EP4061644A1 - Structure en couches structuralement modifiée et sa fabrication - Google Patents

Structure en couches structuralement modifiée et sa fabrication

Info

Publication number
EP4061644A1
EP4061644A1 EP20803874.5A EP20803874A EP4061644A1 EP 4061644 A1 EP4061644 A1 EP 4061644A1 EP 20803874 A EP20803874 A EP 20803874A EP 4061644 A1 EP4061644 A1 EP 4061644A1
Authority
EP
European Patent Office
Prior art keywords
layer
layer structure
engraving
radiation
transparent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20803874.5A
Other languages
German (de)
English (en)
Inventor
Georgios Tziovaras
Roland Kuenzel
Christoph Koehler
Kira PLANKEN
Stefan Janke
Heinz Pudleiner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4061644A1 publication Critical patent/EP4061644A1/fr
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36—Removing material
    • B23K26/362—Laser etching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/328—Diffraction gratings; Holograms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/333—Watermarks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/30—Identification or security features, e.g. for preventing forgery
    • B42D25/351—Translucent or partly translucent parts, e.g. windows

Definitions

  • the present invention relates to a layer structure with a partial structural change and its production as well as security documents containing this layer structure.
  • Plastic-based security and / or value documents, in particular identification documents such as ID cards, are nowadays preferably produced without the use of adhesive layers as multi-layer composites by means of lamination at high temperatures and high pressure in order to subsequently separate the layer structures for the exchange of identification features to prevent.
  • the corresponding security features are introduced into these multilayer composites before or during the lamination process, which consequently have to be designed in such a way that they withstand the lamination process parameters without being destroyed.
  • the security features must not introduce any weak spots into the multi-layer composite that would enable the composite to be opened again later without being destroyed.
  • Identification documents can be introduced and, if a forgery is present, can be easily recognized as such. Ideally, the security feature should still match the data of the
  • Document holder can be associated.
  • Security features in security and / or value documents are usually divided into three security levels:
  • Level 1 security features are those that are visually perceptible to the naked eye without the use of additional aids.
  • Level 2 security features are those that
  • Need aids (such as a magnifying glass, an optical filter, a reader, etc.) in order to become visible.
  • Level 3 security features are those that can only be identified by forensic procedures in a laboratory. As a rule, the analysis is accompanied by at least partial destruction of the document.
  • level 1 security features which can be quickly perceived visually or tactilely, preferably contain personal data of the document holder and, if a deletion is present, this can be recognized as such quickly and without tools or with a few tools.
  • security features are also called personalized security features.
  • the most important personalized security feature is the loto of the document holder.
  • the reason for this is that after the blank document has been completed by means of laser engraving, e.g. as a black and white loto in the Document can be introduced.
  • methods have been developed which enable the photo to be laser-engraved in color, as described in the European patent application with the application number EP 18190363.4.
  • this process enables the photo to be partially structured so that it can be more easily distinguished from a forgery. For example, some areas of the photo can be engraved with more intense laser radiation in order to be able to create additional structuring. With more effort, however, counterfeiters can also create a structure on the photo, for example by partially applying a transparent lacquer.
  • Transparent windows are a popular security feature in polycarbonate ID documents.
  • the improved security against counterfeiting consists in the fact that the transparency of the window is disturbed if a counterfeit attempt is made.
  • the destruction of transparency happens, for example, if an identification document is pasted over with a transparent film, or if the document has been split by mechanical means.
  • the photo or other person-specific information on the document holder is engraved in transparent windows by means of fibers in order to make an attempt at forgery even more difficult. A variant of this is described in WO 2014/151377 A2.
  • a further object was to provide a method for producing a forgery-proof layer structure, or to provide a forgery-proof security document produced by means of the method.
  • a first object of the invention is a layer structure, including:
  • the non-ionizing electromagnetic radiation is preferably fiber radiation;
  • (B) optionally a further transparent radiation-engravable layer (B) with a first surface bl) which points in the direction of the first layer (A) and a further surface b2) which points in the direction facing away from the first layer (A) is and runs essentially parallel to the surface bl); (C) optionally at least one additional transparent plastic layer (C), wherein the layer (C) is optionally arranged, selected from the group consisting of: on the side of the first surface al) of the layer (A), on the side of the further surface b2) of the further layer (B2), between the two layers (A) and (B) or, in the case of several additional layers (C), a combination of at least two thereof, an image of the colored or black partial surface engraving in the form of a Structural change is located on the surface of the layer structure, which forms an outer surface of the layer structure and the first surface al) opposite.
  • the structural change is preferably not transparent.
  • the structural change is also referred to in the following as “non-transparent structural change” or simply “changed structure”.
  • the first layer (A) can be made of any transparent, radiation-engravable material that can be changed in color by means of a laser in the presence of a dye.
  • Layer (A) is preferably a plastic layer. According to the application, its color can be changed by means of a laser that, with an input of a minimum energy of 1 watt in continuous radiation or 5 watts in pulsed radiation, the material of the first layer can be colored with a dye so that this engraving can be done with the bare Visible to the eye.
  • a pulse frequency in a range from 0.5 KHz to 1000 KHz, preferably from 5 KHz to 100 KHz, particularly preferably from 15 KHz to 50 KHz, is preferably used for the pulsed radiation.
  • a pulse duration of 5 ns to 1000 ns, particularly preferably of 10 ns to 200 ns, is preferably selected for the pulsed radiation.
  • Layer (A) is preferably a laser-engravable layer.
  • the transparent radiation-engravable layer (A) preferably has a colored partial area engraving.
  • the engraving preferably includes structures, such as lettering, which have a width in a range in a range from 0.005 to 1 mm, further preferably from 0.01 to 0.5 mm, particularly preferably from 0.02 to 0.1 mm.
  • the engraving preferably has a depth in a range from 0.001 to 2 mm, particularly preferably from 0.002 to 1 mm, very particularly preferably from 0.005 to 0.5 mm, even more preferably from 0.01 to 0.1 mm.
  • the first layer (A) and preferably all further optional layers (B) and (C) are transparent and clear. According to the invention, transparent is understood to mean that they transmit more than 80%, preferably more than 85%, particularly preferably more than 90%, very particularly preferably more than 95% of light in a wavelength range from 400 to 700 nm.
  • the material of the layer structure, in particular of the first layer (A), is preferably clear before treatment with a laser.
  • “Clear” in the sense of the registration means that the layer structure has a cloudiness, also called turbidity, of ⁇ 20%, preferably of ⁇ 15%, more preferably of ⁇ 10%, particularly preferably of ⁇ 5%, measured in accordance with the ASTM D1003: 2013 standard.
  • the optional further layer (B) can be made of any material that allows at least part of the electromagnetic radiation (E) to pass through, so that the electromagnetic radiation (E) is able to apply sufficient energy to the surface a1) of the layer (A ) to make the coloring possible.
  • Layer (B) is preferably a plastic layer.
  • the optional at least one additional layer (C) also preferably contains a transparent plastic.
  • the additional layer (C) preferably has the same material composition as the further layer (B) or as the first layer (A).
  • the layer structure is characterized in that there is an image of the colored or black partial engraving in the form of a structural change on the surface of the layer structure, which forms an outer surface of the layer structure and is opposite the first surface al).
  • An image is to be understood as meaning that there is almost the same shape of the engraving on one side in the form of the structural change on the opposite side of the layer structure.
  • the image can be slightly shifted relative to the engraving or it can be located directly opposite the engraving, that is to say perpendicular through the layer structure, on the surface of the layer structure opposite the engraving.
  • the surface of the layer structure which lies opposite the first surface a1) and which forms a further outer surface of the layer structure has the changed structure at least at the points which are at an angle in a range from 45 to 90 ° to the axis that runs perpendicularly through the layer structure starting from the engraving. It is generally possible to apply the changed structure to the layer structure at least at those points which are at an angle in a range from 0 to 90 °, more preferably from 5 to 80 °, very particularly preferably from 10 to 70 ° to the axis , which runs vertically through the layer structure starting from the engraving.
  • the colored or black engraving is optically covered at least in part, preferably completely, by the nontransparent structural change, at a viewing angle of 45 to 90 ° C from the side of the layer structure that has the nontransparent structural change.
  • the optical coverage of the colored or black engraving by the non-transparent structural change is at least at a viewing angle in a range from 45 to 90 ° from the side of the layer structure that has the non-transparent structural change, preferably in a range from 50 to 100%, more preferably from 60 to 90%, particularly preferably from 70 to 80%, based on the width of the colored or black engraving.
  • the structural change on the outer surface of the layer structure is characterized by the fact that the layer no longer shows any or little transparency at the points with the structural change, but can still be translucent, which is visually expressed in a milky appearance.
  • One explanation for the structural change can be that due to the very rapid melting of the layer at the entry point of the electromagnetic radiation (E), air bubbles are trapped in the material of the layer.
  • Another explanation could be a chemical change in the structure of the material at the point of entry of the electromagnetic radiation (E) into the layer.
  • the changed structure has a cloudy or milky appearance.
  • the areas of the layer structure which contain the changed structure preferably have a turbidity or haze of> 20%, preferably> 50%, more preferably> 80%, measured with a device from BYK-Gardner, model haze gard plus, according to the ASTM D1003: 2013 standard.
  • the changed structure also preferably appears as a white engraving on the layer structure.
  • the changed structure is on a surface of the layer structure that is opposite the surface on which the colored or black partial engraving is present.
  • the colored or black partial engraving thus points in the opposite direction of the layer structure than the changed structure. Since the changed structure is milky, at least a part, preferably the entire colored or black engraving, is covered by the changed structure. It is therefore possible that the colored or black engraving is no longer visible from the side where the changed structure is located.
  • the visibility of the colored or black engraving from the side of the changed structure can be adjusted by selecting the width of the changed structure. Conversely, the changed structure can be covered by the choice of the width of the colored or black engraving if the layer structure is viewed from the side of the colored or black engraving.
  • the layer (B) has a layer thickness at the points with the changed structure which is at least 0.001 mm thicker than at the points without the changed structure.
  • At least one, preferably all of the layers (A), (B) or (C) have one, preferably all of the following properties:
  • At least layer (A), preferably also layer (B), contains a thermoplastic material selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of bifunctional reactive compounds and polyadducts of bifunctional reactive compounds or Combinations of at least two of these.
  • thermoplastics are one or more polycarbonate (s) or copolycarbonate (s) based on diphenols, poly- or copolyacrylate (s) and poly- or copolymethacrylate (s) such as, for example and preferably, polymethyl methacrylate or poly (meth) acrylate (PMMA) ), Poly- or copolymer (s) with styrene such as, for example and preferably, polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), or polystyrene-acrylonitrile (SAN), thermoplastic polyurethane (s), and polyolefin (s), such as for example and preferably polypropylene types or polyolefins based on cyclic olefins (e.g.
  • poly or copolycondensate (s) of terephthalic acid such as, for 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)), polyamide (PA), poly- or copolycondensate (s) of naphthalene dicarbons acid, such as, for example and preferably, polyethylene glycol naphthalate (PEN), poly- or copolycondensate (s) of at least one cycloalkyldicarboxylic acid, such as, for example and preferably, polycyclohexanedimethanolcyclohexanedicarboxylic acid (PCCD), polysulfones (PSU), mixtures of at least two of terephthalic acid, such as, for
  • thermoplastics are one or more polycarbonate (s) or copolycarbonate (s) based on diphenols or blends containing at least one polycarbonate or copolycarbonate.
  • Blends containing at least one polycarbonate or copolycarbonate and at least one polycondensate or copolycondensate of terephthalic acid, naphthalenedicarboxylic acid or a cycloalkyldicarboxylic acid, preferably cyclohexanedicarboxylic acid are very particularly preferred.
  • terephthalic acid preferably from 10,000 to 80,000, particularly preferably from 15,000 to 40,000, or their blends with at least one poly- or copolycondensate of terephthalic acid with average molecular weights Mw of 10,000 to 200,000, preferably from 21,000 to 120,000.
  • polyalkylene terephthalates are suitable as poly- or copolycondensates of terephthalic acid.
  • Suitable polyalkylene terephthalates are, for example Reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g. 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 with 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch, Vol. VIII, p. 695 ff, Karl-Hanser-Verlag, Kunststoff 1973 ).
  • Preferred polyalkylene terephthalates contain at least 80 mol%, preferably 90 mol% terephthalic acid residues, based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol% ethylene glycol and / or 1,4-butanediol and / or 1, 4- Cyclohexanedimethanol residues, based on the diol component.
  • the preferred polyalkylene terephthalates can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid , 4,4'-diphenyldicarboxylic acid, succinic, adipic, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can contain ethylene or butanediol-1,4-glycol residues up to 80 mol% of other aliphatic diols with 3 to 12 carbon atoms or cycloaliphatic diols with 6 to 21 carbon atoms, z. B.
  • the polyalkylene terephthalates can be obtained by incorporating relatively small amounts of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acids, as z. As described in DE-OS 1900270 and US Pat. No. 3,692,744, be branched. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
  • branching agent based on the acid component.
  • polyalkylene terephthalates which are composed solely of terephthalic acid and its reactive derivatives (for example its dialkyl esters) and ethylene glycol and / or 1,4-butanediol and / or 1,4-cyclohexanedimethanol residues have been produced, and mixtures of these polyalkylene terephthalates.
  • Preferred polyalkylene terephthalates are also copolyesters which are produced 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 / 1,4-butanediol) terephthalates.
  • the polyalkylene terephthalates preferably used as a component preferably have an intrinsic viscosity of approx. 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 preferably 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 can preferably be one with 1 to 90% by weight of polycarbonate or copolycarbonate and 99 to 10% by weight of poly- or Copolybutylene terephthalate or glycol-modified poly- or copolycyclohexane-dimethylene terephthalate, preferably with 1 to 90% by weight of polycarbonate and 99 to 10% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, the proportions adding up to 100% by weight.
  • such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate can be one with 20 to 85% by weight of polycarbonate or copolycarbonate and 80 to 15% by weight of poly- 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 up to 100% by weight.
  • Such a blend of polycarbonate or copolycarbonate with poly- or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate can very particularly preferably be one with 35 to 80% by weight of polycarbonate or copolycarbonate and 65 to 20% by weight of poly - 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 up to f00% by weight.
  • blends of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the compositions mentioned above can be involved.
  • particularly suitable polycarbonates or copolycarbonates are aromatic polycarbonates or copolycarbonates.
  • the polycarbonates or copolycarbonates can be linear or branched in a known manner.
  • polycarbonates can be produced in a known manner from diphenols, carbonic acid derivatives, if appropriate chain terminators and if appropriate branching agents. Details of the production of polycarbonates have been laid down in many patents for about 40 years. For example, see Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, to 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 to Drs. U. Grigo, K. Kirchner and PR Müller “Polycarbonate” in Becker / Braun, plastic Handbook, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Kunststoff, Vienna 1992, pages 117-299.
  • Suitable diphenols can be, for example, dihydroxyaryl compounds of the general formula (I),
  • 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, as well as their core alkylated and ring 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) diphenyl methane , 1, 1 -Bis- (4-hydroxyphenyl) -1-phenyl-ethane, 1, 1 -Bis- (4-hydroxyphenyl) -1 - (1 - naphthyl) -ethane, l, l-bis (4- hydroxyphenyl) -l- (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 ) -l-phenyl-propane
  • R 1 and R 2 independently of one another hydrogen, halogen, preferably chlorine or bromine, Ci-Cs- alkyl, Cs-Ce-cycloalkyl, C 6 -Cio-aryl, preferably phenyl, and C7-Ci2-aralkyl, preferably phenyl-Ci- C4-alkyl, in particular benzyl, m is an integer from 4 to 7, preferably 4 or 5,
  • R 3 and R 4 can be selected individually for each X, independently of one another hydrogen or C i -CV alkyl and
  • X is carbon, with the proviso that X, R 3 and R 4 on at least one atom are simultaneously alkyl.
  • the preferred alkyl radical for the radicals R 3 and R 4 in formula (Ia) is methyl.
  • the X atoms in the alpha position to the diphenyl-substituted C atom (Cl) are preferably not dialkyl-substituted, while alkyl disubstitution in the beta position to Cl is preferred.
  • a very particularly preferred dihydroxydiphenylcycloalkane of the forms (Ia) is 1,1-bis (4-hydroxyphcny I) -3, 3, 5-1 rimcthy I - cyc I ohcxan (formula (Ia-1) with R 1 and R 2 equal to H). According to EP-A 359 953, such polycarbonates can be produced from dihydroxydiphenylcycloalkanes of the 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, l, l-bis- (4-hydroxyphenyl) -cyclohexane, l, l-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, l, l- Bis (4-hydroxyphenyl) -3,3,5- trimethyl-cyclohexane, l, r-bis- (4-hydroxyphenyl
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis (4-hydroxyphenyl) propane.
  • Both a dihydroxyaryl compound to form homopolycarbonates and various dihydroxyaryl compounds to form copolycarbonates can be used. It is possible to use both one dihydroxyaryl compound of the formula (I) or (Ia) with the formation of homopolycarbonates and also several dihydroxyaryl compounds of the formula (I) and / or (Ia) with the formation of copolycarbonates.
  • the various dihydroxyaryl compounds can be linked to one another either randomly or in blocks.
  • the molar ratio of dihydroxyaryl compounds of the formula (Ia) to the other dihydroxyaryl compounds of the formula (I) which may also be used is preferably between 99 mol% (Ia) to 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).
  • a very particularly preferred copolycarbonate can be made using l, l-bis (4-h y d r o x y p h c n y I) - 3, 3, 5 - 1 r i m c t h y I - c y c I o h c x a n and 2,2-bis (4-hydroxyphenyl) propane
  • Suitable carbonic acid derivatives can be, for example, diaryl carbonates of the general formula (II), wherein
  • R, R 'and R independently of one another, identically or differently, represent hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl, R can furthermore also mean -COO-R'", where R '"represents hydrogen, linear or branched C1-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
  • Preferred diaryl carbonates are, for example, diphenyl carbonate, methylphenyl phenyl carbonate and di (methylphenyl) carbonate, 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-iso-butylphenyl-phenyl-carbonate, di- (4-iso-butylphenyl) -carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butylphenyl) -carbonate, 4-n- Penty
  • diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl-phenyl-carbonate, di- (4-tert-butyl-phenyl) -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.
  • Diphenyl carbonate is very particularly preferred.
  • one or more monohydroxyaryl compound (s), for example, can additionally be used as chain terminators which were not used to prepare the diaryl carbonate (s) used.
  • chain terminators which were not used to prepare the diaryl carbonate (s) used.
  • These can be those of the general formula (III), in which
  • R A is linear or branched C1-C34- alkyl, C7-C 34 - alkylaryl, C6-C 34 -aryl or represents -COO-R D wherein R D is hydrogen, linear or branched C1-C34- alkyl, C 7 -C 34 -alkylaryl or CV C 34 -aryl, and R B , R c independently of one another, identically or differently, represent hydrogen, linear or branched Ci-C34-alkyl, C7-C34-alkylaryl or C6-C34-aryl.
  • Such monohydroxyaryl compounds are, for example, 1-, 2- or 3-methylphenol, 2,4-dimethylphenol, 4-ethylphenol, 4-n-propylphenol, 4-isopropylphenol, 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- (l-naphthyl) -phenol, 4- (2-naphthyl) -phenol, 4-tritylphenol, methyl salicylate, ethyl salicylate, n-propyl salicylate, iso-propyl salicylate, n-butyl salicylate, isobutyl salicylate
  • Suitable branching agents can be compounds with three or more functional groups, preferably those with three or more hydroxyl groups.
  • Suitable compounds with 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 with three or more functional groups are, for example, 2,4-dihydroxybenzoic acid, trimesic acid (trichloride), cyanuric acid 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 layer (A), preferably also the layer (B), comprises at least one additive which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used, or wherein the layer (A), preferably also the layer (B) is coated with at least one additive in the form of a coating agent which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used.
  • laser-sensitive additives are suitable as additives, so-called laser marking additives, ie those from an absorber in the wavelength range of the radiation to be used (C).
  • the additive preferably comprises at least one or more organic and / or inorganic IR absorbers, preferably inorganic IR absorbers.
  • Such additives and their use in Molding compositions are described, for example, in WO-A 2004/50766 and WO-A 2004/50767 and are commercially available from DSM under the brand name Micabs TM.
  • NIR near infrared
  • infrared absorbers known from the literature such as those described, for. B. in M. Matsuoka, Infrared Absorbing Dyes, Plenum Press, New York, 1990 are described in terms of substance class.
  • Infrared absorbers 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.
  • phthalocyanines and naphthalocyanines are particularly suitable. Due to the improved solubility in thermoplastics, phthalocyanines and naphthalocyanines with bulky side groups are to be preferred.
  • Suitable inorganic IR absorbers are, for example, mixed oxides of metals such as phosphorus-containing tin-copper mixed oxides, as described, for example, in WO-A 2006/042714, those from the group of borides and / or tungstates and mixtures thereof, preferably at least one or more IR absorbers from the group of borides and / or tungstates, and mixtures thereof, particularly preferably at least one or more IR absorbers from the group of tungstates.
  • Bao, 33 W0 3 , Tlo , 33 W0 3 , Ko , 33 W0 3 , Rb 0 are particularly preferred.
  • Cso, 33 W0 3 as inorganic IR absorbers especially preferred.
  • Cs / W ratios of 0.20 and 0.25 are also preferred.
  • the Woframates are to be preferred to the borides due to their low inherent coloration, provided that the method according to the invention is to be carried out on layer structures which have a radiation permeability of> 10% to ⁇ 99%, preferably> 30% to ⁇ 95%, particularly preferred > 40% to ⁇ 93% for the selected radiation, determined according to the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025.
  • tungsten trioxide, tungsten dioxide, a hydrate of tungsten oxide, tungsten hexachloride, ammonium tungstate or tungstic acid and optionally other salts containing the element M, such as cesium carbonate are mixed in certain stoichiometric ratios so that the molar ratios of the individual components are given by the formula M x W y O z are reproduced.
  • This mixture is then treated at temperatures between 100 ° C and 850 ° C in a reducing atmosphere, for example an argon hydrogen atmosphere, and finally the powder obtained is tempered at temperatures between 550 ° C and 1200 ° C under an inert gas atmosphere.
  • the IR absorber can be mixed with the dispersants described below and other organic solvents such as toluene, benzene or similar aromatic hydrocarbons and placed in suitable mills, such as ball mills, with the addition of zirconium oxide (e.g. with a diameter of 0.3 mm) to produce the desired particle size distribution.
  • the nanoparticles are obtained in the form of a dispersion. After grinding, further dispersants can optionally be added. The solvent is removed at elevated temperatures and reduced pressure. Nanoparticles which have an average size of less than 200 nm, particularly preferably less than 100 nm, are preferred.
  • the size of the particles can be determined with the help of transmission electron spectroscopy (TEM).
  • TEM transmission electron spectroscopy
  • the particles thus obtained are dispersed in an organic matrix, for example in an acrylate, and optionally in a mill as described above using suitable auxiliaries such as zirconium dioxide and if necessary, ground using organic solvents such as toluene, benzene or similar hydrocarbons.
  • Suitable polymer-based dispersants are above all dispersants which have a high transmission, such as polyacrylates, polyurethanes, polyethers, polyesters or polyester urethanes and polymers derived therefrom.
  • Preferred dispersants are polyacrylates, polyethers and polyester-based polymers, with polyacrylates such as polymethyl methacrylate and polyester being particularly preferred as high-temperature stable dispersants. Mixtures of these polymers or acrylate-based copolymers can also be used. Such dispersing aids and methods for producing tungstate dispersions are described, for example, in JP 2008214596 and in Adachi et al. J. Am. Ceram. Soc. 2007, 90 4059-4061. Suitable dispersants are commercially available.
  • Dispersants based on polyacrylate are particularly suitable. Such suitable dispersants are available, for example, under the trade names EFKA TM, e.g. EFKA TM 4500 and EFKA TM 4530 from Ciba Specialty Chemicals. Polyester-containing dispersants are also suitable. They are available, for example, under the trade names Solsperse TM, e.g. Solsperse TM 22000, 24000SC, 26000, 27000 from Avecia. Furthermore, polyether-containing dispersants are known, for example, under the trade names Disparlon TM DA234 and DA325 from Kusumoto Chemicals. Polyurethane-based systems are also suitable. Polyurethane-based systems are available under the trade names EFKA TM 4046, EFKA TM 4047 from Ciba Specialty Chemicals. Texaphor TM P60 and P63 are corresponding trade names of Cognis.
  • EFKA TM e.g. EFKA TM 4500 and EFKA
  • the additive preferably comprises at least one or more organic and / or inorganic IR absorbers.
  • the amount of the IR absorber in the dispersant can be 0.2% by weight to 50.0% by weight, preferably 1.0% by weight - 40.0% by weight, more preferably 5.0% by weight. % -35.0% by weight, and most preferably 10.0% -30.0% by weight, based on the dispersion of the inorganic IR absorber used according to the invention.
  • the overall composition of the ready-to-use IR absorber formulation may contain further auxiliaries such as zirconium dioxide and residual solvents such as toluene, benzene or similar aromatic hydrocarbons.
  • inorganic IR absorbers particularly preferably those from the group of tungstates
  • the inorganic IR absorbers can usually be used, however, in an amount of> 0.7% by weight to ⁇ 4.5% by weight, preferably> 0.6% by weight to ⁇ 2% by weight. -% and particularly preferably> 0.7% by weight to ⁇ 1.5% by weight>, calculated as the solids content of inorganic IR absorber, are used in the overall polymer composition.
  • Solid content of inorganic IR absorber, in particular tungstate means in this context the inorganic IR absorber, in particular tungstate, as a pure substance and not a dispersion, suspension or other preparation containing the pure substance, the following information also relating to the content of IR -Additive, especially the tungstate content, always relate to this solid content, unless explicitly stated otherwise.
  • compositions which contain two to five, and particularly preferably two or three, different IR absorbers.
  • the further IR absorber is preferably selected from the group of borides and tin oxides, particularly preferably LaBr, or contains antimony-doped tin oxide or indium tin oxide.
  • the layer structure can be coated with an additive in the form of a coating agent which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used.
  • coating agents preferably comprise an IR absorber, which is in the wavelength range from 0.70 pm to 1000 pm, preferably in the range from 1.0 pm to 50 pm, particularly preferably in the range from 1.0 pm to Absorb ⁇ 2.5 pm.
  • These coating agents are commercially available, for example, under Clearweld TM under the designation LD920, LD930 or LD940.
  • the at least one additive which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used can be contained in the layer structure.
  • Another object of the invention is a method for producing a colored layer structure comprising the steps: i) at least one having a, preferably uncolored layer structure i) l. a first transparent radiation-engravable layer (A) with a first surface a1) and a second surface a2), the surfaces running essentially parallel to one another,
  • a further transparent radiation-engravable layer (B) with a first surface bl) which points in the direction of the first layer (A) and a further surface b2) which faces in the opposite direction and therefore facing away from the first layer (A) has; ii) contacting at least part of the first surface a1) of the first transparent radiation-engravable layer (A) with a coloring agent, preferably with a coloring bath (F) containing the coloring agent; iii) irradiating the layer structure from ii) with focused non-ionizing electromagnetic radiation from the side facing away from the dye bath (F), through the surface a2) or optionally also b2).
  • the layer structure preferably has two outer surfaces which come into contact with the non-ionizing electromagnetic radiation in step iii).
  • One of the outer surfaces is preferably formed by the first surface a1).
  • the further outer surface is preferably formed by the second surface a2) or, if present, by the further surface b2).
  • the layer structure can be overlaid with further layers or coatings on one of the outer sides.
  • the focused non-ionizing radiation strikes the first surface a1) of the first layer (A)
  • a colored or black partial area engraving is produced.
  • the focused non-ionizing radiation hits the outer surface, which is formed by the second surface a2) of the first layer (A) or by the further surface b2) of the further layer (B)
  • an image of the colored or black partial surface engraving is created in Form of a non-transparent structural change on the outer surface, i.e. surface a2) or b2) of the layer structure.
  • the dye bath (B) can comprise at least one colorant, preferably at least one dye, particularly preferably at least one dye from the group of solvent dyes and / or disperse dyes according to the classification of the color index or mixtures of these dyes.
  • Dyes from the group of solvent dyes according to the classification of the Color Index can be, for example, the so-called Macrolex TM dyes from Lanxess AG, Germany.
  • Macrolex TM dyes from Lanxess AG, Germany.
  • Examples include MacrolexTM Blue 3R, MacrolexTM Red H, MacrolexTM Yellow 6G (Solvent Yellow 179 according to CI), MacrolexTM Violet Red R (Dispers Violet 31 according to CI), MacrolexTM Orange R (Solvent Orange 107 according to CI) or mixtures of these dyes.
  • Dyes of the group of the dispers dyes according to the classification of the Color Index can be, for example, diazo, diphenylamine and anthraquinone compounds, acetate dyes, disperse dyes and / or disperse dyes and include disperse blue # 3, disperse blue # 14, disperse yellow # 3, disperse -Rot # 134 and Dispers-Red # 7.
  • the classification and designation of the dyes cited above are consistent with The Color Index, 3rd Edition, jointly published by the Society of Dyes and Colors and the American Association of Textile Chemists and Colorists (1971).
  • the dyes can generally be used either as a single dye ingredient or as a component of a mixture, depending on the color desired. Thus, the term dye used here also includes the dye mixture.
  • Suitable dyes include water-insoluble diazo-diphenylamine and anthraquinone compounds.
  • the preferred dispersed dyes include Dy star's Palanil Blue E-R150 (Anthraquinone / Disperse Blue), DIANIX Orange E-3RN (Azo Dye / CI Disperse Orange 25) and the aforementioned Macrolex TM dyes as solvent dyes.
  • the dye bath preferably comprises: a) solvent and / or dispersant, preferably water and / or organic solvent, particularly preferably water b) colorant, preferably a dye, particularly preferably a dye of the solvent dyes and / or dispersion dyes according to the classification of the color index. c) isopropanol
  • the dye bath therefore also preferably comprises component c) in addition to the components a) and b) already mentioned.
  • Components a) to c) can be present in the following amounts based on the total weight of the dye bath: a) 10 to 90% by weight, preferably 15 to 85% by weight, particularly preferably 35 to 50% by weight, b) 0.01 to 50% by weight, preferably 0.1 to 20% by weight, particularly preferably 0.2 to 15% by weight, c) 5 to 90% by weight, preferably 10 to 80% by weight %, particularly preferably 15 to 60% by weight,
  • the dye bath preferably comprises a dye and / or a dye mixture selected from the group of dispers dyes according to the classification of the Color Index, very particularly a dye selected from the group consisting of azo, diphenylamine and anthraquinone compounds.
  • the dye bath preferably comprises a dye and / or a dye mixture from the group of solvent dyes according to the classification of the Color Index, very particularly preferably a dye and / or dye mixture of Makrolex TM dyes.
  • Water and / or organic solvents can be used as solvents and / or dispersants a). Water is preferably used.
  • organic solvents can be used as organic solvents.
  • examples include butyl alcohol, butylene glycol, diethylene glycol, ethyl alcohol, ethylene glycol, heptane, hexane, pentane, propargyl alcohol, propyl alcohol or mixtures of the aforementioned.
  • the layer structure in step iii) is irradiated with focused non-ionizing electromagnetic radiation, the wavelength range of the focused non-ionizing electromagnetic radiation being selected so that the dye bath has a radiation permeability of> 2% to ⁇ 99%, preferably> 30% to ⁇ 95%, particularly preferably> 40% to ⁇ 93% for the selected radiation, determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025.
  • the irradiation in step iii) is preferably carried out with laser radiation with a wavelength in the range from> 0.1 pm to ⁇ 1000 pm, preferably from> 1.0 pm to ⁇ 50 pm, particularly preferably from> 1.0 pm to ⁇ 2.5 pm.
  • the laser is irradiated, this can be done in continuous wave mode (CW laser), in particular for engraving pixel files or gray-scale files.
  • CW laser continuous wave mode
  • Pulsed laser radiation is particularly preferred for irradiating the layer structures or for vector images or rasterized images.
  • a pulse frequency of 0.5 KHz to 1000 KHz is preferred, Pulse frequencies of 5 KHz to 100 KHz are preferably used, particularly preferably pulse frequencies of 15 KHz to 50 KHz.
  • the intensity of the coloring at the lasered areas can be influenced, depending on the requirements placed on the desired application. The higher the laser power used, the more intense the coloring at the lasered areas of the layer structure.
  • the tactile engraving of the side a1) of layer (A), i.e. the side of the layer structure facing away from the dye bath can be adapted in gray levels.
  • the pulse duration is long enough to allow partial carbonization of the side al) with organic materials. This makes the engraving appear in a dark color. This happens at frequencies of less than 30 KHz, with a laser with a nominal power of 60 watts.
  • the pulse duration is particularly short at frequencies above 30 KHz.
  • the structural change in the material can be seen and felt, but organic materials do not or only to a limited extent carbonization. The structural change appears as a colorless or white engraving.
  • NdYAG lasers neodymium-doped yttrium-aluminum-garnet lasers
  • laser types can also be used for colored laser engraving of layer structures that are suitable for engraving and welding plastic parts, such as layer structures.
  • a CO2 laser can also be used.
  • the color concentration of the color bath can also have an influence on the intensity of the partial coloration of the plastic part, such as the layer structure according to the invention, after irradiation.
  • a concentration of colorant, preferably dye b), is preferred from 0.01 to 50% by weight, particularly preferably from 0.1 to 30% by weight, very particularly preferably from 0.2 to 20% by weight, based on the total weight of the Dye bath.
  • the layer structure is irradiated in step iii), preferably through the further layer (B) onto the first layer (A).
  • At least layer (A), and preferably also layer (B), contains a thermoplastic material selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of bifunctional reactive compounds and polyadducts of bifunctional reactive compounds or combinations of at least two of these.
  • thermoplastic material with regard to preferred embodiments, material, Composition and additives as referred to in connection with the layer structure according to the invention.
  • the layer (A), and optionally also the layer (B) comprises at least one additive which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used, or where the layer (A), and preferably also the layer (B) is coated with at least one additive in the form of a coating agent which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used.
  • the layer (A), and preferably also the layer (B) is coated with at least one additive in the form of a coating agent which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used.
  • Preferred additives and their preferred amounts have already been mentioned.
  • the additive comprises at least one or more organic and / or inorganic IR absorbers.
  • the colorant or the color bath (F) comprises at least one dye from the group of solvent dyes and / or dispers dyes according to the classification of the color index or mixtures of these dyes.
  • the dye bath (F) comprises: a) solvent and / or dispersant, preferably water and / or organic solvent, b) at least one colorant, preferably at least one dye, particularly preferably at least one dye from the Solvent Dyes and / or Dispers Dyes according to the classification of the Color Index or a mixture of the above.
  • the first surface a1) of the layer structure is preferably irradiated through the surface a2) before step ii) with focused non-ionizing electromagnetic radiation (E) in the absence of the dye bath.
  • the layer structure can preferably have at least one layer of a thermoplastic material which comprises at least one additive which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used, and this at least one layer of a thermoplastic material with a radiation permeability of> 10% to ⁇ 99%, preferably from 30% to 95%, particularly preferably 40% to für 93%, for the selected radiation, determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, preferably a inorganic IR absorbers, particularly preferably an inorganic IR absorber from the group of tungstates.
  • this layer forms an outer layer of the layer structure, which is ultimately also colored laser-engraved.
  • the layer structure preferably comprises this at least one outer layer of a thermoplastic material containing at least one additive which has an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used, and this at least one layer of a thermoplastic material has a radiation permeability of> 10% to ⁇ 99%, preferably from> 30% to ⁇ 95%, particularly preferably from> 40% to ⁇ 93%, for the selected radiation, determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, preferably a inorganic IR absorber, particularly preferably an inorganic IR absorber from the group of tungstates, and a further layer containing at least one thermoplastic and at least one laser-sensitive additive, preferably black pigment, particularly preferably carbon black.
  • the layer structure in particular layer (A)
  • the layer structure can be irradiated with E) either before step i) and / or after step iii) in the absence of the dye bath (B) as in step iii).
  • the same radiation (C) can be used for this further irradiation.
  • a black engraving can be applied to the surface, preferably in the underlying transparent layers of the layer structure at the desired location.
  • the high laser reactivity of these layer structures leads to a blackening of the laser-irradiated areas when laser engraved outside the dye bath. If the layer structure is in the coloring bath, the intensity of the laser beam is reduced by the coloring bath so that only coloring occurs at the irradiated areas, but no blackening of the surface of the layer structure is caused.
  • the tactile engraving of the layer structure can be adapted in gray levels.
  • the pulse duration is long enough to allow organic materials to carbonize in the layer. This makes the engraving appear in a dark color. This happens at frequencies of less than 30 KHz, with a laser with a nominal power of 60 watts.
  • the pulse duration is particularly short at frequencies above 30 KHz. This means that a structural change in the material can be seen and felt, with organic materials carbonizing only to a limited extent or not at all. This makes the engraving appear colorless or white.
  • the invention also relates to a security document containing a layer structure according to the invention or a layer structure obtainable by the method according to the invention.
  • a security document containing a layer structure according to the invention or a layer structure obtainable by the method according to the invention.
  • Engraved security documents such as identity cards, passports and driver's licenses as well as other personalized security documents, are characterized by a high level of protection against forgery of the personalized or color-engraved information.
  • blank documents can be personalized in a decentralized and forgery-proof manner in color, also in combination with black and white engravings.
  • Film 1 Makrofol TM ID 6-200000 transparent, made of polycarbonate with a thickness of 600 ⁇ m from Covestro Deutschland AG (corresponding to layer (C) of the layer structure according to the invention).
  • Transparent polycarbonate film with an IR absorber with a thickness of 100 ⁇ m was produced as follows (corresponding to layer (A) or (B) of the layer structure according to the invention):
  • the masterbatch for the production of the film 2 was produced with a conventional twin-screw compounding extruder (ZSK 32) at processing temperatures of 250 to 330 ° C. customary for polycarbonate.
  • ZSK 32 twin-screw compounding extruder
  • a master batch was compounded with the following composition and then granulated:
  • flame black 101 carbon black from Evonik-Degussa GmbH with an average particle size of 95 nm
  • the plant used to produce the extruded film comprises: an extruder for extrusion of the layer containing at least one polycarbonate with a screw of 60 mm diameter (D) and a length of 33 D.
  • the screw has a degassing zone; a melt pump; a deflection head; a slot nozzle with a width of 450 mm; a three-roll smoothing calender with a horizontal roll arrangement, the third roll being pivotable by +/- 45 ° with respect to the horizontal; a roller conveyor;
  • Thickness measurement a device for applying protective film on both sides; a take-off device; a winding station.
  • the granulate of the master batch was conveyed from the dryer into the hopper of the extruder.
  • the material was melted and conveyed in the cylinder / screw plasticizing system of the extruder.
  • the melt reached the smoothing calender from the slot die.
  • the final shaping and cooling of the film took place on the smoothing calender (consisting of three rollers).
  • a structured steel roller (6-sided) and a structured silicone-rubber roller (2-sided) were used to emboss the surfaces.
  • the rubber roller used for structuring the film surface is disclosed in US Pat. No. 4,368,240 from Nauta Roll Corporation.
  • the film was then transported through a take-off and then the film was wound up.
  • the lamination took place on a lamination press from Bürckle, model 50/100.
  • the following layer structure of the laminate was created:
  • an NdYAG laser 1064 nm from Lirma Loba with the model designation D84S was used for the laser irradiation of the laminate A. This was operated with a laser power of approx. 7.5 watts, a laser frequency of 30 kHz in pulse mode and a current of 30 A. The travel speed was set to 60 mm / s.
  • the staining bath (L) with the foil was placed on the workpiece carrier of a Loba D84S laser system. The locus of the laser was adjusted to the foil surface of the laminate A.
  • the laminate A was taken out of the staining bath (L) and cleaned with water.
  • the following could be observed:
  • the laser-engraved elements appeared in a white color, the blue color could not or almost not be perceived, the laser engraving appeared white.
  • the blue appearance could be clearly perceived.
  • a turbidity determination was carried out in accordance with the ASTM D1003: 2013 standard, which is equivalent to ISO 13468-1 , performed.
  • ASTM D1003: 2013 standard which is equivalent to ISO 13468-1
  • a device from BYK-Gardner, model haze gard plus used with which the turbidity was determined in accordance with the ASTM Dl 003: 2013 standard.
  • the measured turbidity reached a value of 87.2%, with 0% standing for no turbidity, which would correspond to a crystal-clear layer.
  • the layer structure showed a haze of 5% at the areas not irradiated with laser light.
  • a light transmission through the laminate A before engraving using a laser was determined to be 81.1%, while the light transmission after the engraving was made using a laser at the engraved areas corresponded to 38.2%.
  • Example 1 was repeated with a red and a yellow dye bath.
  • the composition of the dye bath was the same as in Example 1 except for the dye.
  • For red the following was used: Macrolex® Red H.
  • the laser-engraved elements appeared in a white color, the coloring could not be perceived, the laser engraving appeared white.
  • the red and yellow colors could be clearly seen.
  • a turbidity determination was carried out in accordance with the ASTM D1003: 2013 standard, which is equivalent to ISO 13468-1 , performed.
  • ASTM D1003: 2013 standard which is equivalent to ISO 13468-1
  • the measured turbidity reached a value of 87.2%, with 0% standing for no turbidity, which would correspond to a crystal-clear layer.
  • the layer structure showed a haze of 5% at the areas not irradiated with laser light.
  • the Ligures show in 1a: a schematic representation of a layer structure according to the invention as a side view in which both the colored or black partial surface engraving and the non-transparent structural changes are introduced as a perpendicular image of one another by means of a laser;
  • FIG. 1b a schematic representation of a layer structure according to the invention as in FIG. 1 but with the layer structure rotated by approximately 45 ° relative to the laser;
  • FIG. 1c a schematic representation of a layer structure according to the invention as in FIG. 1 but with the laser rotated by approximately 45 ° relative to the layer structure;
  • Fig. 2 a schematic representation of the manufacturing process.
  • Fig. La shows how on a layer structure 1, produced as described in Examples 1 or 2, on the first surface a1) 10 a coloring 120 and on the further surface a2) 20 a non-transparent structural change 110 under the previously for the conditions described in the examples were introduced.
  • the laser light 100 was first directed perpendicularly onto the further surface a2) 20 of the layer structure 1.
  • the non-transparent structural change 110 was produced.
  • the laser beam 100 then ran perpendicular to the further surface a2) 20 through the thickness D of the layer structure 1.
  • the laser light 100 which was passed through the layer structure 1 after it had made the structural change 110 the colored or black engraving 120 is generated. This coloring could take place because the first surface 10 was in direct contact with a coloring bath 200.
  • Fig. Lb shows the same method as shown in Fig. La, the layer structure 1, but in particular the further surface 20 of the layer structure 1, was rotated by a few degrees relative to the angle of incidence of the fiber, so that the fiber beam 100 at an angle of approx 45 ° impinged on the further surface 20 of the layer structure 1.
  • the beam path of the fiber light 100 is also through the thickness D of the layer structure, the fiber beam covering a somewhat longer path than in the arrangement in FIG. 1.
  • the non-transparent structural change 110 which represents the image of the colored or black partial engraving 120, arranged slightly shifted relative to the Fot by the layer structure 1.
  • Fig. Lc shows the same method as shown in Fig. La, the fiber and thus the fiber light 100 was rotated relative to the further surface 20 of the layer structure 1 by a few degrees, so that the fiber beam 100 at an angle of approximately 45 ° the further surface a2) 20 of the layer structure 1 hit.
  • the beam path of the fiber light 100 is also through the thickness D of the layer structure, the fiber beam traveling a slightly longer path than in the arrangement in FIG. 1.
  • the non-transparent structural change 110 which represents the image of the engraving 120, is through relative to the photo the layer structure 1 arranged slightly shifted.
  • the steps of the method according to the invention are shown in FIG. In step i) 300, the uncolored layer structure 1 in the form of the laminate A was presented. As previously described for Fig.
  • step ii) 400 a coloring bath (F) 200 was placed under the layer structure 1 in such a way that only the first surface al) 10 was in contact with the coloring bath (F) 200.
  • step iii) 500 the layer structure 1 was first introduced into the layer structure 1 by means of a laser beam 100 on the further surface a2) 20 of the layer structure 1, with an intransparent structural change 110 being produced on the further surface a2) when the laser light 100 impinged. The laser light then impinged on the first surface a1) 10 in order to produce the colored or black partial engraving 120 there.

Abstract

L'invention concerne une structure en couches contenant : une première couche (A) transparente pouvant être gravée par rayonnement qui comporte une première surface a1) et une seconde surface a2), laquelle s'étend sensiblement parallèlement à la surface a1), la première couche (A) présentant sur sa première surface a1), qui constitue une première face extérieure de la structure en couches, une gravure à surface partielle colorée ou noire, réalisée au moyen d'un rayonnement électromagnétique non ionisant (E) ; (B) éventuellement une autre couche (B) transparente pouvant être gravée par rayonnement qui comporte une première surface b1) dirigée en direction de la première couche (A), et une autre surface b2) qui est dirigée dans la direction située à l'opposé de la première couche (A) et s'étend sensiblement parallèlement à la surface b1), (C) éventuellement au moins une couche de matière plastique (C) transparente supplémentaire, la couche supplémentaire (C) étant agencée au choix dans le groupe comprenant : sur le côté de la première surface a1) de la couche (A), sur le côté de l'autre surface b2) de l'autre couche (B), entre les deux couches (A) et (B) ou dans le cas de plusieurs autres couches (C) d'une combinaison d'au moins deux desdites autres couches, une image de la gravure partielle colorée ou noire se situant sur la surface de la structure en couches sous la forme d'une modification de structure non transparente, laquelle constitue une autre face extérieure de la structure en couches et se situe à l'opposé de la première surface a1). L'invention concerne également la fabrication de la structure en couches ainsi qu'un document de sécurité contenant la structure en couches selon l'invention.
EP20803874.5A 2019-11-22 2020-11-16 Structure en couches structuralement modifiée et sa fabrication Pending EP4061644A1 (fr)

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EP19210992 2019-11-22
PCT/EP2020/082217 WO2021099248A1 (fr) 2019-11-22 2020-11-16 Structure en couches structuralement modifiée et sa fabrication

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EP (1) EP4061644A1 (fr)
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KR (1) KR20220099549A (fr)
CN (1) CN114650915A (fr)
WO (1) WO2021099248A1 (fr)

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GB2613016B (en) 2021-11-22 2024-03-13 De La Rue Int Ltd A method of manufacturing a security sheet

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KR20220099549A (ko) 2022-07-13
CN114650915A (zh) 2022-06-21
JP2023502425A (ja) 2023-01-24
US20230008490A1 (en) 2023-01-12

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