EP2349733B2 - Cartes id à blocage d'inscriptibilité par gravure laser - Google Patents

Cartes id à blocage d'inscriptibilité par gravure laser Download PDF

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Publication number
EP2349733B2
EP2349733B2 EP09778880.6A EP09778880A EP2349733B2 EP 2349733 B2 EP2349733 B2 EP 2349733B2 EP 09778880 A EP09778880 A EP 09778880A EP 2349733 B2 EP2349733 B2 EP 2349733B2
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EP
European Patent Office
Prior art keywords
laser
layer
laser gravure
inscribed
gravure
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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.)
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EP09778880.6A
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German (de)
English (en)
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EP2349733B1 (fr
EP2349733A1 (fr
Inventor
Heinz Pudleiner
Mehmet-Cengiz Yesildag
Georgios Tziovaras
Dirk Pophusen
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Covestro Deutschland AG
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Covestro Deutschland AG
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Priority to EP09778880.6A priority Critical patent/EP2349733B2/fr
Priority to PL09778880T priority patent/PL2349733T5/pl
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/24—Ablative recording, e.g. by burning marks; Spark recording
    • 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
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers
    • 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
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/43—Marking by removal of material
    • B42D25/435—Marking by removal of material using electromagnetic radiation, e.g. laser
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]

Definitions

  • the invention relates to layer structures for laser engraved ID cards which have an additional layer which is applied after laser engraving on the card body and the subsequent description of the card by laser engraving and thus falsifying the contained identification information restricts or completely prevented, and a method for Blockage of the laser engraving writability of laser engraving-labeled layer structures.
  • plastic films by means of laser engraving is an important step in the production of film composites.
  • Such film composites play e.g. a major role for identification documents such as passports, ID cards, ID cards or credit cards.
  • the black and white personalization of cards by laser engraving i. the application of lettering or illustrations such as black and white photos is well known.
  • the personalization by means of laser engraving is characterized in particular by its high counterfeit security.
  • the image is created inside the card, so that it is not possible to remove the image and create a new image. Separating the cards into their individual layers to access the laser layer is not possible with cards made entirely of polycarbonate.
  • Plastic cards are typically made by lamination of multiple films.
  • films equipped with laser-sensitive additives are laminated in their entirety into the outer layers of the multilayer card structure.
  • the personal data is lasered into the card in the form of textual information and / or image information, i. engraved. Thereafter, the loaded with laser additives film layer but remains active and can also be retrofitted with other data and thus changed content. This possibility opens up the potential of subsequent forgery of identification documents - called ID documents below - by adding data and image information.
  • WO 2003/055638 discloses an identification document in which security information is introduced into a laser-engravable layer by laser engraving, which is a cover layer, ie the surface of the identification document. Although an additional layer described there serves to protect the printed and possibly also lasered information, this is a protection against mechanical damage by abrasion or scratching.
  • US 2004/0198858 A1 describes a laser-writable layer structure, which may also contain a laser radiation, ie IR-opaque laminate layer. About the composition of this laminate layer, however, no further information is disclosed.
  • DE 10 2007 024298 B3 discloses a multi-layer structure for security documents, in which optionally laser-generated luminescent information is introduced into suitable layers and additionally a laser-writable metallization layer and a scratch-resistant coating are provided.
  • the object on which the present invention was based was therefore to find multilayer film composites in which the subsequent writability by means of laser engraving is greatly reduced or completely blocked.
  • a laser-engraved layered structure is laser-engraved with at least one partial or full-area IR radiation reflecting or absorbing cover layer, wherein the partial or full-surface IR radiation reflecting or absorbing cover layer has at least one IR coating. contains absorbent additive or consists of a multi-layer structure.
  • the present invention therefore relates to a laser-engraved layered construction comprising at least one thermoplastic layer which can be inscribed by laser engraving and a partial or full-surface IR radiation reflecting or absorbing cover layer, wherein the covering or full-surface IR radiation reflecting or absorbing at least one IR-absorbing Additive contains and wherein it is the IR-absorbing additive in the topcoat to those selected from the classes of azo, azomethine, methine anthraquinone, indanthrone, pyranthrone, flavanthrone, Benzanthron-, Phtalocyanin-, Pervlen , Dioxazine, thioindigo-isoindoline-isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments and metal complexes of azo, azomethine or methine dyes or metal salts of azo compounds.
  • the invention likewise relates to a laser-engraved layered construction comprising at least one thermoplastic layer which can be inscribed by laser engraving and a partial or full-surface IR radiation-reflecting or absorbing cover layer, wherein the partial or full-surface IR radiation reflecting or absorbing cover layer consists of a multi-layer structure which is a multilayer optical interference film.
  • laser marking The inscription of plastic films by laser engraving is referred to in the art and also in the following as laser marking. Accordingly, the term "laser-marked” is to be understood by laser engraving in the following. The process of laser engraving is known in the art and not to be confused with the Printing with laser printers.
  • the laser-engravable equipped thermoplastic layer contains at least one laser-sensitive additive.
  • the laser-sensitive additive can be suitable both for laser engraving lettering from bright to dark background, from dark to light background or even colored lettering. Laser-sensitive additives are preferred for the lettering for laser engraving inscription from dark to light background.
  • laser-sensitive additives are for example so-called laser marking additives in question, ie those from an absorber in the wavelength range of the laser to be used, preferably in the wavelength range of ND: YAG lasers (neodymium-doped yttrium-aluminum garnet laser).
  • laser marking additives and their use in molding compositions are, for example, in WO-A 2004/50766 and WO-A 2004/50767 described and are commercially available from the Fa. DSM under the trade name Micabs ®.
  • Further absorbers which are suitable as laser-sensitive additives are carbon black, coated sheet silicates, such as, for example, in US Pat DE-A-195 22 397 described and commercially available under the trade name Lazerflair ® , antimony doped tin oxide such as in US 6,693,657 and commercially available under the brand name Mark-it TM and phosphorus-containing tin-copper mixed oxides such as in WO-A 2006/042714 described.
  • the particle size of the laser-sensitive additive is in the range of 100 nm to 10 ⁇ m, and particularly advantageous if it is in the range of 500 nm to 2 ⁇ m.
  • a most preferred laser-sensitive additive is carbon black.
  • thermoplastic plastic of the thermoplastic layer may preferably be at least one thermoplastic selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds and / or polyaddition products of bifunctional reactive compounds. For certain applications, it may be advantageous and therefore preferred to use a transparent thermoplastic.
  • thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or co-polyethacrylates such as, by way of example and by way of preference, polymethyl methacrylate (PMMA), poly- or copolymers with styrene such as by way of example and preferably polystyrene (PS) or polystyrene-acrylonitrile (SAN).
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • SAN polystyrene-acrylonitrile
  • thermoplastic polyurethanes such as by way of example and preferably polypropylene or polyolefins based on cyclic olefins (eg TOPAS ® , Hoechst), poly- or copolycondensates of terephthalic acid, such as by way of example and preferably poly- or copolyethylene terephthalate (PET or CoPET), glycol modified PET (PETG), glycol-modified poly- or copolycyclohexanedimethylene terephthalate (PCTG) or poly- or copolybutylene terephthalate (PBT or CoPBT), poly- or copolycondensates of naphthalenedicarboxylic acid, such as by way of example and preferably polyethylene glycol naphthalate (PEN), poly- or copolycondensates t (e) at least one cycloalkyldicarboxylic acid, such as, by way of example and by
  • thermoplastics are polycarbonates or copolycarbonates or blends containing at least one polycarbonate or copolycarbonate. Particular preference is given to blends containing at least one polycarbonate or copolycarbonate and at least one poly- or copolycondensate of terephthalic acid, of naphthalenedicarboxylic acid or of a cycloalkyldicarboxylic acid, preferably of cyclohexanedicarboxylic acid.
  • polycarbonates or copolycarbonates in particular having average molecular weights M w of from 500 to 100,000, preferably from 10,000 to 80,000, particularly preferably from 15,000 to 40,000, or blends thereof with at least one poly- or copolycondensate of terephthalic acid with medium molecular weight Molecular weights M w from 10,000 to 200,000, preferably from 26,000 to 120,000.
  • Suitable poly- or copolycondensates of terephthalic acid in preferred embodiments of the invention are polyalkylene terephthalates.
  • Suitable polyalkylene terephthalates are, for example, reaction products of aromatic dicarboxylic acids or their reactive derivatives (for example dimethyl esters or anhydrides) and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or cycloaliphatic diols having 2 to 10 carbon atoms by known methods ( Plastics Handbook, Vol. VIII, p. 695 ff, Karl-Hanser-Verlag, Kunststoff 1973 ).
  • Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol%, of terephthalic acid residues, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol%, of ethylene glycol and / or butanediol-1,4- and / or 1,4- Cyclohexanedimethanol radicals, based on the diol component.
  • the preferred polyalkylene terephthalates may contain up to 20 mol% of other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as, for example, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic.
  • other aromatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms such as, for example, phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic, azelaic, cyclohexanediacetic.
  • the preferred polyalkylene terephthalates may contain up to 80 mol% of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, eg. B.
  • the polyalkylene can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, as z. B. in the DE-OS 19 00 270 and the U.S. Patent 3,692,744 are described to be branched.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • not more than 1 mol% of the branching agent, based on the acid component, is used.
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (for example their dialkyl esters) and ethylene glycol and / or butane-1,4-diol and / or 1,4-cyclohexanedimethanol radicals, and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which are prepared from at least two of the abovementioned acid components and / or from at least two of the abovementioned alcohol components; particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4) terephthalates.
  • the polyalkylene terephthalates preferably used as a component preferably have an intrinsic viscosity of about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, each measured in phenol / o-dichlorobenzene (1: 1 wt . Parts) at 25 ° C.
  • the blend of at least one polycarbonate or copolycarbonate with at least one poly- or copolycondensate of terephthalic acid is a blend of at least one polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate.
  • Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate may preferably be one having from 1 to 90% by weight of polycarbonate or copolycarbonate and from 99 to 10% by weight of poly- or Copolybutylene terephthalate or glycol-modified poly- or Copolycyclohexandimethylenterephthalat, preferably with 1 to 90 wt .-% polycarbonate and 99 to 10 wt .-% polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, wherein the proportions add up to 100 wt .-%.
  • Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate is particularly preferably one containing 20 to 85% by weight of polycarbonate or copolycarbonate and 80 to 15% by weight of polycarbonate or copolycarbonate.
  • these may be blends of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the above-mentioned compositions.
  • Particularly suitable polycarbonates or copolycarbonates in preferred embodiments are aromatic polycarbonates or copolycarbonates.
  • the polycarbonates or copolycarbonates may be linear or branched in a known manner.
  • polycarbonates can be carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents. Details of the production of polycarbonates have been laid down in many patents for about 40 years. By way of example, let's look at this Quick, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964 , on D. Freitag, U. Grigo, PR Müller, H. Nouvertne ', BAYER AG, "Polycarbonates” in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718 and finally up Dres. U. Grigo, K. Kirchner and PR Müller “Polycarbonates” in Becker / Braun, Plastics Handbook, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Kunststoff, Vienna 1992, pages 117-299 directed.
  • Suitable diphenols may be, for example, dihydroxyaryl compounds of the general formula (I) HO-Z-OH (I) wherein Z is an aromatic radical having 6 to 34 carbon atoms, the one or more optionally substituted aromatic Cores and aliphatic or cycloaliphatic radicals or alkylaryl or heteroatoms may contain as bridge members.
  • dihydroxyaryl compounds examples include: dihydroxybenzenes, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) -aryls, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) -ketones, Bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, 1,1'-bis (hydroxyphenyl) diisopropylbenzenes, and their kemalkylated and nuclear halogenated compounds.
  • Preferred dihydroxyaryl compounds are, for example, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) diphenylmethane , 1, 1-bis (4-hydroxyphenyl) -1-phenyl-ethane, 1,1-bis (4-hydroxyphenyl) -1- (1-naphthyl) -ethane, 1,1-bis (4-hydroxyphenyl) hydroxyphenyl) -1- (2-naphthyl) ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis - (3,5-dimethyl-4-hydroxyphenyl) -propane, 2,2-bis (4-hydroxyphenyl) -1-phenyl-propane, 2,2-bis (4-hydroxyphen
  • Preferred alkyl radical for the radicals R 3 and R 4 in formula (Ia) is methyl.
  • the X atoms in alpha position to the diphenyl substituted C atom (C-1) are preferably not dialkyl-substituted, while alkyl disubstitution in beta position to C-1 is preferred.
  • a very particularly preferred dihydroxydiphenylcycloalkane of the formula (Ia) is 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (formula (Ia-1) where R 1 and R 2 are H).
  • Such polycarbonates can according to the EP-A 359 953 be prepared from Dihydroxydiphenylcycloalkanen of formula (Ia).
  • dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis- (4-hydroxyphenyl) -diphenyl-methane, 1,1-bis- (4-hydroxyphenyl) -1-phenyl-ethane, bis- (4-hydroxyphenyl) -1- (1-naphthyl) ethane, bis- (4-hydroxyphenyl) -1- (2-naphthyl) -ethane, 2,2-bis (4-hydroxyphenyl) -propane, 2,2-bis (3 , 5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, 1,1- Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1'-bis (4-hydroxyphenyl) -3-di
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
  • Both a dihydroxyaryl compound to form homopolycarbonates and various DihydroxyarylENSen be used to form copolycarbonates. It is possible to use both a dihydroxyaryl compound of the formula (I) or (Ia) to form homopolycarbonates and also a plurality of dihydroxyaryl compounds of the formula (I) and / or (Ia) to form copolycarbonates.
  • the various dihydroxyaryl compounds can be linked to one another both statistically and in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) which may be used is preferably between 99 mol% (Ia) and 1 mol -% (I) and 2 mol% (Ia) to 98 mol% (I), preferably between 99 mol% (Ia) to 1 mol% (I) and 10 mol% (Ia) to 90 mol% ( I) and in particular between 99 mol% (Ia) to 1 mol% (I) and 30 mol% (Ia) to 70 mol% (I).
  • An especially preferred copolycarbonate can be prepared by using 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) propane dihydroxyaryl compounds of the formula (Ia) and (I) are prepared.
  • diaryl carbonates are diphenyl carbonate, methylphenyl phenyl carbonates and di (methylphenyl) carbonates, 4-ethylphenyl phenyl carbonate, di (4-ethylphenyl) carbonate, 4-n-propylphenyl phenyl carbonate, di (4 -n-propylphenyl) carbonate, 4-iso-propylphenyl-phenyl-carbonate, di (4-iso-propylphenyl) -carbonate, 4-n-butylphenyl-phenyl-carbonate, di (4-n-butylphenyl) - carbonate, 4-isobutylphenyl phenyl carbonate, di- (4-isobutylphenyl) carbonate, 4-tert-butylphenyl phenyl carbonate, di- (4-tert-butylphenyl) carbonate, 4-n- Pentylphenyl phenyl carbonate, di (4-n-but
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl phenyl carbonate, di (4-tert-butylphenyl) carbonate, biphenyl-4-yl phenyl carbonate, di (biphenyl-4-yl) carbonate, 4- (1-Methyl-1-phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1-methyl-1-phenylethyl) -phenyl] -carbonate and di- (methyl-salicylate) -carbonate.
  • Such MonohydroxyarylENSen are, for example, 1-, 2- or 3-methylphenol, 2,4-dimethylphenol 4-ethylphenol, 4-n-propylphenol, 4-iso-propylphenol, 4-n-butylphenol, 4-isoButylphenol, 4-tert-butylphenol , 4-n-pentylphenol, 4-n-hexylphenol, 4-iso-octylphenol, 4-n-nonylphenol, 3-pentadecylphenol, 4-cyclohexylphenol, 4- (1-methyl-1-phenylethyl) -phenol, 4-phenylphenol , 4-phenoxyphenol, 4- (1-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, iso-butyl salicylate
  • Suitable branching agents may be compounds having three or more functional groups, preferably those having three or more hydroxyl groups.
  • Suitable compounds having three or more phenolic hydroxyl groups are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-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 and tetra (4-hydroxyphenyl) -methane.
  • Suitable compounds having three and more functional groups are, for example, 2,4-dihydroxybenzoic acid, trimesic acid (trichloride), cyanuric trichloride and 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri (4-hydroxyphenyl) -ethane.
  • the cover layer which reflects or absorbs IR radiation preferably has a transmission for radiation of the wavelength from 800 to 1200 nm, preferably from 850 to 1100 nm, of not greater than 20%, preferably not greater than 15%, particularly preferably not greater than 10% ,
  • the cover layer which reflects or absorbs IR radiation preferably furthermore has a transmission for radiation of the wavelength of 400 to 700 nm greater than 60%, preferably greater than 70%. The transmission is determined according to ASTM D 1003.
  • the IR radiation-reflecting or absorbing cover layer contains at least one IR-absorbing additive.
  • literature-known infrared absorbers are suitable, as they are, for. In M. Matsuoka, Infrared Absorbing Dyes, Plenum Press, New York, 1990 are described in terms of substance class.
  • infrared absorbers from the classes of the azo, azomethine, methine anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone , Pyrrolopyrrol- or Chinophtalonpigmente and metal complexes of azo, azomethine or methine dyes or metal salts of azo compounds.
  • phthalocyanines and naphthalocyanines are particularly suitable. Due to the improved solubility in thermoplastics, phthalocyanines and naphthalocyanines with bulky side groups are preferable.
  • the amount of IR absorbing additives contained in the IR radiation reflecting or absorbing cover layer there are no particular limitations on the amount of IR absorbing additives contained in the IR radiation reflecting or absorbing cover layer, as long as the desired absorption of IR radiation and sufficient transparency are ensured. It has proved to be particularly advantageous if the composition of the IR radiation-reflecting or absorbing covering layer contains the IR-absorbing additive (s) in an amount of from 0.0001 to 10% by weight, in particular from 0.001 to 0.05 Wt .-%, based on the total weight of the composition of the IR radiation reflecting or absorbing cover layer contains. Also particularly suitable are mixtures of IR-absorbing additives. The person skilled in the art can achieve an optimization of the absorption in the near infrared range with dyes of different wavelengths of the absorption maxima.
  • Such IR radiation reflecting or absorbing films or films are known and commercially available.
  • the cover layer which reflects or absorbs IR radiation is a multi-layer structure which is a multilayer optical interference film, which can preferably be produced by coextrusion of alternating polymer layers. These are preferably layers based on coextruded layers IR radiation-reflecting films with a narrow reflection range due to light interference.
  • Such multilayer films are preferably composed of a plurality of parallel layers of transparent thermoplastic materials, for which the above-mentioned thermoplastics come into question, each directly juxtaposed layers of different thermoplastic materials whose refractive indices are at least 0.03, more preferably at least 0.06 different from each other.
  • Such a multilayer film preferably contains at least 10 layers.
  • the individual layers of the multilayer film are preferably very thin with layer thicknesses in the range of about 30 to 500 nm, preferably about 50 to 400 nm, whereby gain interference of light waves reflected at the many interfaces is achieved.
  • layer thicknesses in the range of about 30 to 500 nm, preferably about 50 to 400 nm, whereby gain interference of light waves reflected at the many interfaces is achieved.
  • a dominant wavelength band is reflected, while the remaining light is transmitted by the foil.
  • the amount of reflected light depends on the difference between the two indices of refraction, the ratio of the optical thicknesses of the layers, the number of layers, and the uniformity of the layer thicknesses.
  • the layer structure according to the invention preferably has at least one layer containing at least one thermoplastic and at least one filler ("filled layer").
  • filled layer As thermoplastics for the above-mentioned in question.
  • the filler in the filled layers is preferably at least one color pigment and / or at least one other filler for producing a translucency of the filled layers, preferably titanium dioxide, zirconium dioxide, barium sulfate or glass fibers, more preferably titanium dioxide.
  • the filled layers and the filled films used for their production are preferably those with a transmission in the visible wavelength range from 380 nm to 780 nm of less than 50%, preferably less than 35%, particularly preferably less than 25% most preferred embodiments of less than 15%.
  • the fillers mentioned are preferably used in amounts of from 2 to 45% by weight, more preferably from 5 to 30% by weight, based on the total weight of filler and thermoplastic, of the thermoplastics prior to shaping into the plastic film, which, for example by extrusion or coextrusion added.
  • the filled layers may have further information in preferred embodiments of the invention.
  • This further information can be obtained, for example, by means of conventional printing techniques, e.g. Ink jet, offset or laser printing, be applied.
  • the layer structure according to the invention may comprise further additional layers, via which, for example, further information is introduced into the security document, preferably an identification document.
  • Such further information can be, for example, personalizing portraits or non-personalizing general information, which are contained, for example, in each generic security document, preferably an identification document in the same form.
  • Such layers can be introduced, for example, from previously by means of conventional printing processes, preferably ink-jet or laser printing, particularly preferably color printing equipped with this information films in the layer structure according to the invention.
  • Films which can be printed by means of ink-jet printing processes are known to the person skilled in the art and can be, for example, those from at least one of the above-described thermoplastic plastics optionally containing at least one of the fillers described above.
  • fillers such as e.g. Titanium dioxide, zirconium dioxide, barium sulfate, etc. used white or translucent colored plastic films.
  • plastic films which are to be printed by means of laser printing in particular by means of color laser printing, plastic films of one of the abovementioned thermoplastics which have a surface resistivity of 10 7 to 10 13 ⁇ , preferably of 10 8 to 10 12 ⁇ , are particularly suitable.
  • the specific surface resistance in ⁇ is determined according to DIN IEC 93.
  • thermoplastic resin to achieve the surface resistivity example an additive selected from tertiary or quaternary, preferably quaternary ammonium or phosphonium salts of a partially or perfluorinated organic acid or quaternary ammonium or Phosphoniumhexafluorophosphaten preferred a partially or perfluorinated alkyl sulfonic acid, preferably a perfluoroalkyl sulfonic acid was added.
  • perfluorooctanesulfonic acid tetrapropylammonium salt the perfluorooctanesulfonic acid tetrabutylammonium salt, the perfluorooctanesulfonic acid tetrapentylammonium salt, the perfluorooctanesulfonic acid tetrahexylammonium salt and the perfluorooctanesulfonic acid dimethyldiisopropylammonium salt and the corresponding perfluorobutanesulfonic acid salts.
  • perfluorobutanesulfonic acid dimethyldiisopropylammonium salt (diisopropyldimethylammonium perfluorobutylsulfonate) may be used as an additive.
  • the salts mentioned are known or can be prepared by known methods.
  • the salts of the sulfonic acids can be prepared, for example, by combining equimolar amounts of the free sulfonic acid with the hydroxy form of the corresponding cation in water at room temperature and concentrating the solution.
  • Other manufacturing methods are described, for example in DE-A 1 966 931 and NL-A 7 802 830 ,
  • the salts mentioned are preferably added in amounts of from 0.001 to 2% by weight, preferably from 0.1 to 1% by weight, to the thermoplastics prior to shaping into the plastic film, which can be effected, for example, by extrusion or coextrusion.
  • the layered construction according to the invention may also comprise further additional layers which provide UV protection and / or protection against mechanical damage - such as e.g. Scratch-resistant coatings - etc. have.
  • the layer structure according to the invention is preferably suitable for increasing the security against forgery of security documents, particularly preferably identification documents.
  • the layer structure according to the invention is suitable for increasing the security against counterfeiting of such identification documents in the form of bonded or laminated laminates in the form of plastic cards, such as e.g. Identity documents, passports, driver's licenses, credit cards, bank cards, access control cards or other identity documents, etc.
  • Preferred identification documents in the context of the present invention are multi-layered sheet-like documents with security features such as chips, photographs, biometric data, etc. These security features can be visible from outside or at least be queriable.
  • such an identification document has a size between that of a check card and that of a passport.
  • Such an identification document may also be part of a document of several parts, such as e.g. a plastic identification document in a passport that also contains paper or cardboard parts.
  • the subject matter of the present invention is therefore furthermore a security document, preferably an identification document containing at least one laser-marked layer structure according to the invention.
  • the IR radiation-reflecting or absorbing cover layer is fully or partially applied to the layer structure, preferably the security document or identification document after personalization by means of laser engraving in order to prevent the subsequent change of the laser engraved personalizing data and thus to increase the security against counterfeiting.
  • the invention further provides a method for blocking the laser inscribability of laser-inscribed layer structures, characterized in that a laser-inscribed layer structure containing at least one laser-inscribable thermoplastic layer is provided with a partial or full-surface IR radiation reflecting or absorbing cover layer after laser inscription, wherein the partial or full-surface IR radiation-reflecting cover layer contains at least one IR-absorbing additive and the at least one IR-absorbing additive are those selected from the substance classes of the azo, azomethine, methine-anthraquinone, indanthrone, Pyranthrone, flavanthrone, benzanthrone, phthalocyanine, perylene, dioxazine, thioindigo-isoindoline, isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments and metal complexes of azo, azomethine or methine dyes or metal salts of azo compounds are selected.
  • Another object of the invention is a method for blocking inscribability by means of laser engraving of laser engraving inscribed layer structures, characterized in that a laser-engraved layered structure comprising at least one laser-engravable inscribable thermoplastic layer, after inscription by laser engraving with a partial or full-surface IR radiation or reflective absorbing layer is provided and the IR radiation-reflecting or absorbing cover layer after the lettering by means of laser engraving in the form of a multilayer film, which is a multilayer optical interference film is applied to the laser engraved inscribed layer structure by means of an adhesive or by lamination.
  • This application may be made using an adhesive or by lamination, which may be applied by lamination with both adhesive support and no adhesive.
  • Latent reactive adhesives are known in the art.
  • Preferred latently reactive adhesives are those which have an aqueous dispersion containing a di- or polyisocyanate with a melting or softening temperature of> 30 ° C and an isocyanate-reactive polymer.
  • an aqueous dispersion has a viscosity of at least 2000 mPas.
  • the isocyanate-reactive polymer in this dispersion is a polyurethane, which is composed of crystallizing polymer chains which, when measured by means of thermomechanical analysis (TMA) at temperatures below + 110 ° C, preferably at temperatures below + 90 ° C. , partially or completely recrystallize.
  • TMA thermomechanical analysis
  • the measurement by TMA is carried out analogously to ISO 11359 Part 3 "Determination of the Penetration Temperature".
  • the di- or polyisocyanate is one selected from the group consisting of dimerization products, trimerization products and urea derivatives of TDI (toluene diisocyanate) or IPDI (isophorone diisocyanate).
  • TDI toluene diisocyanate
  • IPDI isophorone diisocyanate
  • an additional increase in anti-counterfeiting security can be achieved in that no water vapor and / or air can diffuse into the interior beyond the edges of the layer structure and thus can no longer lead to a subsequent delamination.
  • Such layer structures can no longer be separated intact.
  • the cover layer which reflects or absorbs IR radiation can no longer be separated without destroying the entire security document or identification document.
  • the same also applies to a covering layer which is reflective or absorbing by means of lamination.
  • Film 1-1 white filled film
  • a film with the same composition as film 1-1 of thickness 400 ⁇ m was produced.
  • Film 3 transparent film
  • a commercially available IR reflection film from 3M (3M Vikuiti® Clear Card IR Filter) was used. It was a transparent, IR-reflective film with less than 20% light transmission in the range between 850 and 1100 nm (determined according to ASTM D 1003).
  • Example 1 Production of a laser-writable layer structure
  • a symmetric layer structure of the card was chosen to avoid bending the card.
  • the above-mentioned film 4 was used.
  • Polyurethane dispersion having a solids content of about 45% by weight .; Isocyanate-reactive polymer of linear polyurethane chains in water
  • Non-ionic, liquid, aliphatic polyurethane-based thickener Viscosity at 23 ° C:> 9,000 mPas; Non-volatile ingredients: 50% by weight.
  • the IR reflection film was coated with a spiral doctor blade with this adhesive dispersion, wherein the wet layer thickness of the adhesive dispersion was 100 microns, so that a dry film thickness of about 30 microns was obtained. Subsequently, the coated film was dried for 90 minutes at about 35 ° C in a drying oven and was then ready for use in the lamination.
  • the left half of the layer (1) of the ID card prepared in Example 1 was laminated in a second lamination step with the adhesive-coated IR reflective sheet of Example 2.
  • the structure according to the invention offers the possibility to prevent the subsequent laser engraving after completion of personalization of an ID card by means of laser engraving by application of an IR radiation reflecting or absorbing cover layer.

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  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Electromagnetism (AREA)
  • General Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Credit Cards Or The Like (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Claims (13)

  1. Structure de couches inscrite par gravure laser contenant au moins une couche plastique thermoplastique inscriptible par gravure laser et une couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface, la couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface contenant au moins un additif absorbant l'IR et l'additif absorbant l'IR dans la couche supérieure étant choisi dans les classes de matières des pigments azo, azométhine, méthine, anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone, phtalocyanine, pérylène, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, pyrrolopyrrole ou quinophtalone, ainsi que des complexes métalliques de colorants azo, azométhine ou méthine, ou des sels métalliques de composés azo.
  2. Structure de couches inscrite par gravure laser contenant au moins une couche plastique thermoplastique inscriptible par gravure laser et une couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface, la couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface étant constituée d'une structure multicouche qui est un film d'interférence optique multicouche.
  3. Structure de couches inscrite par gravure laser selon la revendication 1 ou 2, caractérisée en ce que la couche plastique thermoplastique inscriptible par gravure laser contient au moins un additif sensible aux lasers.
  4. Structure de couches inscrite par gravure laser selon la revendication 3, caractérisée en ce que l'additif sensible aux lasers consiste en un noir de carbone.
  5. Structure de couches inscrite par gravure laser selon au moins l'une quelconque des revendications 1 à 4, caractérisée en ce que le plastique thermoplastique de la couche plastique thermoplastique inscriptible par laser consiste en au moins un plastique thermoplastique choisi parmi les polymères de monomères éthyléniquement insaturés et/ou les polycondensats de composés réactifs bifonctionnels, de préférence en un ou plusieurs polycarbonates ou copolycarbonates à base de diphénols, poly- ou copolyacrylates et poly- ou copolyméthacrylates, poly- ou copolymères avec du styrène, polyuréthanes, ainsi que polyoléfines, poly-ou copolycondensats de l'acide téréphtalique, poly- ou copolycondensats de l'acide naphtalinedicarboxylique, poly- ou copolycondensats d'au moins un acide cycloalkyldicarboxylique, polysulfones ou leurs mélanges, de manière particulièrement préférée en un ou plusieurs polycarbonates ou copolycarbonates à base de diphénols ou des alliages contenant au moins un polycarbonate ou copolycarbonate.
  6. Structure de couches inscrite par gravure laser selon au moins l'une quelconque des revendications 1 à 5, caractérisée en ce que la transmission de la couche supérieure réfléchissant ou absorbant le rayonnement IR pour le rayonnement de longueur d'onde de 800 à 1 200 nm, de préférence de 850 à 1 100 nm, est inférieure ou égale à 20 %, de préférence inférieure ou égale à 15 %, de manière particulièrement préférée inférieure ou égale à 10 %, et la transmission pour le rayonnement de longueur d'onde de 400 à 700 nm est supérieure à 60 %, de préférence supérieure à 70 %.
  7. Structure de couches inscrite par gravure laser selon au moins l'une quelconque des revendications 1 à 6, caractérisée en ce que la structure de couches comprend au moins une couche contenant au moins un plastique thermoplastique et au moins une charge (« couche chargée »).
  8. Structure de couches inscrite par gravure laser selon la revendication 7, caractérisée en ce que la charge consiste en un pigment coloré ou une autre charge permettant de générer une translucidité de la couche chargée, de préférence en du dioxyde de titane, du dioxyde de zirconium, du sulfate de baryum ou des fibres de verre.
  9. Document de sécurité, de préférence document d'identification, contenant au moins une structure de couches inscrite par gravure laser selon au moins l'une quelconque des revendications 1 à 8.
  10. Procédé de blocage de l'inscriptibilité par gravure laser de structures de couches inscrites par gravure laser, caractérisé en ce qu'une structure de couches inscrite par gravure laser contenant au moins une couche plastique thermoplastique inscriptible par gravure laser est munie d'une couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface après l'inscription par gravure laser la couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface contenant au moins un additif absorbant l'IR, et l'additif absorbant l'IR dans la couche supérieure étant choisi dans les classes de matières des pigments azo, azométhine, méthine, anthraquinone, indanthrone, pyranthrone, flavanthrone, benzanthrone, phtalocyanine, pérylène, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, pyrrolopyrrole ou quinophtalone, ainsi que des complexes métalliques de colorants azo, azométhine ou méthine, ou des sels métalliques de composés azo.
  11. Procédé de blocage de l'inscriptibilité par gravure laser de structures de couches inscrites par gravure laser, caractérisé en ce qu'une structure de couches inscrite par gravure laser contenant au moins une couche plastique thermoplastique inscriptible par gravure laser est munie d'une couche supérieure réfléchissant ou absorbant le rayonnement IR sur une partie ou sur l'ensemble de sa surface après l'inscription par gravure laser et la couche supérieure réfléchissant ou absorbant le rayonnement IR est appliquée après l'inscription par gravure laser sous la forme d'une feuille multicouche qui est une feuille d'interférence optique multicouche, sur la structure de couches inscrite par gravure laser par un adhésif ou par stratification.
  12. Procédé selon la revendication 11, caractérisé en ce que l'adhésif consiste en un adhésif réactif latent.
  13. Utilisation d'une feuille réfléchissant ou absorbant le rayonnement IR pour bloquer l'inscription par gravure laser de structures de couches inscrites par gravure laser, de préférence de documents de sécurité, de manière particulièrement préférée de documents d'identification.
EP09778880.6A 2008-10-23 2009-10-10 Cartes id à blocage d'inscriptibilité par gravure laser Not-in-force EP2349733B2 (fr)

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EP09778880.6A EP2349733B2 (fr) 2008-10-23 2009-10-10 Cartes id à blocage d'inscriptibilité par gravure laser
PL09778880T PL2349733T5 (pl) 2008-10-23 2009-10-10 Karty identyfikacyjne z zablokowaną za pomocą grawerowania laserowego zdolnością zapisywania

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EP08018547A EP2179857A1 (fr) 2008-10-23 2008-10-23 Cartes ID dotées d'une fonction d'écriture par gravure au laser bloquée
PCT/EP2009/007269 WO2010046042A1 (fr) 2008-10-23 2009-10-10 Cartes id à blocage d'inscriptibilité par gravure laser
EP09778880.6A EP2349733B2 (fr) 2008-10-23 2009-10-10 Cartes id à blocage d'inscriptibilité par gravure laser

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JP2012506328A (ja) 2012-03-15
ES2407084T3 (es) 2013-06-11
KR20110074558A (ko) 2011-06-30
EP2349733B1 (fr) 2013-03-20
EP2179857A1 (fr) 2010-04-28
ES2407084T5 (es) 2018-02-13
TW201028293A (en) 2010-08-01
EP2349733A1 (fr) 2011-08-03
CN102196920A (zh) 2011-09-21
US20110200801A1 (en) 2011-08-18
US9079443B2 (en) 2015-07-14
PL2349733T3 (pl) 2013-12-31
PL2349733T5 (pl) 2018-12-31
WO2010046042A1 (fr) 2010-04-29

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