EP2349733B2 - Id cards with blocked laser engraving writability - Google Patents

Id cards with blocked laser engraving writability 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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EP09778880.6A
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German (de)
French (fr)
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EP2349733A1 (en
EP2349733B1 (en
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 PL09778880T priority Critical patent/PL2349733T5/en
Priority to EP09778880.6A priority patent/EP2349733B2/en
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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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  • Optics & Photonics (AREA)
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Description

Gegenstand der Erfindung sind Schichtaufbauten für lasergravurbeschreibbare ID-Karten, welche eine zusätzliche Schicht aufweisen, die nach der Lasergravur auf den Kartenkörper aufgebracht wird und das nachträgliche Beschreiben der Karte mittels Lasergravur und damit Verfälschen der enthaltenen Identifikationsinformationen einschränkt bzw. vollständig verhindert, sowie ein Verfahren zur Blockierung der Lasergravurbeschreibbarkeit von lasergravurbeschrifteten Schichtaufbauten.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.

Das Beschreiben von Kunststofffolien mittels Lasergravur ist ein wichtiger Schritt bei der Herstellung von Folienverbunden. Derartige Folienverbunde spielen z.B. eine große Rolle für Identifikationsdokumente wie Pässe, Ausweise, ID-Karten oder Kreditkarten. Das schwarz/weiß Personalisieren von Karten mittels Lasergravur, d.h. das Aufbringen von Schriftzügen oder Abbildungen wie schwarz/weiß-Fotos ist allgemein bekannt. Im Allgemeinen zeichnet sich das Personalisieren mittels Lasergravur insbesondere durch seine hohe Fälschungssicherheit aus. Das Bild entsteht im Inneren der Karte, so dass ein Entfernen des Bildes und Erstellung eines neuen Bildes nicht möglich ist. Ein Trennen der Karten in ihre einzelnen Schichten, um an die LaserSchicht zu gelangen, ist bei Karten, welche vollständig aus Polycarbonat hergestellt werden, nicht möglich.The description of 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. In general, 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.

Kunststoffkarten werden typischerweise durch Lamination von mehreren Folien hergestellt. Um die Personalisierung der Karte mittels Lasergravur durchführen zu können, werden mit Lasersensiblen Additiven ausgerüstete Folien vollflächig in den äußeren Lagen des mehrschichtigen Kartenaufbaus einlaminiert.Plastic cards are typically made by lamination of multiple films. In order to be able to carry out the personalization of the card by means of laser engraving, films equipped with laser-sensitive additives are laminated in their entirety into the outer layers of the multilayer card structure.

Nach der Lamination der Kartenkörper werden die persönlichen Daten in Form von Textinformation und/oder Bildinformation in die Karte eingelasert, d.h. eingraviert. Danach bleibt die mit Laser-Additiven beladene Folienschicht aber weiter aktiv und kann auch noch nachträglich mit weiteren Daten bestückt und damit inhaltlich verändert werden. Diese Möglichkeit eröffnet das Potential der nachträglichen Fälschung von Identifikationsdokumenten - nachstehend ID-Dokumente genannt - durch Hinzufügen von Daten und Bildinformationen.After lamination of the card body, 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 offenbart ein Identifikations-Dokument, in das in eine lasergravierbare Schicht mittels Lasergravur Sicherheitsinformationen eingebracht werden, wobei es sich um eine Deckschicht, d.h. die Oberfläche des Identifikationsdokuments, handelt. Eine dort beschriebene zusätzliche Schicht dient zwar dem Schutz der aufgedruckten und möglicherweise auch eingelaserten Information, jedoch handelt es sich dabei um einen Schutz vor mechanischer Beschädigung durch Abrieb oder Verkratzen. 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 beschreibt einen laserbeschreibbaren Schichtaufbau, der auch eine für Laserstrahlung, d.h. IR-Strahlung undurchlässige Laminatschicht enthalten kann. Über die Zusammensetzung dieser Laminatschicht ist allerdings keinerlei weitere Information offenbart. 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 offenbart einen Mehrschichtaufbau für Sicherheitsdokumente, in welchen gegebenenfalls lasergeneriert lumineszierende Informationen in dafür geeignete Schichten eingebracht werden und zusätzlich eine laserbeschreibbare Metallisierungsschicht sowie eine Kratzschutzversiegelung vorgesehen sind. 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.

Es bestand demnach Bedarf, das nachträgliche Bestücken solcher mehrschichtigen Folienverbunde mit Informationen mittels Lasergravur zu blockieren oder zumindest stark einzuschränken und so die Fälschungssicherheit von Sicherheitsdokumenten, vorzugsweise ID-Dokumenten, zu erhöhen.There was therefore a need to block the subsequent loading of such multilayer film composites with information by means of laser engraving or at least severely limit and thus increase the security against forgery of security documents, preferably ID documents.

Die Aufgabe, die der vorliegenden Erfindung zugrunde lag, bestand demnach darin, mehrschichtigen Folienverbunde aufzufinden, in denen die nachträgliche Beschreibbarkeit mittels Lasergravur stark vermindert oder vollständig blockiert ist.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.

Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, dass ein lasergravurbeschrifteter Schichtaufbau nach der Beschriftung mittels Lasergravur mit wenigstens einer teil- oder vollflächigen IR-Strahlung reflektierenden oder absorbierenden Deckschicht versehen wird, wobei die teil- oder vollflächige IR-Strahlung reflektierende oder absorbierende Deckschicht wenigstens ein IR-absorbierendes Additiv enthält oder aus einem Mehrschichtaufbau besteht.This object is achieved in accordance with the invention in that 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.

In US 2005/0259326A1 ist die Verwendung von multilagigen optischen Folien, die IR-Licht reflektieren, in Karten beschrieben. Die IR-Reflektionsschichten werden innerhalb des Folienverbundes, d.h. zwischen wenigstens zwei weiteren Polymerschichten in der Karte angeordnet, um eine Kartenerkennung mittels Reflektion von IR-Strahlung zu ermöglichen. Dabei handelt es sich um sogenannte VLT (visible light transmissive) Karten. Ein Einsatz von IR-reflektierenden Folien als Deckschichten zur Blockierung der Lasergravurbeschreibbarkeit wird in dieser Anmeldung nicht beschrieben.In US 2005 / 0259326A1 For example, the use of multilayer optical films that reflect IR light is described in Maps. The IR reflection layers are arranged within the film composite, ie between at least two further polymer layers in the card, in order to enable card recognition by means of reflection of IR radiation. These are so-called VLT (visible light transmissive) cards. The use of IR-reflecting films as cover layers for blocking the laser engraving writability is not described in this application.

Gegenstand der vorliegenden Erfindung ist daher ein lasergravurbeschrifteter Schichtaufbau enthaltend wenigstens eine mittels Lasergravur beschriftbar ausgerüstete thermoplastische Kunststoffschicht und eine teil- oder vollflächige IR-Strahlung reflektierende oder absorbierende Deckschicht, wobei die teil- oder vollflächige IR-Strahlung reflektierende oder absorbierende Deckschicht wenigstens ein IR-absorbierendes Additiv enthält und wobei es sich bei dem IR-absorbierenden Additiv in der Deckschicht um solche, die aus den Stoffklassen der Azo-, Azomethin-, Methin- Anthrachinon-, Indanthron-, Pyranthron-, Flavanthron-, Benzanthron-, Phtalocyanin-, Pervlen-, Dioxazin-, Thioindigo- Isoindolin-Isoindolinon-, Chinacridon-, Pyrrolopyrrol- oder Chinophtalonpigmente sowie Metallkomplexe von Azo-, Azomethin- oder Methinfarbstoffen oder Metallsalzen von Azoverbindungen ausgewählt sind, handelt. Ebenfalls Gegenstand der Erfindung ist ein lasergravurbeschrifteter Schichtaufbau enthaltend wenigstens eine mittels Lasergravur beschriftbar ausgerüstete thermoplastische Kunststoffschicht und eine teil- oder vollflächige IR-Strahlung reflektierende oder absorbierende Deckschicht, wobei die teil- oder vollflächigen IR-Strahlung reflektierende oder absorbierende Deckschicht aus einem Mehrschichtaufbau besteht, die ein mehrschichtiger optischer Interferenzfilm ist.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.

Die Beschriftung von Kunststoff-Folien mittels Lasergravur wird in der Fachwelt und auch im Folgenden kurz als Laserbeschriftung bezeichnet. Demnach ist im Folgenden unter dem Begriff "laserbeschriftet" mittels Lasergravur beschriftet zu verstehen. Das Verfahren der Lasergravur ist dem Fachmann bekannt und nicht zu verwechseln mit dem Bedrucken mittels Laserdruckern.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.

Vorzugsweise enthält die mittels Lasergravur beschriftbar ausgerüstete thermoplastische Kunststoffschicht wenigstens ein lasersensibles Additiv. Das lasersensible Additiv kann sowohl zur Lasergravurbeschriftung von hell auf dunklem Untergrund, von dunkel auf hellem Untergrund oder auch von farbigen Beschriftungen geeignet sein. Bevorzugt sind lasersensible Additive für die Beschriftung zur Lasergravurbeschriftung von dunkel auf hellem Untergrund.Preferably, 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.

Als lasersensible Additive kommen beispielsweise sogenannte Laser-Markier-Additive in Frage, d.h. solche aus einem Absorber im Wellenlängenbereich des zu verwendenden Lasers, bevorzugt im Wellenlängenbereich von ND:YAG-Lasern (Neodym-dotierte Yttrium-Aluminium-Granat-Laser). Solche Laser-Markier-Additive und deren Verwendung in Formmassen sind beispielsweise in WO-A 2004/50766 und WO-A 2004/50767 beschrieben und werden von der Fa. DSM unter dem Markennamen Micabs® kommerziell angeboten. Weiterhin als lasersensible Additive geeignete Absorber sind Ruß, beschichtete Schichtsilikate wie z.B. in DE-A-195 22 397 beschrieben und unter den Markennamen Lazerflair® kommerziell erhältlich, antimondotiertes Zinnoxid wie z.B. in US 6,693,657 beschrieben und unter den Markennamen Mark-it™ kommerziell erhältlich sowie phosphorhaltige Zinn-Kupfer-Mischoxide wie z.B. in WO-A 2006/042714 beschrieben.As 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). Such 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 ™ and phosphorus-containing tin-copper mixed oxides such as in WO-A 2006/042714 described.

Bevorzugt ist es, wenn die Korngröße des lasersensiblen Additivs im Bereich von 100 nm bis 10 µm liegt, und besonders vorteilhaft, wenn sie im Bereich von 500 nm bis 2 µm liegt.It is preferred if the particle size of the laser-sensitive additive is in the range of 100 nm to 10 μm, and particularly advantageous if it is in the range of 500 nm to 2 μm.

Ein ganz besonders bevorzugtes lasersensibles Additiv ist Ruß.A most preferred laser-sensitive additive is carbon black.

Bei dem thermoplastischen Kunststoff der thermoplastische Kunststoffschicht kann es sich bevorzugt um wenigstens einen thermoplastischen Kunststoff ausgewählt aus Polymerisaten von ethylenisch ungesättigten Monomeren und/oder Polykondensaten von bifunktionellen reaktiven Verbindungen und/oder Polyadditionaprodukten von bifunktionellen reaktiven Verbindungen, handeln. Für bestimmte Anwendungen kann es vorteilhaft und demnach bevorzugt sein, einen transparenten thermoplastischen Kunststoff einzusetzen.The 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.

Besonders geeignete thermoplastische Kunststoffe sind Polycarbonate oder Copolycarbonate auf Basis von Diphenolen, Poly- oder Copolyacrylate und Poly- oder Copolymethacrylate wie beispielhaft und vorzugsweise Polymethylmethacrylat (PMMA), Poly- oder Copolymere mit Styrol wie beispielhaft und vorzugsweise Polystyrol (PS) oder Polystyrolacrylnitril (SAN), thermoplastische Polyurethane, sowie Polyolefine, wie beispielhaft und vorzugsweise Polypropylentypen oder Polyolefine auf der Basis von cyclischen Olefinen (z.B. TOPAS®, Hoechst), Poly- oder Copolykondensate der Terephthalsäure, wie beispielhaft und vorzugsweise Poly- oder Copolyethylenterephthalat (PET oder CoPET), glycol-modifiziertes PET (PETG), glycol-modifiziertes Poly- oder Copolycyclohexandimethylenterephthalat (PCTG) oder Poly- oder Copolybutylenterephthalat (PBT oder CoPBT), Poly- oder Copolykondensate der Naphthalindicarbonsäure, wie beispielhaft und vorzugsweise Polyethylenglykolnaphthalat (PEN), Poly- oder Copolykondensat(e) wenigstens einer Cycloalkyldicarbonsäure, wie beispielhaft und vorzugsweise Polycyclohexandimethanolcyclohexandicarbonsäure (PCCD), Polysulfone (PSU) oder Mischungen aus den vorangehend genannten.Particularly suitable 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). , thermoplastic polyurethanes, and polyolefins, 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 way of preference, polycyclohexanedimethanolcyclohexanedicarboxylic acid (PCCD), polysulfones (PSU) or mixtures of the abovementioned.

Bevorzugte thermoplastische Kunststoffe sind Polycarbonate oder Copolycarbonate oder Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat. Besonders bevorzugt sind Blends enthaltend wenigstens ein Polycarbonat oder Copolycarbonat und wenigstens ein Poly- oder Copolykondensat der Terephthalsäure, der Naphthalindicarbonsäure oder einer Cycloalkyldicarbonsäure, bevorzugt der Cyclohexandicarbonsäure. Ganz besonders bevorzugt sind Polycarbonate oder Copolycarbonate, insbesondere mit mittleren Molekulargewichten Mw von 500 bis 100 000, bevorzugt von 10 000 bis 80 000, besonders bevorzugt von 15 000 bis 40 000 oder deren Blends mit wenigstens einem Poly- oder Copolykondensat der Terephthalsäure mit mittleren Molekulargewichten Mw von 10.000 bis 200.000, bevorzugt von 26.000 bis 120.000.Preferred 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. Very particular preference is given to 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.

Als Poly- oder Copolykondensate der Terephthalsäure eignen sich in bevorzugten Ausführungformen der Erfindung Polyalkylenterephthalate. Geeignete Polyalkylenterephthalate sind beispielsweise Reaktionsprodukte aus aromatischen Dicarbonsäuren oder ihren reaktionsfähigen Derivaten (z. B. Dimethylestern oder Anhydriden) und aliphatischen, cycloaliphatischen oder araliphatischen Diolen und Mischungen dieser Reaktionsprodukte.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.

Bevorzugte Polyalkylenterephthalate lassen sich aus Terephthalsäure (oder ihren reaktionsfähigen Derivaten) und aliphatischen oder cycloaliphatischen Diolen mit 2 bis 10 C-Atomen nach bekannten Methoden herstellen ( Kunststoff-Handbuch, Bd. VIII, S. 695 ff, Karl-Hanser-Verlag, München 1973 ).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, Munich 1973 ).

Bevorzugte Polyalkylenterephthalate enthalten mindestens 80 Mol-%, vorzugsweise 90 Mol-% Terephthalsäurereste, bezogen auf die Dicarbonsäurekomponente, und mindestens 80 Mol%, vorzugsweise mindestens 90 Mol% Ethylenglykol- und/oder Butandiol-1,4- und/oder 1,4-Cyclohexandimethanol-Reste, bezogen auf die Diolkomponente.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.

Die bevorzugten Polyalkylenterephthalate können neben Terephthalsäureresten bis zu 20 Mol% Reste anderer aromatischer Dicarbonsäuren mit 8 bis 14 C-Atomen oder aliphatischer Dicarbonsäuren mit 4 bis 12 C-Atomen enthalten, wie beispielsweise Reste von Phthalsäure, Isophthalsäure, Naphthalin-2,6-dicarbonsäure, 4,4'-Diphenyldicarbonsäure, Bernstein-, Adipin-, Sebacinsäure, Azelainsäure, Cyclohexandiessigsäure.In addition to terephthalic acid residues, 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.

Die bevorzugten Polyalkylenterephthalate können neben Ethylen- bzw. Butandiol-1,4-glykol-Resten bis zu 80 Mol% anderer aliphatischer Diole mit 3 bis 12 C-Atomen oder cycloaliphatischer Diole mit 6 bis 21 C-Atomen enthalten, z. B. Reste von Propandiol-1,3, 2-Ethylpropandiol-1,3, Neopentylglykol, Pentan-diol-1,5, Hexandiol-1,6, Cyclohexandimethanol-1,4, 3-Methylpentandiol-2,4, 2-Methylpentandiol-2,4, 2,2,4-Trimethylpentandiol-1,3 und 2-Ethylhexandiol-1,6, 2,2-Diethylpropandiol-1,3, Hexandiol-2,5, 1,4-Di-([beta]-hydroxyethoxy)-benzol, 2,2-Bis-(4-hydroxycyclohexyl)-propan, 2,4-Dihydroxy-1,1,3,3-tetramethyl-cyclobutan, 2,2-Bis-(3-[beta]-hydroxyethoxyphenyl)-propan und 2,2-Bis-(4-hydroxypropoxyphenyl)-propan (vgl. DE-OS 24 07 674 , 24 07 776 , 27 15 932 ).In addition to ethylene or butane-1,4-glycol radicals, 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. residues of 1,3-propanediol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-diol-1,5, 1,6-hexanediol, cyclohexanedimethanol-1,4, 3-methylpentanediol-2,4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3 and 2-ethylhexanediol-1,6, 2,2-diethylpropanediol-1,3, hexanediol-2, 5, 1,4-di - ([beta] -hydroxyethoxy) -benzene, 2,2-bis (4-hydroxycyclohexyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, 2,2-bis- (3- [beta] -hydroxyethoxyphenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane (cf. DE-OS 24 07 674 . 24 07 776 . 27 15 932 ).

Die Polyalkylenterephthalate können durch Einbau relativ kleiner Mengen 3- oder 4-wertiger Alkohole oder 3- oder 4-basischer Carbonsäuren, wie sie z. B. in der DE-OS 19 00 270 und der US-PS 3 692 744 beschrieben sind, verzweigt werden. Beispiele bevorzugter Verzweigungsmittel sind Trimesinsäure, Trimellitsäure, Trimethylolethan und -propan und Pentaerythrit.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. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Vorzugsweise wird nicht mehr als 1 Mol% des Verzweigungsmittels, bezogen auf die Säurekomponente, verwendet.Preferably, not more than 1 mol% of the branching agent, based on the acid component, is used.

Besonders bevorzugt sind Polyalkylenterephthalate, die allein aus Terephthalsäure und deren reaktionsfähigen Derivaten (z. B. deren Dialkylestern) und Ethylenglykol und/oder Butandiol-1,4 und/oder 1,4-Cyclohexandimethanol-Reste hergestellt worden sind, und Mischungen dieser Polyalkylenterephthalate.Particularly preferred are 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.

Bevorzugte Polyalkylenterephthalate sind auch Copolyester, die aus mindestens zwei der obengenannten Säurekomponenten und/oder aus mindestens zwei der obengenannten Alkoholkomponenten hergestellt sind, besonders bevorzugte Copolyester sind Poly-(ethylenglykol/butandiol-1,4)-terephthalate.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.

Die als Komponente vorzugsweise verwendeten Polyalkylenterephthalate besitzen bevorzugt eine intrinsische Viskosität von ca. 0,4 bis 1,5 dl/g, vorzugsweise 0,5 bis 1,3 dl/g, jeweils gemessen in Phenol/o-Dichlorbenzol (1: 1 Gew.-Teile) bei 25°C.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.

In besonders bevorzugten Ausführungsformen der Erfindung handelt es sich bei dem Blend von wenigstens einem Polycarbonat oder Copolycarbonat mit wenigstens einem Poly- oder Copolykondensat der Terephthalsäure um einen Blend aus wenigstens einem Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat. Bei einem solchen Blend aus Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat kann es sich bevorzugt um einen solchen mit 1 bis 90 Gew.-% Polycarbonat oder Copolycarbonat und 99 bis 10 Gew.-% Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat, vorzugsweise mit 1 bis 90 Gew.-% Polycarbonat und 99 bis 10 Gew.-% Polybutylenterephthalat oder glycol-modifiziertem Polycyclohexandimethylenterephthalat handeln, wobei sich die Anteile zu 100 Gew.-% addieren. Besonders bevorzugt kann es sich bei einem solchen Blend aus Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertes Poly- oder Copolycyclohexandimethylenterephthalat um einen solchen mit 20 bis 85 Gew.-% Polycarbonat oder Copolycarbonat und 80 bis 15 Gew.-% Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat, vorzugsweise mit 20 bis 85 Gew.-% Polycarbonat und 80 bis 15 Gew.-% Polybutylenterephthalat oder glycol-modifiziertem Polycyclohexandimethylenterephthalat handeln, wobei sich die Anteile zu 100 Gew.% addieren. Ganz besonders bevorzugt kann es sich bei einem solchen Blend aus Polycarbonat oder Copolycarbonat mit Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat um einen solchen mit 35 bis 80 Gew.-% Polycarbonat oder Copolycarbonat und 65 bis 20 Gew.% Poly- oder Copolybutylenterephthalat oder glycol-modifiziertem Poly- oder Copolycyclohexandimethylenterephthalat, vorzugsweise mit 35 bis 80 Gew.-% Polycarbonat und 65 bis 20 Gew.-% Polybutylenterephthalat oder glycol-modifiziertem Polycyclohexandimethylenterephthalat handeln, wobei sich die Anteile zu 100 Gew.-% addieren. In ganz besonders bevorzugten Ausführungsformen kann es sich um Blends aus Polycarbonat und glycol-modifiziertem Polycyclohexandimethylenterephthalat in den vorangehend genannten Zusammensetzungen handeln.In particularly preferred embodiments of the invention, 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. or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate, preferably with 20 to 85% by weight of polycarbonate and 80 to 15% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, the proportions adding to 100% by weight. It is very particularly preferred for such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate to be such with 35 to 80% by weight of polycarbonate or copolycarbonate and 65 to 20% by weight of polycarbonate. or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate, preferably with 35 to 80% by weight of polycarbonate and 65 to 20% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, the proportions adding to 100% by weight. In very particularly preferred embodiments, these may be blends of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the above-mentioned compositions.

Als Polycarbonate oder Copolycarbonate eignen sich in bevorzugten Ausführungsformen besonders aromatische Polycarbonate oder Copolycarbonate.Particularly suitable polycarbonates or copolycarbonates in preferred embodiments are aromatic polycarbonates or copolycarbonates.

Die Polycarbonate oder Copolycarbonate können in bekannter Weise linear oder verzweigt sein.The polycarbonates or copolycarbonates may be linear or branched in a known manner.

Die Herstellung dieser Polycarbonate kann in bekannter Weise aus Diphenolen, Kohlensäurederivaten, gegebenenfalls Kettenabbrechern und gegebenenfalls Verzweigern erfolgen. Einzelheiten der Herstellung von Polycarbonaten sind in vielen Patentschriften seit etwa 40 Jahren niedergelegt. Beispielhaft sei hier nur auf Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964 , auf D. Freitag, U. Grigo, P. R. Müller, H. Nouvertne', BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, Seiten 648-718 und schließlich auf Dres. U. Grigo, K. Kirchner und P. R. Müller "Polycarbonate" in Becker/Braun, Kunststoff-Handbuch, Band 3/1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag München, Wien 1992, Seiten 117-299 verwiesen.The preparation of these 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 Munich, Vienna 1992, pages 117-299 directed.

Geeignete Diphenole können beispielsweise Dihydroxyarylverbindungen der allgemeinen Formel (I) sein,

        HO-Z-OH     (I)

worin Z ein aromatischer Rest mit 6 bis 34 C-Atomen ist, der einen oder mehrere gegebenenfalls substituierte aromatische Kerne und aliphatische oder cycloaliphatische Reste bzw. Alkylaryle oder Heteroatome als Brückenglieder enthalten kann.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.

Beispiele für geeignete Dihydroxyarylverbindungen sind: Dihydroxybenzole, Dihydroxydiphenyle, Bis-(hydroxyphenyl)-alkane, Bis-(hydroxyphenyl)-cycloalkane, Bis-(hydroxyphenyl)-aryle, Bis-(hydroxyphenyl)-ether, Bis-(hydroxyphenyl)-ketone, Bis-(hydroxyphenyl)-sulfide, Bis-(hydroxyphenyl)-sulfone, Bis-(hydroxyphenyl)-sulfoxide, 1,1'-Bis-(hydroxyphenyl)-diisopropylbenzole, sowie deren kemalkylierte und kernhalogenierte Verbindungen.Examples of suitable dihydroxyaryl compounds are: 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.

Diese und weitere geeignete andere Dihydroxyarylverbindungen sind z.B. in DE-A 3 832 396 , FR-A 1 561 518 , in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, S. 28 ff.; S.102 ff . und in D.G. Legrand, J.T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, S. 72 ff . beschrieben.These and other suitable other Dihydroxyarylverbindungen are eg in DE-A 3 832 396 . FR-A 1 561 518 , in H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, p. 28 ff .; P.102 ff , and in DG Legrand, JT Bendler, Handbook of Polycarbonates Science and Technology, Marcel Dekker New York 2000, pp. 72 et seq , described.

Bevorzugte Dihydroxyarylverbindungen sind beispielsweise Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(4-hydroxyphenyl)-methan, Bis-(3,5-dimethyl-4-hydroxyphenyl)-methan, Bis-(4-hydroxyphenyl)-diphenyl-methan, 1, 1-Bis-(4-hydroxyphenyl)-1-phenyl-ethan, 1,1-Bis-(4-hydroxyphenyl)-1-(1-naphthyl)-ethan, 1,1-Bis-(4-hydroxyphenyl)-1-(2-naphthyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis-(3-methyl-4-hydroxyphenyl)-propan, 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan, 2,2-Bis-(4-hydroxyphenyl)-1-phenyl-propan, 2,2-Bis-(4-hydroxyphenyl)-hexafluor-propan, 2,4-Bis-(4-hydroxyphenyl)-2-methyl-butan, 2,4-Bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutan, 1,1-Bis-(4-hydroxyphenyl)-cyclohexan, 1,1-Bis-(3,5-dimethyl-4-hydroxyphenyl)-cylohexan, 1,1-Bis-(4-hydroxyphenyl)-4-methyl-cylohexan, 1,3-Bis-[2-(4-hydroxyphenyl)-2-propyl]-benzol, 1,1'-Bis-(4-hydroxyphenyl)-3-diisopropyl-benzol, 1,1'-Bis-(4-hydroxyphenyl)-4-diisopropyl-benzol, 1,3-Bis-[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]-benzol, Bis-(4-hydroxyphenyl)-ether, Bis-(4-hydroxyphenyl)-sulfid, Bis-(4-hydroxyphenyl)-sulfon, Bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfon und 2,2',3,3'-Tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi-[1H-inden]-5,5'-diol oderPreferred 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-hydroxyphenyl) -hexafluoro-propane, 2 , 4-bis (4-hydroxyphenyl) -2-methylbutane, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cylohexane, 1,1-bis (4-hydroxyphenyl) -4-methylcyclohexane, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] -benzene, 1,1'-bis (4-hydroxyphenyl) -3-diisopropylbenzene, 1,1'-bis (4-hydroxyphenyl) -4-diisopropylbenzene , 1,3-Bis- [2- (3,5-dimethyl-4-hydroxyphenyl) -2-propyl] -benzene, bis (4-hydro xyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone and 2,2 ', 3,3' -Tetrahydro-3,3,3 ', 3'-tetramethyl-1,1'-spirobi- [1H-indene] -5,5'-diol or

Dihydroxydiphenylcycloalkane der Formel (Ia)

Figure imgb0001
worin

R1 und R2
unabhängig voneinander Wasserstoff, Halogen, bevorzugt Chlor oder Brom, C1-C8-Alk-yl, C5-C6-Cycloalkyl, C6-C10-Aryl, bevorzugt Phenyl, und C7-C12-Aralkyl, bevorzugt Phenyl-C1-C4-Alkyl, insbesondere Benzyl,
m
eine ganze Zahl von 4 bis 7, bevorzugt 4 oder 5,
R3 und R4
für jedes X individuell wählbar, unabhängig voneinander Wasserstoff oder C1-C6-Alkyl und
X
Kohlenstoff bedeuten,
mit der Maßgabe, dass an mindestens einem Atom X, R3 und R4 gleichzeitig Alkyl bedeuten. Bevorzugt sind in der Formel (Ia) an einem oder zwei Atom(en) X, insbesondere nur an einem Atom X R3 und R4 gleichzeitig Alkyl.Dihydroxydiphenylcycloalkanes of the formula (Ia)
Figure imgb0001
 wherein
R 1 and R 2
independently of one another are hydrogen, halogen, preferably chlorine or bromine, C 1 -C 8 -alkyl, C 5 -C 6 -cycloalkyl, C 6 -C 10 -aryl, preferably phenyl, and C 7 -C 12 -aralkyl Phenyl-C 1 -C 4 -alkyl, in particular benzyl,
m
an integer from 4 to 7, preferably 4 or 5,
R 3 and R 4
individually selectable for each X independently hydrogen or C 1 -C 6 alkyl and
X
Mean carbon,
with the proviso that on at least one atom X, R 3 and R 4 are simultaneously alkyl. Are preferred in the formula (Ia) at one or two atom (s) X, in particular only on one atom X, R 3 and R 4 are simultaneously alkyl.

Bevorzugter Alkylrest für die Reste R3 und R4 in Formel (Ia) ist Methyl. Die X-Atome in alpha - Stellung zu dem Diphenylsubstituierten C-Atom (C-1) sind bevorzugt nicht dialkylsubstituiert, dagegen ist die Alkyldisubstitution in beta-Stellung zu C-1 bevorzugt.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.

Besonders bevorzugte Dihydroxydiphenylcycloalkane der Formeln (Ia) sind solche mit 5 und 6 Ring-C-Atomen X im cycloaliphatischen Rest (m = 4 oder 5 in Formel (Ia)), beispielsweise die Diphenole der Formeln (Ia-1) bis (Ia-3d),

Figure imgb0002
Figure imgb0003
Figure imgb0004
 Particularly preferred dihydroxydiphenylcycloalkanes of the formulas (Ia) are those having 5 and 6 ring C atoms X in the cycloaliphatic radical (m = 4 or 5 in formula (Ia)), for example the diphenols of the formulas (Ia-1) to (Ia) 3d)
Figure imgb0002
Figure imgb0003
Figure imgb0004

Ein ganz besonders bevorzugtes Dihydroxydiphenylcycloalkan der Formel (Ia) ist 1,1-Bis-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexan (Formel (Ia-1) mit R1 und R2 gleich H).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).

Solche Polycarbonate können gemäss der EP-A 359 953 aus Dihydroxydiphenylcycloalkanen der Formel (Ia) hergestellt werden.Such polycarbonates can according to the EP-A 359 953 be prepared from Dihydroxydiphenylcycloalkanen of formula (Ia).

Besonders bevorzugte Dihydroxyarylverbindungen sind Resorcin, 4,4'-Dihydroxydiphenyl, Bis-(4-hydroxyphenyl)-diphenyl-methan, 1,1-Bis-(4-hydroxyphenyl)-1-phenyl-ethan, Bis-(4-hydroxyphenyl)-1-(1-naphthyl)-ethan, Bis-(4-hydroxyphenyl)-1-(2-naphthyl)-ethan, 2,2-Bis-(4-hydroxyphenyl)-propan, 2,2-Bis(3,5-dimethyl-4-hydroxyphenyl)-propan, 1,1-Bis-(4-hydroxyphenyl)-cyclohexan, 1, 1-Bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexan, 1,1 -Bis-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexan, 1,1'-Bis-(4-hydroxyphenyl)-3-diisopropyl-benzol und 1,1'- Bis-(4-hydroxyphenyl)-4-diisopropyl-benzol.Particularly preferred 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-diisopropylbenzene and 1,1'-bis (4-hydroxyphenyl) - 4-diisopropyl-benzene.

Ganz besonders bevorzugte Dihydroxyarylverbindungen sind 4,4'-Dihydroxydiphenyl und 2,2-Bis-(4-hydroxyphenyl)-propan.Very particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.

Es können sowohl eine Dihydroxyarylverbindung unter Bildung von Homopolycarbonaten als auch verschiedene Dihydroxyarylverbindungen unter Bildung von Copolycarbonaten verwendet werden. Es können sowohl eine Dihydroxyarylverbindung der Formel (I) oder (Ia) unter Bildung von Homopolycarbonaten als auch mehrere Dihydroxyarylverbindungen der Formel (I) und/oder (Ia) unter Bildung von Copolycarbonaten verwendet werden. Dabei können die verschiedenen Dihydroxyarylverbindungen sowohl statistisch als auch blockweise miteinander verknüpft sein. Im Falle von Copolycarbonaten aus Dihydroxyarylverbindungen der Formel (I) und (Ia), beträgt das molare Verhältnis von Dihydroxyarylverbindungen der Formel (Ia) zu den gegebenenfalls mitzuverwendenden anderen Dihydroxyarylverbindungen der Formel (I) vorzugsweise zwischen 99 Mol-% (Ia) zu 1 Mol-% (I) und 2 Mol-% (Ia) zu 98 Mol-% (I), vorzugsweise zwischen 99 Mol% (Ia) zu 1 Mol-% (I) und 10 Mol% (Ia) zu 90 Mol% (I) und insbesondere zwischen 99 Mol% (Ia) zu 1 Mol-% (I) und 30 Mol-% (Ia) zu 70 Mol% (I).Both a dihydroxyaryl compound to form homopolycarbonates and various Dihydroxyarylverbindungen 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. In the case of copolycarbonates of dihydroxyaryl compounds of the formula (I) and (Ia), 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).

Ein ganz besonders bevorzugtes Copolycarbonat kann unter Verwendung von 1,1-Bis-(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexan und 2,2-Bis-(4-hydroxyphenyl)-propan Dihydroxyarylverbindungen der Formel (Ia) und (I) hergestellt werden.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.

Geeignete Kohlensäurederivate können beispielsweise Diarylcarbonate der allgemeinen Formel (II) sein,

Figure imgb0005
worin

R, R' und R"
unabhängig voneinander gleich oder verschieden für Wasserstoff, lineares oder verzweigtes C1-C34-Alkyl, C7-C34-Alkylaryl oder C6-C34-Aryl stehen, R weiterhin auch -COO-R'" bedeuten kann, wobei R'" für Wasserstoff, lineares oder verzweigtes C1-C34-Alkyl, C7-C34-Alkylaryl oder C6-C34-Aryl steht.
Suitable carbonic acid derivatives may be, for example, diaryl carbonates of the general formula (II)
Figure imgb0005
 wherein
R, R 'and R "
independently of one another denote hydrogen, linear or branched C 1 -C 34 -alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl, R can furthermore also denote -COO-R '", where R 3 '"is hydrogen, linear or branched C 1 -C 34 alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl.

Bevorzugte Diarylcarbonate sind beispielsweise Diphenylcarbonat, Methylphenyl-phenylcarbonate und Di-(methylphenyl)-carbonate, 4-Ethylphenyl-phenyl-carbonat, Di-(4-ethylphenyl)-carbonat, 4-n-Propylphenyl-phenyl-carbonat, Di-(4-n-propylphenyl)-carbonat, 4-iso-Propylphenyl-phenyl-carbonat, Di-(4-iso-propylphenyl)-carbonat, 4-n-Butylphenyl-phenyl-carbonat, Di-(4-n-butylphenyl)-carbonat, 4-iso-Butylphenyl-phenyl-carbonat, Di-(4-iso-butylphenyl)-carbonat, 4-tert-Butylphenyl-phenyl-carbonat, Di-(4-tert-butylphenyl)-carbonat, 4-n-Pentylphenyl-phenyl-carbonat, Di-(4-n-pentylphenyl)-carbonat, 4-n-Hexylphenyl-phenyl-carbonat, Di-(4-n-hexylphenyl)-carbonat, 4-iso-Octylphenyl-phenyl-carbonat, Di-(4-iso-octylphenyl)-carbonat, 4-n-Nonylphenyl-phenyl-carbonat, Di-(4-n-nonylphenyl)-carbonat, 4-Cyclohexylphenyl-phenyl-carbonat, Di-(4-cyclohexylphenyl)-carbonat, 4-(1-Methyl-1-phenylethyl)-phenyl-phenyl-carbonat, Di-[4-(1-methyl-1-phenylethyl)-phenyl]-carbonat, Biphenyl-4-yl-phenyl-carbonat, Di-(biphenyl-4-yl)-carbonat, 4-(1-Naphthyl)-phenyl-phenyl-carbonat, 4-(2-Naphthyl)-phenyl-phenyl-carbonat, Di-[4-(1-naphthyl)-phenyl]-carbonat, Di-[4-(2-naphthyl)phenyl]-carbonat, 4-Phenoxyphenyl-phenyl-carbonat, Di-(4-phenoxyphenyl)-carbonat, 3-Pentadecylphenyl-phenyl-carbonat, Di-(3-pentadecylphenyl)-carbonat, 4-Tritylphenyl-phenyl-carbonat, Di-(4-tritylphenyl)-carbonat, Methylsalicylat-phenyl-carbonat, Di-(methylsalicylat)-carbonat, Ethylsalicylat-phenyl-carbonat, Di-(ethylsalicylat)-carbonat, n-Propylsalicylat-phenyl-carbonat, Di-(n-propylsalicylat)-carbonat, iso-Propylsalicylat-phenyl-carbonat, Di-(iso-propylsalicylat)-carbonat, n-Butylsalicylat-phenyl-carbonat, Di-(n-butylsalicylat)-carbonat, iso-Butylsalicylat-phenyl-carbonat, Di-(iso-butylsalicylat)-carbonat, tert-Butylsalicylat-phenyl-carbonat, Di-(tert-butylsalicylat)-carbonat, Di-(phenylsalicylat)-carbonat und Di-(benzylsalicylat)-carbonat.Examples of preferred 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-pentylphenyl) carbonate, 4-n-hexylphenyl phenyl carbonate, di (4-n-hexylphenyl) carbonate, 4-iso-octylphenyl phenyl carbonate, Di- (4-iso-octylphenyl) -carbonate, 4-n-nonylphenyl-phenyl-carbonate, di- (4-n-nonylphenyl) -carbonate, 4-cyclohexylphenyl-phenyl-carbonate, di (4-cyclohexylphenyl) - carbonate, 4- (1-methyl-1-phenylethyl) -phenyl-phenyl-carbonate, di- [4- (1-methyl-1-phenylethyl) -phenyl] -carbonate, biphenyl-4-yl-phenyl-carbonate, di (biphenyl 4-yl) carbonate, 4- (1-naphthyl) phenyl phenyl carbonate, 4- (2-naphthyl) phenyl phenyl carbonate, di- [4- (1-naphthyl) phenyl] - carbonate, di- [4- (2-naphthyl) phenyl] carbonate, 4-phenoxyphenyl phenyl carbonate, di- (4-phenoxyphenyl) carbonate, 3-pentadecylphenyl phenyl carbonate, di (3-pentadecylphenyl) carbonate, 4-trityl phenyl phenyl carbonate, di (4-trityl phenyl) carbonate, methyl salicylate phenyl carbonate, di (methyl salicylate) carbonate, ethyl salicylate phenyl carbonate, di (ethyl salicylate) carbonate, n Propyl salicylate phenyl carbonate, di (n-propyl salicylate) carbonate, iso-propyl salicylate phenyl carbonate, di (iso-propyl salicylate) carbonate, n-butyl salicylate phenyl carbonate, di- (n-butylsalicylate) carbonate, iso-butyl salicylate phenyl carbonate, di- (iso-butylsalicylate) carbonate, tert-butyl salicylate phenyl carbonate, di- (tert-butylsalicylate) carbonate, di (phenyl salicylate) carbonate and di- ( benzyl salicylate) carbonate.

Besonders bevorzugte Diarylverbindungen sind Diphenylcarbonat, 4-tert-Butylphenyl-phenyl-carbonat, Di-(4-tert-butylphenyl)-carbonat, Biphenyl-4-yl-phenyl-carbonat, Di-(biphenyl-4-yl)-carbonat, 4-(1-Methyl-1-phenylethyl)-phenyl-phenyl-carbonat, Di-[4-(1-methyl-1-phenylethyl)-phenyl]-carbonat und Di-(methylsalicylat)-carbonat.Particularly preferred 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.

Ganz besonders bevorzugt ist Diphenylcarbonat.Very particular preference is given to diphenyl carbonate.

Es können sowohl ein Diarylcarbonat als auch verschiedene Diarylcarbonate verwendet werden.Both a diaryl carbonate and various diaryl carbonates can be used.

Zur Steuerung bzw. Veränderung der Endgruppen können zusätzlich beispielsweise eine oder mehrere Monohydroxyarylverbindung(en) als Kettenabbrecher eingesetzt werden, die nicht zur Herstellung des oder der verwendeten Diarylcarbonat(e) verwendet wurde(n). Dabei kann es sich um solche der allgemeinen Formel (IR) handeln,

Figure imgb0006
wobei

RA
für lineares oder verzweigtes C1-C34-Alkyl, C7-C34-Alkylaryl, C6-C34-Aryl oder für -COO-RD steht, wobei RD für Wasserstoff, lineares oder verzweigtes C1-C34-Alkyl, C7-C34-Alkylaryl oder C6-C34-Aryl steht, und
RB, RC
unabhängig voneinander gleich oder verschieden für Wasserstoff, lineares oder verzweigtes C1-C34-Alkyl, C7-C34-Alkylaryl oder C6-C34-Aryl stehen.
In addition, for example, one or more monohydroxyaryl compound (s) may be used as a chain terminator for controlling or changing the end groups, which was not used to prepare the diaryl carbonate (s) used. These may be those of the general formula (IR),
Figure imgb0006
 in which
R A
is linear or branched C 1 -C 34 -alkyl, C 7 -C 34 -alkylaryl, C 6 -C 34 -aryl or -COO-R D , where R D is hydrogen, linear or branched C 1 -C 34 Alkyl, C 7 -C 34 alkylaryl or C 6 -C 34 aryl, and
R B , R C
independently of one another are identical or different and represent hydrogen, linear or branched C 1 -C 34 -alkyl, C 7 -C 34 -alkylaryl or C 6 -C 34 -aryl.

Solche Monohydroxyarylverbindungen sind beispielsweise 1-, 2- oder 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, Methylsalicylat, Ethylsalicylat, n-Propylsalicylat, iso-Propylsalicylat, n-Butylsalicylat, iso-Butylsalicylat, tert-Butylsalicylat, Phenylsalicylat und Benzylsalicylat.Such Monohydroxyarylverbindungen 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, tert Butyl salicylate, phenyl salicylate and benzyl salicylate.

Bevorzugt sind 4-tert-Butylphenol, 4-iso-Octylphenol und 3-Pentadecylphenol.Preference is given to 4-tert-butylphenol, 4-iso-octylphenol and 3-pentadecylphenol.

Geeignete Verzweiger können Verbindungen mit drei und mehr funktionellen Gruppen, vorzugsweise solche mit drei oder mehr Hydroxylgruppen.Suitable branching agents may be compounds having three or more functional groups, preferably those having three or more hydroxyl groups.

Geeignete Verbindungen mit drei oder mehr phenolischen Hydroxylgruppen sind beispielsweise Phloroglucin, 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hepten-2, 4,6-Dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptan, 1,3,5-Tri-(4-hydroxyphenyl)-benzol, 1,1,1-Tri-(4-hydroxyphenyl)-ethan, Tri-(4-hydroxyphenyl)-phenylmethan, 2,2-Bis-(4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propan, 2,4-Bis-(4-hydroxyphenyl-isopropyl)-phenol und Tetra-(4-hydroxyphenyl)-methan.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.

Sonstige geeignete Verbindungen mit drei und mehr funktionellen Gruppen sind beispielsweise 2,4-Dihydroxybenzoesäure, Trimesinsäure(trichlorid), Cyanursäuretrichlorid und 3,3-Bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol.Other 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.

Bevorzugte Verzweiger sind 3,3-Bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindol und 1,1,1 -Tri-(4-hydroxyphenyl)-ethan.Preferred branching agents are 3,3-bis (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-tri (4-hydroxyphenyl) -ethane.

Die IR-Strahlung reflektierende oder absorbierende Deckschicht weist vorzugsweise eine Transmission für Strahlung der Wellenlänge von 800 bis 1200 nm, bevorzugt von 850 bis 1100 nm von nicht größer als 20 %, bevorzugt nicht größer als 15 %, besonders bevorzugt nicht größer als 10 % auf. Die IR-Strahlung reflektierende oder absorbierende Deckschicht weist vorzugsweise weiterhin eine Transmission für Strahlung der Wellenlänge von 400 bis 700 nm größer als 60 %, bevorzugt größer als 70 % auf. Die Transmission wird nach ASTM D 1003 bestimmt.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.

In einer Ausführungsform der Erfindung enthält ödie IR-Strahlung reflektierenden oder absorbierende Deckschicht weigstens ein IR-absorbierendes Additiv. Erfmdungsegemäß kommen hier organische IR-absorbierende Additive in Frage. Geeignete organische IR-absorbierende Additive sind Verbindungen, welche zwischen 700 und 1500 nm (Nahes Infrarot = NIR) eine möglichst hohe Absorption aufweisen. Geeignet sind beispielsweise literaturbekannte Infrarot-Absorber, wie sie z. B. in M. Matsuoka, Infrared Absorbing Dyes, Plenum Press, New York, 1990 stoffklassenmässig beschrieben sind. Erfindungsgemäß werden Infrarot-Absorber aus den Stoffklassen der Azo-, Azomethin-, Methin- Anthrachinon-, Indanthron-, Pyranthron-, Flavanthron-, Benzanthron-, Phtalocyanin-, Perylen-, Dioxazin-, Thioindigo- Isoindolin-, Isoindolinon-, Chinacridon-, Pyrrolopyrrol- oder Chinophtalonpigmente sowie Metallkomplexe von Azo-, Azomethin- oder Methinfarbstoffen oder Metallsalzen von Azoverbindungen. Davon sind ganz besonders Phthalocyanine und Naphthalocyanine geeignet. Aufgrund der verbesserten Löslichkeit in thermoplastischen Kunststoffen sind Phthalocyanine und Naphthalocyanine mit sperrigen Seitengruppen vorzuziehen.In one embodiment of the invention, the IR radiation-reflecting or absorbing cover layer contains at least one IR-absorbing additive. According to the invention, organic IR-absorbing additives are suitable here. Suitable organic IR-absorbing additives are compounds which have the highest possible absorption between 700 and 1500 nm (near infrared = NIR). For example, 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. According to the invention, 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. Of these, phthalocyanines and naphthalocyanines are particularly suitable. Due to the improved solubility in thermoplastics, phthalocyanines and naphthalocyanines with bulky side groups are preferable.

Hinsichtlich der Menge der in der IR-Strahlung reflektierenden oder absorbierenden Deckschicht enthaltenen IR-absorbierenden Additive liegen keine besonderen Beschränkungen vor, solange die gewünschte Absorption von IR-Strahlung und eine ausreichende Transparenz gewährleistet ist. Als besonders vorteilhaft hat es sich erwiesen, wenn die Zusammensetzung der IR-Strahlung reflektierenden oder absorbierenden Deckschicht das oder die IR-absorbierende(n) Additive in einer Menge von 0,0001 bis 10 Gew.-%, insbesondere von 0,001 bis 0,05 Gew.-%, bezogen auf das Gesamtgewicht der Zusammensetzung der IR-Strahlung reflektierenden oder absorbierenden Deckschicht enthält. Besonders geeignet sind auch Mischungen von IR-absorbierenden Additiven. Der Fachmann kann mit Farbstoffen unterschiedlicher Wellenlängen der Absorptionsmaxima eine Optimierung der Absorption im nahen Infrarotbereich erreichen.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.

Solche IR-Strahlung reflektierende oder absorbierende Folien bzw. Filme sind bekannt und kommerziell erhältlich.Such IR radiation reflecting or absorbing films or films are known and commercially available.

In einer weiteren Ansfiihrungsform der Erfindung handelt es sich bei der IR-Strahlung reflektierenden oder absorbierenden Deckschicht um einen Mehrschichtaufbau, die, ein mehrschichtiger optischer Interferenzfilm ist, welcher vorzugsweise durch Coextrusion sich abwechselnder Polymerschichten hergestellt werden kann Dabei handelt es sich vorzugsweise um Schichten basierend auf coextrudierten IR-Strahlung reflektierenden Folien mit einem schmalen Reflexionsbereich infolge Licht-Interferenz.In a further embodiment of the invention, 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.

Solche mehrschichtigen Folien sind vorzugsweise aus mehreren parallelen Schichten aus transparenten thermoplastischen Kunststoffen aufgebaut, wofür die oben genannten thermoplastischen Kunststoffe in Frage kommen, wobei jeweils unmittelbar aneinander liegende Schichten aus unterschiedlichen thermoplastischen Kunststoffen bestehen, deren Brechungsindices sich mindestens um 0,03, besonders bevorzugt um mindestens 0,06 voneinander unterscheiden. Eine solche mehrschichtige Folie enthält vorzugsweise mindestens 10 Schichten.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.

Die einzelnen Schichten der mehrschichtigen Folie sind vorzugsweise sehr dünn mit Schichtdicken im Bereich von etwa 30 bis 500 nm, vorzugsweise ungefähr 50 bis 400 nm, wodurch eine Verstärkungsinterferenz von an den vielen Grenzflächen reflektierten Lichtwellen zustande kommt. Abhängig von der Schichtdicke und dem Brechungsindex der thermoplastischen Kunststoffe wird ein vorherrschendes Wellenlängenband reflektiert, während das übrige Licht von der Folie durchgelassen wird.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. Depending on the layer thickness and the refractive index of the thermoplastics, a dominant wavelength band is reflected, while the remaining light is transmitted by the foil.

Die Menge des reflektierten Lichts (Reflektionsvermögen) hängt vom Unterschied zwischen den zwei Brechungsindices, vom Verhältnis der optischen Dicken der Schichten, von der Anzahl der Schichten und von der Gleichförmigkeit der Schichtdicken ab.The amount of reflected light (reflectance) 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.

Solche mehrschichtigen Folien sind dem Fachmann bekannt und beispielsweise beschrieben in US 3.610.729 , US 3.711.176 , US 4.446.305 , US Patent 4.540.623 , US 5.448.404 , US 5.882.774 , US 6.531.230 , US Patent 6.783.349 , WO-A 99/39224 und WO-A 03/100521 Such multilayer films are known to the person skilled in the art and are described, for example, in US Pat US 3,610,729 . US 3,711,176 . US 4,446,305 . U.S. Patent 4,540,623 . US 5,448,404 . US 5,882,774 . US 6,531,230 . US Patent 6,783,349 . WO-A 99/39224 and WO-A 03/100521

Der erfindungsgemäße Schichtaufbau weist bevorzugt wenigstens eine Schicht enthaltend wenigstens einen thermoplastischen Kunststoff und wenigstens einen Füllstoff ("gefüllte Schicht") auf. Als thermoplastische Kunststoffe kommen dafür die vorangehend genannten in Frage.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"). As thermoplastics for the above-mentioned in question.

Bei dem Füllstoff in den gefüllten Schichten handelt es sich bevorzugt um wenigstens ein Farbpigment und/oder wenigstens einen sonstigen Füllstoff zur Erzeugung einer Transluzenz der gefüllten Schichten, bevorzugt um Titandioxid, Zirkoniumdioxid, Bariumsulfat oder Glasfasern, besonders bevorzugt um Titandioxid.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.

Bevorzugt handelt es sich bei den gefüllten Schichten sowie bei den zu deren Herstellung eingesetzten gefüllten Folien um solche mit einer Transmission im sichtbaren Wellenlängenbereich von 380 nm bis 780 nm von kleiner 50%, bevorzugt von kleiner 35 %, besonders bevorzugt von kleiner 25 %, in ganz besonders bevorzugten Ausführungsformen von kleiner als 15 %.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%.

Die genannten Füllstoffe werden vorzugsweise in Mengen von 2 bis 45 Gew.-%, besonders bevorzugt von 5 bis 30 Gew.-%, bezogen auf das Gesamtgewicht Füllstoff und thermoplastischem Kunststoff, den thermoplastischen Kunststoffen vor der Formgebung zur Kunststoff-Folie, welche zum Beispiel durch Extrusion oder Coextrusion erfolgen kann, zugegeben.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.

Die gefüllten Schichten können in bevorzugten Ausführungsformen der Erfindung weitere Informationen aufweisen. Diese weiteren Informationen können beispielsweise mittels herkömmlicher Drucktechniken, wie z.B. Ink-Jet-, Offset- oder Laserdruck, aufgebracht sein.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.

Der erfindungsgemäße Schichtaufbau kann weitere zusätzliche Schichten aufweisen, über die beispielsweise weitere Informationen in das Sicherheitsdokument, bevorzugt Identifikationsdokument eingebracht werden.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.

Bei solchen weiteren Informationen kann es sich beispielsweise um personalisierende Porträts oder nicht personalisierende allgemeine Informationen handeln, die beispielsweise in jedem gattungsgleichen Sicherheitsdokument, bevorzugt Identifikationsdokument in gleicher Form enthalten sind.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.

Solche Schichten können beispielsweise aus vorher mittels herkömmlicher Druckverfahren, vorzugsweise Ink-Jet- oder Laserdruck, besonders bevorzugt Farbdruck mit diesen Informationen bestückten Folien in den erfindungsgemäßen Schichtaufbau eingebracht werden.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.

Mittels Ink-Jet-Druckverfahren bedruckbare Folien sind dem Fachmann bekannt und können beispielsweise solche aus wenigstens einem der oben beschriebenen thermoplastischen Kunststoffe gegebenenfalls enthaltend wenigstens einen der oben beschriebenen Füllstoffe sein. In besonders bevorzugten Ausführungsformen werden zur besseren Sichtbarkeit der aufgedruckten Informationen mittels Füllstoffen wie z.B. Titandioxid, Zirkoniumdioxid, Bariumsulfat etc. weiß oder transluzent eingefärbte Kunststoff-Folien verwendet.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. In particularly preferred embodiments, for better visibility of the printed information, fillers such as e.g. Titanium dioxide, zirconium dioxide, barium sulfate, etc. used white or translucent colored plastic films.

Für mittels Laserdruck, insbesondere mittels Farblaserdruck zu bedruckende Folien eignen sich insbesondere solche Kunststoff-Folien aus einem der oben genannten thermoplastischen Kunststoffe, die einen spezifischen Oberflächenwiderstand von 107 bis 1013 Ω, bevorzugt von 108 bis 1012 Ω aufweisen. Der spezifische Oberflächenwiderstand in Ω wird gemäß DIN IEC 93 bestimmt.For 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 Ω, preferably of 10 8 to 10 12 Ω, are particularly suitable. The specific surface resistance in Ω is determined according to DIN IEC 93.

Dabei kann es sich vorzugsweise um solche Folien handeln, bei denen dem thermoplastischen Kunststoff zur Erzielung des spezifischen Oberflächenwiderstandes beispielsweise ein Additiv ausgewählt aus tertiären oder quaternären, bevorzugt quaternären Ammonium- oder Phosphoniumsalzen einer teil- oder perfluorierten organischen Säure oder quaternären Ammonium- oder Phosphoniumhexafluorophosphaten, bevorzugt einer teil- oder perfluorierten Alkylsulfonsäure, vorzugsweise einer Perfluoralkylsulfonsäure zugegeben wurde.These may preferably be those films in which the 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.

Bevorzugte geeignete quarternäre Ammonium- oder Phosphoniumsalze sind:

  • Perfluoroctansulfonsäuretetrapropylammoniumsalz,
  • Perfluorbutansulfonsäuretetrapropylammoniumsalz,
  • Perfluoroctansulfonsäuretetrabutylammoniumsalz,
  • Perfluorbutansulfonsäuretetrabutylammoniumsalz,
  • Perfluoroctansulfonsäuretetrapentylammoniumsalz,
  • Perfluorbutansulfonsäuretetrapentylammoniumsalz,
  • Perfluoroctansulfonsäuretetrahexylammoniumsalz,
  • Perfluorbutansulfonsäuretetrahexylammoniumsalz,
  • Perfluorbutansulfonsäuretrimethylneopentylammoniumsalz,
  • Perfluoroctansulfonsäuretrimethylneopentylammoniumsalz,
  • Perfluorbutansulfonsäuredimethyldineopentylammoniumsalz,
  • Perfluoroctansulfonsäuredimethyldineopentylammoniumsalz,
  • N-Methyl-tripropylammoniumperfluorbutylsulfonat,
  • N-Ethyl-tripropylammoniumperfluorbutylsulfonat,
  • Tetrapropylammoniumperfluorbutylsulfonat,
  • Diisopropyldimethylammoniumperfluorbutylsulfonat,
  • Diisopropyldimethylammoniumperfluoroctylsulfonat,
  • N-Methyl-tributylammoniumperfluoroctylsulfonat
  • Cyclohexyldiethylmethylammoniumperfluoroctylsulfonat,
  • Cyclohexyltrimethylammoniumperfluoroctylsulfonat,
sowie die entsprechenden Phosphoniumsalze. Bevorzugt sind die Ammoniumsalze.Preferred suitable quaternary ammonium or phosphonium salts are:
  • Perfluoroctansulfonsäuretetrapropylammoniumsalz,
  • Perfluorbutansulfonsäuretetrapropylammoniumsalz,
  • Perfluoroctansulfonsäuretetrabutylammoniumsalz,
  • Perfluorbutansulfonsäuretetrabutylammoniumsalz,
  • Perfluoroctansulfonsäuretetrapentylammoniumsalz,
  • Perfluorbutansulfonsäuretetrapentylammoniumsalz,
  • Perfluoroctansulfonsäuretetrahexylammoniumsalz,
  • Perfluorbutansulfonsäuretetrahexylammoniumsalz,
  • Perfluorbutansulfonsäuretrimethylneopentylammoniumsalz,
  • Perfluoroctansulfonsäuretrimethylneopentylammoniumsalz,
  • Perfluorbutansulfonsäuredimethyldineopentylammoniumsalz,
  • Perfluoroctansulfonsäuredimethyldineopentylammoniumsalz,
  • N-methyl perfluorobutyl sulfonate,
  • N-ethyl perfluorobutyl sulfonate,
  • Tetrapropylammoniumperfluorbutylsulfonat,
  • Diisopropyldimethylammoniumperfluorbutylsulfonat,
  • Diisopropyldimethylammoniumperfluoroctylsulfonat,
  • N-methyl-tributylammoniumperfluoroctylsulfonat
  • Cyclohexyldiethylmethylammoniumperfluoroctylsulfonat,
  • Cyclohexyltrimethylammoniumperfluoroctylsulfonat,
and the corresponding phosphonium salts. The ammonium salts are preferred.

Bevorzugt können auch ein oder mehrere der vorstehend genannten quartären Ammonium- oder Phosphoniumsalze, also auch Mischungen eingesetzt werden.It is also possible to use one or more of the abovementioned quaternary ammonium or phosphonium salts, ie also mixtures.

Ganz besonders geeignet ist das Perfluoroctansulfonsäuretetrapropylammoniumsalz, das Perfluoroctansulfonsäuretetrabutylammoniumsalz, das Perfluoroctansulfonsäuretetrapentylammoniumsalz, das Perfluoroctansulfonsäuretetrahexylammoniumsalz und das Perfluoroctansulfonsäuredimethyldiisopropylammoniumsalz sowie die entsprechenden Perfluorbutansulfonsäuresalze.Especially suitable is the 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.

In einer ganz besonders bevorzugten Ausführungsform kann Perfluorbutansulfonsäuredimethyldiisopropylammoniumsalz (Diisopropyldimethylammonium-perfluorbutylsulfonat) als Additiv verwendet werden.In a most preferred embodiment, perfluorobutanesulfonic acid dimethyldiisopropylammonium salt (diisopropyldimethylammonium perfluorobutylsulfonate) may be used as an additive.

Die genannten Salze sind bekannt oder können nach bekannten Methoden hergestellt werden. Die Salze der Sulfonsäuren lassen sich beispielsweise durch Zusammengeben äquimolarer Mengen der freien Sulfonsäure mit der Hydroxyform des entsprechenden Kations in Wasser bei Raumtemperatur und Einengen der Lösung darstellen. Andere Herstellungsverfahren sind beschrieben z.B. in DE-A 1 966 931 und NL-A 7 802 830 .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 ,

Die genannten Salze werden vorzugsweise in Mengen von 0.001 bis 2 Gew.%, bevorzugt von 0.1 bis 1 Gew.% den thermoplastischen Kunststoffen vor der Formgebung zur Kunststoff-Folie, welche zum Beispiel durch Extrusion oder Coextrusion erfolgen kann, zugegeben.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.

Der erfindungsgemäße Schichtaufbau kann zudem weitere zusätzliche Schichten aufweisen, die UV-Schutz und/oder Schutz vor mechanischer Beschädigung - wie z.B. Kratzfestbeschichtungen - etc. aufweisen.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.

Der erfindungsgemäße Schichtaufbau kann beispielsweise derart hergestellt werden, dass

  • den einzelnen Schichten entsprechende Folien mit Ausnahme der IR-Strahlung reflektierenden oder absorbierenden Deckschicht in einem Folienstapel zusammengelegt und zu einem Schichtverbund laminiert werden,
  • anschließend auf den laminierten Schichtverbund die mittels Lasergravur aufzubringenden Daten bzw. Informationen, vorzugsweise personalisierende Daten bzw. Informationen, in den Schichtverbund durch Laserbeschriftung eingebracht werden und
  • anschließend mittels Verklebung und/oder Laminieren die IR-Strahlung reflektierenden oder absorbierenden Deckschicht aufgebracht wird.
The layer structure according to the invention can be produced for example in such a way that
  • the films corresponding to the individual layers, with the exception of the cover layer which reflects or absorbs IR radiation, are combined in a film stack and laminated to form a layer composite,
  • Subsequently, the data to be applied by means of laser engraving or information, preferably personalizing data or information, are introduced into the laminated composite by laser inscription on the laminated layer composite and
  • then by gluing and / or laminating the IR radiation reflecting or absorbing cover layer is applied.

Der erfindungsgemäße Schichtaufbau eignet sich bevorzugt für die Erhöhung der Fälschungssicherheit von Sicherheitsdokumenten, besonders bevorzugt Identifikationsdokumenten. Ganz besonders bevorzugt eignet sich der erfindungsgemäße Schichtaufbau für die Erhöhung der Fälschungssicherheit von solchen Identifikationsdokumenten in Form verklebter oder laminierter Schichtverbunde in Form von Kunststoffkarten, wie z.B. Personalausweisen, Reisepässen, Führerscheinen, Kreditkarten, Bankkarten, Karten für die Zugangskontrolle oder sonstigen Ausweisdokumenten etc.. Bevorzugte Identifikationsdokumente sind im Rahmen der vorliegenden Erfindung mehrschichtige flächenförmige Dokumente mit Sicherheitsmerkmalen wie Chips, Fotografien, biometrischen Daten etc. Diese Sicherheitsmerkmale können von außen sichtbar oder zumindest abfragbar sein. Vorzugsweise hat ein solches Identifikationsdokument eine Größe zwischen der einer Scheckkarte und der eines Reisepasses. Ein solches Identifikationsdokument kann auch Teil eines Dokumentes aus mehreren Teilen sein, wie z.B. ein Identifikationsdokument aus Kunststoff in einem Reisepass, der auch Papier- oder Pappanteile enthält.The layer structure according to the invention is preferably suitable for increasing the security against forgery of security documents, particularly preferably identification documents. Most preferably, 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. Preferably, 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.

Gegenstand der vorliegenden Erfindung ist daher weiterhin ein Sicherheitsdokument, bevorzugt ein Identifikationsdokument enthaltend wenigstens einen erfindungsgemäßen laserbeschrifteten Schichtaufbau.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.

Die IR-Strahlung reflektierenden oder absorbierenden Deckschicht wird auf den Schichtaufbau, vorzugsweise das Sicherheitsdokument bzw. Identifikationsdokument nach dem Personalisieren mittels Lasergravur voll- oder teilflächig aufgebracht, um die nachträgliche Veränderung der mittels Lasergravur aufgebrachten personalisierenden Daten zu verhindern und damit die Fälschungssicherheit zu erhöhen.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.

Weiterhin Gegenstand der Erfindung ist demnach ein Verfahren zur Blockierung der Laserbeschriftbarkeit von laserbeschrifteten Schichtaufbauten, dadurch gekennzeichnet, dass ein laserbeschrifteter Schichtaufbau enthaltend wenigstens eine laserbeschriftbar ausgerüstete thermoplastische Kunststoffschicht nach der Laserbeschriftung mit einer teil- oder vollflächigen IR-Strahlung reflektierenden oder absorbierenden Deckschicht versehen wird, wobei die teil- oder vollflächigen IR-Strahlung reflektierende Deckschicht mindestens ein IR-absorbierenden Additiv enthält und es sich bei dem mindestens einen IR-absorbierenden Additiv um solche, die aus den Stoffklassen der Azo-, Azomethin-, Methin-Anthrachinon-, Indanthron-, Pyranthron-, Flavanthron-, Benzanthron-, Phtalocyanin-, Perylen-, Dioxazin-, Thioindigo- Isoindolin-, Isoindolinon-, Chinacridon-, Pyrrolopyrrol- oder Chinophtalonpigmente sowie Metallkomplexe von Azo-, Azomethin- oder Methinfarbstoffen oder Metallsalzen von Azoverbindungen ausgewählt sind, handelt.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.

Unter Blockierung der Laserbeschriftbarkeit ist im Rahmen der Erfindung sowohl eine deutliche Verringerung der weiteren Laserbeschriftbarkeit als auch die vollständige Verhinderung der weiteren Laserbeschriftbarkeit zu verstehenBy blocking the laser inscribability is to be understood in the context of the invention both a significant reduction in the further laser inscribability and the complete prevention of further laser inscribability

Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Blockierun der Beschriftbarkeit mittels Lasergravur von lasergravurbeschrifteten Schichtaufbauten, dadurch gekennzeichnet, dass ein lasergravurbeschrifteter Schichtaufbau, enthaltend wenigstens eine lasergravurbeschriftbar ausgerüstete thermoplastische Kunststoffschicht, nach der Beschriftung mittels Lasergravur mit einer teil- oder vollflächigen IR-Strahlung reflektierenden oder absorbierenden Deckschicht versehen wird und die IR-Strahlung reflektierende oder absorbierende Deckschicht nach der Beschriftung mittels Lasergravur in Form einer mehrschichtigen Folie, die eine mehrschichtige optische Interferenzfolie ist, auf den lasergravurbeschrifteten Schichtaufbau mittels eines Klebstoffes oder mittels Lamination aufgebracht wird.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.

Diese Aufbringung kann unter Einsatz eines Klebstoffes oder mittels Lamination erfolgen, wobei die Aufbringung mittels Lamination sowohl mit Unterstützung durch einen Klebstoff als auch unter vollständigem Verzicht auf einen Klebstoff erfolgen kann.This application may be made using an adhesive or by lamination, which may be applied by lamination with both adhesive support and no adhesive.

Im Falle der Aufbringung unter Verwendung eines Klebers ist ganz besonders bevorzugt die Verwendung eines latent reaktiven Klebstoffs.In the case of application using an adhesive, the use of a latently reactive adhesive is most preferred.

Latent reaktive Klebstoffe sind dem Fachmann bekannt. Bevorzugte latent reaktive Klebstoffe sind solche, die eine wässrige Dispersion aufweisen, die ein Di- oder Polyisocyanat mit Schmelz- bzw. Erweichungstemperatur von > 30°C und ein mit Isocyanat-reaktives Polymer enthalten. Vorzugsweise weist eine solche wässrige Dispersion eine Viskosität von mindestens 2000 mPas auf. Weiterhin bevorzugt handelt es sich bei dem Isocyanat-reaktive Polymer in dieser Dispersion um ein Polyurethan, das aus kristallisierenden Polymerketten aufgebaut ist, welche bei Messung mittels thermomechanischer Analyse (TMA) bei Temperaturen unter +110°C, bevorzugt bei Temperaturen unter +90°C, partiell oder vollständig dekristallisieren. Die Messung mittels TMA wird analog zu ISO 11359 Teil 3 "Bestimmung der Penetrationstemperatur" durchgeführt. Weiterhin bevorzugt handelt es sich bei dem Di- oder Polyisocyanat um ein solches ausgewählt aus der Gruppe bestehend aus Dimerisierungsprodukten, Trimerisierungsprodukten und Harnstoff-Derivaten des TDI (Toluylen-diisocyanat) bzw. IPDI (Isophorondiisocyanat). Solche latent reaktiven Klebstoffe sind beispielsweise in DE-A 10 2007 054 046 beschrieben.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. Preferably, such an aqueous dispersion has a viscosity of at least 2000 mPas. Further preferably, 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. The measurement by TMA is carried out analogously to ISO 11359 Part 3 "Determination of the Penetration Temperature". Further preferably, 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). Such latent reactive adhesives are for example in DE-A 10 2007 054 046 described.

Durch die Verwendung solcher latent reaktiver Klebstoffe kann eine zusätzliche Erhöhung der Fälschungssicherheit dadurch bewirkt werden, dass über die Kanten des Schichtaufbaus kein Wasserdampf und/oder Luft mehr ins Innere hinein diffundieren können und somit nicht mehr zu einer nachträglichen Delamination führen können. Solche Schichtaufbauten können nicht mehr unzerstört getrennt werden. Demnach kann die IR-Strahlung reflektierenden oder absorbierenden Deckschicht ohne Zerstörung des gesamten Sicherheitsdokuments bzw. Identifikationsdokuments nicht mehr abgetrennt werden. Gleiches gilt im Übrigen auch für eine mittels Auflaminieren aufgebrachte IR-Strahlung reflektierende oder absorbierende Deckschicht.By using such latently reactive adhesives, 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. Accordingly, the cover layer which reflects or absorbs IR radiation can no longer be separated without destroying the entire security document or identification document. Incidentally, the same also applies to a covering layer which is reflective or absorbing by means of lamination.

Die Verwendung einer IR-Strahlung reflektierenden oder absorbierenden Folie zur Blockierung der Laserbeschriftbarkeit von laserbeschrifteten Schichtaufbauten, bevorzugt von Sicherheitsdokumenten, besonders bevorzugt von Identifikationsdokumenten ist bisher nicht bekannt und demnach ebenfalls Gegenstand der vorliegenden Erfindung.The use of a film which reflects or absorbs IR radiation to block the laser inscribability of laser-printed layer structures, preferably of security documents, particularly preferably of identification documents, is hitherto unknown and accordingly likewise the subject of the present invention.

Die folgenden Beispiele dienen der exemplarischen Erläuterung der Erfindung und sind nicht als Beschränkung aufzufassen.The following examples serve to exemplify the invention and are not to be considered as limiting.

BeispieleExamples Für den erfindungsgemäßen Karten-Schichtaufbau eingesetzte FolienFilms used for the card layer construction according to the invention Folie 1-1: weiß gefüllte FolieFilm 1-1: white filled film

Es wurde eine Polycarbonatfolie der Dicke 100 µm auf Basis Polycarbonat Makrolon 3108® der Bayer MaterialScience AG und Titandioxid (Kronos® 2230 der Fa. Kronos Titan) als Weißpigment-Füllstoff mit einer Zusammensetzung von 85 Gew.-% Makrolon 3108® und 15 Gew.% Titandioxid bei einer Massetemperatur von ca. 280°C mittels Extrusion hergestellt.It was 100 microns based on polycarbonate Makrolon 3108 ® of Bayer Material Science AG and titanium dioxide (Kronos® 2230 Fa. Kronos Titan) as a white pigment filler by weight having a composition of 85 wt .-% Makrolon 3108 ® and 15 is a polycarbonate sheet of thickness. % Titanium dioxide produced at a melt temperature of about 280 ° C by extrusion.

Folie 1-2: weiß gefüllte FolieSlide 1-2: white filled foil

Es wurde eine Folie mit der gleichen Zusammensetzung wie Folie 1-1 der Dicke 400 µm hergestellt.A film with the same composition as film 1-1 of thickness 400 μm was produced.

Folie 2: lasergravierbare FolieSlide 2: laser-engravable film

Es wurde eine Polycarbonatfolie der Dicke 50 µm auf Basis Polycarbonat Makrolon 3108® der Bayer MaterialScience AG und Ruß (Flammruß 101 der Fa. Degussa) mit einem mittleren Teilchengrö-βe von 95 nm als lasersensibles Additiv bei einer Massetemperatur von ca. 280°C mittels Extrusion hergestellt. Dazu wurde ein Compound aus 85 Gew.-% Polycarbonat Makrolon 3108® und 15 Gew.-% eines Masterbatches mit einer Zusammensetzung von 99,004 Gew.-% Makrolon 3108® und 0,006 Gew.-% (60 ppm) Ruß verwendet.There was a polycarbonate film of thickness 50 microns on the basis of the polycarbonate Makrolon 3108 ®, Bayer MaterialScience AG, and carbon black (lampblack 101 of Messrs. Degussa) having an average Teilchengrö-βe of 95 nm as a laser-sensitive additive at a melt temperature of about 280 ° C by means of Extrusion produced. For this purpose, a compound of 85 wt .-% was polycarbonate Makrolon ® 3108 and 15 wt .-% of a masterbatch having a composition of 99.004 wt .-% Makrolon 3108 ® and 0.006 wt .-% (60 ppm) of carbon black used.

Folie 3: transparente FolieFilm 3: transparent film

Es wurde eine Polycarbonatfolie der Dicke 50 µm auf Basis Polycarbonat Makrolon 3108® der Bayer MaterialScience AG bei einer Massetemperatur von ca. 280°C mittels Extrusion hergestellt.There was prepared 50 microns based on polycarbonate Makrolon ® 3108 from Bayer MaterialScience AG at a melt temperature of about 280 ° C by means of extrusion, a polycarbonate sheet of thickness.

Folie 4:IR-Reflektionsfolie:Slide 4: IR Reflective Film:

Es wurde eine kommerziell erhältliche IR-Reflektionsfolie der Firma 3M (3M Vikuiti® Clear Card IR Filter) verwendet. Dabei handelte es sich um eine transparente, IR reflektierende Folie mit weniger als 20% Lichttransmission im Bereich zwischen 850 und 1100 nm (bestimmt nach ASTM D 1003).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).

Beispiel 1: Herstellung eines laserbeschreibbaren SchichtaufbausExample 1: Production of a laser-writable layer structure

Aus den oben aufgeführten Folien wurde wie im Folgenden aufgeführt ein laserbeschreibbarer Schichtaufbau in Form einer ID-Karte laminiert:

  1. (1) Folie 3; 50 µm
  2. (2) Folie 2; 50 µm
  3. (3) Folie 1-1; 100 µm
  4. (4) Folie 1-2; 400 µm
  5. (5) Folie 1-1; 100 µm
  6. (6) Folie 2; 50 µm
  7. (7) Folie 3; 50 µm
From the films listed above, a laser-writable layer structure in the form of an ID card was laminated as follows:
  1. (1) film 3; 50 μm
  2. (2) film 2; 50 μm
  3. (3) film 1-1; 100 μm
  4. (4) slide 1-2; 400 μm
  5. (5) slide 1-1; 100 μm
  6. (6) film 2; 50 μm
  7. (7) film 3; 50 μm

Es wurde ein symmetrischer Schichtaufbau der Karte gewählt, um ein Verbiegen der Karte zu vermeiden.A symmetric layer structure of the card was chosen to avoid bending the card.

Dazu wurde aus den Folien ein Stapel in der oben genannten Reihenfolge gebildet und die Lamination wurde auf einer Laminationspresse der Firma Bürkle mit folgenden Parametern durchgeführt:

  • Vorheizen der Presse auf 170-180°C
  • Pressen für 8 Minuten bei einem Druck von 15 N/cm2
  • Pressen für 2 Minuten bei einem Druck von 200 N/cm2
  • Abkühlen der Presse auf 38°C und öffnen der Presse.
For this purpose, a stack was formed from the films in the above-mentioned order and the lamination was carried out on a lamination press from Bürkle with the following parameters:
  • Preheat the press to 170-180 ° C
  • Press for 8 minutes at a pressure of 15 N / cm 2
  • Press for 2 minutes at a pressure of 200 N / cm 2
  • Cool the press to 38 ° C and open the press.

Beispiel 2: Herstellung einer Klebebeschichtung auf der IR-Reflektionsfolie für die nachträgliche Lamination auf diese ID-KarteExample 2: Preparation of an adhesive coating on the IR reflection film for subsequent lamination to this ID card

Als IR-Reflektionsfolie wurde die oben genannte Folie 4 verwendet.As the IR reflection film, the above-mentioned film 4 was used.

Zur Herstellung der Klebstoffdispersion für die Klebebeschichtung wurden die folgenden Komponenten verwendet:To prepare the adhesive dispersion for the adhesive coating, the following components were used:

A) Polyurethandispersion: A) Polyurethane dispersion:

Polyurethandispersion mit einem Feststoffgehalt von ca. 45 Gew.%.; Isocyanat-reaktives Polymer aus linearen Polyurethanketten in WasserPolyurethane dispersion having a solids content of about 45% by weight .; Isocyanate-reactive polymer of linear polyurethane chains in water

B) Verdicker: Borchi® Gel L 75 NB) Thickener : Borchi® Gel L 75 N

Nicht-ionischer, flüssiger, aliphatischer Polyurethan-basierter Verdicker: Viskosität bei 23°C: > 9.000 mPas; Nicht flüchtige Bestandteile: 50 Gew.-%.Non-ionic, liquid, aliphatic polyurethane-based thickener: Viscosity at 23 ° C:> 9,000 mPas; Non-volatile ingredients: 50% by weight.

C) Deaktiviertes Polyisocyanat: Dispercoll® BL XP 2514C) Deactivated polyisocyanate: Dispercoll® BL XP 2514

Suspension von oberflächendeaktiviertem TDI-Uretdion (TDI-Dimer) in Wasser mit einem Feststoffgehalt von ca. 40 Gew.-%.Suspension of surface-deactivated TDI uretdione (TDI dimer) in water with a solids content of about 40 wt .-%.

Für die Herstellung der Klebstoffdispersion wurden zunächst 700 Gewichtsteile der Polyurethandispersion A) unter Rühren mit 7 Gewichtsteilen des Verdickers B) versetzt, um die Viskosität zu erhöhen.For the preparation of the adhesive dispersion, first 700 parts by weight of the polyurethane dispersion A) were added while stirring to 7 parts by weight of the thickener B) in order to increase the viscosity.

Anschließend wurden unter Rühren zu 100 Gewichtsteilen dieser verdickten Dispersion 10 Gewichtsteile des deaktivierten Polyisocyanats C) zugegeben, so dass eine wässrige Dispersion erhalten wurde.Then, with stirring, 100 parts by weight of this thickened dispersion was added with 10 parts by weight of the deactivated polyisocyanate C), so that an aqueous dispersion was obtained.

Anschließend wurde die IR-Reflektionsfolie mit einem Spiral-Rakel mit dieser Klebstoffdispersion beschichtet, wobei die Nassschichtdicke der Klebstoffdispersion 100 µm betrug, so dass eine Trockenschichtdicke von ca. 30 µm erhalten wurde. Anschließend wurde die beschichtete Folie 90 min bei ca. 35°C im Trockenschrank getrocknet und war dann fertig zum Einsatz in der Lamination.Subsequently, 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.

Beispiel 3Example 3

Die linke Hälfte der Schicht (1) der in Beispiel 1 hergestellten ID-Karte wurde in einem zweiten Laminationsschritt mit der klebstoffbeschichteten IR-Reflektionsfolie aus Beispiel 2 laminiert.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.

Dazu wurde die Lamination auf einer Laminationspresse der Firma Bürkle mit folgenden Parametern durchgerührt:

  • Vorheizen der Presse auf 90°C
  • Pressen für 8 Minuten bei einem Druck von 15 N/cm2
  • Abkühlen der Presse auf 38°C und Öffnen der Presse.
For this purpose, the lamination was carried out on a lamination press of Bürkle with the following parameters:
  • Preheat the press to 90 ° C
  • Press for 8 minutes at a pressure of 15 N / cm 2
  • Cool the press to 38 ° C and open the press.

Beispiel 4Example 4

Auf der zur Hälfte mit der IR-Refektionsfolie beschichteten ID-Karte aus Beispiel 3 wurde eine Lasergravierung auf einer Laser-Anlage der Firma Foba mit folgenden Parametern durchgeführt: Laser Medium: Nd:YAG Wellenlänge: 1064 nm Leistung: 40 Watt Strom: 30 A Pulsfrequenz: 14 KHz. Vorschubgeschwindigkeit: 200 mm/sek. Laser engraving on a Foba laser system was carried out on the ID card from Example 3, which was coated halfway with the IR refection film, with the following parameters: Laser medium: Nd: YAG Wavelength: 1064 nm Power: 40 watts Electricity: 30 A pulse rate: 14 KHz. Feed speed: 200 mm / sec.

Bei der Lasergravierung wurde die Information nur auf eine laserbeschreibbare Folienschicht (Schicht (2)) der ID-Karte geschrieben. Als Information sollte das vollständige Portrait einer Frau mittels Lasergravierung in die laserbeschreibbare Schicht geschrieben werden. Dabei wurde folgendes Ergebnis erzielt:

  • Auf der linken Hälfte der ID-Karte, auf der die IR-Reflektionsfolie auflaminiert war, konnte keine Lasergravur der darunter liegenden laserbeschreibbaren Folienschicht erzielt werden. Auf der rechten Seite konnte kontrastreich die rechte Gesichtshälfte in die laserbeschreibbare Folienschicht eingeschrieben werden, was die grundsätzliche Beschreibbarkeit der Laserschicht nachweist.
In laser engraving, the information was only written on a laser-writable film layer (layer (2)) of the ID card. As information, the full portrait of a woman should be laser engraved into the laser-writeable Be written layer. The result was as follows:
  • On the left half of the ID card on which the IR reflection foil was laminated, no laser engraving of the underlying laser writable film layer could be achieved. On the right side, the right half of the face could be inscribed into the laser-writable film layer with high contrast, which proves the fundamental writability of the laser layer.

Somit bietet der erfindungsgemäße Aufbau die Möglichkeit, nach abgeschlossener Personalisierung einer ID-Karte mittels Lasergravur durch Aufbringung einer IR-Strahlung reflektierenden oder absorbierenden Deckschicht die nachträgliche Lasergravur zu verhindern.Thus, 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.

Claims (13)

  1. Laser gravure inscribed layer structure comprising at least one thermoplastic polymer layer modified so as to be inscribable by means of laser gravure and a top layer which reflects or absorbs IR radiation over part or all of its area, the top layer which reflects or absorbs IR radiation over part or all of its area comprising at least one IR-absorbing additive, and the IR-absorbing additive in the top layer being one 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.
  2. Laser gravure inscribed layer structure comprising at least one thermoplastic polymer layer modified so as to be inscribable by means of laser gravure and a top layer which reflects or absorbs IR radiation over part or all of its area, the top layer which reflects or absorbs IR radiation over part or all of its area consisting of a multilayer structure which is a multilayer optical interference film.
  3. Laser gravure inscribed layer structure according to Claim 1 or 2, characterized in that the thermoplastic polymer layer modified so as to be inscribable by means of laser gravure comprises at least one laser-sensitive additive.
  4. Laser gravure inscribed layer structure according to Claim 3, characterized in that the laser-sensitive additive is carbon black.
  5. Laser gravure inscribed layer structure according to at least one of Claims 1 to 4, characterized in that the thermoplastic polymer of the thermoplastic polymer layer modified so as to be laser-inscribable is at least one thermoplastic polymer selected from polymers of ethylenically unsaturated monomers and/or polycondensates of bifunctional reactive compounds, preferably one or more polycarbonate(s) or copolycarbonate(s) based on diphenols, poly- or copolyacrylate(s) and poly- or copolymethacrylate(s), poly- or copolymer(s) with styrene, polyurethane(s), and polyolefin(s), poly- or copolycondensate(s) of terephthalic acid, poly- or copolycondensates of naphthalenedicarboxylic acid, poly- or copolycondensate(s) of at least one cycloalkyl-dicarboxylic acid, polysulphones or mixtures of these, more preferably one or more polycarbonate (s) or copolycarbonate(s) based on diphenols or blends comprising at least one polycarbonate or copolycarbonate.
  6. Laser gravure inscribed layer structure according to at least one of Claims 1 to 5, characterized in that the transmission of the top layer which reflects or absorbs IR radiation for radiation of wavelength from 800 to 1200 nm, preferably from 850 to 1100 nm, is not greater than 20%, preferably not greater than 15%, more preferably not greater than 10%, and the transmission for radiation of wavelength from 400 to 700 nm is greater than 60%, preferably greater than 70%.
  7. Laser gravure inscribed layer structure according to at least one of Claims 1 to 6, characterized in that the layer structure has at least one layer comprising at least one thermoplastic polymer and at least one filler ("filled layer").
  8. Laser gravure inscribed layer structure according to Claim 7, characterized in that the filler is a colour pigment or another filler for generation of translucence of the filled layer, preferably titanium dioxide, zirconium dioxide, barium sulphate or glass fibres.
  9. Security document, preferably identification document, comprising at least one laser gravure inscribed layer structure according to at least one of Claims 1 to 8.
  10. Process for blocking inscribability by means of laser gravure of laser gravure inscribed layer structures, characterized in that a laser gravure inscribed layer structure comprising at least one thermoplastic polymer layer modified so as to be laser gravure inscribable, after inscription by means of laser gravure, is provided with a top layer which reflects or absorbs IR radiation over part or all of its area, the top layer which reflects or absorbs IR radiation over part or all of its area comprising at least one IR-absorbing additive and the at least one IR-absorbing additive being one 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.
  11. Process for blocking inscribability by means of laser gravure of laser gravure inscribed layer structures, characterized in that a laser gravure inscribed layer structure comprising at least one thermoplastic polymer layer modified so as to be laser gravure inscribable, after inscription by means of laser gravure, is provided with a top layer which reflects or absorbs IR radiation over part or all of its area and the top layer which reflects or absorbs IR radiation, after inscription by means of laser gravure, is applied in the form of a multilayer film which is a multilayer optical interference film, to the laser gravure inscribed layer structure by means of an adhesive or by means of lamination.
  12. Process according to Claim 11, characterized in that the adhesive is a latently reactive adhesive.
  13. Use of a film which reflects or absorbs IR radiation for blocking of inscription by means of laser gravure of laser gravure inscribed layer structures, preferably of security documents, more preferably of identification documents.
EP09778880.6A 2008-10-23 2009-10-10 Id cards with blocked laser engraving writability Active EP2349733B2 (en)

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9168696B2 (en) 2012-06-04 2015-10-27 Sabic Global Technologies B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
US9662833B2 (en) 2012-06-04 2017-05-30 Sabic Global Technologies B.V. Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof
WO2014084289A1 (en) * 2012-11-30 2014-06-05 富士フイルム株式会社 Curable resin composition, and image-sensor-chip production method and image sensor chip using same
US9209443B2 (en) 2013-01-10 2015-12-08 Sabic Global Technologies B.V. Laser-perforated porous solid-state films and applications thereof
US9713915B2 (en) 2013-01-18 2017-07-25 Covestro Deutschland Ag Bird protection glazing
DE102013218751A1 (en) * 2013-09-18 2015-03-19 Bundesdruckerei Gmbh Method for producing a security feature of a value or security product and method for producing such a product
EP2955029B1 (en) * 2014-06-13 2018-01-31 Agfa-Gevaert Laser markable materials and documents
US10687588B2 (en) 2014-10-22 2020-06-23 3M Innovative Properties Company Printed components and methods for making the same
EP3436284B1 (en) 2016-03-29 2023-04-05 Covestro Deutschland AG Method for the partial colouring of plastic parts
KR102507562B1 (en) * 2016-12-22 2023-03-09 코베스트로 도이칠란트 아게 Plastic film for ID-documents with improved laser engraving properties and improved chemical resistance
US11242464B2 (en) 2017-06-28 2022-02-08 Covestro Deutschland Ag Method for the partial colouring of plastic parts
DE102017223464A1 (en) * 2017-12-20 2019-06-27 Tesa Se Temperature-resistant laser-inscribable film
CN109504053B (en) * 2018-07-12 2021-02-09 江苏华信新材料股份有限公司 Polycarbonate laser etching film for smart card and preparation method thereof
EP3892473A1 (en) 2020-04-09 2021-10-13 Gemalto AG Data carrier with protection against subsequent laser marking
JP6941209B1 (en) * 2020-08-18 2021-09-29 三菱瓦斯化学株式会社 Resin sheets, multi-layers, and cards
CN114953641B (en) * 2022-04-12 2023-06-30 桂林市啄木鸟医疗器械有限公司 Laser blocking glass, laser therapeutic instrument handle thereof and laser therapeutic instrument

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232502A2 (en) † 1985-12-14 1987-08-19 4P Folie Forchheim GmbH Identification cards
WO1994015319A1 (en) † 1992-12-23 1994-07-07 GAO Gesellschaft für Automation und Organisation mbH Identity card with a visible authenticating mark and a process for manufacturing the same
WO2003055638A1 (en) † 2001-12-24 2003-07-10 Digimarc Id Systems, Llc Laser etched security features for identification documents and methods of making same

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE99693C (en)
DE271932C (en)
NL152889B (en) 1967-03-10 1977-04-15 Gen Electric PROCESS FOR PREPARING A LINEAR POLYCARBONATE COPOLYMER AND ORIENTABLE TEXTILE FIBER OF THIS COPOLYMER.
FR1580834A (en) 1968-01-04 1969-09-12
DE1966931C3 (en) 1969-06-11 1978-11-02 Bayer Ag, 5090 Leverkusen Perfluoroalkyl-substituted quaternary ammonium salts
US3610729A (en) 1969-06-18 1971-10-05 Polaroid Corp Multilayered light polarizer
US3711176A (en) 1971-01-14 1973-01-16 Dow Chemical Co Highly reflective thermoplastic bodies for infrared, visible or ultraviolet light
JPS5039599B2 (en) 1973-03-30 1975-12-18
DE2407776A1 (en) 1974-02-19 1975-09-04 Licentia Gmbh Voltage regulator for TV receiver line output stage - has booster diode with transducer as variable regulating impedance
DE2715932A1 (en) * 1977-04-09 1978-10-19 Bayer Ag FAST CRYSTALLIZING POLY (AETHYLENE / ALKYLENE) TEREPHTHALATE
NL189707C (en) 1978-03-15 1993-07-01 Bayer Ag PROCESS FOR PREPARING TETRA-ETHYLAMMONIUM PERFLUORALKYL SULFONATE.
US4446305A (en) 1981-03-02 1984-05-01 Polaroid Corporation Optical device including birefringent polymer
US4540623A (en) 1983-10-14 1985-09-10 The Dow Chemical Company Coextruded multi-layered articles
EP0155780B1 (en) * 1984-03-21 1990-03-28 Imperial Chemical Industries Plc Infra-red absorber
NO170326C (en) * 1988-08-12 1992-10-07 Bayer Ag DIHYDROKSYDIFENYLCYKLOALKANER
DE3832396A1 (en) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkanes, their preparation, and their use for the preparation of high-molecular-weight polycarbonates
US5227458A (en) * 1988-08-12 1993-07-13 Bayer Aktiengesellschaft Polycarbonate from dihydroxydiphenyl cycloalkane
US5103337A (en) * 1990-07-24 1992-04-07 The Dow Chemical Company Infrared reflective optical interference film
DE4033300C2 (en) * 1990-10-19 1994-06-23 Gao Ges Automation Org Multi-layer, card-shaped data carrier and method for producing the same
US5225314A (en) * 1991-04-17 1993-07-06 Polaroid Corporation Imaging process, and imaging medium for use therein
EP0666993B1 (en) 1992-10-29 1999-06-09 Minnesota Mining And Manufacturing Company Formable reflective multilayer body
US5882774A (en) 1993-12-21 1999-03-16 Minnesota Mining And Manufacturing Company Optical film
DE19522397A1 (en) * 1995-06-23 1997-01-02 Merck Patent Gmbh Laser-markable plastics
US6531230B1 (en) 1998-01-13 2003-03-11 3M Innovative Properties Company Color shifting film
US6808658B2 (en) 1998-01-13 2004-10-26 3M Innovative Properties Company Method for making texture multilayer optical films
JP2002519725A (en) 1998-01-28 2002-07-02 ミネソタ マイニング アンド マニュファクチャリング カンパニー Infrared interference filter
DE10117786A1 (en) * 2001-04-10 2002-10-17 Bayer Ag Heat absorbing layer system useful for heat radiation screening of synthetic plastic displacement (sic) elements having outstanding long term weathering resistance, and high transparency, glaze and heat resistance
US6693657B2 (en) 2001-04-12 2004-02-17 Engelhard Corporation Additive for YAG laser marking
US20030012902A1 (en) * 2001-07-10 2003-01-16 Kim Hyun Jin Compositions for sports equipment having laser-sensitive additives and methods of marking
US7728048B2 (en) * 2002-12-20 2010-06-01 L-1 Secure Credentialing, Inc. Increasing thermal conductivity of host polymer used with laser engraving methods and compositions
US6991695B2 (en) 2002-05-21 2006-01-31 3M Innovative Properties Company Method for subdividing multilayer optical film cleanly and rapidly
DE60311594T2 (en) 2002-12-04 2007-11-15 Dsm Ip Assets B.V. LASER LIGHT ABSORBENT ADDITIVE
EP1751700B1 (en) 2004-05-22 2012-10-24 3M Innovative Properties Company Cards and laminates incorporating multilayer optical films
DE102004050557B4 (en) * 2004-10-15 2010-08-12 Ticona Gmbh Laser-markable molding compounds and products and methods for laser marking obtainable therefrom
DE102007024298B3 (en) * 2007-05-23 2008-10-16 Zahedi Fariborz Martin Loessl Film element for authentication, security paper, security document, security document, coin, token, commodity, design element and method for producing a film element for authentication and method for producing a security paper, a security document and a value document such as a banknote
DE102007054046A1 (en) 2007-11-13 2009-06-18 Bayer Materialscience Ag Latent reactive adhesives for identification documents

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0232502A2 (en) † 1985-12-14 1987-08-19 4P Folie Forchheim GmbH Identification cards
WO1994015319A1 (en) † 1992-12-23 1994-07-07 GAO Gesellschaft für Automation und Organisation mbH Identity card with a visible authenticating mark and a process for manufacturing the same
WO2003055638A1 (en) † 2001-12-24 2003-07-10 Digimarc Id Systems, Llc Laser etched security features for identification documents and methods of making same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RANKL W. ET AL: "Handbuch der Chipkarten", vol. 5. AUF., August 2008, CARL HANSER VERLAG, MÜNCHEN, pages: 42 - 45 †

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