US20140291495A1 - Electro-optical security element - Google Patents

Electro-optical security element Download PDF

Info

Publication number
US20140291495A1
US20140291495A1 US14/362,257 US201214362257A US2014291495A1 US 20140291495 A1 US20140291495 A1 US 20140291495A1 US 201214362257 A US201214362257 A US 201214362257A US 2014291495 A1 US2014291495 A1 US 2014291495A1
Authority
US
United States
Prior art keywords
security
pigments
matrix
bis
security element
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.)
Abandoned
Application number
US14/362,257
Other languages
English (en)
Inventor
Joerg Fischer
Manfred Paeschke
Oliver Muth
Arthur Mathea
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
Assigned to BUNDESDRUCKEREI GMBH reassignment BUNDESDRUCKEREI GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MUTH, OLIVER, MATHEA, ARTHUR, PAESCHKE, MANFRED, FISCHER, JOERG
Publication of US20140291495A1 publication Critical patent/US20140291495A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/364—Liquid crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/373—Metallic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
    • B42D25/378—Special inks
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D169/00—Coating compositions based on polycarbonates; Coating compositions based on derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
    • G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
    • G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
    • G06K19/06046—Constructional details
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
    • G06K7/00—Methods or arrangements for sensing record carriers, e.g. for reading patterns
    • G06K7/10—Methods or arrangements for sensing record carriers, e.g. for reading patterns by electromagnetic radiation, e.g. optical sensing; by corpuscular radiation
    • G06K7/14—Methods or arrangements for sensing record carriers, e.g. for reading patterns by electromagnetic radiation, e.g. optical sensing; by corpuscular radiation using light without selection of wavelength, e.g. sensing reflected white light
    • 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
    • H01L51/52—
    • H01L51/56—
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • B42D2033/20—
    • B42D2033/30—
    • B42D2033/32—
    • B42D2035/20—
    • B42D2035/34—
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • C08G2261/3142—Condensed aromatic systems, e.g. perylene, anthracene or pyrene fluorene-based, e.g. fluorene, indenofluorene, or spirobifluorene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/90—Applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds

Definitions

  • the invention relates to a security element, particularly for a security and/or valuable document, comprising a matrix based on an organic polymeric material, at least one electrically conductive pigment dispersed in the matrix, and at least one luminescent substance dispersed in the matrix, which luminescent substance is capable, in the presence of the conductive pigment, of non-contact excitation of light emission, and a printable composition for the preparation of such a security element, a security and/or valuable document having such a security element, as well as methods for the preparation and verification of such a security and/or valuable document.
  • Safety and/or security documents identity cards, passports, ID cards, access control cards, visas, control characters, tickets, driver's licenses, motor vehicle documents, bank notes, checks, postage stamps, credit cards, any smart cards and adhesive labels (e.g. for product protection) often comprise at least one substrate and a partially or completely transparent cover layer.
  • Substrate and cover layer may in turn consist of a plurality of layers.
  • security elements For example, bank notes and postage stamps may consist of one substrate or substrate layer only, to which security elements can then be applied, for example in the form of a printing ink.
  • Some security elements include substances being luminescent under certain physical conditions, and a verification can be carried out by visual inspection or automatic detection of the luminescence under these conditions.
  • Particulate luminescent substances are used, which may be encapsulated, i.e. have a core/shell structure. These core/shell structures are embedded in a polymeric matrix. In general, the substances having the electroluminescent properties are always present in a particulate form, with particle sizes above 200 nm.
  • polycarbonates based on a geminally disubstituted dihydroxydiphenyl cycloalkane are per se known.
  • such polycarbonates are used as binders for screen-printing inks.
  • This document also describes methods for making such polycarbonates.
  • the invention is therefore based on the technical object of specifying a security element, which can be produced at relatively low cost and satisfies all requirements in view of the observable and/or measurable luminescence under excitation conditions and may also have other advantages, in particular have an increased diversity in the selection of radiation-emitting substances (UV, VIS, IR) and/or an increased security against counterfeiting.
  • a security element which can be produced at relatively low cost and satisfies all requirements in view of the observable and/or measurable luminescence under excitation conditions and may also have other advantages, in particular have an increased diversity in the selection of radiation-emitting substances (UV, VIS, IR) and/or an increased security against counterfeiting.
  • FIG. 1 shows an illustrative spectrum arising from one embodiment of the invention.
  • the invention teaches a preferably machine-readable or machine-detectable security element for a security and/or valuable document comprising a (non-conductive) matrix based on an organic polymeric material, at least one electrically conductive pigment dispersed in the matrix, and at least one luminescent substance dispersed in the matrix, which luminescent substance is capable, in the presence of the conductive pigment, of non-contact excitation of light emission, and wherein the luminescent substance is preferably not encapsulated and is directly surrounded by the matrix and is embedded therein.
  • the term “in the presence” means that the luminescent substance can in any case be stimulated for non-contact emission when the conductive pigment, in addition to the luminescent substance, is also present in a sufficient quantity in the matrix.
  • the organic polymeric material may be an arbitrary polymeric material used in the field of security and/or valuable documents.
  • examples are: transparent, opaque, or non-transparent polymeric materials, such as 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), polystyrene, polyacrylates and methacrylates, vinyl esters, ABS 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
  • PVC polyviny
  • the polymer for example the polycarbonate derivative has an average molecular weight (weight average) of at least 10,000, preferably 20,000 to 300,000.
  • polycarbonate derivative may contain functional carbonate structural units of formula (I),
  • R 1 and R 2 are independently from each other 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 can be individually selected for each X, and independently represent hydrogen or C 1 -C 6 alkyl; X is carbon and n an integer greater than 20, with the proviso that at least at one atom X, R 3 and R 4 are both alkyl.
  • R 3 and R 4 both are alkyl.
  • R 3 and R 4 may in particular be methyl.
  • the X atoms in the alpha position to the diphenyl-substituted C atom (C1) cannot be dialkyl-substituted.
  • the X atoms in the beta position to C1 can be disubstituted with alkyl.
  • m 4 or 5.
  • the polycarbonate derivative may for instance be formed based on monomers, such as 4,4′-(3,3,5-trimethyl cyclohexane-1,1-diyl)diphenol, 4,4′-(3,3-dimethyl cyclohexane-1,1-diyl)diphenol, or 4,4′-(2,4,4-trimethyl cyclopentane-1,1-diyl)diphenol.
  • monomers such as 4,4′-(3,3,5-trimethyl cyclohexane-1,1-diyl)diphenol, 4,4′-(3,3-dimethyl cyclohexane-1,1-diyl)diphenol, or 4,4′-(2,4,4-trimethyl cyclopentane-1,1-diyl)diphenol.
  • a polycarbonate derivative according to the invention may for instance be made from diphenols of formula (Ia) according to the document DE 38 32 396.6, the scope of disclosure of which with its complete contents is hereby included in the scope of disclosure of this description.
  • a diphenol of formula (Ia) under formation of homopolycarbonates as well as several diphenols of formula (Ia) under formation of copolycarbonates can be used (the meaning of radicals, groups and parameters same as in formula I).
  • diphenols of formula (Ia) can also be used in a mixture with other diphenols, for instance with those of formula (Ib)
  • Suitable other diphenols of formula (Ib) are those, wherein Z is an aromatic radical with 6 to 30 C atoms, which may contain one or several aromatic nuclei, be substituted and contain aliphatic radicals or other cycloaliphatic radicals than those of formula (Ia) or heteroatoms as bridge members.
  • diphenols of formula (Ib) examples include hydroquinone, resorcin, dihydroxydiphenyls, bi-(hydroxyphenyl)alkanes, bis-(hydroxyphenyl)cycloalkanes, bis-(hydroxyphenyl) sulfides, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones, bis-(hydroxyphenyl) sulfoxides, alpha,alpha′-bis-(hydroxyphenyl)diisopropylbenzenes and their nuclear-alkylated and nuclear-halogenated compounds.
  • Preferred other diphenols are for instance: 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-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)cyclohexane,
  • diphenols of formula (Ib) are for instance: 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 may be used individually as well as in a mixture.
  • the molar ratio of diphenols of formula (Ia) to, if applicable, the optionally also used other diphenols of formula (Ib) should be between 100 mol-% (Ia) to 0 mol-% (Ib) and 2 mol-% (Ia) to 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), especially between 100 mol-% (Ia) to 0 mol-% (Ib) and 50 mol-% (Ia) to 50 mol-% (Ib).
  • the high-molecular polycarbonates from the diphenols of formula (Ia), if applicable, in combination with other diphenols, may be made according to the known polycarbonate production methods.
  • the different diphenols may be linked in a statistical manner as well as also block-wise.
  • the polycarbonate derivatives used according to the invention may be branched in a per se known manner. If branching is desired, this can be achieved in a per se known manner by condensation of small amounts, preferably amounts between 0.05 and 2.0 mol-% (referred to the used diphenols), of three or more than three-functional compounds, in particular such with three or more than three phenolic hydroxyl groups.
  • Some branching agents with three or more than three phenolic hydroxyl groups are: phloroglucin, 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-is-(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane, hexa-[4-(4-hydroxyphenyl
  • Some of the other three-functional compounds are 2,4-dihydroxy benzoic acid, trimesic acid, cyanuric chloride, and 3,3-bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.
  • Suitable compounds are e.g. phenol, tert-butylphenols or other alkyl-substituted phenols.
  • phenols of formula (Ic) are suitable
  • R is a branched C8 and/or C9-alkyl radical.
  • the share of the CH 3 protons in the alkyl radical R is between 47 and 89% and the share of the CH and CH 2 protons is between 53 and 11%; also preferably R is in an o and/or p position to the OH group, and particularly preferably the upper limit of the ortho share is 20%.
  • the chain stoppers are used in general in amounts from 0.5 to 10, preferably 1.5 to 8 mol-%, referred to the used diphenols.
  • the polycarbonate derivatives may preferably be made according to the phase boundary method (cf. H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Vol. IX, page 33ff., Interscience Publ. 1964) in a per se known manner.
  • the diphenols of formula (Ia) are dissolved in an aqueous alkaline phase.
  • mixtures of diphenols of formula (Ia) and the other diphenols, for instance those of formula (Ib), are used.
  • chain stoppers e.g. of formula (Ic) may be added.
  • a reaction is performed in presence of an inert, preferably polycarbonate-dissolving, organic phase with phosgene according to the method of the phase boundary condensation.
  • the reaction temperature is between 0° C. and 40° C.
  • the optionally also used branching agents may either be presented with the diphenols in the aqueous alkaline phase or may be added dissolved in the organic solvent before the phosgenation. Beside the diphenols of formula (Ia) and, if applicable, other diphenols (Ib), their mono and/or bis-chlorocarbonic acid esters can also be used, the latter being added dissolved in organic solvents.
  • the amount of chain stoppers and of branching agents then depends on the molar amount of diphenolate radicals corresponding to formula (Ia) and, if applicable, formula (Ib); when chlorocarbonic acid esters are also used, the amount of phosgene can correspondingly be reduced in a known manner.
  • Suitable organic solvents for the chain stoppers and, if applicable, for the branching agents and the chlorocarbonic acid esters are for instance methylene chloride, chlorobenzene and in particular mixtures of methylene chloride and chlorobenzene. If applicable, the used chain stoppers and branching agents can be dissolved in the same solvent.
  • an organic phase for the phase boundary polycondensation serves for instance methylene chloride, chlorobenzene and mixtures of methylene chloride and chlorobenzene.
  • aqueous alkaline phase serves for instance a NaOH solution.
  • Making the polycarbonate derivatives according to the phase boundary method can by catalyzed in a usual manner by catalysts such as tertiary amines, in particular tertiary aliphatic amines such as tributylamine or triethylamine; the catalysts can be used in amounts from 0.05 to 10 mol-%, referred to the moles of used diphenols.
  • the catalysts can be added before the phosgenation or during or also after the phosgenation.
  • the polycarbonate derivatives can be made according to the prior art method in a homogeneous phase, the so-called “pyridine method” and according to the prior art method for the melt transesterification by using for instance diphenyl carbonate instead of phosgene.
  • the polycarbonate derivatives may be linear or branched, they are homopolycarbonates or copolycarbonates based on the diphenols of formula (Ia).
  • the polycarbonate properties can be varied in a favorable manner.
  • the diphenols of formula (Ia) are contained in polycarbonate derivatives in amounts from 100 mol-% to 2 mol-%, preferably in amounts from 100 mol-% to 10 mol-% and in particular in amounts from 100 mol-% to 30 mol-%, especially in amounts from 100 mol-% to 50 mol-% referred to the total amount of 100 mol-% of diphenol units.
  • the polycarbonate derivative comprises a copolymer in particular consisting of monomer units M1 based on bisphenol A, and monomer units M2 based on the geminally disubstituted dihydroxydiphenyl cycloalkane, preferably of the 4,4′-(3,3,5-trimethyl cyclohexane-1,1-diyl)diphenol, wherein the molar ratio M2/M1 is preferably greater than 0.5, in particular greater than 0.8, for instance greater than 1.0.
  • the glass temperature Tg is below 150° C. after a first heating cycle and may be increased in a second heating cycle, which substantially improves the stability of the obtained structure.
  • liquid preparation comprising: A) 1 to 30 wt-% of a polycarbonate derivative used according to the invention, and B) 70 to 99 wt-% of an organic solvent or of a mixture of organic solvents.
  • the used organic solvents are preferably halogen-free solvents. These may in particular be aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene; esters, such as methylacetate, ethylacetate, butylacetate, methoxypropylacetate, ethyl-3-ethoxypropionate.
  • halogen-free solvents may in particular be aliphatic, cycloaliphatic, aromatic hydrocarbons, such as mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha, toluene, xylene; esters, such as methylacetate, ethylacetate, butylacetate, methoxypropylacetate, ethyl-3-ethoxypropionate.
  • mesitylene, 1,2,4-trimethylbenzene, cumene and solvent naphtha toluene, xylene, acetic acid methyl ester, acetic acid ethyl ester, methoxypropylacetate, ethyl-3-ethoxypropionate.
  • a suitable mixture of solvents comprises for instance, L1) 0 to 10 wt-%, preferably 1 to 5 wt-%, in particular 2 to 3 wt-% mesitylene, L2) 10 to 50 wt-%, preferably 25 to 50 wt-%, in particular 30 to 40 wt-% 1-methoxy-2-propanolacetate, 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-%, preferably 0.01 to 2 wt-%, in particular 0.05 to 0.5 wt-% cumene, and L6) 0 to 80 wt-%, preferably 1 to 40 wt-%, in particular 15 to 25 wt-
  • the solvent mixture may also contain L7) with 10 to 50 wt-%, preferably 25 to 50 wt-%, in particular 30 to 60 wt-% butyl glycol acetate, the relative amounts of the components L1) to L7) always totaling 100 wt-%.
  • matrix means, for the purpose of the invention, that the polymeric material forming the matrix forms the main structural component, in which the other components are embedded and dispersed, preferably homogeneously dispersed.
  • a homogeneous distribution is defined by that the amounts of the other components, be it on a molecular basis or as particles, are equal in each volume element, at least, referred to volume elements of the matrix of 1000 ⁇ m 3 , differ from each other by less than 10%.
  • the luminescent substance may preferably be an organic substance, in particular an organic light-emitting semiconductor, for example an OLED material.
  • This organic substance is non-particulate, and preferably is homogeneously dispersed in the matrix, in particular dissolved.
  • small molecules typically ⁇ 3000 da
  • triplet emitters and luminescent polymers, for example having a HOMO-LUMO gap in the range from 1.5 to 3.5 eV.
  • small molecules include N,N-diphenylaniline and derivatives thereof, 9H-fluorenes and derivatives thereof, anthracene and derivatives thereof, 4,4′-bis[(9-ethyl-3-carbazoyl) vinylenyl)]anthracene, 9,10-bis(9-ethyl-3-carbazovinylene)-1,1′-biphenyl, 4,4′-bis-(diphenylvinylenyl) biphenyl, 1,4-bis(9-ethyl-3-carbazovinylene)-2-methoxy-5-(2-thylhexyloxy)benzene, 4,4′-bis(diphenylvinylenyl) anthracene, 1,4-bis(9-ethyl-3-carbazovinylene)-9,9-dihexyl fluorene, 9,9,9′,9′,9′′,9′′-hexakis(hexyl)
  • Small molecules may also be derivatized with functional groups, which improve the solubility in organic solvents, such as toluene, or in the solvents mentioned in context with the matrix.
  • polymers being capable of luminescing include poly(p-phenylene vinylene), alkyl-substituted, particularly dialkyl-, for example dimethyl-, diethyl- or dibutyl-substituted poly(p-phenylene vinylene) derivatives (substituents in para to each other), poly[2-methoxy-5-(3,7-di-methyloctyloxy)-p-phenylene vinylene), poly[2-methoxy-5-(3,7-dimethyloctyloxy)-p-phenylene vinylene) with POSS (polyoctahedral oligomeric silsesquioxane), DMP (dimethyl phenyl), N,N-bis-(4-methyl-phenyl)-4-aniline or 2,5-diphenyl-1,2,4-oxadiazole end caps, poly[2-methoxy-5-(2′-ethylhexyloxy)-p-pheny
  • Suitable copolymers are, for example, poly[9,9-dioctyl-2,7-divinylene fluoreneylene)-alt-co (9,10-anthracene)], poly[9,9-dioctyl-2,7-divinylene fluoreneylene)-alt-co- ⁇ 2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene ⁇ ], poly[(9,9-dioctylfluoreneyl-2,7-diyl)-co-(1,4-vinylene phenylene)], poly[(9,9-dioctylfluoreneyl-2,7-diyl)-co-1,4-benzo ⁇ 2,1′-3 ⁇ -thiadiazole)], poly[(9,9-2-dihexylfluoreneyl,7-diyl)-co-(2-methoxy-5- ⁇ 2-ethylhexyloxy
  • the luminescent substance is a particulate quantum dot material, and wherein the quantum dot material is preferably homogeneously dispersed in the matrix.
  • Quantum dots are small (crystalline) particles the exciton propagation of which is limited in all three spatial directions to values in the order of or less than the exciton Bohr radius. This ultimately leads to a width of the band gap between the valence band and the conduction band, which is variable depending on the geometric size of the particle. The smaller the particle, the greater the band gap, and the correspondingly higher the energy emitted after excitation, for example color. By reduction, for example, the color can be shifted from the long-wavelength range to ranges of shorter wavelengths.
  • the size of the quantum dots is typically in the range from 1 to 20 nm, in particular 2 to 10 nm, and then the number of atoms of a particle is between 20 and 500,000, or between 100 and 100,000.
  • Quantum dots can uniformly consist of one material, but core/shell structures may also be formed, wherein core and shell are made of different materials, typically semiconductor materials having different band-gap widths, the material having a higher band gap generally forming the shell.
  • all materials may be used for quantum dots that have band gaps or exciton energies in the range from 1.5 to 3.5 eV for the above-mentioned particle sizes.
  • Typical materials include CdSe, ZnS, ZnSe, CdZnSe, CdS, InAr, InP, CdSeS, generally all the semiconductor materials, which are found in the field of luminescent diodes, particularly group III/V semiconductors with the group III elements Al, Ga and In, and the group V elements N, P, As and Sb. From the mentioned elements can be formed binary, ternary and quaternary (and higher complexity) compounds in any combination, and the molar ratio of the group III elements to the group V elements is 1:1.
  • dopings are possible, if applicable, with atoms, which belong to none of the mentioned groups of elements.
  • Other materials include phosphorus nanoparticles, which are doped with a rare earth element.
  • Various Cd-free quantum dots are for example available from the company Nanoco Technologies Ltd., Manchester, UK, or from Aldrich Materials Science.
  • mixtures of at least two, but also three, four or more substances being capable of light emission can be used, especially substances emitting with different colors, then mixed colors being formed, which makes the analysis and consequently counterfeiting even more difficult. If, for example, blue, green, and red luminescent materials are used, practically every color of the spectrum can be obtained by varying the proportions of the different substances.
  • a pigment containing an electrically conductive material or a mixture of such pigments is provided in the matrix.
  • Electrically conductive pigments comprise at least one electrically conductive layer or electrically conductive particles, or consist thereof. It is not necessary, though preferable, that the pigment is homogeneously dispersed in the matrix. These pigments may be both so-called leafing pigments (when curing the matrix, they will be oriented toward the surface) and non-leafing pigments. In principle, the pigment may be transparent or non-transparent.
  • electrically conductive pigments is particularly advantageous when using electroluminophores as a luminescent substance, as therewith a reliable and non-contact excitation of the luminescence with electric fields can be secured.
  • platelet-shaped conductive pigments act as field amplifiers due to the sharp edges or points present in this pigment form.
  • the electrically conductive layer and an electrically conductive particle may, for example, comprise or consist of one or a plurality of metal oxides made conductive by doping, for example, tin oxide, zinc oxide, indium oxide, and/or titanium oxide.
  • metal oxides made conductive by doping
  • Ga, Al, In, Th, Ge, Sn, P, Ar, Sb, Se, Te, W, and/or F can be used.
  • materials can be used, which are based on a carrier layer, for example based on titanium dioxide, synthetic or natural mica, other phyllosilicates, glass, silicon dioxide, and/or Al 2 O 3 , and carry thereon the electrically conductive layer, preferably are enwrapped by this layer.
  • the carrier layer and the electrically conductive layer may be present, for example containing metal oxides, metal oxide hydrates, metal suboxides, metal fluorides, metal nitrides, metal oxynitrides, or mixtures of such substances.
  • the carrier layer and/or the other layers, if provided, and/or the electrically conductive layer are optically transparent or substantially transparent, i.e., they transmit at least 10%, preferably at least 70% of the incident light.
  • the transparent or semi-transparent layers may be colorless or colored.
  • the color properties of the electrically conductive pigments can also be modified by the additional layers, particularly if they are located below the conductive layer or between the carrier layer and the conductive layer.
  • the electrically conductive pigment is preferably mica coated with at least one electrically conductive metal oxide layer, especially mica coated with antimony-doped tin oxide.
  • one or a plurality of metal oxide layers may be provided, such as a titanium oxide layer.
  • the diameter of an electrically conductive pigment is preferably in the range from 0.1 ⁇ m to 500 ⁇ m, preferably from 2 ⁇ m to 100 ⁇ m, more preferably from 5 ⁇ m to 70 ⁇ m. A narrow particle size distribution is preferred.
  • platelet-shaped electrically conductive pigments are used.
  • the aspect ratio (diameter/thickness) for platelet-shaped conductive pigments is typically at least 2:1, in particular at least 10:1, better at least 100:1.
  • Particularly transparent with high conductivity are electrically conductive platelet-shaped pigments, the number-weighted mean grain area F50 (grain area: size of a main surface) of which is at least 150 ⁇ m 2 , in particular at least 200 ⁇ m 2 . It is advantageous, if the number-weighted rate of pigments having a particle size preferably less than 80 ⁇ m 2 is not more than 33%, in particular less than 25%, based on the total amount of electrically conductive pigment. Even better is a rate with a grain area less than 40 ⁇ m 2 of not more than 15%, particularly not more than 10%. This reduction of fine portions reduces light scattering and thus an opacity of the marking layer.
  • the average grain area, based on the transparency ideally is 1,000 ⁇ m 2 , and may be up to 4,000 ⁇ m 2 or even more.
  • Suitable electrically conductive pigments are commercially available for example from Germany's leading providers of specialized pigments.
  • metallic effect pigments being established for the technology of coating agents, for example, Al-based, such as Al—MgF.
  • base metals include copper, bronze, gold, silver, lead, zinc, and tin.
  • platelets of carbon as they are available, for example, from pseudo-single crystals of carbon.
  • nanorods can also be used.
  • materials in particular metals (in particular silver-colored), alloys and semiconductors can be used, but also carbon.
  • the lengths are typically in the range from 1 to 200 nm, the aspect ratio (length to diameter) being in the range from 3 to 100, usually from 3 to 20.
  • nanotubes can be used, the diameter of which is typically less than 100 nm, in most cases less than 10 nm.
  • nanotubes with a carbon structure are suitable.
  • Nanotubes may have one or a plurality of walls. The ends may be open or closed. The interior may be empty, but also filled. The latter is recommended for tubular structures, which themselves are not conductive or semi-conductive. Filling will then include a conductive species, in particular metal, such as lead.
  • the electrically conductive pigments are arranged in the matrix preferably substantially in parallel to a main surface or a surface of the (cured) matrix, respectively.
  • the matrix itself is typically formed as a film, coating agent layer, printing layer, or foil.
  • the layer thickness is usually in the range from 5 ⁇ m to 500 ⁇ m, in particular from 20 ⁇ m to 500 ⁇ m.
  • a charge carrier transport material may also be provided in the matrix. This is particularly advisable, for example, for triplet emitters, which will then reduce the required amount of triplet emitter substance for a given luminescence intensity. That is typically a hole transport material and an electron transport material.
  • hole transport materials include arylamines, isoindoles, N,N′-bis-(3-methylphenyl)-N,N′-bis-(phenyl)benzidine, N,N′-bis-(4-methylphenyl)-N,N′-bis-(phenyl)benzidine, N,N′-bis-(2-naphtalenyl)-N,N′-bis-(phenyl)benzidine, 1,3,5-tris-(3-methyldiphenylamino)benzene, N,N′-bis-(1-naphtalenyl)-N,N′-bis-(phenyl)benzidine, N,N′-bis-(2-naphtalenyl)-N,N′-bis-(phenyl)benzidine, 4,4′,4′′-tris-(N,N-phenyl-3-methylphenylamino)triphenylamines, 4,4′, N,N′-diphenylcarba
  • N,N,N′,N′-tetrakis(4-methylphenyl)benzidine is suitable.
  • an additional matrix polymer is preferably also employed, such as polyvinylcarbazole (PVK) or polystyrene (PS).
  • electron transporting materials include oxadiazole, imidazole, 8-hydroxyquinolinolato-lithium, 2-(4-biphenyl)-5-(4-tert.-butylphenyl)-1,3,4-oxadiazole, 4,7-diphenyl-1,10-phenanthroline, 2,2′,2′′-(1,3,5-benzenetriyl)tris-(1-phenyl-1-H-benzimidazole), 2,9-dimethyl-4,7-di-phenyl-a,10-phenanthroline, bis-(2-methyl-8-quinolinolate)-4-(phenylphenolato)aluminum.
  • An exemplary combination is tris-(2-(4-tolyl) pyridinato-N,C2) iridium (III) as an electroluminescent material, N,N′-bis-(4-methylphenyl)-N,N′-bis-(phenyl)benzidine as a hole transport material, and 2,2′,2′′-(1,3,5-benzinetriyl)-tris-(1-phenyl-1-H-benzimidazole) as an electron transport material.
  • the matrix may additionally comprise converting phosphors.
  • Conversion phosphors convert at least a portion of the primary radiation into a secondary radiation having a different wavelength. Thereby, a displacement of the emission spectrum is obtained.
  • conversion phosphors still enable a variation of the emission wavelength, i.e., a defined predetermined modification thereof, whereby a greater variability with regard to the observable color or emission wavelength is achieved.
  • the matrix may additionally contain one or a plurality of substances or materials selected from the group consisting of color pigments, effect pigments, optically variable pigments, UV blockers, preservatives, and stabilizers.
  • the pigments are in particular laser-sensitive pigments, such as, for example, described in the document WO 2010/006583 A, which also allows a modulation of the luminescence in the manner described therein.
  • the matrix additionally comprises an organic or inorganic (absorbing) color pigment and/or effect pigment, or a mixture of such pigments.
  • organic or inorganic (absorbing) color pigment and/or effect pigment or a mixture of such pigments.
  • These may be, for example, at least one platelet-shaped effect pigment and/or an organic or inorganic color pigment.
  • Platelet-shaped effect pigments are designated platelet-shaped pearlescent pigments, predominantly transparent or semi-transparent interference pigments, and metallic effect pigments.
  • Liquid crystal pigments so-called LCPs, or structured polymeric platelets, so-called holographic pigments, are also included here.
  • LCPs Liquid crystal pigments
  • holographic pigments are also included here.
  • These platelet-shaped pigments are composed of one or a plurality of layers of different materials, if appropriate.
  • Pearlescent pigments consist of transparent platelets of a high refractive index and show, in a parallel orientation, a characteristic pearly luster by multiple reflection. Those pearlescent pigments, which in addition also show interference colors, are referred to as interference pigments.
  • interference pigments or metallic effect pigments are used as platelet-shaped effect pigments, which have on an inorganic platelet-shaped carrier at least one coating of a metal, metal oxide, metal oxide hydrate or mixtures thereof, a mixed metal oxide, metal suboxide, metal oxynitride, metal fluoride, BiOCl, or a polymer.
  • the metallic effect pigments preferably comprise at least one metal layer.
  • the inorganic platelet-shaped carrier is preferably made of natural or synthetic mica, kaolin or other phyllosilicates, of glass, SiO 2 , TiO 2 , Al 2 O 3 , Fe 2 O 3 , polymeric platelets, graphite platelets, or metal platelets, such as aluminum, titanium, bronze, silver, copper, gold, steel, or various metal alloys. Carriers made of mica, glass, graphite, SiO 2 , TiO 2 , and Al 2 O 3 , or mixtures thereof are preferred.
  • the size of these carriers is not critical. They generally have a thickness between 0.01 and 5 ⁇ m, in particular between 0.05 and 4.5 ⁇ m.
  • the extension in length or width is typically between 1 and 250 ⁇ m, preferably between 2 and 200 ⁇ m and in particular between 2 and 100 ⁇ m. They generally have an aspect ratio (ratio of the average diameter to the average particle thickness) from 2:1 to 25,000:1, in particular from 3:1 to 2,000:1.
  • a coating applied to the carrier consists of metals, metal oxides, mixed metal oxides, metal suboxides, and metal fluorides, and in particular of a colorless or colored metal oxide selected from TiO 2 , titanium suboxides, titanium oxynitrides, Fe 2 O 3 , Fe 3 O 4 , SnO 2 , Sb 2 O 3 , SiO 2 , Al 2 O 3 , ZrO 2 , B 2 O 3 , Cr 2 O 3 , ZnO, CuO, NiO, or mixtures thereof.
  • a colorless or colored metal oxide selected from TiO 2 , titanium suboxides, titanium oxynitrides, Fe 2 O 3 , Fe 3 O 4 , SnO 2 , Sb 2 O 3 , SiO 2 , Al 2 O 3 , ZrO 2 , B 2 O 3 , Cr 2 O 3 , ZnO, CuO, NiO, or mixtures thereof.
  • Coatings of metals are preferably made of aluminum, titanium, chromium, nickel, silver, zinc, molybdenum, tantalum, tungsten, palladium, copper, gold, platinum, or alloys comprising these.
  • the preferred metal fluoride is MgF 2 .
  • platelet-shaped effect pigments are preferably used multi-layer effect pigments. These have multiple layers on a platelet-shaped, preferably non-metallic carrier, said layers preferably consisting of the materials mentioned above and having different refractive indexes in such a way that there are at least two layers each having a different refractive index alternately on the carrier, the refractive indices in the individual layers differing by at least 0.1 and preferably by at least 0.3.
  • the layers on the carrier may be nearly transparent and colorless as well as transparent and colored or semi-transparent.
  • LCPs consisting of crosslinked, aligned cholesteric liquid crystals, or also structured polymeric platelets designated holographic pigments may be used as platelet-shaped effect pigments.
  • the platelet-shaped effect pigments used are (same as the electrically conductive pigments) preferably transparent or semi-transparent.
  • Semi-transparent pigments transmit at least 10%, transparent pigments, however, at least 70% of the incident visible light.
  • Such platelet-shaped effect pigments are preferably used, since in a security and/or valuable product, their transparency contributes to a wide variety of possible background or subsurface colors and at the same time does not affect the intensity of the light emission generated by electroluminescence.
  • a platelet-shaped effect pigment is used, which has at least one metal layer.
  • some pigments, such as described herein, can form or complement the electrically conductive pigments.
  • a platelet-shaped effect pigment may be used, which creates a different visually perceivable color and/or brightness impression under different lighting and/or viewing angles. In the case of different color impressions, this property is referred to as color flop. In particular those pigments that have a color flop, create in the security element or security and/or valuable products made therewith color and gloss impressions that cannot be copied and that are well visible to the naked eye without vision aids. Such pigments are also referred to as optically variable.
  • the optically variable platelet-shaped effect pigments comprise, for example, under at least two different lighting or viewing angles, at least two and not more than four, but preferably, under two different lighting or viewing angles, two or under three different lighting or viewing angles, three optically clearly distinguishable discrete colors.
  • the discrete colors there are only the discrete colors, but no intermediate stages, that is, a clear change from one color to a different color is detectable when tilting the security element comprising the optically variable pigments.
  • This property helps the viewer to recognize the security element as such, and at the same time, makes copying of this feature difficult, since in the commercial color copiers, color flop effects cannot be copied and reproduced.
  • optically variable platelet-shaped effect pigments can also be used that, when tilting over different lighting and/or viewing angles, have a color gradient, i.e. many different shades, such as the typical pearlescent luster. Such diffuse color changes, too, are readily detectable by the human eye.
  • the platelet-shaped effect pigments used according to the invention are present in the marking layer or the security and/or valuable product in an oriented form, i.e. they are approximately parallel to the surfaces of the security product provided with the security element.
  • Such alignment normally is obtained by means of the usual methods for applying the security element, such as for example by conventional printing processes.
  • the electrically conductive pigments are aligned in a corresponding manner.
  • the commercially available interference pigments can be used, which are sold, for example, by Mearl under the name Mearlin®, metallic effect pigments from Eckhard and goniochromatic (optically variable) effect pigments such as Variochrom® from BASF, Chromafflair® from Flex Products Inc., Helicone® from Wacker, or holographic pigments from Spectratec, and other similar commercially available pigments.
  • Mearlin® metallic effect pigments from Eckhard and goniochromatic (optically variable) effect pigments
  • Variochrom® from BASF
  • Chromafflair® from Flex Products Inc.
  • Helicone® Helicone® from Wacker
  • holographic pigments from Spectratec
  • inorganic color pigments all common, transparent and opaque, white, colored and black pigments, such as Prussian blue, bismuth vanadate, goethite, magnetite, hematite, chromium oxide, chromium hydroxide, cobalt aluminate, ultramarine, chromium-iron mixed oxides, spinels such as cobalt blue, cadmium sulfides and selenides, chromate pigments or carbon black are suitable, whereas as organic pigments, in particular quinacridones, benzimidazoles, copper phthalocyanine, azo pigments, perinones, anthanthrones, other phthalocyanines, anthraquinones, indigo, thioindigo and their derivatives, or carmine can be used. Generally, all organic or inorganic color pigments are suitable, in particular those being conventional in the printing field.
  • pigments can be used, which absorb UV light.
  • examples are titanium dioxide and zinc oxide.
  • a security element according to the invention can be prepared in various ways. On the one hand, it is for example possible to produce a mixture of the polymeric material of the matrix and the other components described above and to extrude a film, wherein the extrusion is carried out in a conventional manner in accordance with the polymeric material used. The film thus obtained can then optionally be separated into individual film pieces and laminated or glued into or onto a security and/or valuable document.
  • a printable composition according to the invention in particular a printing ink, can be produced. It will contain the organic polymeric material of the matrix, the at least one luminescent substance, which is capable of non-contact excitation of light emission in the presence of the conductive pigment, the at least one electrically conductive pigment, and optionally at least one aqueous and/or organic solvent (preferred are organic solvents), the luminescent substance not being encapsulated.
  • the composition may contain at least one charge carrier transport material, as well as the other components described above, such as color pigments, effect pigments, optically variable pigments, UV blockers, preservatives, rheology-modifying agents, and stabilizers.
  • Suitable organic solvents are the solvents described above in connection with the polymeric material of the matrix and its preparation, and all conventional solvents and solvent mixtures being conventional in the printing technology, in particular the ink jet printing technology.
  • aqueous dispersions which contain less than 10 wt-% organic solvents, is also possible.
  • the matrix with its further components according to the invention consists of dispersed film-forming particles.
  • the composition may, depending on the intended application, be a solution, dispersion, emulsion, or paste.
  • a security element according to the invention (if applicable, after drying) comprises, for example: A) 0.1 to 5 wt-%, particularly 1 to 5 wt-% luminescent substance, B) 60 to 95 wt-%, in particular 85 to 95 wt-% matrix, C) 2 to 15 wt-%, particularly 5 to 10 wt-%, electrically conductive pigment, D) 0 to 37.9 wt-%, particularly 0.1 to 9 wt-% additives, and/or pigments different from C), the relative amounts of the components A) to D) always totaling 100%.
  • the invention further relates to a security and/or valuable document, comprising a substrate layer, optionally one or a plurality of additional layers, as well as at least one printing layer or film according to the invention, the printing layer or film being applied over the entire surface or over part of the surface of the substrate layer or an additional layer.
  • the printing layer or film may be incorporated in so far in the layer structure of a security and/or valuable document or be stacked thereon.
  • Such a document can be produced by that the substrate layer and/or the additional layer is formed from an organic polymeric material (e.g., as a film), wherein on the substrate layer or the additional layer, a printing layer or a film according to the invention is applied, and wherein, if applicable, the substrate layer and additional layer, optionally with a cover layer, are laminated together, before or after the application of the printing layer or film.
  • a security and/or valuable document is verifiable or authenticatable by exposing the security and/or valuable document to physical conditions, which stimulate the luminescent substance to emit light, wherein the light emission is observed or measured, and wherein the security and/or valuable document, in accordance with the observation or measurement, is classified as genuine or forged.
  • Such conditions include, for example, that the document is introduced in a gap electrode, which is supplied with an alternating electric field being dimensioned for the excitation of light emission.
  • a machine-readable security element with the greatest variety of usable electroluminescences, preferably in the UV, visible light and IR ranges is provided.
  • Emitter materials having different emission characteristics (color/wavelengths) at different excitations can be used, for example in the visible range, UV, or electrical excitation.
  • colors/wavelengths can be used, for example in the visible range, UV, or electrical excitation.
  • effects being time-resolved and accordingly detectable and thus evaluable by measurement are achieved by that different lifetimes of excited states and the corresponding selection of the emitter materials are provided.
  • the local luminescence then also depends, for example, on the random lateral distribution of the electrically conductive particles, which may be statistically uniform, while in the micro range (5 to 100 times the lateral dimension of the electrically conductive particles) they may be laterally dispersed in an uneven manner.
  • These patterns can be also used to generate random patterns, such as they are necessary for the generation of cryptographic keys, or can serve as the basis for material-based PUFs (physical unclonable functions).
  • these random patterns allow an electro-optical personalization and machine-detectable information/identification as a “serial number”, such as described in the document WO 2010/006583.
  • the polycarbonate derivative exhibited a relative solution viscosity of 1.255.
  • the polycarbonate derivative exhibited a relative solution viscosity of 1.263.
  • Example 2 As in Example 1, a mixture of 149.0 g (0.65 mol) of bisphenol A and 107.9 g (0.35 mol) of 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane was reacted to polycarbonate.
  • the polycarbonate derivative exhibited a relative solution viscosity of 1.263.
  • liquid composition to be applied by printing for example by screen printing
  • the following solution was prepared: 17.5 parts by weight of the polycarbonate of Example 1.3, 82.5 parts by weight of the following solvent mixture, consisting of:
  • the preparation was made analogous to Example 2.1, except that instead of the polyfluorene solution, the same amount of the following solution was used.
  • a polycarbonate film Makrofol® 6-2 (thickness approx. 100 ⁇ m) was imprinted, for example, with the preparation of Example 2.1 or 2.2 using digital printing, such as ink printing. Alternatively, screen printing may be used.
  • the printed film contains 0.5 wt-% luminescent substance, 90 wt-% organic polymeric material of the matrix, 8 wt-% conductive pigments.
  • the imprinted polycarbonate film thus obtained can be then laminated with other polycarbonate films, and that directly, i.e. without the use of interposed adhesive layers.
  • the individual film layers practically form a continuous piece of polycarbonate, as the materials laminated together, including the printed structures, are all based on polycarbonate. The layers can no longer be detached from one another, thus an extremely high protection against forgery being achieved, since access to the printed structures is practically impossible.
  • a security and/or valuable document prepared according to the invention may contain within the printing layer (identical or different) luminescent substances, which at different excitation modes emit at different wavelengths or show a center wavelength. In any case, an emission takes place with non-contact electrical stimulation.
  • FIG. 1 spectra of an embodiment according to the invention are shown.
  • the spectrum shown by the solid line is the light component reflected in the visible range (or not absorbed) and reproduces the color impression of the security element without any other excitation.
  • the short-dashed spectrum represents the emission of the security element for non-contact electrical excitation.
  • the long-dashed spectrum shows the emission when excited with UV. As can be seen, a different color, depending on the type of excitation, is detected by the viewer (or an automatic test device). Depending on the type of excitation, a shift or change in the shape of the spectrally dispersed emission takes place.
US14/362,257 2011-12-01 2012-11-30 Electro-optical security element Abandoned US20140291495A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102011119821.4 2011-12-01
DE102011119821A DE102011119821A1 (de) 2011-12-01 2011-12-01 Elektrooptisches Sicherheitselement
PCT/DE2012/001196 WO2013079056A2 (de) 2011-12-01 2012-11-30 Elektrooptisches sicherheitselement

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE2012/001196 A-371-Of-International WO2013079056A2 (de) 2011-12-01 2012-11-30 Elektrooptisches sicherheitselement

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/400,242 Continuation US10167402B2 (en) 2011-12-01 2017-01-06 Electro-optical security element for securtiy and/or valuable document

Publications (1)

Publication Number Publication Date
US20140291495A1 true US20140291495A1 (en) 2014-10-02

Family

ID=47748363

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/362,257 Abandoned US20140291495A1 (en) 2011-12-01 2012-11-30 Electro-optical security element
US15/400,242 Active 2033-01-26 US10167402B2 (en) 2011-12-01 2017-01-06 Electro-optical security element for securtiy and/or valuable document

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/400,242 Active 2033-01-26 US10167402B2 (en) 2011-12-01 2017-01-06 Electro-optical security element for securtiy and/or valuable document

Country Status (8)

Country Link
US (2) US20140291495A1 (pt)
EP (1) EP2734602B1 (pt)
CN (1) CN104093813B (pt)
BR (1) BR112014006645B1 (pt)
DE (2) DE102011119821A1 (pt)
EA (1) EA028223B1 (pt)
WO (1) WO2013079056A2 (pt)
ZA (1) ZA201403578B (pt)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160141540A1 (en) * 2014-11-17 2016-05-19 Samsung Display Co., Ltd. Organic light emitting diode display
WO2016120383A1 (en) 2015-01-30 2016-08-04 Sicpa Holding Sa Simultaneous authentication of a security article and identification of the security article user
WO2016120382A1 (en) 2015-01-30 2016-08-04 Sicpa Holding Sa Simultaneous authentication of a security article and identification of the security article user
WO2016162479A1 (en) 2015-04-10 2016-10-13 Sicpa Holding Sa Mobile, portable apparatus for authenticating a security article and method of operating the portable authentication apparatus
US20170340518A1 (en) * 2016-05-31 2017-11-30 Corning Incorporated Anti-counterfeiting measures for glass articles
KR20180018521A (ko) * 2015-06-18 2018-02-21 시크파 홀딩 에스에이 열발광 및 초상자성 복합 입자 및 이를 포함하는 마킹
WO2019002046A1 (en) 2017-06-26 2019-01-03 Sicpa Holding Sa PRINTING SECURITY ELEMENTS
US11952499B2 (en) 2018-02-12 2024-04-09 Hubergroup Italia Layer sequence with colour flop effect including platelet-shaped effect pigments

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10526501B2 (en) * 2015-04-09 2020-01-07 Basf Se Composition comprising silver nanowires in an alcohol/water mixture and dispersed styrene/(meth)acrylic copolymers for the preparation of electroconductive transparent layers
CN111751336B (zh) * 2019-03-27 2021-08-31 天津大学 D-a型有机掺杂晶体余辉材料在防伪中的应用
ES2803848A1 (es) * 2019-07-24 2021-01-29 Signe Sa Film para empaquetado de productos y uso del mismo
CN116162361B (zh) * 2021-11-25 2024-04-09 广东中塑新材料有限公司 低介电lcp树脂材料及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221144B1 (en) * 1998-03-18 2001-04-24 Merck Patent Gmbh Conductive pigments
US20060115110A1 (en) * 2004-11-09 2006-06-01 Rodriguez Tony F Authenticating identification and security documents
WO2010037638A2 (en) * 2008-10-03 2010-04-08 Sicpa Holding Sa Paired optically variable security element
US20100260985A1 (en) * 2007-12-07 2010-10-14 Bundesdruckerei Gmbh Polymer layer composite for a security and/or valuable document

Family Cites Families (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2970131A (en) 1961-01-31 polycarbonate process
NL104015C (pt) 1953-10-16
DE1007996B (de) 1955-03-26 1957-05-09 Bayer Ag Verfahren zur Herstellung thermoplastischer Kunststoffe
US3275601A (en) 1956-01-04 1966-09-27 Bayer Ag Manufacture of polycarbonates using tertiary amines, quaternary amines and salts thereof as catalysts
US2991273A (en) 1956-07-07 1961-07-04 Bayer Ag Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates
US3148172A (en) 1956-07-19 1964-09-08 Gen Electric Polycarbonates of dihydroxyaryl ethers
US2999846A (en) 1956-11-30 1961-09-12 Schnell Hermann High molecular weight thermoplastic aromatic sulfoxy polycarbonates
US3062781A (en) 1958-07-02 1962-11-06 Bayer Ag Process for the production of polycarbonates
US2999835A (en) 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
GB1122003A (en) 1964-10-07 1968-07-31 Gen Electric Improvements in aromatic polycarbonates
NL152889B (nl) 1967-03-10 1977-04-15 Gen Electric Werkwijze ter bereiding van een lineair polycarbonaatcopolymeer, alsmede orienteerbare textielvezel van dit copolymeer.
DE2063050C3 (de) 1970-12-22 1983-12-15 Bayer Ag, 5090 Leverkusen Verseifungsbeständige Polycarbonate, Verfahren zu deren Herstellung und deren Verwendung
DE2063052A1 (de) 1970-12-22 1972-07-13 Bayer Verseifungsbeständige Polycarbonate
DE2211956A1 (de) 1972-03-11 1973-10-25 Bayer Ag Verfahren zur herstellung verseifungsstabiler blockcopolycarbonate
DE3832396A1 (de) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkane, ihre herstellung und ihre verwendung zur herstellung von hochmolekularen polycarbonaten
DE4421561A1 (de) 1994-06-20 1995-12-21 Bayer Ag Hochtemperaturbeständige flexible Siebdruckfarben
DE19811693A1 (de) 1998-03-18 1999-09-23 Merck Patent Gmbh Leitfähige Pigmente
ITMI20012434A1 (it) 2001-11-20 2003-05-20 Dompe Spa Acidi 2-aril-propionici e composizioni farmaceutiche che li contengono
US20030215602A1 (en) 2002-02-26 2003-11-20 Anders Andersson Method and device for producing a multi-ply web of flexible material, such as paper and nonwoven, and multi-ply material and product produced by the method
DE10304805A1 (de) 2003-02-05 2004-08-19 Informium Ag Verfahren zur Herstellung von Sicherheitskennzeichen
DE10326644A1 (de) * 2003-06-11 2005-01-13 Bundesdruckerei Gmbh Wertdokument mit einem Sicherheitselement und Verfahren zur Herstellung des Wertdokuments
ATE488375T1 (de) * 2003-09-12 2010-12-15 American Dye Source Inc Verfahren zur aufzeichnung von informationen in lumineszierenden zusammensetzungen und verwendungen davon in herstellungsartikeln
KR100682860B1 (ko) 2004-01-27 2007-02-15 삼성에스디아이 주식회사 스피로플루오렌계 고분자 및 이를 이용한 유기 전계 발광소자
DE102004025373A1 (de) * 2004-05-24 2005-12-15 Merck Patent Gmbh Maschinenlesbares Sicherheitselement für Sicherheitserzeugnisse
US7838858B2 (en) * 2005-05-31 2010-11-23 Nikon Corporation Evaluation system and method of a search operation that detects a detection subject on an object
US20090116753A1 (en) 2005-09-12 2009-05-07 Ultradots, Inc. Authenticating and identifying objects using nanoparticles
DE102007056342A1 (de) 2007-11-22 2009-05-28 Merck Patent Gmbh Oberflächenmodifizierte Konversionsleuchtstoffe
DE102008034022A1 (de) 2008-07-16 2010-01-21 Merck Patent Gmbh Verfahren zur Herstellung eines Sicherheits- und/oder Wertprodukts mit Teilbereichen mit unterschiedlicher Lumineszenzemission
DE102008034021A1 (de) * 2008-07-16 2010-01-21 Merck Patent Gmbh Verfahren zur Herstellung eines Sicherheits- und/oder Wertprodukts mit Zufallsmuster und korrelierter Identzeichenfolge
DE102010005632A1 (de) * 2010-01-25 2011-07-28 Siemens Aktiengesellschaft, 80333 Phosphoreszente Metallkomplexverbindung, Verfahren zur Herstellung und lichtemittierendes Bauelement
US8252494B2 (en) 2010-05-03 2012-08-28 Xerox Corporation Fluorescent toner compositions and fluorescent pigments
US9754341B2 (en) * 2015-03-20 2017-09-05 Digimarc Corporation Digital watermarking and data hiding with narrow-band absorption materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6221144B1 (en) * 1998-03-18 2001-04-24 Merck Patent Gmbh Conductive pigments
US20060115110A1 (en) * 2004-11-09 2006-06-01 Rodriguez Tony F Authenticating identification and security documents
US20100260985A1 (en) * 2007-12-07 2010-10-14 Bundesdruckerei Gmbh Polymer layer composite for a security and/or valuable document
WO2010037638A2 (en) * 2008-10-03 2010-04-08 Sicpa Holding Sa Paired optically variable security element
US8998265B2 (en) * 2008-10-03 2015-04-07 Sicpa Holding Sa Paired optically variable security element

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9806275B2 (en) * 2014-11-17 2017-10-31 Samsung Display Co., Ltd. Organic light emitting diode display
US20160141540A1 (en) * 2014-11-17 2016-05-19 Samsung Display Co., Ltd. Organic light emitting diode display
US10403061B2 (en) 2015-01-30 2019-09-03 Sicpa Holding Sa Simultaneous authentication of a security article and identification of the security article user
WO2016120383A1 (en) 2015-01-30 2016-08-04 Sicpa Holding Sa Simultaneous authentication of a security article and identification of the security article user
WO2016120382A1 (en) 2015-01-30 2016-08-04 Sicpa Holding Sa Simultaneous authentication of a security article and identification of the security article user
US10445955B2 (en) 2015-01-30 2019-10-15 Sicpa Holding Sa Simultaneous authentication of a security article and identification of the security article user
WO2016162479A1 (en) 2015-04-10 2016-10-13 Sicpa Holding Sa Mobile, portable apparatus for authenticating a security article and method of operating the portable authentication apparatus
US10713347B2 (en) 2015-04-10 2020-07-14 Sicpa Holding Sa Mobile, portable apparatus for authenticating a security article and method of operating the portable authentication apparatus
US11629264B2 (en) * 2015-06-18 2023-04-18 Sicpa Holding Sa Thermoluminescent and superparamagnetic composite particle and marking comprising same
US20180155564A1 (en) * 2015-06-18 2018-06-07 Sicpa Holding Sa Thermoluminescent and superparamagnetic composite particle and marking comprising same
KR20180018521A (ko) * 2015-06-18 2018-02-21 시크파 홀딩 에스에이 열발광 및 초상자성 복합 입자 및 이를 포함하는 마킹
AU2016280744B2 (en) * 2015-06-18 2020-07-16 Sicpa Holding Sa Thermoluminescent and superparamagnetic composite particle and marking comprising same
KR102595143B1 (ko) * 2015-06-18 2023-10-30 시크파 홀딩 에스에이 열발광 및 초상자성 복합 입자 및 이를 포함하는 마킹
US10676240B2 (en) * 2016-05-31 2020-06-09 Corning Incorporated Anti-counterfeiting measures for glass articles
US20170340518A1 (en) * 2016-05-31 2017-11-30 Corning Incorporated Anti-counterfeiting measures for glass articles
US11667434B2 (en) 2016-05-31 2023-06-06 Corning Incorporated Anti-counterfeiting measures for glass articles
US11932445B2 (en) 2016-05-31 2024-03-19 Corning Incorporated Anti-counterfeiting measures for glass articles
WO2019002046A1 (en) 2017-06-26 2019-01-03 Sicpa Holding Sa PRINTING SECURITY ELEMENTS
US11124006B2 (en) 2017-06-26 2021-09-21 Sicpa Holding Sa Printing of security features
US11952499B2 (en) 2018-02-12 2024-04-09 Hubergroup Italia Layer sequence with colour flop effect including platelet-shaped effect pigments

Also Published As

Publication number Publication date
BR112014006645B1 (pt) 2021-03-23
EA028223B1 (ru) 2017-10-31
US20170122873A1 (en) 2017-05-04
WO2013079056A2 (de) 2013-06-06
CN104093813B (zh) 2017-06-06
EP2734602B1 (de) 2017-02-01
DE112012005043A5 (de) 2014-11-27
US10167402B2 (en) 2019-01-01
EA201400630A1 (ru) 2014-11-28
ZA201403578B (en) 2015-11-25
CN104093813A (zh) 2014-10-08
BR112014006645A2 (pt) 2017-04-04
EP2734602A2 (de) 2014-05-28
DE112012005043B4 (de) 2021-09-09
WO2013079056A3 (de) 2013-07-25
DE102011119821A1 (de) 2013-06-06

Similar Documents

Publication Publication Date Title
US10167402B2 (en) Electro-optical security element for securtiy and/or valuable document
Abdollahi et al. Photoluminescent and chromic nanomaterials for anticounterfeiting technologies: recent advances and future challenges
JP4916636B2 (ja) 視角に依存するカラー・シフトを有する顔料、該顔料を製造する方法、該顔料のセキュリティ用途での利用、該顔料を含むコーティング組成物および検出用デバイス
US20100062194A1 (en) Anti-counterfeiting methods and devices using substantially transparent fluorescent materials
CN102099198B (zh) 用于制造具有随机图案和相关识别符号序列的安全和/或有价产品的方法
KR101206658B1 (ko) 보안 제품용의 기계-판독가능한 보안 요소
US6572784B1 (en) Luminescent pigments and foils with color-shifting properties
CN102002365B (zh) 透明纳米荧光材料组合物及其在隐形防伪产品中的应用
US8642161B2 (en) Optically variable security element
CN105142924B (zh) 带电致发光防伪元件的安全产品或有价产品及其制造方法
CN110028948A (zh) 无镉量子点、其制造方法、包括其的组合物、量子点-聚合物复合物和显示器件
US20070225402A1 (en) Ultraviolet luminescent ink and security system using the same
US20160194507A1 (en) Quantum Dot Ink Formulation for Heat Transfer Printing Applications
US11186768B2 (en) Use of 4-bora-3A,4A-diaza-s-indacenes for security purposes
TW201823242A (zh) 經2-苯基苯氧基取代之苝雙醯亞胺化合物及其用途
US20190023905A1 (en) Perylene bisimides with rigid 2,2'-biphenoxy bridges
AU2014203815A1 (en) Safety and/or valuable document having a photonic crystal
TW201833109A (zh) 經１，６，７，１２-四-（２-異丙基苯氧基）取代之苝四羧酸二醯亞胺
EP3342601B1 (en) A security document
JP4240963B2 (ja) ホログラム転写シートとホログラム被転写媒体
US20170037260A1 (en) Photo-Activated Polymers and Use in Articles, and Methods of 2D and 3D Printing
RU2725599C1 (ru) Композиционный материал для маркировки материального объекта
KR20210041917A (ko) 양자점, 이를 포함하는 표시장치 및 그 표시장치의 제조방법

Legal Events

Date Code Title Description
AS Assignment

Owner name: BUNDESDRUCKEREI GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:FISCHER, JOERG;PAESCHKE, MANFRED;MUTH, OLIVER;AND OTHERS;SIGNING DATES FROM 20140211 TO 20140219;REEL/FRAME:033217/0796

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION