Layered structure with modified structure and its manufacturing

Abstract

The present invention provides: (A) a first transparent, radiation-engravable layer (A) having a first surface a1) and a second surface a2) extending substantially parallel to surface a1), said first layer (A) having a colored or black partial engraving, said engraving being produced by non-ionizing electromagnetic radiation (E) on first surface a1), which forms a first outer surface of the layer structure; (B) optionally an additional transparent, radiation-engravable layer (B) having a first surface b1) facing towards the first layer (A) and another surface b2) facing away from the first layer (A) and extending substantially parallel to first surface b1); and (C) optionally and at least one additional transparent plastic layer (C) (wherein the additional layer (C) is provided on the face of the first surface a1) of the layer (A), on the face of the additional surface b2) of the additional layer (B), in one of the group of options consisting of between the two layers (A) and (B), or in the case of the additional layer (C), in one of the group of options consisting of a combination of at least two of said options, and wherein a colored or black partially engraved image is located on the additional surface of the layer structure in the form of an opaque structural change forming an additional outer surface of the layer structure and located opposite the first surface a1). The invention also relates to the production of a layer structure, as well as to a security document comprising a layer structure according to the invention.

Description

[Technical Field]

[0001] The present invention relates to a layered structure having structural changes over a portion of a region, a method for manufacturing the same, and a security document having the layered structure. [Background technology]

[0002] Plastic-based security documents and / or documents of value, particularly identity cards, such as ID cards, are now preferably manufactured by lamination at high temperature and pressure without the use of adhesive layers as multilayer composites to prevent subsequent delamination of the layered structure for replacing identification functions. Since the corresponding security features are incorporated into these multilayer composites before or during the lamination process, they must be configured to withstand the lamination process parameters without destruction. Furthermore, the security features must not introduce any weaknesses into the multilayer composite that would allow for subsequent non-destructive opening of the composite. Of particular interest are security features that can be introduced after the lamination process or into the completed ID document and that can be easily identified as such in the event of forgery. Ideally, it should be possible to link the security features to the document holder's data.

[0003] Security features in security documents and / or documents of value are typically divided into three levels of security: - Level 1 security features are those that are purely visually perceptible to the naked eye without the use of additional auxiliary means.

[0004] - Level 2 security features require auxiliary tools (e.g., magnifying glasses, optical filters, readers, etc.) to be visible.

[0005] - Level 3 security features are those that can only be identified in a laboratory setting by forensic methods. Generally, the analysis involves at least partial destruction of the document.

[0006] Therefore, there is a growing need for Level 1 security features that can be quickly perceived, preferably by visual or tactile means, preferably including the personal data of the document holder, and that can be perceived so quickly, without or with little assistance, in the case of forgery. Such security features will also be referred to below as personalized security features.

[0007] For ID documents made of plastic, particularly polycarbonate, the most important personalized security feature is the document holder's photograph. This is because, after a blank document is completed, it can be added to the document, for example, as a black and white photograph, by laser engraving. To improve the prevention of forgery of laser-engraved photographs, a method has been developed that enables laser engraving of photographs in color, as described in the European patent application EP18190363.4. Apart from color laser engraving, this method allows for partial structuring of the photograph, making it easier to distinguish a photograph from a forgery. In this way, for example, it is possible to engrave certain areas of the photograph using stronger laser radiation to create further structuring. However, with much effort, forgers can also create structures on photographs, for example, by partially applying clear lacquer.

[0008] A common security feature in ID documents made of polycarbonate is a transparent window. An improvement in evidence against forgery is the destruction of the window's transparency when attempting to forge it. This destruction can occur, for example, when a transparent film is affixed to the ID document or when the document is divided by mechanical means. In some cases, a laser is used to engrave a photograph of the document holder or other personally identifiable information onto the transparent window to make attempted forgery more difficult. One variation of this is described in WO2014 / 151377A2.

[0009] However, in order to counter forgery, there is still a need to further improve the method of color laser engraving.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0011] Therefore, an object of the present invention was to provide a layer structure with anti-counterfeiting engraving in a layer structure and an anti-counterfeiting security document produced therefrom. A further object was to provide a method for manufacturing a more anti-counterfeiting layer structure or a more anti-counterfeiting security document produced by that method.

Means for Solving the Problems

[0012] The present invention firstly provides the following: (A) A first transparent radiation-engravable layer (A) having a first surface a1) and a second surface a2) extending essentially parallel to the surface a1), wherein the first layer (A) on its first surface a1) forming the first outer surface of the layer structure has a colored or black engraving over a part of the region generated by non-ionizing electromagnetic radiation (E). The non-ionizing electromagnetic radiation is preferably laser radiation; (B) Optionally, a further transparent radiation-engravable layer (B) having a first surface b1) facing in the direction of the first layer (A) and a further surface b2) facing away from the first layer (A) and extending essentially parallel to the surface b1); (C) Optionally, at least one additional transparent polymer layer (C), where the arrangement of layer (C) is selected from the group consisting of at least two combinations of the following: on the side of the first surface a1) of layer (A), on the side of the further surface b2) of the further layer (B2), between two layers (A) and (B), or, in the case of multiple further layers (C), A layered structure having the following characteristics is provided: Here, the colored or black engraved image over a portion of the region forms the outer surface of the layered structure and exists in the form of a structural change on the surface of the layered structure opposite to the first surface a1). The structural change is preferably opaque. [Modes for carrying out the invention]

[0013] Hereafter, structural changes will also be referred to as "opaque structural changes" or simply "changed structures."

[0014] The first layer (A) can be manufactured from any transparent radiation-engravable material, and its coloring can be altered by a laser in the presence of a dye. Layer (A) is preferably a polymer layer. "Laser-alterable coloring" as used in this application means that, in the material of the first layer, coloring with a dye is achievable with a minimum energy input of 1 watt of sustained radiation or 5 watts of pulsed laser radiation, and as a result, the engraving is visible to the naked eye. For pulsed radiation, it is preferable to use a pulse frequency in the range of 0.5 kHz to 1000 kHz, preferably 5 kHz to 100 kHz, and more preferably 15 kHz to 50 kHz. For pulsed radiation, it is preferable to select a pulse duration of 5 ns to 1000 ns, more preferably 10 ns to 200 ns.

[0015] Layer (A) is preferably a laser-engravable layer. The transparent laser-engravable layer (A) preferably has a colored engraving over part of the area. The engraving is a structure, such as a written inscription, preferably having a width in the range of 0.005 to 1 mm, more preferably 0.01 to 0.5 mm, and more preferably 0.02 to 0.1 mm. The engraving has a depth in the range of 0.001 to 2 mm, more preferably 0.002 to 1 mm, very preferably 0.005 to 0.5 mm, and even more preferably 0.01 to 0.1 mm.

[0016] The first layer (A), and preferably all other arbitrary layers (B) and (C), are transparent and clear. "Transparent" as understood in this invention means transmitting light in the wavelength range of 400 to 700 nm to a degree greater than 80%, preferably greater than 85%, more preferably greater than 90%, and most preferably greater than 95%.

[0017] The layered material, particularly the material of the first layer (A), is preferably clear before laser treatment. In the context of this application, “clear” means that the layered structure has a turbidity (also called turbidity) of ≤20%, preferably ≤15%, more preferably ≤10%, and especially preferably ≤5%, as measured according to the ASTM D1003:2013 standard.

[0018] Any further layer (B) may be made from any material that transmits electromagnetic radiation (E) at least partially so that the electromagnetic radiation (E) can strike the surface a1) of layer (A) with enough energy to allow coloring. Layer (B) is preferably a polymer layer.

[0019] Any at least one additional layer (C) also preferably comprises a transparent plastic. The additional layer (C) preferably has the same material composition as the further layer (B) or the first layer (A).

[0020] The layered structure is characterized in that a colored or black engraved image, extending over a portion of the region, forms the outer surface of the layered structure and exists in the form of a structural variation on the surface of the layered structure opposite to the first surface a1). To be understood by “image” is that substantially the same form of the engraving on one side exists on the opposite side of the layered structure in the form of a structural variation. The image may be slightly shifted relative to the engraving, or it may be on the opposite side of the engraving, i.e., perpendicular to the layered structure, on the surface opposite the engraving to the layered structure.

[0021] In a preferred embodiment of the layered structure, the surface of the layered structure opposite the first surface a1) and forming a further outer surface of the layered structure has a variation structure at least in areas at angles in the range of 45° to 90° with respect to an axis extending perpendicularly through the layered structure starting from the carving. It is generally possible to introduce a variation structure in areas within the layered structure at angles in the range of 0° to 90°, more preferably 5° to 80°, and most preferably 10° to 70°, with respect to an axis extending perpendicularly through the layered structure starting from the carving.

[0022] This achieves the effect that the colored or black sculpture is at least partially, preferably completely, optically covered by the opaque structural change at a viewing angle of 45° to 90° from the side of the layer structure having the opaque structural change. The optical coverage of the colored or black sculpture by the opaque structural change is preferably in the range of 50% to 100%, more preferably 60% to 90%, and particularly preferably 70% to 80%, based on the width of the colored or black sculpture, at a viewing angle within the range of 45° to 90° from the side of the layer structure having the opaque structural change.

[0023] Structural changes on the outer surface of a layered structure are characterized by the fact that the layer may no longer exhibit transparency, or exhibit little transparency, at the site of the structural change, but may still be semi-transparent, which visually manifests as a milky white appearance. One explanation for the structural change may be that bubbles are trapped in the layer's material due to the very rapid melting of the layer at the site of electromagnetic radiation (E) entry. Another explanation may be a chemical structural change in the material at the site where electromagnetic radiation (E) enters the layer.

[0024] In a preferred embodiment of the layered structure, the altered structure has a cloudy or milky appearance. The region of the layered structure containing the altered structure has a turbidity or haze of preferably ≥20%, preferably ≥50%, and more preferably ≥80%, as measured with a BYK-Gardner HazeGuard Plus instrument according to standard ASTM D1003:2013.

[0025] More preferably, the variation structure appears as a white engraving on the layered structure. As already mentioned, the variation structure is located on the surface of the layered structure opposite to the surface where the colored or black engraving is present over a portion of the area. Thus, the colored or black engraving over a portion of the area points away from the variation structure in the opposite direction to the layered structure. Since the variation structure is milky white and cloudy, preferably at least a portion, preferably all, of the colored or black engraving is covered by the variation structure. Therefore, it is possible that the colored or black engraving is no longer visible from the side where the variation structure is present. The visibility of the colored or black engraving from the side of the variation structure can be adjusted by selecting the width of the variation structure. Conversely, if the layered structure is viewed from the side of the colored or black engraving, the variation structure can be covered by selecting the width of the colored or black engraving.

[0026] In a preferred embodiment of the layered structure, the layer (B) in the portion with the modified structure has a layer thickness at least 0.001 mm thicker than the portion without the modified structure.

[0027] In a preferred embodiment of the layered structure, at least one, preferably all, of layers (A), (B), and (C) have one, preferably all, of the following characteristics: I. Layer thickness in the range of 10 μm to 10,000 μm, preferably 20 μm to 7,000 μm, more preferably 30 μm to 5,000 μm, and most preferably 70 μm to 2,000 μm, as determined by thickness measurement using a micrometer screw or by microtome section and subsequent microscopic observation; II. Radiation transmittance of ≥2% to ≤99.95%, preferably ≥4% to ≤90%, and more preferably ≥5% to ≤85%, for selected radiation, preferably determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025.

[0028] In a preferred embodiment of the layer configuration, at least layer (A), and preferably layer (B), also comprises a thermoplastic material selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of difunctional reactive compounds, and polyaddition products of difunctional reactive compounds, or at least two combinations thereof.

[0029] Preferred thermoplastic materials include one or more polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or copolymethacrylates, for example, and preferably, polymethyl methacrylate or poly(meth)acrylate (PMMA), polymers or copolymers with styrene, for example, and preferably, polystyrene (PS), acrylonitrile-butadiene-styrene (ABS), or polystyrene-acrylonitrile (SAN), thermoplastic polyurethanes, and polyolefins, for example, and preferably, polyolefins based on polypropylene type or cyclic olefins (TOPAS®, Hoechst), poly- or copolycondensates of terephthalic acid, for example For example, and preferably, these include 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 copoly condensates of naphthalenedicarboxylic acid, for example, and preferably polyethylene glycol naphthalate (PEN), poly- or copoly condensates of at least one cycloalkyldicarboxylic acid, for example, and preferably polycyclohexanedimethanol cyclohexanedicarboxylic acid (PCCD), polysulfone (PSU), a mixture of at least two of the above, or a blend thereof.

[0030] Particularly preferred thermoplastics are one or more polycarbonates or copolycarbonates based on a blend containing diphenol or at least one polycarbonate or copolycarbonate. Very particularly preferred are blends containing at least one polycarbonate or copolycarbonate and at least one poly- or copolycondensate of terephthalic acid, naphthalenedicarboxylic acid, or cycloalkyldicarboxylic acid, preferably cyclohexanedicarboxylic acid. Very particularly preferred are polycarbonates or copolycarbonates, especially those having an average molecular weight Mw of 500 to 100,000, preferably 10,000 to 80,000, more preferably 15,000 to 40,000, or blends thereof with at least one poly- or copolycondensate of terephthalic acid having an average molecular weight Mw of 10,000 to 200,000, preferably 21,000 to 120,000.

[0031] In preferred embodiments of the present invention, suitable poly- or copolymer condensates of terephthalic acid are polyalkylene terephthalates. Suitable polyalkylene terephthalates are, for example, reaction products of aromatic dicarboxylic acids or their reactive derivatives (e.g., dimethyl esters or anhydrides) with aliphatic, alicyclic, or aromatic aliphatic diols, and mixtures thereof.

[0032] Preferred polyalkylene terephthalates can be prepared from terephthalic acid (or its reactive derivatives) and aliphatic or alicyclic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch [Plastics Handbook], Vol. VIII, p. 695ff, Karl-Hanser-Verlag, Munich 1973).

[0033] A preferred polyalkylene terephthalate contains at least 80 mol%, preferably 90 mol%, of terephthalic acid groups based on the dicarboxylic acid component, and at least 80 mol%, preferably at least 90 mol%, of ethylene glycol and / or butane-1,4-diol and / or cyclohexane-1,4-dimethanol groups based on the diol component.

[0034] Preferred polyalkylene terephthalates may contain, in addition to the terephthalic acid group, 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 phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and cyclohexanediacetic acid.

[0035] Preferred polyalkylene terephthalates include, in addition to the ethylene and / or butane-1,4-diol group, other aliphatic diols having 3 to 12 carbon atoms or alicyclic diols having 6 to 21 carbon atoms, such as propane-1,3-diol, 2-ethylpropane-1,3-diol, neopentyl glycol, pentane-1,5-diol, hexane-1,6-diol, cyclohexane-1,4-dimethanol, 3-methylpentane-2,4-diol, 2-methylpentane-2,4-diol, 2,2 It may contain up to 80 mol% of the groups of ,4-trimethylpentane-1,3-diol and 2-ethylhexane-1,6-diol, 2,2-diethylpropane-1,3-diol, hexane-2,5-diol, 1,4-di([beta]-hydroxyethoxy)benzene, 2,2-bis(4-hydroxycyclohexyl)propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis(3-[beta]-hydroxyethoxyphenyl)propane and 2,2-bis(4-hydroxypropoxyphenyl)propane (see DE-A 24 07 674, 24 07 776, 27 15 932).

[0036] Polyalkylene terephthalates can be branched by the incorporation of relatively small amounts of trivalent or tetravalent alcohols, or tribasic or tetrabasic carboxylic acids, as described, for example, in DE-A 19 00 270 and US Patent 3 692 744. Examples of preferred branching agents include trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane, and pentaerythritol.

[0037] It is preferable to use a branching agent at a concentration of 1 mol% or less relative to the acid component.

[0038] Polyalkylene terephthalates prepared solely from terephthalic acid and its reactive derivatives (e.g., dialkyl esters thereof), as well as ethylene glycol and / or butane-1,4-diol and / or cyclohexane-1,4-dimethanol groups, and mixtures thereof of these polyalkylene terephthalates are particularly preferred.

[0039] Preferred polyalkylene terephthalates further include copolyesters produced from at least two of the above acidic components and / or at least two of the above alcoholic components; a particularly preferred copolyester is poly(ethylene glycol / butane-1,4-diol) terephthalate.

[0040] The polyalkylene terephthalate, which is preferably used as an ingredient, has an intrinsic viscosity of preferably about 0.4 to 1.5 dl / g, preferably 0.5 to 1.3 dl / g, which is measured in each case in phenol / o-dichlorobenzene (1:1 parts by weight) at 25°C.

[0041] A blend of at least one polycarbonate or copolycarbonate and at least one poly- or copolycondensate of terephthalic acid is preferably a blend of at least one polycarbonate or copolycarbonate and poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate. Such blends of polycarbonate or copolycarbonate and poly- or copolybutylene terephthalate or glycol-modified poly or copolycyclohexanedimethylene terephthalate may preferably contain 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 copolycyclohexanedimethylene terephthalate, and preferably contain 1% to 90% by weight of polycarbonate and 99% to 10% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, where the proportions may total 100% by weight. Such blends of polycarbonate or copolycarbonate and poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate may more preferably contain 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, and more preferably contain 20% to 85% by weight of polycarbonate and 80% to 15% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, where the proportions may total 100% by weight.Such blends of polycarbonate or copolycarbonate and poly- or copolybutylene terephthalate or glycol-modified poly- or copolycyclohexanedimethylene terephthalate may most preferably contain 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 containing 35% to 80% by weight of polycarbonate and 65% to 20% by weight of polybutylene terephthalate or glycol-modified polycyclohexanedimethylene terephthalate, where the proportions may total 100% by weight. A particularly preferred embodiment may include the blend of polycarbonate and glycol-modified polycyclohexanedimethylene terephthalate in the aforementioned composition.

[0042] Preferred polycarbonates or copolymers in preferred embodiments are, in particular, aromatic polycarbonates or copolymers.

[0043] Polycarbonates or copolymers may be linear or branched in known ways.

[0044] These polycarbonates can be produced by known methods from diphenols, carbon dioxide derivatives, optionally chain arresters, and optionally branching agents. Details of polycarbonate production have been described in numerous patent specifications over the past 40 years or so. Here, as mere examples, we refer to Schnell, "Chemistry and Physics of Polycarbonates," Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964; D. Freitag, U. Grigo, PRMueller, H. Nouvertne, BAYER AG, "Polycarbonates" in the Encyclopedia of Polymer Science and Engineering, Vol. 11, 2nd edition, 1988, pp. 648-718; and finally, Dres. U. Grigo, K. Kirchner and PRMueller, Becker / Braun, "Polycarbonate" in the Kunststoff-Handbuch [Plastics Handbook], Vol. 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester [Polycarbonates, Polyacetals, Polyesters, Cellulose Esters], Carl Hanser Verlag You can refer to Munich, Vienna 1992, pp. 117-299.

[0045] Suitable diphenols may include, for example, dihydroxyaryl compounds of general formula (I). [ka]

[0046] [In the formula, Z is an aromatic group having 6 to 34 carbon atoms, and may contain one or more substituted aromatic rings and aliphatic or alicyclic groups or alkylaryl or heteroatoms as bridging elements.] Suitable examples of dihydroxyaryl compounds include dihydroxybenzene, dihydroxydiphenyl, 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)diisopropylbenzene, and their cyclic alkylated and cyclic halogenated compounds.

[0047] These and other more suitable dihydroxyaryl compounds are described, for example, DE-A 3 832 396, FR-A 1 561 518, H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pp. 28 ff; pp. 102 ff, and DGLegrand, JTBendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker, New York 2000, pp. 72 ff.

[0048] Preferred dihydroxyaryl compounds include, 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-phenylethane, 1,1-bis(4-hydroxyphenyl)-1-(1-naphthyl)ethane, and 1,1-bis(4-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-phenylpropane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 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)cyclohexane, 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 The dihydroxydiphenylcycloalkanes of formula (Ia) are dimethyl-4-hydroxyphenyl)-2-propyl]benzene, bis(4-hydroxyphenyl) 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 of formula (Ia). [ka]

[0049] [During the ceremony, R 1and R 2 is, independently, hydrogen, halogen, preferably chlorine or bromine, C1-C8-alkyl, C5-C6-cycloalkyl, C6-C 10 -aryl, preferably phenyl, and C7-C 12 -aralkyl, preferably phenyl-C1-C4-alkyl, especially benzyl, m is an integer from 4 to 7, preferably 4 or 5, R 3 and R 4 can be individually selected for each X and is, independently, hydrogen or C1-C6-alkyl, and X is carbon, provided that on at least one atom X, R 3 and R 4 are both alkyl. Preferably, in formula (Ia), on one or two X atoms, especially only on one X atom, R 3 and R 4 are both alkyl) The preferred alkyl group for R 3 and R 4 groups in formula (Ia) is methyl. The X atoms in the alpha position to the diphenyl-substituted carbon atom (C-1) are preferably not dialkyl-substituted; in contrast, a beta-position alkyl disubstitution to C-1 is suitable.

[0050] Particularly preferred dihydroxydiphenylcycloalkanes of formula (Ia) are those having a 5- and 6-membered alicyclic group (m = 4 or 5 in formula (Ia)) with ring carbon atoms X, for example the diphenols of formula (Ia-1) to (Ia-3).

Chemical formula

Chemical formula

Chemical formula

[0051] A particularly preferred dihydroxydiphenylcycloalkane of formula (Ia) is 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (formula (Ia-1) (wherein R 1 and R 2 =H))

[0052] Such polycarbonates can be prepared from the dihydroxydiphenylcycloalkane of formula (Ia) according to EP-A 359 953.

[0053] Particularly preferred dihydroxyaryl compounds are resorcinol, 4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)diphenylmethane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, 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-diisopropylbenzene.

[0054] Particularly preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl and 2,2-bis(4-hydroxyphenyl)propane.

[0055] It is possible to form a homopolycarbonate using one dihydroxyaryl compound, or a copolymer using different dihydroxyaryl compounds. It is possible to form a homopolycarbonate using one dihydroxyaryl compound of formula (I) or (Ia), or to form a copolymer using two or more dihydroxyaryl compounds of formula (e)(I) and / or (Ia). Various dihydroxyaryl compounds can be interconnected randomly or in a block-like manner. In the case of a copolycarbonate composed of dihydroxyaryl compounds of formulas (I) and (Ia), the molar ratio of the dihydroxyaryl compound of formula (Ia) to other dihydroxyaryl compounds of formula (I) that can be optionally used is preferably between 99 mol% of (Ia) and 1 mol% of (I) to 2 mol% of (Ia) and 98 mol% of (I), preferably between 99 mol% of (Ia) and 1 mol% of (I) to 10 mol% of (Ia) and 90 mol% of (I), and in particular between 99 mol% of (Ia) and 1 mol% of (I) to 30 mol% of (Ia) and 70 mol% of (I).

[0056] Very particularly preferred copolymers can be prepared using the 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 2,2-bis(4-hydroxyphenyl)propanedihydroxyaryl compounds of formulas (Ia) and (I).

[0057] Suitable carbonate derivatives may be, for example, diaryl carbonates of general formula (II). [ka]

[0058] [During the ceremony, R, R', and R'' are identical or different, and independently represent hydrogen, linear or branched C1-C 34 -Alkyl, C7-C 34 -alkylaryl or C6-C 34-aryl, where R may further be -COO-R'''', where R'''' is hydrogen, linear or branched C1-C 34 -Alkyl, C7-C 34 -alkylaryl or C6-C 34 -Aryl] Preferred diaryl carbonates include, for example, diphenyl carbonate, methylphenyl carbonate and di(methylphenyl) carbonate, 4-ethylphenyl carbonate, di(4-ethylphenyl) carbonate, 4-n-propylphenyl carbonate, di(4-n-propylphenyl) carbonate, 4-isopropylphenyl carbonate, di(4-isopropylphenyl) carbonate, 4-n-butylphenyl carbonate, di(4-n-butylphenyl) carbonate, and 4-isobutylphenyl. Phenylphenyl carbonate, di(4-isobutylphenyl) carbonate, 4-tert-butylphenylphenyl carbonate, di(4-tert-butylphenyl) carbonate, 4-n-pentylphenylphenyl carbonate, di(4-n-pentylphenyl) carbonate, 4-n-hexylphenylphenyl carbonate, di(4-n-hexylphenyl) carbonate, 4-isooctylphenylphenyl carbonate, di(4-isooctylphenyl) carbonate, 4-n-nonylphenylphenyl carbonate, di(4-n-nonyl Phenyl) carbonate, 4-cyclohexylphenylphenyl carbonate, di(4-cyclohexylphenyl) carbonate, 4-(1-methyl-1-phenylethyl)phenylphenyl carbonate, di[4-(1-methyl-1-phenylethyl)phenyl] carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl) carbonate, 4-(1-naphthyl)phenylphenyl carbonate, 4-(2-naphthyl)phenylphenyl carbonate, di[4-(1-naphthyl)phenyl] carbonate, di[4-(2-naphthyl] [Tyl)phenyl]carbonate, 4-phenoxyphenylphenyl carbonate, di(4-phenoxyphenyl)carbonate, 3-pentadecylphenylphenyl carbonate, di(3-pentadecylphenyl)carbonate, 4-tritylphenylphenyl carbonate, di(4-tritylphenyl)carbonate, (methyl salicylate)phenyl carbonate, di(methyl salicylate)carbonate, (ethyl salicylate)phenyl carbonate, di(ethyl salicylate)carbonate, (n-propyl salicylate)phenylcarbonate,These are di(n-propyl salicylate)carbonate, (isopropyl salicylate)phenyl carbonate, di(isopropyl salicylate)carbonate, (n-butyl salicylate)phenyl carbonate, (n-butyl salicylate)phenyl carbonate, di(n-butyl salicylate)carbonate, (isobutyl salicylate)phenyl carbonate, di(isobutyl salicylate)carbonate, (tert-butyl salicylate)phenyl carbonate, di(tert-butyl salicylate)carbonate, di(phenyl salicylate)carbonate, and di(benzyl salicylate)carbonate.

[0059] Particularly preferred diaryl compounds are diphenyl carbonate, 4-tert-butylphenyl carbonate, di(4-tert-butylphenyl) carbonate, biphenyl-4-ylphenyl carbonate, di(biphenyl-4-yl) carbonate, 4-(1-methyl-1-phenylethyl)phenylphenyl carbonate, di[4-(1-methyl-1-phenylethyl)phenyl] carbonate, and di(methyl salicylate) carbonate. Diphenyl carbonate is especially preferred.

[0060] It is possible to use either one diaryl carbonate or different diaryl carbonates.

[0061] For control or mutation of the terminal groups, it is further possible to use one or more monohydroxyaryl compounds not used in the preparation of the diaryl carbonate to be used as chain termination agents. These may be of general formula (III). [ka]

[0062] [During the ceremony, R A C1-C is linear or branched. 34 -Alkyl, C7-C 34 -alkylaryl, C6-C34 -aryl or -COO-R D And here, R D This consists of hydrogen, linear or branched C1-C 34 -Alkyl, C7-C 34 -alkylaryl or C6-C 34 -aryl, and R B , R C These are identical or different, independently, linear or branched C1-C 34 -Alkyl, C7-C 34 -Alkylaryl, or C6-C 34 -Aryl] Examples of such monohydroxyaryl compounds include 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-isooctylphenol, 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, isopropyl salicylate, n-butyl salicylate, isobutyl salicylate, tert-butyl salicylate, phenyl salicylate, and benzyl salicylate.

[0063] 4-tert-butylphenol, 4-isooctylphenol, and 3-pentadecylphenol are preferred.

[0064] Suitable branching agents include compounds having three or more functional groups, preferably compounds having three or more hydroxyl groups.

[0065] Suitable compounds having three or more phenolic hydroxyl groups include, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hept-2-ene, 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-hydroxyphenylisopropyl)phenol, and tetra(4-hydroxyphenyl)methane.

[0066] Other suitable compounds having three or more functional groups include, for example, 2,4-dihydroxybenzoic acid, trimesic acid / trimesoyl trichloride, cyanuryl trichloride, and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

[0067] Preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tri(4-hydroxyphenyl)ethane.

[0068] In a preferred embodiment of the layered structure, layer (A), and preferably layer (B), also comprises at least one additive having an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used, or layer (A), and preferably layer (B), both are coated with at least one additive in the form of a coating composition having an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used.

[0069] Suitable additives include, in principle, all laser-sensitive additives, so-called laser marking additives, i.e., additives consisting of absorbers in the wavelength range of the radiation (C) used. The additives preferably contain at least one organic and / or inorganic IR absorber, preferably an inorganic IR absorber. The use of such additives and in molding compounds is described, for example, in WO-A 2004 / 50766 and WO-A 2004 / 50767 and is commercially available from DSM under the trade name Micabs®.

[0070] Suitable organic IR absorbers are, for example, compounds that have the highest possible absorption between 700 and 2500 nm (near-infrared = NIR). Suitable infrared absorbers include those known from literature, such as those described by substance class in M. Matsuoka, Infrared Absorbing Dyes, Plenum Press, New York, 1990. Particularly preferred are infrared absorbers from the substance class containing azo, azomethine, methine, anthraquinone, indanthron, pyrantron, flavanthron, benzantron, phthalocyanine, perylene, dioxazine, thioindigo, isoindoline, isoindolinone, quinacridone, pyrrolopyrrole or quinophthalone pigments, as well as metal complexes of azo, azomethine or methine dyes or metal salts of azo compounds. Among these, phthalocyanine and naphthalocyanine are particularly preferred. Phthalocyanine and naphthalocyanine with bulky side groups are preferred because they have improved solubility in thermoplastics.

[0071] Suitable inorganic IR absorbers include, for example, mixed oxides of metals such as phosphorus-containing tin-copper mixed oxides, such as those described in WO-A 2006 / 042714, from the group of borides and / or tungstates, and mixtures thereof, preferably at least one IR absorber from the group of borides and / or tungstates and mixtures thereof, more preferably at least one IR absorber from the group of tungstates.

[0072] Suitable inorganic IR absorbers from the group of borides include, for example, M x B y (M = La, Ce, Pr, Nd, Tb, Dy, Ho, Y, Sm, Eu, Er, Tm, Yb, Lu, Sr, Ti, Zr, Hf, V, Ta, Cr, Mo, W, and Ca; x and y are integers from 1 to 6) This includes compounds of the type, such as lanthanum hexaboride (LaB6), praseodymium boride (PrB6), neodymium boride (NdB6), cerium boride (CeB6), terbium boride (TbB6), dysprosium boride (DyB6), holmium boride (HoB6), yttrium boride (YB6), samarium boride (SmB6), europieu boride These include mer (EuB6), erbium boride (ErB6), thulium boride (TmB6), ytterbium boride (YbB6), lutetium boride (LuB6), strontium boride (SrB6), calcium boride (CaB6), titanium boride (TiB2), zirconium boride (ZrB2), hafnium boride (HfB2), vanadium boride (VB2), tantalum boride (TaB2), chromium boride (CrB and CrB2), molybdenum boride (MoB2, Mo2B5 and MoB), tungsten boride (W2B5), or combinations thereof.

[0073] Furthermore, suitable inorganic IR absorbers from the tungstate group include, for example, W y O z (W=tungsten, O=oxygen; z / y=2.20-2.99) and / or M x W y O zThere are tungsten compounds of the type (M=H, He, alkali metals, alkaline earth metals, metals from rare earth elements, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi; x / y=0.001-1.000; z / y=2.2-3.0), and preferred elements are H, Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, and Sn, among which Cs is very particularly preferred. Ba is particularly preferred. 0.33 WO3, Tl 0.33 WO3, K 0.33 WO3, Rb 0.33 WO3, Cs 0.33 WO3, Na 0.33 WO3, Na 0.75 WO3 and mixtures thereof are particularly preferred. In a particularly preferred embodiment of the present invention, Cs is used as the inorganic IR absorber. 0.33 It is very preferable to use WO3 alone. Equally preferred are Cs / W ratios of 0.20 and 0.25.

[0074] When the method of the present invention is carried out on a layered structure having a radiation transmittance of ≥10% to ≤99%, preferably ≥30% to ≤95%, and more preferably ≥40% to ≤93%, for selected radiation determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, tungstates are preferred over borides among inorganic IR absorbers because they have less inherent coloration.

[0075] Such tungstates include, for example, tungsten trioxide, tungsten dioxide, hydrated tungsten oxide, tungsten hexachloride, ammonium tungstate or tungstic acid, and further salts optionally containing element M, such as cesium carbonate, in particular, stoichiometric ratios where the molar ratios of the individual components are given by formula M x W y O zIt is prepared by mixing as given by [method]. Next, this mixture is treated in a reducing atmosphere, e.g., an argon-hydrogen atmosphere, at a temperature of 100°C to 850°C, and finally the resulting powder is heat-treated in an inert gas atmosphere at a temperature of 550°C to 1200°C. The inorganic IR absorber nanoparticles of the present invention can be produced by mixing the IR absorber with a dispersant described below and a further organic solvent, e.g., toluene, benzene, or a similar aromatic hydrocarbon, grinding in a suitable mill, e.g., a ball mill, and adding zirconium oxide (e.g., having a diameter of 0.3 mm) to produce a desired particle size distribution. The nanoparticles are obtained in the form of a dispersion. After grinding, further dispersants may optionally be added. The solvent is removed at high temperature and under reduced pressure. Nanoparticles having an average size of less than 200 nm, more preferably less than 100 nm, are preferred. The particle size can be determined using a transmission electron microscope (TEM). This type of measurement concerning IR-absorbing nanoparticles is described, for example, in Adachi et al., J.Am.Ceram.Soc., 2008, 91, 2897-2902.

[0076] The preparation of tungstates is described in detail, for example, EP-A 1 801 815, and these are commercially available, for example, under the name YMDS874 from Sumitomo Metal Mining Co., Ltd. (Japan).

[0077] For example, for use in a layered structure (A) comprising a transparent thermoplastic material having a radiotransmittance to selected radiation of ≥10% to ≤99%, preferably ≥30% to ≤95%, more preferably ≥40% to ≤93%, as determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, the particles thus obtained are dispersed in an organic matrix, for example in an acrylate, and optionally pulverized in a mill as described above, using a suitable auxiliary agent, for example zirconium dioxide, and optionally an organic solvent, for example toluene, benzene, or a similar hydrocarbon.

[0078] Suitable polymer-based dispersants are, in particular, dispersants having high permeability, such as polyacrylates, polyurethanes, polyethers, polyesters or polyester urethanes, and polymers derived therefrom.

[0079] Preferred dispersants are polyacrylate, polyether, and polyester-based polymers, with particularly preferred dispersants having high thermal stability being polyacrylates, e.g., polymethyl methacrylate, and polyesters. Mixtures of these polymers or copolymers based on acrylates can also be used. Methods for producing this type of dispersant and tungstate dispersion are described, for example, in JP 2008214596 and Adachi et al., J.Am.Ceram.Soc., 2007, 90 4059-4061. Suitable dispersants are commercially available.

[0080] Polyacrylate-based dispersants are particularly preferred. Such preferred dispersants are available, for example, from Ciba Specialty Chemicals under the trademark EFKA®, e.g., EFKA® 4500 and EFKA® 4530. Polyester-containing dispersants are similarly preferred. These are available, for example, from Avecia under the trademark Solsperse®, e.g., Solsperse® 22000, 24000SC, 26000, and 27000. Polyether-containing dispersants are also known, for example, from Kusumoto Chemicals under the trademarks Disparlon® DA234 and DA325. Polyurethane-based systems are also preferred. Polyurethane-based systems are available from Ciba Specialty Chemicals under the trademarks EFKA® 4046 and EFKA® 4047. Texaphor® P60 and P63 are corresponding trademarks from Cognis.

[0081] The additive preferably includes at least one organic and / or inorganic IR absorber.

[0082] The amount of IR absorbent in the dispersant may be 0.2% to 50.0% by weight, preferably 1.0% to 40.0% by weight, more preferably 5.0% to 35.0% by weight, and most preferably 10.0% to 30.0% by weight, relative to the dispersion of the inorganic IR absorbent used according to the present invention. The overall composition of the ready-to-use IR absorbent formulation may include not only the pure IR absorbent material and dispersant, but also further additives, such as zirconium dioxide, and residual solvents, such as toluene, benzene, or similar aromatic hydrocarbons.

[0083] There are no restrictions on the amount of inorganic IR absorbers, more preferably tungstates, in a layered polymer composition. However, inorganic IR absorbers, particularly tungstates, can typically be used in amounts of ≥0.7% to ≤4.5% by weight, preferably ≥0.6% to ≤2% by weight, and more preferably ≥0.7% to ≤1.5% by weight, calculated as the solid content of inorganic IR absorbers in the total polymer composition.

[0084] In this context, “solid component of inorganic IR absorber,” particularly tungstate, means inorganic IR absorber, particularly tungstate, as a pure substance, not as a dispersion, suspension or other preparation containing the pure substance, where the content of the IR additive, particularly the tungstate, is reported below and always relates to this solid component unless explicitly stated otherwise.

[0085] Preferably, in addition to tungstate as an IR absorbent, further IR absorbents may be optionally used, the proportion of such absorbents in the mixture is always less than the proportion of the tungstate. In the case of a mixture, the composition preferably contains 2 to 5 (including both ends), particularly preferably 2 or 3 different IR absorbents. The further IR absorbents are preferably selected from the group of borides and tin oxides, more preferably LaB6 or antimond-doped tin oxide or indium tin oxide.

[0086] Alternatively, the layer structure may be coated with additives in the form of a coating composition having an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used. These coating compositions preferably contain an IR absorber that absorbs in the wavelength range of ≥0.70 μm to ≤1000 μm, preferably ≥1.0 μm to ≤50 μm, and more preferably ≥1.0 μm to ≤2.5 μm. These coating compositions are commercially available, for example, under the Clearweld® brand name, LD920, LD930, or LD940.

[0087] At least one additive having an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used may be present in the layer structure.

[0088] The present invention further involves the following steps: i) at least i) 1. A first transparent radiation-engravable layer (A) having a first surface a1) and a second surface a2) (where these surfaces extend essentially parallel to each other), i)2. Optionally, a further transparent, radiation-engravable layer (B) having a first surface b1) facing the direction of the first layer (A) and a further surface b2) facing the opposite direction, and therefore away from the first layer (A). Starting from a preferably uncolored layered structure having; ii) At least a portion of the first surface a1) of the first transparent radiation-engravable layer (A) is brought into contact with a coloring agent, preferably a coloring bath (F) containing a coloring agent; iii) Irradiate the layered structure from ii) with focused non-ionizing electromagnetic radiation from the side away from the colored bath (F) via surface a2), or optionally via b2). The present invention provides a method for producing a colored layer structure, including [a specific element].

[0089] The layered structure preferably has two outer surfaces that come into contact with non-ionizing electromagnetic radiation in step iii). One of the outer surfaces is preferably formed by a first surface a1). Further outer surfaces are preferably formed by a second surface a2) or, if present, by further surfaces b2). The layered structure may be superimposed on one of the outer surfaces by a further layer or coating in step iv).

[0090] As already described above in relation to the layer structure of the present invention, the incidence of focused non-ionizing radiation on the first surface a1) of the first layer (A) results in a colored or black engraved area over a portion of the region. When focused non-ionizing radiation is incident on the outer surface formed by the second surface a2) of the first layer (A) or by the further surface b2) of the further layer (B), the result is a colored or black engraved image over a portion of the region in the form of an opaque structural change on the outer surface of the layer structure, i.e., surface a2) or b2).

[0091] The coloring bath (B) may include at least one colorant, preferably at least one dye, more preferably at least one dye from the group of solvent dyes and / or disperse dyes according to color index classification, or a mixture of these dyes.

[0092] The Color Index (CI) of the British Dye and Color Society and the American Textile Chemical Technology and Dyeing Technology Association clearly characterizes all colorants through group names and numbers of chemical composition / chemical structure.

[0093] Dyes from the group of solvent dyes classified by the Color Index may be, for example, what are called Macrolex® dyes from Lanxess AG, Germany. Examples include Macrolex® Blue 3R, Macrolex® Red H, Macrolex® Yellow 6G (CI Solvent Yellow 179), Macrolex® Violet Red R (CI Disperse Violet 31), Macrolex® Orange R (CI Solvent Orange 107), or mixtures of these dyes.

[0094] Dyes from the group of disperse dyes according to the Color Index classification may include, for example, diazo, diphenylamine and anthraquinone compounds, acetate dyes, disperse dyes and / or dispersol dyes, including disperse blue #3, disperse blue #14, disperse yellow #3, disperse red #134, and disperse red #7. The above classification and description of dyes is based on "Color Index," 3rd edition, jointly published by the British Dye and Color Society and the American Society of Textile Chemical Technology and Dyeing Technology (1971). Very generally, dyes can be used as a single dye component or as a component of a mixture according to the desired color. Thus, the term "dye" as used herein also includes dye mixtures.

[0095] Suitable dyes include water-insoluble diazo-diphenylamines and anthraquinone compounds. Particularly preferred are acetate dyes, dispersed acetate dyes, disperse dyes, and dispersol dyes, as disclosed in the Color Index, 3rd edition, Volume 2, British Dye and Color Society, 1971, pp. 2479 and 2187-2743.

[0096] Preferred disperse dyes include Dystar's Palanil Blue E-R150 (anthraquinone / disperse blue), DIANIX Orange E-3RN (azo dye / Cl disperse-orange 25), and the above Macrolex® dyes as solvent dyes.

[0097] The coloring bath is preferably: a) Solvent and / or dispersant, preferably water and / or an organic solvent, preferred water b) Colorants, preferably dyes, more preferably dyes from solvent dyes and / or disperse dyes according to color index classification. c) Isopropanol Includes.

[0098] Advantageous coloring baths have been found to be suitable for the simultaneous coloring of polycarbonate layer structures at temperatures >80°C. These are described, for example, in WO-A 03 / 040461, EP-A 2050866, and WO-A 03 / 083207. Under the conditions of the method of the present invention, essentially partial coloring of the layer structure occurs in the irradiated area, resulting in strong engraving being precisely visible in these areas.

[0099] Therefore, more preferably, the coloring bath includes component c) in addition to components a) and b) already described.

[0100] Components a) to c) may be present in the following amounts based on the total weight of the colored bath: a) 10% to 90% by weight, preferably 15% to 85% by weight, more preferably 35% to 50% by weight. b) 0.01% to 50% by weight, preferably 0.1% to 20% by weight, more preferably 0.2% to 15% by weight. c) 5% to 90% by weight, preferably 10% to 80% by weight, more preferably 15% to 60% by weight.

[0101] The coloring bath preferably contains dyes and / or dye mixtures selected from the group of disperse dyes according to the color index classification, and more particularly, dyes selected from the group consisting of azo, diphenylamine, and anthraquinone compounds.

[0102] The coloring bath preferably contains dyes and / or dye mixtures selected from the group of solvent dyes according to the color index classification, most preferably Makrolex® dyes and / or dye mixtures.

[0103] The solvent and / or dispersant a) used may be water and / or an organic solvent. Water is preferred.

[0104] Useful organic solvents include all standard solvents that do not attack the layer structure upon contact, particularly chemically, i.e., do not affect its optical properties in more detail. Examples include butyl alcohol, butylene glycol, diethylene glycol, ethyl alcohol, ethylene glycol, heptane, hexane, pentane, propargyl alcohol, propyl alcohol, or mixtures of the above solvents.

[0105] In the method of the present invention, it is preferable to use water and c).

[0106] In step iii), the layer structure is irradiated with focused non-ionizing electromagnetic radiation, where the wavelength range of the focused non-ionizing electromagnetic radiation is selected for the selected radiation, determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, such that the colored bath has a radiation transmittance of ≥2% to ≤99%, preferably ≥30% to ≤95%, and more preferably ≥40% to ≤93%.

[0107] Preferably, the irradiation in step iii) is carried out with laser radiation having a wavelength in the range of ≥0.1 μm to ≤1000 μm, preferably ≥1.0 μm to ≤50 μm, and more preferably ≥1.0 μm to ≤2.5 μm.

[0108] When illumination is performed by laser, this can be done in continuous wave (CW) operation, particularly for engraving pixel files or gray-shade files. For illumination of layered structures, or for vector images or halftone images, pulsed laser emission is particularly preferred. Preferably, pulse frequencies of 0.5 kHz to 1000 kHz are used; preferably, pulse frequencies of 5 kHz to 100 kHz, and particularly preferably, pulse frequencies of 15 kHz to 50 kHz are used.

[0109] In step iii), by changing the power of the laser beam used for irradiation, it is possible to influence the intensity of coloration at the laser-irradiated area according to the requirements of the desired application. The higher the laser power used, the stronger the coloration at the laser-irradiated area of ​​the layered structure.

[0110] In step iii), by changing the frequency of the laser beam used for irradiation, the tactile sculpture on the side a1) of layer (A), i.e., the side of the layer structure away from the coloring bath, can be made to match shades of gray. At low frequencies, the pulse duration is long enough to allow partial carbonization of side a1) in the case of organic materials. This causes the sculpture to appear dark. This is achieved at frequencies below 30 kHz using a laser with a nominal output of 60 watts. At frequencies above 30 kHz, the pulse duration is particularly short. Thus, structural changes in the material become visible and perceptible, but carbonization, if any, occurs only to a limited extent in the case of organic materials. Therefore, the structural changes appear as colorless or white sculptures.

[0111] In this method, it is preferable to use an NdYAG laser (neodymium-doped yttrium aluminum garnet laser). However, for layered color laser engraving, it is also possible to use a laser type suitable for engraving and welding plastic parts such as layered structures. For example, a CO2 laser can be used.

[0112] Furthermore, the color density of the coloring bath may affect the intensity of partial coloring of plastic parts, such as the layered structure of the present invention, after irradiation. Based on the total weight of the coloring bath, a concentration of colorant, preferably dye b), of 0.01% to 50% by weight, more preferably 0.1% to 30% by weight, and most preferably 0.2% to 20% by weight is preferred.

[0113] In a preferred embodiment of this method, the layer structure in step iii) is preferably irradiated onto the first layer (A) through a further layer (B).

[0114] In a preferred embodiment of this method, at least layer (A), and preferably layer (B), also comprises a thermoplastic material selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of difunctional reactive compounds, and polyaddition products of difunctional reactive compounds, or at least two combinations thereof.

[0115] To avoid repetition, the following details relating to thermoplastic materials, preferred embodiments, materials, compositions, and additives in connection with the layer structure of the present invention will be referenced below.

[0116] In a preferred embodiment of this method, layer (A), and optionally layer (B), also comprises at least one additive having an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used, or layer (A), and preferably layer (B), is coated with at least one additive in the form of a coating composition having an absorption maximum in the wavelength range of the focused non-ionizing electromagnetic radiation used. Preferred additives and their preferred amounts have already been described above.

[0117] In a preferred embodiment of this method, the additive comprises at least one organic and / or inorganic IR absorber.

[0118] In a preferred embodiment of this method, the colorant or color bath (F) comprises at least one dye or a mixture of these dyes from the group of solvent dyes and / or disperse dyes, according to the color index classification.

[0119] In a preferred embodiment of this method, the coloring bath (F) is: a) Solvent and / or dispersant, preferably water and / or organic solvent b) At least one colorant, preferably at least one dye, more preferably at least one dye from solvent dyes and / or disperse dyes according to color index classification, or a mixture of the aforementioned dyes. Includes.

[0120] Layer (A), and preferably layer (B), also preferably comprises at least one thermoplastic material and / or at least one black pigment, preferably carbon black.

[0121] The first surface a1) of the layered structure is preferably irradiated through surface a2) with focused non-ionizing electromagnetic radiation (E) in the absence of the coloring bath, prior to step ii).

[0122] The layered structure may preferably have at least one layer of thermoplastic material containing at least one additive having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used, where the at least one layer of thermoplastic material has a radiation transmittance of ≥10% to ≤99%, preferably ≥30% to ≤95%, more preferably ≥40% to ≤93%, for selected radiation determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, and is preferably an inorganic IR absorber, more preferably an inorganic IR absorber from the group of tungstates. This layer preferably forms the outer layer of the layered structure, which is also eventually color laser engraved.

[0123] The layer structure preferably comprises at least one outer layer of thermoplastic material having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used for selected radiation determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025, wherein this at least one layer of thermoplastic material has a radiation transmittance of ≥10% to ≤99%, preferably ≥30% to ≤95%, more preferably ≥40% to ≤93%, preferably an inorganic IR absorber, more preferably an inorganic IR absorber from the group of tungstates, and further comprises at least one thermoplastic material and at least one laser-sensitive additive, preferably a black pigment, more preferably carbon black.

[0124] This embodiment enables, for example, a combination of color laser engraving and black laser engraving according to the present invention. For this purpose, the layered structure, in particular layer (A), may be irradiated with (E) in the absence of the coloring bath (B), either before step i) and / or after step iii), as in step iii). The same radiation (C) can ideally be used for this further irradiation. Irradiating with (C) in the absence of the coloring bath (F) makes it possible to black engrave on the surface of the desired area, preferably on the transparent layer of the layered structure beneath it. When laser engraving is performed outside the coloring bath, the high laser reactivity of these layered structures results in blackening at the laser-irradiated area. When the layered structure is inside the coloring bath, the intensity of the laser beam is attenuated by the coloring bath so that coloring occurs only at the irradiated area and does not result in blackening of the surface of the layered structure.

[0125] To create black or white laser engravings outside a coloring bath, the procedure is preferably as follows: By changing the frequency of the laser beam used, it is possible to adjust the layered tactile engraving in gray shades. At low frequencies, the pulse duration is long enough to allow carbonization within the layers in the case of organic materials. This makes the engraving appear dark. This is achieved at frequencies below 30 kHz using a laser with a nominal output of 60 watts. At frequencies above 30 kHz, the pulse duration is particularly short. This makes structural changes in the material visible and perceptible, and if there is carbonization in the case of organic materials, it is limited. This means that the engraving has a colorless or white appearance.

[0126] The present invention further relates to security documents having a layered structure or a layered structure obtained by the method of the present invention. More specifically, security documents personalized or color-engraved by the method of the present invention, such as ID cards, passports and driver's licenses, and other personalized security documents, feature a high degree of forgery proof of the personalized or color-engraved information applied. The method of the present invention can be used to personalize blank documents in a distributed and anti-counterfeiting manner, with coloring including combination with black and white engraving. Furthermore, it is possible to produce tactile laser engraving in color, or in combination with black and white engraving, which until today was only possible in black. [Examples]

[0127] example Film 1: Makrofol (trademark) ID 6-2 00000 is made of transparent, 600 μm thick polycarbonate from Covestro Deutschland AG (corresponding to layer (C) of the layered structure of the present invention).

[0128] Film 2:A transparent polycarbonate film having an IR absorbent with a thickness of 100 μm was manufactured as follows (corresponding to layer (A) or (B) of the layer structure of the present invention): Masterbatch: Formulated with a high-concentration IR masterbatch. The masterbatch for manufacturing film 2 was produced using a conventional twin-screw compounding extruder (ZSK 32) at a processing temperature of 250°C to 330°C, which is conventional for polycarbonate.

[0129] A masterbatch having the following composition was formulated and then pelletized: • 94.69% by weight of Makrolon® 3108 polycarbonate from Covestro Deutschland AG • 0.75% by weight of YMDS 874 IR absorbent from Sumitomo • 4.5% by weight of Makrolon® 3108 powder from Covestro Deutschland AG • Lamp Black 101 (carbon black from Evonik-Degussa GmbH) with an average particle size of 95 nm at 0.006 wt% (60 ppm).

[0130] Manufacturing of extruded film 2 The equipment used for manufacturing extruded film includes the following: An extruder for extruding layers containing at least one polycarbonate, equipped with a screw with a diameter (D) of 60 mm and a length of 33 mm. The screw has a volatile matter removal zone; • Melting pump; Crosshead; • 450mm wide slot die; • A three-roller smoothing calendar with a horizontal roll arrangement, in which the third roll is capable of swiveling + / 45° relative to the horizontal; • Roll conveyor; • Thickness measurement means • Apparatus for coating both sides of a protective film; • Collection device; • Winding station.

[0131] The masterbatch pellets were transported from the dryer to the extruder's filling hopper. The material was melted and transported to the extruder's barrel / screw plasticizing system. The molten material was sent from the slot die to the smoothing calender. Final shaping and cooling of the film was performed on the smoothing calender (consisting of three rolls). The surface was embossed using a non-planarizing steel roll (side 6) and a non-planarizing silicone rubber roll (side 2). The rubber rolls used to texture the film surface are disclosed in Nauta Roll Corporation's US-4 368 240. The film was then transported through a take-up and subsequently wound up.

[0132] Lamination of films 1 and 2 is used to obtain laminate A. : Lamination was performed using a Buerckle 50 / 100 lamination press.

[0133] The following layered structure was fabricated: Film 2, 100 μm Film 1,600μm Film 2, 100 μm The layered structure described above was constructed using the following press settings: Preheat the press to 170-180°C. 15 N / cm 2 Pressurize for 8 minutes 100 N / cm 2 Pressurize for 2 minutes Cool the press to 38°C and then open the press. High-gloss laminating sheets were used for lamination; in this way, the laminate received high-gloss surfaces on both sides and thus had a glass-clear appearance.

[0134] Composition of the coloring bath 5% by weight of water 15% by weight of Macrolex® Blue 3R (dye, from Lanxess AG Deutschland) 80% by weight isopropanol Example 1: Four spacers were placed in a coloring bath (F) of the above composition. The layer structure of the present invention, in the form of laminate A having the characteristics described above, was placed on the spacers. The height of the spacers was adjusted so that laminate A was wetted by the coloring bath (F) only from below.

[0135] Laser irradiation of laminate A was performed using a Foba D84S NdYAG 1064nm laser. This was operated with a laser output of approximately 7.5 watts, a pulsed laser frequency of 30 kHz, and a current of 30 A. The travel speed was set to 60 mm / s. A colored bath (F) with a film was placed on the workpiece carrier of the Foba D84S laser system. The laser focus was aligned with the film surface of laminate A.

[0136] After irradiation, laminate A was removed from the coloring bath (F) and washed with water. When laminate A was viewed from the side facing the irradiation source, the following observations were made: against a dark background, the laser-engraved elements appeared white; it was impossible or nearly impossible to perceive blue; the laser engraving appeared white. Against a white background, it was possible to clearly perceive blue.

[0137] When laminate A was viewed from the side facing the colored bath (F), it was possible to clearly perceive the color against both a white or light-colored background and a black or dark-colored background.

[0138] This effect has already been explained in the definition of structural change.

[0139] To measure the haze of the layer structure on the surface that the laser first contacts during irradiation, in this case surface a2), turbidity was measured according to the standard ASTM D1003:2013, which corresponds to ISO 13468-1. For this purpose, a BYK-Gardner HazeGuard Plus instrument was used to determine the haze according to the standard ASTM D1003:2013. The measured haze reached a value of 87.2%, with 0% indicating zero haze, corresponding to the glass clear layer. The layer structure had 5% haze in the areas not irradiated by laser light. Using the same standard, it was found that the transmittance through laminate A before laser engraving was 81.1%, while the transmittance after introducing laser engraving to the engraving area was 38.2%.

[0140] Example 2 Example 1 was repeated with a red coloring bath and a yellow coloring bath.

[0141] The composition of the coloring bath was the same as in Example 1, except for the dye. The red dye used was Macrolex® Red H.

[0142] The yellow dye used was Macrolex® Yellow 6G.

[0143] When the laminate was observed against a dark background, the laser-engraved elements appeared white, making it impossible to perceive any color. However, when viewed against a white background, red and yellow colors were clearly perceptible.

[0144] When the laminate was viewed from the side facing the colored bath (F), it was possible to clearly perceive the color against both a white or light-colored background and a black or dark-colored background.

[0145] To measure the haze of the layer structure on the surface that the laser first contacts during irradiation, in this case surface a2), turbidity measurements were performed according to the standard ASTM D1003:2013, which corresponds to ISO 13468-1. For this purpose, a BYK-Gardner HazeGuard Plus instrument was used to determine the haze according to the standard ASTM D1003:2013. The measured haze reached a value of 87.2%, with 0% indicating zero haze, corresponding to the glass clear layer. The layer structure had 5% haze in the areas not irradiated by the laser light. [Brief explanation of the drawing]

[0146] figure The following figures illustrate, without limiting to these embodiments, how structural changes and coloring or black engraving across a portion of a region are simultaneously introduced into a layered structure by laser. The figures show: [Figure 1] Figure 1a: Schematic diagram of the layered structure of the present invention as a side view, in which both colored or black engraved and opaque structural changes are introduced by a laser as images perpendicular to each other across a portion of the region.

[0147] Figure 1b: This is a schematic diagram of the layer structure of the present invention as shown in Figure 1, but the layer structure is rotated by approximately 45° with respect to the laser.

[0148] Figure 1c: A schematic diagram of the layer structure of the present invention as shown in Figure 1, but with a laser rotated approximately 45° relative to the layer structure. [Figure 2] Figure 2: Schematic diagram of the manufacturing process.

[0149] Figure 1a shows how, on a layered structure 1 manufactured as described in Example 1 or 2, color 120 is introduced onto a first surface a1)10 and an opaque structural change 110 is introduced onto a further surface a2)20 under the conditions described above for the example. For laser irradiation of the layered structure 1 in the form of laminate A, the laser beam 100 was first directed perpendicularly onto the further surface a2)20 of the layered structure 1. When the laser beam 100 struck the further surface a2)20 of the layered structure 1, an opaque structural change 110 was generated. The laser beam 100 then traveled perpendicularly through the thickness D of the layered structure 1 to the further surface a2)20. Upon striking the first surface a1)10, the laser beam 100, having passed through the layered structure 1, first created the structural change area 110, and then created a colored or black engraving 120. This coloring was possible because the first surface 10 was in direct contact with the coloring bath 200.

[0150] Figure 1b shows the same method as shown in Figure 1a, but with the layer structure 1, particularly the further surface 20 of the layer structure 1, rotated by a few degrees with respect to the angle of incidence of the laser, so that the laser beam 100 strikes the further surface 20 of the layer structure 1 at an angle of approximately 45°. The beam path of the laser light 100 similarly passes through the thickness D of the layer structure, and the laser beam covers a somewhat larger distance than in the arrangement in Figure 1. As a result, the opaque structural changes 110 that constitute the image of the colored or black engraving 120 over a portion of the region are in an arrangement that is slightly shifted with respect to the normal passing through the layer structure 1.

[0151] Figure 1c shows the same method as shown in Figure 1a, but with the laser and therefore the laser beam 100 rotated by a few degrees relative to the further surface a2)20 of the layer structure 1, so that the laser beam 100 strikes the further surface a2)20 of the layer structure 1 at an angle of approximately 45°. The beam path of the laser beam 100 similarly passes through the thickness D of the layer structure, and the laser beam covers a somewhat larger distance than in the arrangement in Figure 1. As a result, the opaque structural changes 110 that constitute the image of the engraving 120 are positioned slightly offset with respect to the normal passing through the layer structure 1.

[0152] Figure 2 shows the steps of the method of the present invention. In step i) 300, the uncolored layer structure 1 was provided in the form of a laminate A. As described above with respect to Figure 1a, this is done on the workpiece carrier of the Foba D84S laser apparatus. In step ii) 400, the coloring bath (F) 200 was placed beneath the layer structure 1 such that only the first surface a1) 10 was in contact with the coloring bath (F) 200. In the third step iii) 500, the layer structure 1 was first irradiated with a laser beam 100 onto a further surface a2) 20 of the layer structure 1, and when the laser light 100 struck, an opaque structural change 110 was generated on the further surface a2). Subsequently, the laser light struck the first surface a1) 10, generating a colored or black engraving 120 on a portion of the area thereon. This invention encompasses the following: [Item 1] (A) The first transparent radiation-engravable layer (A) (wherein the first surface a1 that forms the first outer surface of the layered structure) has a first surface a1) and a second surface a2) that extends essentially parallel to surface a1), and the first layer (A) on the first surface a1) has colored or black engraving over a portion of the area generated by non-ionizing electromagnetic radiation (E); (B) Optionally, a further transparent, radiation-engravable layer (B) having a first surface b1) facing the direction of the first layer (A) and a further surface b2) facing away from the first layer (A) and extending essentially parallel to surface b1); (C) Optionally, at least one additional transparent polymer layer (C) (where the arrangement of layer (C) is selected from the group consisting of at least two combinations of the following: on the side of the first surface a1 of layer (A), on the side of the further surface b2 of the further layer (B), between two layers (A) and (B), or, in the case of multiple further layers (C), on the side of the further surface b2 of the further layer (B)). A layered structure having, Herein, the layered structure is characterized in that a colored or black engraved image over a portion of the region forms a further outer surface of the layered structure, and exists in the form of an opaque structural change on the surface of the layered structure opposite to the first surface a1). [Item 2] The layered structure according to item 1, wherein the surface of the layered structure, which is on the opposite side of the first surface a1) and forms a further outer surface of the layered structure, has a varied structure in a portion where it is at an angle in the range of 45° to 90° with respect to an axis extending perpendicularly through the layered structure, starting at least from the carving. [Item 3] The layer structure according to any of the preceding claims, wherein the modified structure has a cloudy or milky appearance and preferably has a turbidity in the range of 20 to 500 NTU, more preferably in the range of 50 to 450 NTU. [Item 4] The layer structure according to any of the preceding claims, wherein the layer (B) of the portion having the modified structure has a layer thickness at least 0.001 mm thicker than the portion without the modified structure. [Item 5] At least one, preferably all, of layers (A), (B), and (C) has the following characteristics: I. Layer thickness in the range of 10 μm to 10,000 μm; II. Radiation transmittance of ≥2% to ≤99.95%, preferably ≥4% to ≤90%, and more preferably ≥5% to ≤85%, for selected radiation, as determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025. A layer structure according to any of the preceding claims, having one, preferably two, more preferably three, and most preferably all of the above. [Item 6] The layer structure according to any of the preceding claims, wherein at least layer (A), and preferably layer (B), also comprises a thermoplastic material selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of difunctional reactive compounds, and polyaddition products of difunctional reactive compounds, or at least two combinations thereof. [Item 7] The layer structure according to any of the preceding claims, wherein layer (A), and preferably layer (B), also comprises at least one additive having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used, or layer (A), and preferably layer (B), both are coated with at least one additive in the form of a coating composition having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used. [Item 8] The following steps: i) at least i) 1. A first transparent radiation-engravable layer (A) having a first surface a1) and a second surface a2) (where these surfaces extend essentially parallel to each other). i)2. Optionally, a further transparent, radiation-engravable layer (B) having a first surface b1) facing the direction of the first layer (A) and a further surface b2) facing the opposite direction, and therefore away from the first layer (A). Starting from a preferably uncolored layered structure having; ii) At least a portion of the first surface a1) of the first transparent radiation-engravable layer (A) is brought into contact with a coloring agent, preferably a coloring bath (F) containing a coloring agent; iii) Irradiate the layered structure from ii) with focused non-ionizing electromagnetic radiation from the side away from the colored bath (F) via surface a2), or optionally via b2). A method for producing a colored layer structure, including the above. [Item 9] The method according to item 8, wherein the layer structure in step iii) is preferably irradiated onto the first layer (A) through a further layer (B). [Item 10] The method according to any one of items 8 and 9, wherein at least layer (A), and preferably layer (B), also comprises a thermoplastic selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of difunctional reactive compounds, and polyaddition products of difunctional reactive compounds, or at least two combinations thereof. [Item 11] The method according to any one of items 8 to 10, wherein layer (A) and optionally layer (B) also contain at least one additive having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used, or layer (A) and preferably layer (B) also are coated with at least one additive in the form of a coating composition having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used. [Item 12] The method according to item 11, wherein the additive comprises at least one organic and / or inorganic IR absorber. [Item 13] The method according to any one of items 8 to 12, wherein the colorant or color bath (F) comprises at least one dye or a mixture of these dyes from the group of solvent dyes and / or disperse dyes according to the Color Index classification. [Item 14] Coloring bath (F): a) Solvent and / or dispersant, preferably water and / or an organic solvent, b) At least one colorant, preferably at least one dye, more preferably at least one dye from solvent dyes and / or disperse dyes according to color index classification, or a mixture of the aforementioned dyes. The method described in any of items 8-13, including the method described in item 8-13. [Item 15] A security document having a layered structure as described in any of items 1-7, or obtainable by any of the methods described in items 8-14.

Claims

1. (A) A first transparent radiation-engravable layer (A) having a first surface a1) and a second surface a2) extending parallel to surface a1) (where the first layer (A) on its first surface a1) which forms the first outer surface of the layered structure has colored or black engraving over a portion of the area generated by non-ionizing electromagnetic radiation (E); (B) A further transparent, radiation-engravable layer (B) having a first surface b1) facing the direction of the first layer (A) and a further surface b2) facing away from the first layer (A) and extending essentially parallel to surface b1); (C) at least one additional transparent polymer layer (C) (where the arrangement of layer (C) is selectively selected from the group consisting of at least two combinations of the following: on the side of the first surface a1) of layer (A), on the side of the further surface b2) of the further layer (B), between two layers (A) and (B), or, in the case of multiple further layers (C), on the side of the further surface b2) of the further layer (B)). A layered structure having, Here, the colored or black engraved image across a portion of the region forms a further outer surface of the layered structure, existing in the form of an opaque structural change on the surface of the layered structure opposite to the first surface a1), Regions of the layered structure, including opaque structural changes on the surface, have turbidity or haze of ≥20% when measured according to the standard ASTM D1003:2013. The surface of the layered structure, which is opposite to the first surface a1) and forms a further outer surface of the layered structure, has an opaque structural change on its surface at least in the portion where it is at an angle in the range of 0° to 70° with respect to an axis extending perpendicularly from the sculpture through the layered structure. The aforementioned layered structure.

2. The layered structure according to claim 1, wherein the surface of the layered structure, which is on the opposite side of the first surface a1) and forms a further outer surface of the layered structure, has an opaque structural change of its surface in a portion where it is at an angle in the range of 10° to 70° with respect to an axis extending perpendicularly from the sculpture through the layered structure.

3. The layer structure according to claim 1 or 2, wherein the opaque structural change on the surface has a cloudy or milky white appearance.

4. The layer structure according to any one of claims 1 to 3, wherein the layer (B) of the portion having an opaque structural change on the surface has a layer thickness at least 0.001 mm thicker than the portion of the surface without an opaque structural change.

5. At least one of layers (A), (B), and (C) has the following characteristics: I. Layer thickness in the range of 10 μm to 10,000 μm; II. The layer structure according to any one of claims 1 to 4, having one of a range of radiation transmittances from 2% to 99.95% for selected radiation, as determined by the UV-VIS-NIR-MIR method according to DIN EN ISO / IEC 17025.

6. The layer structure according to any one of claims 1 to 5, wherein at least layer (A) comprises a thermoplastic material selected from the group consisting of polymers of ethylenically unsaturated monomers, polycondensates of difunctional reactive compounds, and polyaddition products of difunctional reactive compounds, or at least two combinations thereof.

7. The layer structure according to any one of claims 1 to 6, wherein layer (A) comprises at least one additive having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used, or layer (A) is coated with at least one additive in the form of a coating composition having an absorption maximum in the wavelength range of focused non-ionizing electromagnetic radiation used.

8. The layered structure according to any one of claims 1 to 7, wherein the opaque structural change of the surface appears as a white sculpture.

9. A security document having the layered structure described in any one of claims 1 to 8.

Images