Document de sécurité et/ou de valeur à cristal photonique Active EP2118855B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007007029A DE102007007029A1 (de) 2007-02-08 2007-02-08 Sicherheits- und/oder Wertdokument mit photonischem Kristall
PCT/DE2008/000228 WO2008095481A2 (fr) 2007-02-08 2008-02-06 Document de sécurité et/ou de valeur à cristal photonique

Publications (2)

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EP2118855A2 EP2118855A2 (fr) 2009-11-18
EP2118855B1 true EP2118855B1 (fr) 2020-09-23

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CN (1) CN101652800B (fr)
AU (3) AU2008213463A1 (fr)
CA (1) CA2677418C (fr)
DE (1) DE102007007029A1 (fr)
WO (1) WO2008095481A2 (fr)

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DE102007012042A1 (de) 2007-03-13 2008-09-18 Giesecke & Devrient Gmbh Sicherheitselement
GB0720550D0 (en) 2007-10-19 2007-11-28 Rue De Int Ltd Photonic crystal security device multiple optical effects
CA2656506A1 (fr) * 2009-02-27 2010-08-27 Bank Of Canada Dispositif de verification des caracteristiques de securite
DE102011112696B4 (de) * 2011-08-31 2016-02-18 Martin-Luther-Universität Halle-Wittenberg Solarzelle mit Folie zur Rückseitenkontaktierung, Verfahren zu deren Herstellung und Verwendung einer Folie als Rückseitenkontaktierung
ES2632808T3 (es) * 2014-09-04 2017-09-15 Nicox Science Ireland Compuestos de carnosina donadores de óxido nítrico
EP3109060B1 (fr) 2015-06-23 2018-08-15 Hueck Folien Gesellschaft m.b.H. Element de securite et procede destines a la fabrication d'un element de securite
WO2020192579A1 (fr) * 2019-03-22 2020-10-01 苏州科技大学 Marque anti-contrefaçon et papier anti-contrefaçon

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FR2554122B1 (fr) 1983-11-02 1987-03-20 Rhone Poulenc Spec Chim Nouvelle composition destinee au marquage de documents et procede de verification de l'authenticite de ces documents
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Also Published As

Publication number Publication date
WO2008095481A3 (fr) 2008-12-11
EP2118855A2 (fr) 2009-11-18
CN101652800A (zh) 2010-02-17
CA2677418A1 (fr) 2008-08-14
AU2016225899B2 (en) 2018-02-01
AU2016225899A1 (en) 2016-09-29
CA2677418C (fr) 2016-09-20
DE102007007029A1 (de) 2008-08-14
WO2008095481A2 (fr) 2008-08-14
AU2008213463A1 (en) 2008-08-14
AU2014203815A1 (en) 2014-07-31
CN101652800B (zh) 2013-02-06

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