EP0753623A2 - Sicherheitsblatt, insbesondere vom Typ der ein elektrisch leitendes Element beinhaltet - Google Patents
Sicherheitsblatt, insbesondere vom Typ der ein elektrisch leitendes Element beinhaltet Download PDFInfo
- Publication number
- EP0753623A2 EP0753623A2 EP96111103A EP96111103A EP0753623A2 EP 0753623 A2 EP0753623 A2 EP 0753623A2 EP 96111103 A EP96111103 A EP 96111103A EP 96111103 A EP96111103 A EP 96111103A EP 0753623 A2 EP0753623 A2 EP 0753623A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- sheet according
- conductive polymer
- intrinsically conductive
- security
- polyaniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000001514 detection method Methods 0.000 claims abstract description 10
- 229920001940 conductive polymer Polymers 0.000 claims description 75
- 229920000767 polyaniline Polymers 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 32
- 239000011159 matrix material Substances 0.000 claims description 30
- 229920001169 thermoplastic Polymers 0.000 claims description 27
- 238000007639 printing Methods 0.000 claims description 22
- 239000000835 fiber Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 229920003043 Cellulose fiber Polymers 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 12
- -1 polyphenylene Polymers 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000696 magnetic material Substances 0.000 claims description 6
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000265 Polyparaphenylene Polymers 0.000 claims description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229920000123 polythiophene Polymers 0.000 claims description 3
- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
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- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
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- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000012544 monitoring process Methods 0.000 abstract description 3
- 239000000976 ink Substances 0.000 description 20
- 239000000843 powder Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229920000914 Metallic fiber Polymers 0.000 description 7
- 239000004922 lacquer Substances 0.000 description 7
- 239000002966 varnish Substances 0.000 description 7
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- 239000002131 composite material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
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- 239000000049 pigment Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000002322 conducting polymer Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000003981 vehicle Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005325 percolation Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
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- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920005822 acrylic binder Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 230000005611 electricity Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000005012 oleoresinous Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- 238000005507 spraying Methods 0.000 description 1
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- 239000000758 substrate Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/48—Elements suited for physical verification, e.g. by irradiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
-
- 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
- B42D25/355—Security threads
-
- 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
- G07D7/004—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 digital security elements, e.g. information coded on a magnetic thread or strip
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
Definitions
- the present invention relates to a security sheet, particularly of the type that includes an electrically conducting element.
- the present invention relates to a security sheet that includes an electrically conducting element that can be detected by virtue of means for detecting electrical conductivity.
- Said security sheet by allowing precise detection and simple monitoring, is particularly useful in the production of security documents such as currency bills, checks, identification documents, and credit cards.
- conducting polymers which can be roughly classified into two different groups: filled conducting polymers in which a polymer is made conductive by the addition of a conductive filler, such as for example carbon black, graphite, carbon fiber, metal powder, etcetera, and intrinsically conducting polymers that are made conductive through a chemical process.
- a conductive filler such as for example carbon black, graphite, carbon fiber, metal powder, etcetera
- intrinsically conducting polymers that are made conductive through a chemical process.
- Filled conducting polymers are known since a long time; they present however certain problems derived from the presence of the powder itself in the polymer structure.
- Intrinsically conductive polymers are a class of molecules that was created when it was discovered that polyacetylene could be made to conduct electricity by "doping" (H. Shirakawa, E.J. Louis, A.G. Mac Diarmid, C.K. Chiang, A.J. Heeger, J. Chem. Soc., Chem. Commun., 1977).
- ICPs are conjugated polymers that can be obtained from the respective monomers by virtue of normal polymerization reactions combined with, or followed by, chemical "doping" processes, and have particular properties that consist, in particular, in electrical conductivity.
- Known ICPs include polyaniline, which has high conductivity and high environmental stability.
- doping polyaniline bases described in the literature (Y. Cao, P. Smith and A.J. Heeger, Sinth. Met. 48, 1992)
- the mixtures of polyanilines with conventional polymers or with their respective copolymers R.W. Gumbs, Sinth. Met. 64, 1994
- polyaniline Another specific characteristic of polyaniline is that during the production process it is possible to preset and control, by means of the oxidation and protonation state, the electrical properties of the polymer that is produced (E.M. Geniès, A. Boyle, M. Capkowski, C. Tsintavis, Sinth. Met. 36 (1990); A.G. MacDiarmid, A.J. Epstein, Faraday Discuss. Chem. Soc. 88, 1989).
- the percolation threshold is reached for very low polyaniline contents, on the order of 1% or even less (C.Y. Yang, Y. Cao, P. Smith, A.J. Heeger, Sinth. Met. 53, 1993).
- Conductivity increases continuously as the concentration of polyaniline in the polymer matrix increases, starting from the percolation threshold, until it reaches values that are higher by several orders of magnitude (C. O. Yoon, M. Reghn, D. Moses, A.J. Heeger, Y. Cao, Sinth. Met. 63, 1994).
- the low percolation threshold and the continuous increase in conductivity starting from the threshold are particularly important characteristics, since they allow to produce, in a reproducible and controlled manner, conducting composites having electrical properties whose values can vary and can be preset over a wide range, and they also allow to obtain, for said blends, excellent mechanical properties that are very similar to those of the polymer that acts as matrix.
- CH-PS 472 081 describes how to provide currency bills with metal security threads.
- Anti-forgery systems for currency bills are also known which insert a surface-metallized plastic strip or thread in the bill paper.
- Metallization has been restricted, in practice, to aluminum, since in this case the process for the evaporation and deposition of the metal on the plastics is easy and relatively inexpensive, whereas other metals require the use of sophisticated and expensive techniques and facilities, since it is necessary to work in high vacuum.
- Metallic pigments of various kinds are also known which can be included in printing ink varnishes.
- copperplate-printing inks containing metallic pigments constituted by iron particles in the form of microspheres have been used to print security documents and currency bills.
- the iron pigment can react with the acid components of the varnish of the ink and, in the presence of condensation water, can produce gaseous hydrogen inside the container.
- a principal aim of the present invention is to avoid or substantially reduce the above described drawbacks.
- Another object is to provide an ink that is adapted for the copperplate printing of valued paper and security documents, constitutes a sophisticated anti-forgery system and is not abrasive for printing machine rollers.
- a security sheet comprising a supporting matrix and an intrinsically conductive polymer.
- support matrix refers to matrices that are conventionally used as basic material in the production of security sheets and documents, i.e., of documents that include an anti-forgery system.
- security sheets refers to sheets used as base to produce currency bills, checks, shares, identification documents such as ID cards, passports, credit cards, restricted-area passes, and all documents used in everyday life that require an anti-forgery system.
- said support matrix is a structure made of natural or synthetic fibers preferably chosen from the group including cellulose fibers and synthetic fibers, and is preferably constituted by synthetic polymers.
- said support matrix consists of paper based of cellulose fibers, for example of the type that is commonly used in the production of currency bills.
- the security sheet according to the present invention can also comprise additives, such as for example fillers, impregnating agents, and other agents known in the art of making paper and derived products.
- said support matrix is a thermoplastic polymer, preferably chosen from the group comprising polyester, polyvinyl chloride, polyvinyl acetate, polyethylene, ABS, polystyrene, polycarbonate, polymethyl methacrylate, polyethylene glycol, and mixtures thereof, polyester being the most preferred one.
- said intrinsically conductive polymer is chosen from the group comprising polyaniline, polypyrrole, polythiophene, polyphenylene vinylidene, polydiphenylamine, in substituted and unsubstituted forms, polyaniline being the most preferred one.
- the intrinsically conductive polymers of the invention are polymers or copolymers whose relative molecular mass is such that they can form films or fibers, derived from the polymerization of substituted or unsubstituted anilines, in positions and with radicals of a known type, as described for example for polyaniline in WO 92/22911.
- the intrinsically conductive polymers used in the invention also advantageously have a relative molecular mass of more than 10,000.
- said intrinsically conductive polymers are present in the form of a blend with a conventional thermoplastic polymer.
- Intrinsically conductive polymers produce, together with thermoplastic polymers, blends that have high conductivity even at low concentrations of the conducting polymer-dopant species.
- the high conductivity of the polymer blend that comprises the intrinsically conductive polymers according to the invention indicates that said conductive polymers are advantageously present as a continuous phase rather than as a phase of disperse particles.
- thermoplastic polymer/intrinsically conductive polymer blend has good mechanical and workability properties that can be likened to those of the thermoplastic polymer.
- the amount of conductive polymer that is present is preferably between 0.1% and 40% by weight, more preferably between 0.5% and 20% by weight, even more preferably between 1% and 5% by weight, with respect to the weight of the thermoplastic polymer.
- thermoplastic polymer/intrinsically conductive polymer blend can be advantageously varied over a wide range and is advantageously between 10 -8 and 10 S.cm -1 , more preferably between 10 -5 S.cm -1 and 10 S.cm -1 , and even more preferably between 10 -3 S.cm -1 and 1 S.cm -1 , as a function of the amount of intrinsically conductive polymer which is present in the blend.
- the use of intrinsically conductive polymers allows to provide different conductivity values and therefore allows to provide unequivocal information for detection of the document and selective recognition thereof according to the specific conductivity value of the polymer included therein, by using conventional detector device that are described hereinafter.
- the sheet according to the present invention comprises a support matrix made of cellulose fibers and a security thread which is constituted by a intrinsically conductive polymer/thermoplastic polymer blend of the type described above, included in said support matrix.
- the security thread according to the present embodiment has conductive properties and high resistance to mechanical traction, and can be detected, as regards electrical conductivity, by virtue of conventional means used for detecting metallic threads inserted in paper, as described for example in EP-0 057 972.
- said thread has a thickness between 10 and 50 microns.
- said security thread is transparent or semitransparent and allows, by applying printing ink, to produce symbols, images and the like that can be perceived against the light.
- the transparency of the thread varies according to the content of polyaniline and of the thermoplastic polymer used as host-matrix. Higher transparency values are obtained with polymethyl methacrylate and polystyrene.
- the use of a blend with a polyaniline content between 0.1% and 40% by weight with respect to the matrix of thermoplastic polymer advantageously allows to obtain transparency values in the range between 25% and 95%, whereas by using polyaniline values between 0.5% and 20% one obtains transparency values between 60% and 85%.
- the security thread or strip comprises a support matrix made of thermoplastic polymeric material, which advantageously consists of polyester, on which a continuous or discontinuous layer of an intrinsically conductive polymer of the above described type is deposited.
- said intrinsically conductive polymer is in the form of a dispersion in a compatible vehicle.
- Said vehicle is constituted by a medium or binder in which the intrinsically conductive polymer can be dissolved or dispersed and is advantageously a polymer, preferably of the acrylic type; the concentration of said intrinsically conductive polymer being preferably between 1% and 40% by weight with respect to the weight of the binder.
- the non-conductive thermoplastic polymeric material has a continuous or discontinuous covering layer that is constituted by an intrinsically conductive polymer, preferably polyaniline dispersed on a binder, with a thickness between 1 and 10 ⁇ m, more preferably between 1.5 and 5 ⁇ m.
- this covering layer one advantageously has transparency values between 25% and 95%, more preferably between 60% and 85%.
- the deposition of an intrinsically conductive polymer dispersed in an appropriate vehicle on a support matrix can be achieved by spreading with conventional means, for example by spraying, followed by evaporation of the solvent, or by means of a printing process.
- said security thread or strip can be produced with various controlled conductivity values, so as to allow its selective recognition on the basis of the specific conductivity value of the intrinsically conductive polymer deposited on said strip.
- the conductivity values vary generally over a wide range between 10 -8 and 10 S.cm -1 .
- the conductivity values are between 10 -5 S.cm -1 and 5 S.cm -1 , preferably between 10 -3 S.cm -1 and 1 S.cm -1 , as a function of the amount of intrinsically conductive polymer that is present.
- said conductive polymer When said conductive polymer is constituted by polyaniline, it has a green coloring that can be modified by adding dyes or fluorescent substances without compromising the transparency and conductivity of the film.
- these materials are applied in such a manner as to leave continuous regions exposed along the strip of thermoplastic polymer, so as to allow to detect conductivity and a characteristic that is visible against the light.
- said strip/thread can include regions that are covered by a printing ink so as to form portions (symbols or images) that can be detected visually against the light.
- figure 1 is a view of a security thread constitued by a support matrix made of nonconductive transparent polymeric material (polyester) 1, on the surface whereof there is a continuous layer of intrinsically conductive polymer (polyaniline) 2 and a magnetic material 3 deposited thereon so as to form transversal bands.
- polyaniline intrinsically conductive polymer
- Figure 2 is a view of a security thread constitued by a support matrix made of nonconductive transparent polymeric material (polyester) 10, on the surface whereof there is a continuous layer of intrinsically conductive polymer (polyaniline or polypyrrole) 20, and a magnetic material 30 deposited thereon so as to form two longitudinal bands.
- the first digit corresponds to the single-digit numbering used in figure 1 in order to indicate corresponding components.
- Figure 3 illustrates a security thread that is constitued by a support matrix made of nonconductive transparent polymeric material (polyester) 100, on the surface of which there is a coloured layer of intrinsically conductive polymer (polyaniline) 200, applied by a printing method, for example rotogravure, so as to form in the regions not covered by the coloured layer images like symbols 100', or letters 100'', allowing thus to detect a characteristic that is visible against the light.
- a magnetic material 300 is applied so as to form two longitudinal bands.
- the first digit corresponds to the single-digit numbering used in figure 1 and to the first digit of the two-digit numbering used in figure 2 in order to indicate corresponding components.
- said intrinsically conductive polymers or blends thereof with thermoplastic polymers are present in the form of fibers dispersed in the support matrix, which is advantageously constituted by paper.
- Said fibers are preferably between 1 and 20 mm long and their diameter advantageously varies between 3 and 30 ⁇ m.
- Said intrinsically conductive polymers and their blends with thermoplastic polymers have a relative density that is advantageously between 1.4 and 1.5 g/ml, which corresponds to a fraction of the relative density of metals.
- a significant advantage with respect to the use of metallic fibers is constituted by the fact that these values are similar to those of the cellulose fibers used in the production of paper, facilitating the uniform and easy dispersion of said conductive fibers in the mix without having to provide particular technical refinements.
- said fibers constituted by blends of intrinsically conductive polymers and thermoplastic polymers have the main properties of metallic fibers, such as electrical conductivity and the ability to absorb electromagnetic waves. Furthermore, when polyaniline is used in a blend with thermoplastic polymers (for example polystyrene, polycarbonate, methyl methacrylate%), other properties, such as coloring and transparency, have been observed which make the fibers detectable by using commonly employed detection methods.
- thermoplastic polymers for example polystyrene, polycarbonate, methyl methacrylate
- microwave absorption ability with a device that is commonly used in detection technology (according to the ASTM D4935-89 standard method) and comprises a source of electromagnetic waves, to which the sheet according to the invention is exposed through a tube that acts as waveguide, and a detector that measures the amount of radiation transmitted by the sheet, which is preferably made of cellulose.
- Electrical conductivity can be measured by measuring surface resistivity with a device that has two electrodes that rest, according to a specific geometrical arrangement, on the surface of the sheet (according to the ASTM D4496-87 method).
- Said intrinsically conductive polymer which is advantageously in fiber form, can be treated, with particular reference to polyaniline blended with at least one thermoplastic polymer, so as to vary the optical properties, modifying its transparency, color, and fluorescence. Furthermore, by varying the amount of doping of the conductive polymer and therefore its electrical properties, it is possible to vary the response of the microwave absorption signal that can be detected for document identification.
- the sheet according to the invention therefore has a high security value, allowing to assign an unequivocal identification for its recognition by means of an adapted device, differently from techniques that entail the use of metallic fibers, which produce a standard response for a given content of fibers in the paper.
- the intrinsically conductive polymer can be advantageously deposited in a controlled manner, i.e., in preset and limited regions of the sheet, with preset concentrations.
- said intrinsically conductive polymer in fiber form is included on the surface of the support matrix, preferably so as to form straight bands or stripes.
- the inclusion of the conductive polymer fibers in regions of the surface of the sheet is performed by means of methods that are known in the art, for example by depositing said fibers from an aqueous disperse system on a portion of the sheet in the wet section of conventional paper-making machine.
- particles of a film of intrinsically conductive polymer blended with a thermoplastic polymer are deposited on the surface of the support matrix, for example in a circular or hexagonal shape (so-called "planchettes").
- a synthetic lacquer preferably of the vinyl type
- said lacquer increases the wettability of said particles and develops, during the drying of the sheet, a sufficient heat-sealing property, as described for example in EP-A-0 544 917. Since the particles have the properties of electrical conduction and microwave absorption, detection is possible with conventional means of the previously described type.
- an intrinsically conductive polymer in powder form is embedded in said support matrix, which is advantageously constituted by cellulose fibers.
- the intrinsically conductive polymeric component in powder form is blended with fillers of the type used commonly in the paper-making process.
- the sheet of paper comprising the intrinsically conductive polymer is interposed, by virtue of conventional methods, between two sheets of paper that do not contain the conductive polymer.
- said intrinsically conductive polymer is included as powder in a printing ink for detection with conventional means.
- a printing ink for detection with conventional means.
- said intrinsically conductive polymer which is preferably constituted by polyaniline, is blended in solution or in the melted state with conventional polymers and receives the addition of dyes that allow to give the resulting conductive powder a wide range of colorings and fluorescence characteristics.
- Said conductive polymer which is advantageously constituted by polyaniline, preferably blended with dyes, is dispersed in powder form in the varnishes of printing inks at concentrations preferably between 1% and 30% by weight with respect to said ink.
- the particle size of the powder of said conductive polymer is preferably in the range between 0.5 and 10 ⁇ m, more preferably between 1 and 2.5 ⁇ m.
- Films of polymeric blends constituted by blends of conductive polyaniline and conventional thermoplastic polymers are prepared by using conventional extrusion techniques, starting from the dissolved or melted polymeric composite.
- the polyaniline fraction in the composite varies between 1% and 40% and the composite correspondingly assumes values between 10 -8 and 10 S.cm -1 .
- the transparency and color of the film vary according to the polyaniline content and as a function of the thermoplastic polymer used as matrix. Higher transparency values (70-85%) are obtained with polymethyl methacrylate and polystyrene.
- the film thus obtained is cut into a strip that is 1.2 mm wide and said strip is embedded in a paper sheet with conventional methods.
- a 20- ⁇ m film or thread of polyester is covered with layers of varying thickness of conductive composite (example 1), according to the data listed in Tables 1, 2, and 3.
- the conductive composite was applied by spreading lacquers containing polyaniline with a vehicle, followed by evaporation of the solvent.
- lacquers Two types of disperse systems (lacquers) of VersiconTM polyaniline in an acrylic binder, produced by the company Zipperling Kessler & Co under the trade names Incoblend Lacquer 910002 and 9100016/43, were used.
- a wire with a diameter of 20 ⁇ m, having a conductivity of 1.10 -1 S.cm -1 is obtained from a solution of a blend that contains 2% polyaniline in polymethyl methacrylate.
- the wire is cut so as to obtain fibers that are approximately 5 mm long.
- the fibers are then dispersed in a mix of cellulose fibers until a 5% concentration by weight is obtained.
- a sheet of paper having an average surface resistivity on the order of 10 8 ohm/square is formed from the mix thus obtained.
- a powder of a conductive polymer based on polyaniline is finely ground until an average particle size of approximately 1 ⁇ m is obtained.
- the relative density of the powder is 1.4 g/cu cm and the conductivity is 10 S.cm -1 .
- the powder is then dispersed, by using techniques that are commonly used in the production of printing inks, in a varnish for copperplate-printing inks, in such amounts as to constitute 20% by weight with respect to the produced ink.
- a typical varnish for copperplate-printing inks in paste form contains: 20% to 40% of unsaturated oleo-resinous compounds that can polymerize due to oxidation reactions; 10% to 40% extenders such as calcium carbonate, barium sulfate, titanium oxide, aluminum silicates; 15% to 30% organic solvents constituted by a mixture of hydrocarbon mineral oils with a boiling range up to 300 o C, glycol ethers, and small amounts of specific additives.
- the conductive polymer powder of Example 4 is dispersed in varnishes used to produce letterpress, lithography, screen-printing, and rotogravure inks so as to thus obtain the respective inks.
Landscapes
- Engineering & Computer Science (AREA)
- Computer Security & Cryptography (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Conductive Materials (AREA)
- Laminated Bodies (AREA)
- Paper (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI951540A IT1275558B (it) | 1995-07-14 | 1995-07-14 | Foglio di sicurezza in particolare del tipo incorporante un elemento conduttore dell'elettricita' |
ITMI951540 | 1995-07-14 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0753623A2 true EP0753623A2 (de) | 1997-01-15 |
EP0753623A3 EP0753623A3 (de) | 1997-08-20 |
Family
ID=11371992
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96111103A Withdrawn EP0753623A3 (de) | 1995-07-14 | 1996-07-10 | Sicherheitsblatt, insbesondere vom Typ der ein elektrisch leitendes Element beinhaltet |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0753623A3 (de) |
IT (1) | IT1275558B (de) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2771111A1 (fr) * | 1997-11-20 | 1999-05-21 | Arjo Wiggins Sa | Document de securite comportant des particules magnetiques |
NL1008929C2 (nl) * | 1998-04-20 | 1999-10-21 | Vhp Ugchelen Bv | Uit papier vervaardigd substraat voorzien van een geïntegreerde schakeling. |
WO1999066128A1 (de) * | 1998-06-16 | 1999-12-23 | WHD elektronische Prüftechnik GmbH | Merkmalsstoffe und sicherheitsmerkmale und verfahren zur integration dieser in die papierstoffbahn sowie verfahren zur prüfung |
US6031457A (en) * | 1998-06-09 | 2000-02-29 | Flex Products, Inc. | Conductive security article and method of manufacture |
EP0914970A3 (de) * | 1997-11-11 | 2000-03-22 | MANTEGAZZA ANTONIO ARTI GRAFICHE S.r.l. | Sicherheitsstreifen mit optischen und magnetischen Informationen |
US6118377A (en) * | 1998-06-09 | 2000-09-12 | Flex Products, Inc. | Conductive security article with detector apparatus |
DE19915440A1 (de) * | 1998-06-16 | 2000-09-28 | Whd Elektron Prueftech Gmbh | Elektrisch leitender Merkmalsstoff |
NL1011860C2 (nl) | 1999-04-22 | 2000-10-24 | Vhp Ugchelen Bv | Veiligheidsvoorziening en toepassingen daarvan. |
DE19928060A1 (de) * | 1999-06-15 | 2000-12-21 | Whd Elektron Prueftech Gmbh | Optisch variables Sicherheitsmerkmal und Verfahren zu seiner Herstellung |
EP1074599A1 (de) * | 1998-12-25 | 2001-02-07 | Tokushu Paper Manufacturing Co. | Fluoreszierende partikel, verfahren zur herstellung und verwendung in fälschungssicheren papieren |
WO2002070367A1 (de) * | 2001-03-01 | 2002-09-12 | WHD elektronische Prüftechnik GmbH | Sicherheitsmerkmale |
WO2002070368A3 (de) * | 2001-03-01 | 2002-12-12 | Whd Elektron Prueftech Gmbh | Sicherheitsmerkmale |
WO2004049268A1 (de) * | 2002-11-28 | 2004-06-10 | Hueck Folien Ges.M.B.H | Sicherheitselemente mit kombinierten maschinell erkennbaren merkmalen |
WO2004111338A1 (de) * | 2003-06-17 | 2004-12-23 | Hueck Folien Ges.M.B.H | Sicherheitselemente mit visuell erkennbaren und maschinenlesbaren merkmalen |
WO2006042568A1 (de) * | 2004-10-20 | 2006-04-27 | Hueck Folien Ges.M.B.H | Substrate mit elektrisch leitfähigen schichten |
EP1693802A1 (de) * | 2005-02-22 | 2006-08-23 | Hueck Folien GmbH & Co. KG | Elektronische Merkmale für Wertdokumente |
WO2007144657A2 (en) | 2006-06-15 | 2007-12-21 | D. W. Spinks (Embossing) Limited | Planchette for use in couterfeit protection |
US20130139982A1 (en) * | 2011-12-06 | 2013-06-06 | Fuji Xerox Co., Ltd. | Paper and paper production method |
DE102016004429A1 (de) | 2016-04-12 | 2017-10-12 | Dätwyler Cabling Solutions Ag | Steckbuchsenmodul für Datenübertragungskabel und Montageverfahren zum Verbinden des Steckbuchsenmoduls mit dem Datenübertragungskabel |
WO2020224800A1 (de) * | 2019-05-09 | 2020-11-12 | Giesecke+Devrient Currency Technology Gmbh | Elektrisch leitendes papiergefüge, verfahren zum herstellen desselben und verwendung |
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DE2909731A1 (de) * | 1978-03-15 | 1979-09-20 | Oesterr Nationalbank | Papier, verfahren zur pruefung von papieren und vorrichtung zur durchfuehrung des pruefverfahrens |
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US4183989B1 (de) * | 1976-12-07 | 1990-05-08 | Portals Ltd | |
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DE2909731A1 (de) * | 1978-03-15 | 1979-09-20 | Oesterr Nationalbank | Papier, verfahren zur pruefung von papieren und vorrichtung zur durchfuehrung des pruefverfahrens |
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Cited By (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0914970A3 (de) * | 1997-11-11 | 2000-03-22 | MANTEGAZZA ANTONIO ARTI GRAFICHE S.r.l. | Sicherheitsstreifen mit optischen und magnetischen Informationen |
US6126076A (en) * | 1997-11-11 | 2000-10-03 | Mantegazza Antonio Arti Grafiche S.R.L. | Security strip with optical and magnetic information, insertable in documents in general |
FR2771111A1 (fr) * | 1997-11-20 | 1999-05-21 | Arjo Wiggins Sa | Document de securite comportant des particules magnetiques |
WO1999027185A1 (fr) * | 1997-11-20 | 1999-06-03 | Arjo Wiggins S.A. | Papier de securite comportant des particules magnetiques |
EP1034536B1 (de) * | 1997-11-20 | 2002-06-19 | Arjo Wiggins | Sicherheitsinformationsträger |
WO1999054842A1 (en) * | 1998-04-20 | 1999-10-28 | Vhp Veiligheidspapierfabriek Ugchelen B.V. | Substrate which is made from paper and is provided with an integrated circuit |
US7032828B2 (en) | 1998-04-20 | 2006-04-25 | Vhp Veiligheidspapierfabriek Ugchelen B.V. | Substrate which is made from paper and is provided with an integrated circuit |
NL1008929C2 (nl) * | 1998-04-20 | 1999-10-21 | Vhp Ugchelen Bv | Uit papier vervaardigd substraat voorzien van een geïntegreerde schakeling. |
US6830192B1 (en) | 1998-04-20 | 2004-12-14 | Vhp Veiligheidspapierfabriek Ugchelen B.V. | Substrate which is made from paper and is provided with an integrated circuit |
US6031457A (en) * | 1998-06-09 | 2000-02-29 | Flex Products, Inc. | Conductive security article and method of manufacture |
US6118377A (en) * | 1998-06-09 | 2000-09-12 | Flex Products, Inc. | Conductive security article with detector apparatus |
WO1999066128A1 (de) * | 1998-06-16 | 1999-12-23 | WHD elektronische Prüftechnik GmbH | Merkmalsstoffe und sicherheitsmerkmale und verfahren zur integration dieser in die papierstoffbahn sowie verfahren zur prüfung |
BG64397B1 (bg) * | 1998-06-16 | 2004-12-30 | Whd Electronische Prueftechnik Gmbh | Маркиращи субстанции и защитни знаци, метод за интегрирането им в хартиеното платно и метод за проверяването им |
DE19915440A1 (de) * | 1998-06-16 | 2000-09-28 | Whd Elektron Prueftech Gmbh | Elektrisch leitender Merkmalsstoff |
EP1074599A4 (de) * | 1998-12-25 | 2001-10-17 | Tokushu Paper Mfg Co | Fluoreszierende partikel, verfahren zur herstellung und verwendung in fälschungssicheren papieren |
EP1074599A1 (de) * | 1998-12-25 | 2001-02-07 | Tokushu Paper Manufacturing Co. | Fluoreszierende partikel, verfahren zur herstellung und verwendung in fälschungssicheren papieren |
US6663960B1 (en) | 1998-12-25 | 2003-12-16 | Tokushu Paper Mfg. Co., Ltd. | Fluorescent particles, method for preparing the same and paper preventing forgery using the fluorescent particle |
WO2000065545A1 (en) | 1999-04-22 | 2000-11-02 | Vhp Veiligheidspapierfabriek Ugchelen B.V. | Security facility and uses thereof |
NL1011860C2 (nl) | 1999-04-22 | 2000-10-24 | Vhp Ugchelen Bv | Veiligheidsvoorziening en toepassingen daarvan. |
US7301682B1 (en) | 1999-06-15 | 2007-11-27 | Whd Elektronische Prueftechnik Gmbh | Optically variable security attribute |
BG64546B1 (bg) * | 1999-06-15 | 2005-07-29 | Whd Elektronische Prueftechnik Gmbh | Оптично променящ се защитен елемент |
CZ298221B6 (cs) * | 1999-06-15 | 2007-07-25 | WHD elektronische Prüftechnik GmbH | Opticky variabilní bezpecnostní prvek |
WO2000076778A1 (de) * | 1999-06-15 | 2000-12-21 | WHD elektronische Prüftechnik GmbH | Optisch variables sicherheitsmerkmal |
DE19928060A1 (de) * | 1999-06-15 | 2000-12-21 | Whd Elektron Prueftech Gmbh | Optisch variables Sicherheitsmerkmal und Verfahren zu seiner Herstellung |
WO2002070368A3 (de) * | 2001-03-01 | 2002-12-12 | Whd Elektron Prueftech Gmbh | Sicherheitsmerkmale |
WO2002070367A1 (de) * | 2001-03-01 | 2002-09-12 | WHD elektronische Prüftechnik GmbH | Sicherheitsmerkmale |
WO2004049268A1 (de) * | 2002-11-28 | 2004-06-10 | Hueck Folien Ges.M.B.H | Sicherheitselemente mit kombinierten maschinell erkennbaren merkmalen |
WO2004111338A1 (de) * | 2003-06-17 | 2004-12-23 | Hueck Folien Ges.M.B.H | Sicherheitselemente mit visuell erkennbaren und maschinenlesbaren merkmalen |
WO2006042568A1 (de) * | 2004-10-20 | 2006-04-27 | Hueck Folien Ges.M.B.H | Substrate mit elektrisch leitfähigen schichten |
EP1693802A1 (de) * | 2005-02-22 | 2006-08-23 | Hueck Folien GmbH & Co. KG | Elektronische Merkmale für Wertdokumente |
WO2007144657A3 (en) * | 2006-06-15 | 2008-02-28 | Dw Spinks Embossing Ltd | Planchette for use in couterfeit protection |
WO2007144657A2 (en) | 2006-06-15 | 2007-12-21 | D. W. Spinks (Embossing) Limited | Planchette for use in couterfeit protection |
US20130139982A1 (en) * | 2011-12-06 | 2013-06-06 | Fuji Xerox Co., Ltd. | Paper and paper production method |
US8597465B2 (en) * | 2011-12-06 | 2013-12-03 | Fuji Xerox Co., Ltd. | Paper and paper production method |
DE102016004429A1 (de) | 2016-04-12 | 2017-10-12 | Dätwyler Cabling Solutions Ag | Steckbuchsenmodul für Datenübertragungskabel und Montageverfahren zum Verbinden des Steckbuchsenmoduls mit dem Datenübertragungskabel |
WO2020224800A1 (de) * | 2019-05-09 | 2020-11-12 | Giesecke+Devrient Currency Technology Gmbh | Elektrisch leitendes papiergefüge, verfahren zum herstellen desselben und verwendung |
CN113811653A (zh) * | 2019-05-09 | 2021-12-17 | 捷德货币技术有限责任公司 | 导电的纸结构、用于制造导电的纸结构的方法和应用 |
US20220213651A1 (en) * | 2019-05-09 | 2022-07-07 | Giesecke+Devrient Currency Technology Gmbh | Electrically conductive paper structure, method for manufacturing same and use |
CN113811653B (zh) * | 2019-05-09 | 2023-11-07 | 捷德货币技术有限责任公司 | 导电的纸结构、用于制造导电的纸结构的方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
EP0753623A3 (de) | 1997-08-20 |
IT1275558B (it) | 1997-08-07 |
ITMI951540A0 (it) | 1995-07-14 |
ITMI951540A1 (it) | 1997-01-14 |
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