EP2307203A2 - Document de sécurité comprenant un guide de lumière - Google Patents

Document de sécurité comprenant un guide de lumière

Info

Publication number
EP2307203A2
EP2307203A2 EP09777264A EP09777264A EP2307203A2 EP 2307203 A2 EP2307203 A2 EP 2307203A2 EP 09777264 A EP09777264 A EP 09777264A EP 09777264 A EP09777264 A EP 09777264A EP 2307203 A2 EP2307203 A2 EP 2307203A2
Authority
EP
European Patent Office
Prior art keywords
light
security
lichtleitstruktur
document
document body
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.)
Granted
Application number
EP09777264A
Other languages
German (de)
English (en)
Other versions
EP2307203B1 (fr
Inventor
Malte Pflughoefft
Christian Kunath
Oliver Muth
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.)
Bundesdruckerei GmbH
Original Assignee
Bundesdruckerei GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bundesdruckerei GmbH filed Critical Bundesdruckerei GmbH
Priority to PL09777264T priority Critical patent/PL2307203T3/pl
Publication of EP2307203A2 publication Critical patent/EP2307203A2/fr
Application granted granted Critical
Publication of EP2307203B1 publication Critical patent/EP2307203B1/fr
Priority to CY20121100782T priority patent/CY1113389T1/el
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • B42D25/20—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
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G—PHYSICS
    • G07—CHECKING-DEVICES
    • G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
    • G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
    • G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
    • G07D7/12—Visible light, infrared or ultraviolet radiation
    • G07D7/1205—Testing spectral properties

Definitions

  • the invention relates to a value and / or security document, comprising a document body, which comprises a laminate formed from a plurality of substrate layers, in which a Lichtleit Quilt is formed.
  • the invention further relates to a method for producing such a value and / or security document.
  • the manner of embodiment of the optical waveguide structure constitutes a security feature for the value and / or security document.
  • the invention further relates to a method for verifying the value and / or security document with regard to its authenticity and / or integrity against manipulation and / or falsification an apparatus for verifying such a value and / or security document and an assistance device for aiding the verification of a value and / or security document.
  • Security and / or security documents have security features that make it difficult or even impossible to imitate, forge or falsify the security and / or value document.
  • the prior art discloses a large number of such security features.
  • a part of the security features is characterized by how they influence an interaction of the value and / or security document with electromagnetic radiation, in particular light in the visible wavelength range. It is known, for example, to integrate diffractive structures, which may be formed, for example, as holograms, into the value and / or security document. Inhaled light is diffracted by such a diffractive structure. A resulting diffraction pattern is compared with an expected diffraction pattern to verify the value and / or security feature or value and / or security document.
  • luminescent substances for example fluorescent colors
  • security documents it is known to integrate luminescent substances, for example fluorescent colors
  • luminescent substances for example fluorescent colors
  • properties of light transmission By way of example, there may be mentioned transparency that consists of two mutually corresponding structures, which are arranged on different sides of a translucent layer in the security document and complement each other when the document is scanned to form a pattern.
  • a security substrate which comprises a carrier having a front side which extends from a first edge to a second edge opposite the first edge and comprises a rear side opposite the front side and wherein the front side and the back side are mutually adjacent are arranged so that they form a light guide.
  • the security substrate further comprises a luminescent label disposed in the carrier between the front and the back and between the first and second edges such that luminescence of the security label is directed through the optical fiber to at least one of the first and second edges. so that a verification of the security document can be carried out by reading out the luminescence light stimulated by the front or the back at the edges.
  • the invention is based on the technical problem of providing an improved value and / or security document which uses a light guide as a security feature, but is insensitive to surface treatment, for example printing, and offers greater security against counterfeiting. Furthermore, an improved method and a device and an assistance device for verifying such a value and / or security document are needed. Broad features of the invention
  • a value and / or security document comprising a document body is proposed, which comprises a laminate formed from a plurality of substrate layers, in which a light guide structure is formed, wherein the light guide structure is a printed structure printed on one of the substrate layers.
  • Such a security and / or security document is obtained by a method for producing a security and / or security document, which comprises the steps of: providing substrate layers; Gathering the substrate layers into a substrate layer stack in which the substrate layers overlap one another; Laminating the substrate layers by applying heat and pressure to a document body in which a Lichtleit Cook is formed, characterized in that on one of the substrate layers before lamination, the Lichtleit Cook is printed in the form of a print pattern.
  • a security and / or security document having such a security feature can be verified by a method comprising the steps of: coupling light into the light guiding structure of the document body, spatially resolved sensing of the guided in the light guiding structure and coupling areas on one or more side surfaces Connecting top and bottom, escaping light and comparing a light exit pattern derived from the spatially resolved detected escaping light with an expected pattern.
  • a structuring of the optical waveguide ie the optical waveguide structure, defines a characteristic light emission pattern.
  • the light-guiding structure is printed flat on one of the substrate layers.
  • a structure of the light guide structure defines a light exit at edges of the document body.
  • An apparatus for verifying the security feature of a value and / or security document formed by the light guide structure comprises an excitation source for effecting coupling of light into the light guide structure of the document body, a detection unit for spatially resolved detection of the guided in the light guide structure and coupling areas on one or more Side surfaces connecting a top and a bottom, exiting light, and a comparison unit for comparing a light emission pattern derived from the spatially resolved detected outgoing light with an expected pattern.
  • An apparatus for supporting the verification of a security document merely comprises an excitation source for coupling the light into the light guiding structure of the document body. Detection of a light emission pattern in such an embodiment is performed by a human observer, who compares the observed light emission pattern to an expected light emission pattern for verification.
  • the invention makes use of the fact that the printing structure has a refractive index which is different from the refractive index (s) of the surrounding material or materials.
  • the light guiding structure is arranged between two of the substrate layers.
  • a major advantage of the manufacturing method is that the optical waveguide structure can be printed by printing on one of the substrate layers before lamination. This makes it possible to print a variety of structures.
  • any printable composition or material is considered as defined herein. This means that any composition or material that is printed on a substrate layer surface will be a (printed) ink or ink.
  • a resulting ink layer or ink layer constitutes a print layer. It does not necessarily have to have a perceivable color to the human observer.
  • a transparent print layer is therefore in this sense also a color layer.
  • a structured printing layer in turn represents a printing structure.
  • a light guide structure is a structure capable of guiding electromagnetic radiation, preferably light in the visible wavelength range, due to total reflection at an interface of the light guide structure.
  • Luminescent substances are materials or substances which, upon excitation of an atomic or molecular excited state, emit electromagnetic energy Radiation, preferably in the visible wavelength range in a low-energy state. Even more complex electronic transitions with the emission of photons are considered here as luminescence processes. Depending on the physical and / or chemical processes different luminescence processes are distinguished. In the context of the described here, it does not matter which luminescence process the luminescent substance uses.
  • these can be electroluminescence, cathodoluminescence, photoluminescence, in particular fluorescence or phosphorescence or also more-photon processes (eg so-called upconversion processes), chemiluminescence, bioluminescence, triboluminescence, thermoluminescence, sonoluminescence, radioluminescence and piezo luminescence.
  • the printing-technical application of the light guiding structure or of the pressure structure which forms the light guiding structure can be carried out by means of any printing method, for example high pressure, planographic printing, throughprint, gravure printing or particularly preferably by means of digital printing, for example by means of an inkjet printing.
  • the light guiding structure is printed with an ink or ink comprising particles of a material having a refractive index greater than the refractive index of the materials adjacent to the light guiding structure, the particles having an average diameter smaller than half Wavelength of a radiation provided for the light pipe, preferably less than one fifth of this wavelength, and more preferably less than one-tenth of this wavelength.
  • Particularly suitable as particles are metal chalcogenides, for example metal oxides, preferably titanium dioxide, zirconium dioxide, metal sulfides, for example zinc sulfide, but also diamond, in each case in nanoscale form.
  • a substance, which is present in nanoscale form, consists of particles whose particle distribution in the grain size range between 1 and 100 nm. Also conceivable are amorphous material forms, in particular high-index (lead) glasses.
  • the printing structure which forms the light guiding structure becomes in the document body, which has an upper side and a lower side and one or more side surfaces connecting the upper side and the lower side printed so printed on the one substrate layer that the Lichtleit Cook in the finished document body comprises a plurality of coupling regions, which are each formed along the one or more side surfaces of the document body and separated from each other, via coupling regions light, in the Lichtleit Cook total reflection at interfaces the light guiding structure is passed, one and / or can be coupled out.
  • the light guide structure is formed so that when light is coupled into at least one of the coupling regions, this light is conducted via a light guide in the light guide structure to one or more other coupling regions. It is preferably provided that the light is conducted to a plurality of coupling regions. Since these are formed separately from each other along the side surfaces or the side surfaces of the document body, the light coupled into the light guide exits the light guide structure and the document body at different locations. This results in a light emission pattern, which is characteristic for the structure of the light guide structure.
  • Such a coding is preferably carried out in an individualizing, preferably personalizing manner.
  • An individualizing information is information that makes two otherwise identical objects distinguishable.
  • An individualizing information in the field of value and / or security documents is, for example, a serial number.
  • An individualizing information that encodes information associated with a person to whom the security document is associated is referred to as personalizing information.
  • personalizing information are merely exemplified a name, a date of birth, a first name, a place of birth, a place of residence, a height, an eye color, biometric information such as a face image and / or a fingerprint or iris pattern, etc.
  • the light guiding structure is thus structured such that it has information about a number of coupling regions, positioning of the coupling regions, relative distances of the coupling regions from one another and / or their respective extent along the one or more side surfaces, preferably an individualizing or personalizing one Information encoded in the document body or will.
  • the light guide structure is surrounded by transparent material.
  • a material thickness is desirable, which preferably carries about one wavelength, particularly preferably a multiple of the wavelength of the light conducted via the light guide structure. Typically, material thicknesses of a few micrometers are sufficient for visible light.
  • the optical waveguide structure In order to be able to apply the optical waveguide structure to a printed substrate layer surface which is already printed with opaque or transparent or translucent colors, it is provided in one embodiment that initially a transparent ink layer or printing layer is printed. On the transparent printing layer, which has a low refractive index, then the printing layer forming the light guiding structure can then be printed. Likewise, the patterned printed layer, which forms the optical waveguide structure, can be overprinted with a transparent, low-refractive-index print layer in order to preclude the adverse effects of a substrate layer arranged thereon in the document body, for example printed on it.
  • the light guiding structure is printed in several layers in some embodiments.
  • a monolithic optical waveguide structure is formed even in the case of a construction comprising a plurality of printed layers. This means that there are no boundaries between the separately applied portions of the optical waveguide structure.
  • the optical waveguide structure is preferably structured into a plurality of strands which each begin at a coupling region.
  • the optical waveguide structure comprises a strand beginning at one of the coupling regions, which branches off into a plurality of further strands, each terminating at one of the plurality of coupling regions.
  • This pressure structure or optical waveguide structure is preferably designed such that a coupling of light is possible at the coupling region at which the branching strand begins, which is then conducted to the multiple coupling regions at which the multiple strands terminate.
  • an opaque release structure is formed in the printing plane.
  • This release structure can also be applied by printing.
  • a transparent material is arranged in each case between the separating structure and the strands in a preferred embodiment.
  • a coupling of light into the optical waveguide structure can take place, on the one hand, via coupling in of an external light source via a coupling region on the one or one of the several lateral surfaces into the optical waveguide structure.
  • the printing structure comprises at least one luminescent substance.
  • a coupling of light can thus take place via an excitation of the luminescence.
  • the luminescent substance can be any luminescent substance that can be integrated into the ink or ink by printing technology, which is used to form the printing structure that forms the light-guiding structure. Of these, particular preference is given to luminescent substances which have electroluminescence and photoluminescence.
  • Excitation of the luminescence can take place over the entire surface.
  • decoupling of the light preferably takes place from the coupling regions, since the light is conducted via light conduits to these regions.
  • between the top and the light guide structure and / or the underside of the document body and the light guide structure is arranged in each case an opaque element. This means that between the upper side of the document body and the light guide structure, an opaque element and / or between the underside of the document body and the Lichtleit Modell another opaque element are arranged.
  • the opaque element and / or the further opaque element may each be a printing layer or also an opaque substrate layer or another element introduced into the security and / or security document, for example a metallized region.
  • the printing structure is produced from a plurality of sections which are coupled to one another in a light-conducting manner.
  • the pressure structure comprises mutually coupled sections, some of which comprise luminescent substances and others are free of luminescent substances. In such an embodiment, in the case of a local excitation, an occurrence of the luminescence, ie a coupling of light into the light guide structure, depends on the excitation location.
  • the detection unit is designed to be movable relative to the document body in order to detect a light exit locally along the one or more side surfaces.
  • the detection unit may comprise a plurality of detection elements coupled to one another, which at the same time can detect a light emission at different locations of the one of the several side surfaces.
  • the excitation source is movable relative to the document body.
  • the excitation source may comprise a plurality of excitation elements.
  • the excitation source is designed as a UV light source.
  • other embodiments may provide other sources of excitation, each of which, adapted to the respective luminescent substances, can make an excitation for them.
  • the excitation source is rigidly mounted relative to a guide into which the document body is insertable and defined relative to the excitation source positionable.
  • the detection unit is also rigidly fixed relative to this guide.
  • the excitation of the luminescence is performed locally and that the resulting light emission pattern is evaluated as a function of the excitation location.
  • the excitation location of the locally induced excitation of the luminescence is varied and the resulting light exit pattern sequence is evaluated.
  • polymer layers which are customarily used in the field of security and / or value documents can be used as materials for the substrate layers.
  • the polymer layers can, identically or differently, be based on a polymer material from the group comprising PC (polycarbonate, especially bisphenol A polycarbonate), PET (polyethylene glycol terephthalate), PMMA (polymethyl methacrylate), TPU (thermoplastic polyurethane elastomers), PE (polyethylene), PP (Polypropylene), PI (polyimide or poly-trans-isoprene), PVC (polyvinyl chloride) and copolymers of such polymers.
  • PC polycarbonate, especially bisphenol A polycarbonate
  • PET polyethylene glycol terephthalate
  • PMMA polymethyl methacrylate
  • TPU thermoplastic polyurethane elastomers
  • PE polyethylene
  • PP Polypropylene
  • PI polyimide or poly-trans-isoprene
  • PVC polyviny
  • Low-T g -Materials are polymers whose glass transition temperature is below 140 0 C.
  • the base polymer of at least one of the polymer layers to be joined contains identical or different mutually reactive groups, wherein react at a laminating temperature of less than 200 0 C reactive groups of a first polymer layer with each other and / or with reactive groups of a second polymer layer.
  • the lamination temperature can be lowered without jeopardizing the intimate bond of the laminated layers.
  • various polymer layers having reactive groups this is due to the fact that the various polymer layers can no longer be readily delaminated due to the reaction of the respective reactive groups. Because there is a reactive coupling between the polymer layers, as it were a reactive lamination.
  • the glass transition temperature T 9 of at least one Polymer layer before thermal lamination is less than 120 0 C (or less than 11O 0 C or less than 100 0 C), wherein the glass transition temperature of this polymer layer after thermal lamination by reacting reactive groups of the polymer base polymer layer by at least 5 ° C. , preferably at least 20 ° C., is higher than the glass transition temperature before the thermal lamination.
  • the lamination temperature when using such polymer materials less than 180 ° C, more preferably still less than 150 ° C.
  • suitable reactive groups is readily possible for a person skilled in the art of polymer chemistry.
  • reactive groups are of course possible. These include the reaction partners of the Diels-Alder reaction or a metathesis.
  • the reactive groups may be attached directly to the base polymer or linked to the base polymer via a spacer group. Suitable spacer groups are all spacer groups known to the person skilled in the art of polymer chemistry.
  • the spacer groups may also be oligomers or polymers which impart elasticity, whereby a risk of breakage of the security and / or value document is reduced. Such elasticity-promoting spacer groups are known to the person skilled in the art and therefore need not be further described here.
  • base polymer in the context of the above statements designates a polymer structure which does not bear any groups reactive under the lamination conditions used. These may be homopolymers or copolymers. There are also modified polymers compared to said polymers.
  • ink or ink are preferably added to 10% to 90%, more preferably 30% to 70% by volume of particles of a material having a high refractive index.
  • materials are, for example, titanium dioxide or zirconium dioxide and other metal oxides.
  • a preparation comprising: A) 0.1 to 20 wt .-% of a binder with a polycarbonate derivative, B) 30 to 99.9 wt .-% of a preferably organic solvent or solvent mixture, C) 0 to 10 wt D) 0 to 10 wt .-% of a functional material or a mixture of functional materials, E) 0 to 30 wt .-% of additives and / or auxiliaries, or a mixture thereof Substances, wherein the sum of the components A) to E) always gives 100 wt .-%, as a printing ink.
  • polycarbonate derivatives are highly compatible with polycarbonate materials, in particular with polycarbonates based on bisphenol A, such as, for example, Makrofol® films.
  • polycarbonate derivative used is stable to high temperatures and shows no discoloration at lamination typical temperatures up to 200 0 C and more, whereby the use of the above-described low-Tg materials is not necessary.
  • the polycarbonate derivative may contain functional carbonate structural units of the formula (I)
  • R 1 and R 2 independently of one another are hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl, preferably phenyl, and C 7 C 12 aralkyl, preferably phenyl-C 1 -C 4 alkyl, in particular benzyl;
  • m is an integer from 4 to 7, preferably 4 or 5;
  • R 3 and R 4 are individually selectable for each X, independently of one another is hydrogen or C 1 -C 6 alkyl;
  • X is carbon and n is an integer greater than 20, with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl.
  • X, R 3 and R 4 may be simultaneously alkyl at 1 to 2 atoms, in particular only at one atom.
  • R 3 and R 4 may be in particular methyl.
  • the X atoms alpha to the diphenyl-substituted C atom (C1) may not be dialkyl-substituted.
  • the X atoms beta to C1 may be disubstituted with alkyl.
  • m 4 or 5.
  • the polycarbonate derivative can be prepared, for example, on the basis of monomers, such as 4,4 ' - (3,3,5-trimethylcyclohexane-1,1-diyl) diphenol, 4,4 ' - (3,3-) dimethylcyclohexane-1, 1-diyl) diphenol, or 4,4 ' - (2,4,4-trimethylcyclopentane-1, 1-diyl) diphenol.
  • Such a polycarbonate derivative can be prepared, for example, according to the document DE 38 32 396.6 from diphenols of the formula (Ia), the disclosure of which is hereby incorporated in full in the disclosure of this description. It is possible to use both a diphenol of the formula (Ia) to form homopolycarbonates and a plurality of diphenols of the formula (Ia) to form copolycarbonates (meaning of radicals, groups and parameters, as in formula I).
  • diphenols of the formula (Ia) may also be mixed with other diphenols, for example with those of the formula (Ib)
  • thermoplastic aromatic polycarbonate derivatives
  • Suitable other diphenols of the formula (Ib) are those in which Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted, and aliphatic radicals or cycloaliphatic radicals other than those of the formula (II) Ia) or heteroatoms may contain as bridge members.
  • diphenols of the formula (Ib) are hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ether, bis ( hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, alpha, alpha'-bis (hydroxyphenyl) diisopropylbenzenes and their nuclear alkylated and chemically halogenated compounds.
  • diphenols of the formula (Ib) are hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ether, bis ( hydroxyphenyl) ketones, bis
  • Preferred other diphenols are, for example: 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis ( 4-hydroxyphenyl) cyclohexane, alpha, alpha-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3-methyl) chloro-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, bis- (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1, 1-bis (3,5-dimethyl-4-hydroxyphenyl
  • diphenols of the formula (Ib) are, for example, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane and 1, 1-bis (4-hydroxyphenyl) -cyclohexane.
  • 2,2-bis (4-hydroxyphenyl) propane is preferred.
  • the other diphenols can be used both individually and in a mixture.
  • the molar ratio of diphenols of the formula (Ia) to the other diphenols of the formula (Ib) which may optionally be used should be between 100 mol% (Ia) to 0 mol% (Ib) and 2 mol% (Ia) 98 mol% (Ib), preferably between 100 mol% (Ia) to 0 mol% (Ib) and 10 mol% (Ia) to 90 mol% (Ib) and in particular between 100 mol% (Ia ) to 0 mol% (Ib) and 30 mol% (Ia) to 70 mol% (Ib).
  • the high molecular weight polycarbonate derivatives from the diphenols of the formula (Ia), optionally in combination with other diphenols, can be prepared by the known polycarbonate production processes.
  • the various diphenols can be linked together both statistically and in blocks.
  • the polycarbonate derivatives used can be branched in a manner known per se. If the branching is desired, this can in known manner by condensing small amounts, preferably amounts of 0.05 to 2.0 mol% (based on diphenols), of trifunctional or more than trifunctional compounds, in particular those with three or more than three phenolic hydroxyl groups can be achieved.
  • Some branching agents having three or more than three phenolic hydroxyl groups are phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,6-dimethyl-2,4,6-tri - (4-hydroxyphenyl) heptane, 1, 3,5-tri (4-hydroxyphenyl) benzene, 1,1,1-tri (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) phenylmethane , 2,2-bis [4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis (4-hydroxyphenyl-isopropyl) -phenol, 2,6-bis (2-bis) hydroxy-5-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, hexa- [4- (4-hydroxyphenyl-isopropyl) -phen
  • R represents a branched C 8 and / or C 9 alkyl radical.
  • R the proportion of CH 3 protons between 47 and 89% and the proportion of CH and CH 2 - protons between 53 and 11%; also preferably R is in the o- and / or p-position to the OH group, and more preferably the upper limit of the ortho-portion is 20%.
  • the chain terminators are generally used in amounts of 0.5 to 10, preferably 1, 5 to 8 mol%, based on diphenols used.
  • the polycarbonate derivatives can preferably be prepared in a manner known per se according to the phase interface behavior (compare H. Schnell in. Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol.
  • the diphenols of the formula (Ia) are dissolved in an aqueous alkaline phase.
  • mixtures of diphenols of the formula (Ia) and the other diphenols, for example those of the formula (Ib), are used.
  • chain terminators of, for example, the formula (Ic) can be added.
  • organic phase is reacted with phosgene by the method of interfacial condensation.
  • the reaction temperature is in the range of 0 0 C to 40 ° C.
  • the optionally used with branching agents can be presented either with the diphenols in the aqueous alkaline phase or dissolved in the organic solvent added before phosgenation.
  • their mono- and / or bis-chlorocarbonic acid esters may also be used, these being added dissolved in organic solvents.
  • the amount of chain terminators and branching then depends on the molar amount of diphenolate radicals corresponding to formula (Ia) and optionally formula (Ib); with the concomitant use of Chlorocarbonic esters, the amount of phosgene can be reduced accordingly in a known manner.
  • Suitable organic solvents for the chain terminators and optionally for the branching agents and the chloroformates are, for example, methylene chloride, chlorobenzene and in particular mixtures of methylene chloride and chlorobenzene.
  • the chain terminators and branching agents used can be dissolved in the same solvent.
  • methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene serve as the organic phase for the interfacial polycondensation.
  • the aqueous alkaline phase used is, for example, NaOH solution.
  • the preparation of the polycarbonate derivatives by the interfacial process can be catalyzed in a conventional manner by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts of 0.05 to 10 mol%, based on moles of diphenols used.
  • the catalysts can be added before the beginning of the phosgenation or during or after the phosgenation.
  • the polycarbonate derivatives can be prepared by the known method in the homogeneous phase, the so-called "pyridine process" and by the known melt transesterification process using, for example, diphenyl carbonate instead of phosgene.
  • the polycarbonate derivatives may be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of the formula (Ia).
  • the diphenols of the formula (Ia) are present in amounts of from 100 mol% to 2 mol%, preferably in amounts of from 100 mol% to 10 mol% and in particular in amounts of from 100 mol% to 30 mol% %, based on the total amount of 100 mol% of diphenol units contained in polycarbonate derivatives.
  • the polycarbonate derivative may be a copolymer containing, in particular consisting thereof, monomer units M1 based on the formula (Ib).
  • monomer units M1 based on the formula (Ib).
  • bisphenol A, and monomer units M2 based on the geminally disubstituted dihydroxydiphenylcycloalkane, preferably the 4,4 ' - (3,3,5 - Trimethylcyclohexan-1, 1-diyl) diphenols, wherein the molar ratio M2 / M1 is preferably greater than 0.3, in particular greater than 0.4, for example greater than 0.5.
  • the polycarbonate derivative has a weight average molecular weight of at least 10,000, preferably from 20,000 to 300,000.
  • component B may be substantially organic or aqueous.
  • Substantially aqueous means that up to 20% by weight of component B) is organic Solvent can be.
  • Substantially organic means that up to 5% by weight of water may be present in component B).
  • Component B preferably contains one or consists of a liquid aliphatic, cycloaliphatic and / or aromatic hydrocarbon, a liquid organic ester and / or a mixture of such substances.
  • the organic solvents used are preferably halogen-free organic solvents.
  • aliphatic, cycloaliphatic, aromatic hydrocarbons such as mesitylene, 1, 2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene; (organic) esters such as methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, ethyl 3-ethoxypropionate.
  • mesitylene, 1, 2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene methyl acetate, ethyl acetate, methoxypropyl acetate.
  • Ethyl 3-ethoxypropionate is particularly suitable.
  • a suitable solvent mixture comprises, for example, L1) 0 to 10% by weight, preferably 1 to 5% by weight, in particular 2 to 3% by weight, mesitylene, L2) 10 to 50% by weight, preferably 25 to 50% by weight %, in particular 30 to 40 wt.%, 1-methoxy-2-propanol acetate, L3) 0 to 20 wt.%, preferably 1 to 20 wt.%, in particular 7 to 15 wt.%, 1 , 2,4-trimethylbenzene, L4) 10 to 50 wt.%, Preferably 25 to 50 wt.%, In particular 30 to 40 wt.%, Ethyl 3-ethoxypropionate, L5) 0 to 10 wt.
  • the preparation may contain in detail: A) 0.1 to 10 wt .-%, in particular 0.5 to 5 wt .-%, of a binder with a polycarbonate derivative based geminal disubstituted
  • Dihydroxydiphenylcycloalkanes B) 40 to 99.9% by weight, in particular 45 to 99.5% by weight, of an organic solvent or solvent mixture, C) 0.1 to 6% by weight, in particular 0.5 to 4% by weight D) 0.001 to 6 wt .-%, in particular 0.1 to 4 wt .-%, of a functional material or a mixture of functional materials, E) 0.1 to 30 wt .-% , in particular 1 to 20 wt .-%, additives and / or auxiliaries, or a mixture of such substances.
  • component C if a colorant is to be provided, basically any colorant or colorant mixture comes into question. Colorants are all colorants.
  • Dyes should be soluble or (stably) dispersible or suspendible in the component B solvents. Furthermore, it is advantageous if the colorant at temperatures of 160 0 C and more for a period of more than 5 min. stable, in particular color-stable.
  • the colorant is subjected to a predetermined and reproducible color change under the processing conditions and is selected accordingly.
  • pigments must be present in particular in the finest particle size distribution. For inkjet printing, this means in practice that the particle size should not exceed 1, 0 microns, otherwise blockages in the printhead are the result.
  • nanoscale solid-state pigments and dissolved dyes have proven their worth.
  • the colorants may be cationic, anionic or even neutral. Just as examples of colorants that can be used in ink-jet printing are called its: Brilliant Black Cl. No. 28440, Chromogen Black Cl. No. 14645, direct deep black E Cl. No. 30235, true black salt B Cl. No.
  • Bayscript® Black Liquid (Cl mixture, sold by Bayer AG Germany), Cartasol® Black MG liquid (Cl., Basic Black 11, Registered Trade Mark of Clariant GmbH Germany), Flexonyl Black® PR 100 (E Cl., No. 30235, marketed by Hoechst AG), Rhodamine B, Cartasol® Orange K3 GL, Cartasol® Yellow K4 GL, Cartasol® K GL 1 or Cartasol® Red K-3B.
  • anthraquinone, azo, quinophthalone, coumarin, methine, perinone, and / or pyrazole dyes eg available under the trade name Macrolex®, can be used as soluble colorants.
  • colorants are described in the reference Ullmann 's Encyclopedia of Industrial Chemistry, Electronic Release 2008, Wiley Verlag, chapter "Colorants Used in Ink Jet Inks".
  • Well-soluble colorants lead to an optimal integration into the matrix or the binder of the print layer.
  • the colorants may be added either directly as a dye or pigment or as a paste, a mixture of dye and pigment together with another binder.
  • This additional Binder should be chemically compatible with the other components of the preparation. If such a paste is used as a colorant, the amount of component B refers to the colorant without the other components of the paste. These other components of the paste are then subsumed under the component E.
  • Component D comprises substances that can be seen directly by the human eye or by the use of suitable detectors using technical aids.
  • luminescent substances include photoluminophores, electroluminophores, Antistokes luminophores, fluorophores but also magnetizable, photoacoustically addressable or piezoelectric materials.
  • Raman-active or Raman-reinforcing materials can be used, as well as so-called barcode materials.
  • the preferred criteria are either the solubility in the component B or pigmented systems particle sizes ⁇ 1 micron and a temperature stability for temperatures> 160 0 C in the sense of the comments on component C.
  • Functional materials can be added directly or via a paste, ie a mixture with a further binder, which then forms part of component E, or the binder of component A.
  • the component E comprises inks for inkjet printing usually furnished substances such as anti-foaming agents, adjusting agents, wetting agents, surfactants, flow agents, dryers, catalysts, (Light) stabilizers, preservatives, biocides, surfactants, organic polymers for viscosity adjustment, buffer systems, etc.
  • Suitable adjusting agents are commercially available actuating salts in question. An example of this is sodium lactate.
  • biocides all commercially available preservatives which are used for inks come into question. Examples are ProxelOGXL and Parmetol® A26.
  • Suitable surfactants are all commercially available surfactants which are used for inks. Preferred are amphoteric or nonionic surfactants.
  • surfactants which do not alter the properties of the dye.
  • suitable surfactants are betaines, ethoxylated diols, etc.
  • Surfynol® and Tergitol® are betaines, ethoxylated diols, etc.
  • a buffer system can be set up which stabilizes the pH in the range from 2.5 to 8.5, in particular in the range from 5 to 8.
  • Suitable buffer systems are lithium acetate, borate buffer, triethanolamine or acetic acid / sodium acetate.
  • a buffer system will be considered in particular in the case of a substantially aqueous component B.
  • To adjust the viscosity of the ink (possibly water-soluble) polymers can be provided. Here all suitable for conventional ink formulations polymers come into question.
  • Examples are water-soluble starch, in particular with an average molecular weight of 3,000 to 7,000, polyvinylpyrrolidone, in particular with an average molecular weight of 25,000 to 250,000, polyvinyl alcohol, in particular with an average molecular weight of 10,000 to 20,000, xanthan gum, carboxymethylcellulose, ethylene oxide / propylene oxide Block copolymer, especially having an average molecular weight of 1,000 to 8,000.
  • An example of the latter block copolymer is the product series Pluronic®.
  • the proportion of biocide, based on the total amount of ink may be in the range of 0 to 0.5% by weight, preferably 0.1 to 0.3% by weight.
  • the proportion of surfactant can range from 0 to 0.2 wt .-%.
  • the proportion of adjusting agents based on the total amount of ink, 0 to 1 wt .-%, preferably 0.1 to 0.5 wt .-%, amount.
  • the auxiliaries also include other components, such as, for example, acetic acid, formic acid or n-methylpyrolidone or other polymers from the dye solution or paste used.
  • substances which are suitable as component E reference is additionally made, for example, to Ullmann's Encyclopedia of Chemical Industry, Electronic Release 2008, Wiley Verlag, chapter “Paints and Coatings", section “Paint Additives”.
  • the materials which increase a refractive index of the ink are assigned to the additives and auxiliaries of the component E.
  • inks which do not contain pigments greater than 250 nm as the colorant are preferred since they have a negative effect on light conduction as scattering centers.
  • Fig. 1 is a plan view of a substrate layer, on a one
  • Fig. 2 layered substrate layers to be joined together to form a laminate
  • FIG. 3 shows the laminate resulting from the lamination of the substrate layers of FIG. 2;
  • FIG. 4 is a schematic illustration of an apparatus for assisting verification of the security feature provided by the light guide structure
  • Fig. 5 is a plan view of a substrate layer to which another
  • Printed structure is printed
  • Fig. 6 shows several substrate layers to be laminated to another document body
  • Fig. 7 shows the resulting document body
  • the light-conducting structure comprises luminescent substances
  • Fig. 9 shows several substrate layers laminated to another document body
  • FIG. 10 shows the resulting further document body
  • FIG. Fig. 11 is a plan view of a substrate layer printed with a partially printed printed structure, with some portions containing luminescent materials and other portions;
  • FIGS. 12a, 12b, 12c schematically show a verification of a safety body formed with the substrate layer according to FIG. 11;
  • Fig. 13 is a plan view of a substrate layer printed with a partially printed printed structure, wherein the sections have different colors.
  • a substrate layer 1 is shown schematically in plan view, on which a printing structure 2 is printed, which forms a Lichtleit Quilt in a value and / or security document to be produced.
  • the printing structure 2 is made of a material, i. an ink or printing ink having a larger refractive index than the substrate layer 1 and other substrate layers disposed adjacent to the printing pattern 2 in a finished document body.
  • the pressure structure 2 has a strand 3, which branches into a plurality of further strands 4.
  • the strands 3, 4 respectively start and end at one of the edges 5 of the substrate layer, which form a side surface of the document body formed after lamination. These areas of the pressure structure 2 adjacent to the side surface are referred to as coupling regions 6.
  • the areas between the strands 3, 4 can also be printed, preferably with a transparent printing ink, which has a lower refractive index than the printing ink or ink with which the printing structure 2 is produced. It is also possible to form 4 opaque separating elements between the further strands, which however are preferably likewise separated from the strands 4 by transparent material regions.
  • the substrate layer 1 After the substrate layer 1 has been printed with the printing structure, it is combined with further substrate layers 7 - 10 to form a substrate layer stack, as shown in FIG. 2.
  • the same technical features are provided in all figures with identical reference numerals.
  • the collation takes place such that the printed surface 12 of the substrate layer 1 is an inner substrate layer surface. This means that this substrate layer surface 12 is not a top or bottom of the substrate layer stack.
  • Fig. 3 the finished laminate is shown, which forms the document body 13 of the security and / or security document. It is understood by those skilled in the art that any other security features in the value and / or security document forming document body 13 can be incorporated, as long as they do not affect the photoconductive properties of the printing structure 2, which is a Lichtleit Geneva.
  • the coupling regions 6 are located on side surfaces 14 which connect an upper side 15 and a lower side 16 of the document body 13.
  • the document body 13 is inserted into an assistant apparatus 20 for verifying the security and / or security document.
  • the assistance device 20 comprises a guide 21, into which the document body 13 can be inserted, so that the light guide structure, ie the pressure structure 2, can be positioned in a defined manner relative to an excitation source 22.
  • the excitation source 22 is a light source in the example shown. This can be, for example, a light emitting diode.
  • a spatially resolving light detection unit is preferably used.
  • This can for example comprise a CCD chip, which can determine a positioning and / or expansion of the coupling regions with the aid of an evaluation software and can compare with an expected pattern.
  • FIG. 5 shows a plan view of a further substrate layer 1 'on which a differently structured light structure 2' is printed.
  • the ink or ink constituting the conductive structure comprises a luminescent substance.
  • FIG. 6 the substrate layer stack formed by collation is shown schematically analogously to the illustration according to FIG. 2.
  • FIG. 7 shows a side view of the resulting document body 13.
  • the decoupling regions 6 in the side surfaces 14 of the document body 13 are again clearly visible.
  • Fig. 8 the verification of the value and / or security document is shown schematically.
  • an excitation source 22 for example, UV light 24 is irradiated through the upper substrate layers 7, 8 into the light guide structure 2 ', which is formed by the printing layer.
  • the luminescent substances are excited to luminescence.
  • the light thus coupled into the light guiding structure emerges partly through the upper side 15 or the lower side 16, since it is usually imitated isotropically in space by the luminescent substances.
  • part of the light strikes the interface of the light guide structure at an acute angle and can leave it.
  • a majority 26 of the light strikes the interface at an obtuse angle and is directed to one of the coupling regions 6. Therefore, they appear brighter than the remaining side surface 14 of the document body 13.
  • a verification of the security document can be made.
  • a substrate layer stack is shown showing another arrangement of the substrate layers 7-10. In this arrangement, only one substrate layer 7 is arranged above the substrate layer 1 "printed with the light guide structure 2 '".
  • the resulting document body 13 is shown schematically in FIG. 11 shows the top view of another substrate layer 1 '", in which the printing structure 2 is printed in three sections 2a, 2b and 2c
  • the sections 2a and 2c are printed with a color containing luminescent substances
  • it is printed with color that contains no luminescent substances.
  • FIGS. 12a to 12c respectively show the resulting document body 13, which is locally excited at different positions by means of UV light.
  • luminescence i. a light extraction from the coupling regions 6, on. This is due to the fact that the excitation in the areas 2a and 2b (see Fig. 11) each result in luminescence.
  • an excitation in the center of the document body which causes an excitation of the section 2b (see Fig. 11)
  • no luminescence occurs, so that no light leakage from the coupling regions 6 can be observed.
  • a substrate layer sequence of a manufactured document body may be different in various embodiments.
  • an uppermost layer is transparent, for example, and has a layer thickness (layer thickness) of 50 ⁇ m to 100 ⁇ m.
  • a second substrate layer viewed from above is preferably opaque and has a layer thickness of, for example, 100 / ym.
  • two transparent substrate layers of preferably 300 microns thickness are arranged together. One of these two substrate layers is printed on a surface, which faces the other of these transparent substrate layers, with a printing structure that represents a light-conducting structure.
  • a refractive index of the material from which the print pattern is printed is greater than the refractive index or refractive indices of the two transparent substrate layers immediately adjacent to the print pattern in the finished document body.
  • these two transparent print layers and other components or security features can be embedded or be.
  • a microchip and / or an antenna structure may be inserted into recesses of the transparent substrate layers.
  • a further opaque substrate layer of, for example, 100 microns layer thickness and a further transparent substrate layer of 50 microns to 100 / ym layer thickness are arranged in the following sequence.
  • three or more substrate layers are arranged in the center of the document body instead of the two transparent substrate layers. Between at least two of these three or more substrate layers, a light guide structure in the form of a pressure structure is formed.
  • the printing structure is printed on one of the centrally arranged transparent substrate layers in such a way that the printing structure adjoins an opaque substrate layer.
  • the print pattern formed as a light guide structure is preferably overprinted with a transparent material having a lower refractive index than the print pattern of the light guide structure. This ensures that no scattering centers, as in opaque material, eg. B: the opaque substrate layers usually occur, directly adjacent to the light guide structure. Nevertheless, such scattering centers often cause a partial decoupling of light at this scattering center, independently of the refractive index difference between the pressure structure formed as a light guide structure and the adjacent material.
  • a further embodiment provides that the printing structure that forms the light-guiding structure is printed on a transparent substrate layer which, for example, has a layer thickness of 100 ⁇ m.
  • a transparent substrate layer which is often referred to as an overlay film and preferably has a layer thickness of about 50 ⁇ m, is arranged over the printing structure for its protection. This protects the print structure from damage and manipulation.
  • the two transparent substrate layers have a refractive index which is lower than the refractive index of the printed structure.
  • the described arrangement is connected to further substrate layers to a document body, which are arranged below. These preferably comprise an opaque substrate layer which adjoins the described arrangement and further preferably transparent substrate layers, which of course may be printed on one or two sides.
  • a plurality of substrate layers are printed with a printing structure which is in each case embodied as a light-conducting structure, ie has a higher refractive index than the adjacent substrate layers or materials.
  • These pressure structures are preferably in different levels of arranged several substrate layers document body. This makes it possible to form more complex light emission patterns.
  • FIG. 13 shows the plan view of a further substrate layer 1 "", in which the printing structure is printed in sections 2a to 2f.
  • the sections 2a to 2e have at least two different colors, which are generated via colorant.
  • white light is injected via the coupling region 6 1 . This results in the coupling regions 6 ", 6"', 6 "", 6 1 "", 6 at least two different colors
  • the substrate layer 1, 1 ', 1 "" and the further substrate layer 7 immediately adjacent to the pressure structure 2 are formed of a transparent material, however, embodiments are also conceivable in which the immediately adjacent layer is opaque.
  • the structure of the document body formed as a laminate may vary greatly from the structure described herein In particular, a number of the substrate layers used and a thickness of the substrate layers may vary widely, especially for the integration of electronic components such as chips , Contact elements, antennas, displays and the like.

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  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Business, Economics & Management (AREA)
  • Accounting & Taxation (AREA)
  • Finance (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Credit Cards Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Optical Integrated Circuits (AREA)

Abstract

L'invention concerne un document de valeur et/ou de sécurité comprenant un corps (13) qui comporte un stratifié composé d'une ou de plusieurs couches de substrat (1, 1', 1'", 1"", 7-10), une structure de guidage de lumière étant formée dans ce stratifié. Ce document de valeur et/ou de sécurité se caractérise en ce que la structure de guidage de lumière est une structure d'impression (2, 2', 2'") imprimée sur une des couches de substrat (1, 1', 1'", 1"", 7-10). L'invention concerne en outre un procédé pour vérifier l'authenticité du document de valeur et/ou de sécurité et/ou l'absence de manipulations et/ou de falsifications sur ce document, ainsi qu'un dispositif pour vérifier un tel document de valeur et/ou de sécurité et un dispositif d'assistance destiné à faciliter le processus de vérification d'un document de valeur et/ou de sécurité.
EP09777264A 2008-07-14 2009-07-14 Document de sécurité comprenant un guide de lumière Active EP2307203B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL09777264T PL2307203T3 (pl) 2008-07-14 2009-07-14 Dokument bezpieczeństwa ze światłowodem
CY20121100782T CY1113389T1 (el) 2008-07-14 2012-08-30 Εγγραφο ασφαλειας με εναν οπτικο κυματαγωγο

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008033718.8A DE102008033718B4 (de) 2008-07-14 2008-07-14 Sicherheitsdokument mit einem Lichtleiter
PCT/EP2009/005208 WO2010006805A2 (fr) 2008-07-14 2009-07-14 Document de sécurité comprenant un guide de lumière

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Publication Number Publication Date
EP2307203A2 true EP2307203A2 (fr) 2011-04-13
EP2307203B1 EP2307203B1 (fr) 2012-06-06

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CY (1) CY1113389T1 (fr)
DE (1) DE102008033718B4 (fr)
PL (1) PL2307203T3 (fr)
PT (1) PT2307203E (fr)
WO (1) WO2010006805A2 (fr)

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US9889698B2 (en) 2012-09-03 2018-02-13 Assa Abloy Ab Secure laminate with security feature on the edge
DE102012111113B4 (de) 2012-11-19 2019-03-28 Bundesdruckerei Gmbh Wert- und/oder Sicherheitsdokument sowie Sicherheitselement hierfür
DE102014015282A1 (de) * 2014-10-16 2016-04-21 Giesecke & Devrient Gmbh Datenträger mit Lichtleiter
DE102015012616A1 (de) 2014-10-16 2016-04-21 Giesecke & Devrient Gmbh Kartenkörper für einen Datenträger und Inlay für einen Teil-Kartenkörper
WO2021151459A1 (fr) 2020-01-27 2021-08-05 Orell Füssli AG Document de sécurité avec guide de lumière présentant une structure de coupleur de sortie peu dense

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Publication number Publication date
CY1113389T1 (el) 2016-06-22
EP2307203B1 (fr) 2012-06-06
DE102008033718B4 (de) 2021-07-29
WO2010006805A2 (fr) 2010-01-21
PL2307203T3 (pl) 2013-01-31
WO2010006805A3 (fr) 2010-06-10
PT2307203E (pt) 2012-07-10
DE102008033718A1 (de) 2010-01-21

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