Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/0005—Adaptation of holography to specific applications
  • G03H1/0011—Adaptation of holography to specific applications for security or authentication
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/142—Laminating of sheets, panels or inserts, e.g. stiffeners, by wrapping in at least one outer layer, or inserting into a preformed pocket
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
  • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
  • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
  • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
  • B32B37/182—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only one or more of the layers being plastic
  • B32B37/185—Laminating sheets, panels or inserts between two discrete plastic layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/04—Punching, slitting or perforating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
  • B42D25/29—Securities; Bank notes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/328—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
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
  • B42D25/378—Special inks
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
  • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
  • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
  • B42D25/30—Identification or security features, e.g. for preventing forgery
  • B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
  • B42D25/378—Special inks
  • B42D25/387—Special inks absorbing or reflecting ultraviolet light
• • 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
  • B42D25/415—Marking using chemicals
  • B42D25/42—Marking using chemicals by photographic processes
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
  • G03H1/024—Hologram nature or properties
  • G03H1/0248—Volume holograms
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
  • G03H1/0252—Laminate comprising a hologram layer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
  • G03H1/0252—Laminate comprising a hologram layer
  • G03H1/0256—Laminate comprising a hologram layer having specific functional layer
• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
  • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
  • G11B7/2403—Layers; Shape, structure or physical properties thereof
  • G11B7/24035—Recording layers
  • G11B7/24044—Recording layers for storing optical interference patterns, e.g. holograms; for storing data in three dimensions, e.g. volume storage
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B38/00—Ancillary operations in connection with laminating processes
  • B32B38/04—Punching, slitting or perforating
  • B32B2038/042—Punching
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/412—Transparent
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/416—Reflective
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2398/00—Unspecified macromolecular compounds
  • B32B2398/20—Thermoplastics
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2554/00—Paper of special types, e.g. banknotes
• • B42D2033/04—
• • B42D2033/08—
• • B42D2033/14—
• • B42D2033/22—
• • B42D2033/30—
• • 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
  • B42D25/45—Associating two or more layers
  • B42D25/455—Associating two or more layers using heat
• • 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
  • B42D25/45—Associating two or more layers
  • B42D25/46—Associating two or more layers using pressure
• • 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
  • B42D25/475—Cutting cards
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/0005—Adaptation of holography to specific applications
  • G03H1/0011—Adaptation of holography to specific applications for security or authentication
  • G03H2001/0016—Covert holograms or holobjects requiring additional knowledge to be perceived, e.g. holobject reconstructed only under IR illumination
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H1/00—Holographic processes or apparatus using light, infrared or ultraviolet waves for obtaining holograms or for obtaining an image from them; Details peculiar thereto
  • G03H1/02—Details of features involved during the holographic process; Replication of holograms without interference recording
  • G03H2001/026—Recording materials or recording processes
  • G03H2001/0264—Organic recording material
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2210/00—Object characteristics
  • G03H2210/63—Environment affecting the recording, e.g. underwater
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2250/00—Laminate comprising a hologram layer
  • G03H2250/12—Special arrangement of layers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2250/00—Laminate comprising a hologram layer
  • G03H2250/33—Absorbing layer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2250/00—Laminate comprising a hologram layer
  • G03H2250/37—Enclosing the photosensitive material
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2260/00—Recording materials or recording processes
  • G03H2260/12—Photopolymer
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03H—HOLOGRAPHIC PROCESSES OR APPARATUS
  • G03H2260/00—Recording materials or recording processes
  • G03H2260/50—Reactivity or recording processes
  • G03H2260/52—Photochromic reactivity wherein light induces a reversible transformation between two states having different absorption spectra
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
  • Y10T156/1052—Methods of surface bonding and/or assembly therefor with cutting, punching, tearing or severing
  • Y10T156/108—Flash, trim or excess removal

Definitions

• the present invention relates to a security and / or value document with a hologram in a visually switchable window as a novel security element and to a method for the production thereof.
• Plastic-based security and / or value document, in particular identification documents, e.g. ID cards are nowadays preferably produced without the use of adhesive layers as multilayers by means of lamination at high temperatures and high pressure in order to prevent a subsequent separation of the layer structures for the exchange of identification features.
• the appropriate security features are introduced, which must therefore be designed so that they withstand the lamination process parameters nondestructive.
• no weaknesses in the multi-layer composite must be introduced by the security features, which would enable a non-destructive subsequent opening of the composite again.
• Security features in security and / or value documents are usually divided into three security levels:
• Tier 1 security features are those that are purely visually perceptible without the use of additional resources.
• Level 2 security features are those that require aids (such as a magnifying glass, an optical filter, a reader, etc.) to become visible.
• Tier 3 security features are those that can only be identified in a laboratory by forensic procedures. As a rule, at least partial destruction of the document is accompanied by the analysis.
• Level 1 security features can be perceived quickly, they are disadvantageous in that sufficiently complex counterfeits can result with limited effort.
• Level 3 security features can only be counterfeited at extremely high cost, but for their identification, at least partial destruction of the secure document can not be avoided.
• holograms in security and / or value documents has for many years been a popular means of increasing the counterfeit security of these documents.
• the holograms are usually glued by means of hot stamping on the documents.
• the holgrams used are mostly embossed holograms, which are provided on the back with a heat-activated adhesive. In the hot stamping process, the adhesive is activated by the heat of the stamping die, the hologram bonds to the document and can then be released from its carrier film.
• Embossed holograms themselves are formed in a stamping step from a precision mold (Nickelshim) in a thermoplastic material. Such surface holograms typically have an embossing thickness of less than one micron. However, the nature of these holograms limits their light efficiency to about 30%, i. A maximum of 30% of the incident light is diffracted by the hologram in the direction of the viewer. For this reason, these are usually metallized subsequently or immediately imprinted in metallized films in order to increase their visual visibility.
• holograms display a "rainbow" -like polychromatic color image.
• holograms are also laminated in plastic documents, where the holograms are imprinted on the internal foils and then covered with transparent foils to ensure their visibility.
• volume holograms because their diffractive structure was inscribed in the total layer thickness (usually 10-20 ⁇ ). Volume holograms show a pronounced angle-dependent light diffraction behavior. So they are transparent at certain angles (off Brugg) and among others clearly visible (on Bragg).
• some security and / or value documents especially in card form, contain a transparent window at one point, eg the current driver's license from Sweden.
• a transparent window has the security function that in an attempt to delaminate the card or to open in any way, the film composite in the transparent window is disturbed and there is a clouding or other visible error, which is easily recognizable by the lack of clarity in the window.
• thermochromic and / or photochromic materials have been used.
• thermochromic materials in conjunction with embossed holograms for better authentication is known from the applications JP 2012008313 A and JP 2012008315 ⁇ . Nevertheless, such holograms are not suitable for use in security and / or value documents due to their low counterfeit security.
• the subject of the present invention is therefore a security and / or value document containing at least one window, the window being formed from a multi-layer composite, characterized in that the multi-layer composite comprises at least one layer (P) containing at least one photopolymer into which at least one
• Hologram (H) is introduced and at least one transparent optically switchable layer (O), which is non-transparent by heat or radiation having.
• the window in the security and / or value document according to the invention provides both a security feature of level 1, since the transparency of the window is tarnished in a counterfeiting attempt, as well as a security feature of level 2, since the use of tools for switching the optically switchable layer is required.
• the hologram (H) is a volume hologram, more preferably a retraction hologram.
• Such preferred holograms have the advantage that they are completely transparent at certain angles (off Bragg) due to their angle-dependent light diffraction behavior, so that the window appears completely transparent in itself. At other angles, such holograms are then at least so clearly visible that they can be perceived as security features of level I at least visually without aids (on Bragg).
• an optically switchable layer (O) is to be understood as meaning that the layer (O) changes in such a way when an auxiliary device is used that it can be clearly perceived by the naked eye from all angles of view.
• the layer (O) is switchable by irradiation or the action of heat between completely transparent and a clearly visible hologram with a preferably dark background, more preferably under the action of UV radiation, heat or other radiation, most preferably under the action of UV radiation or heat.
• the layer (P) and the optically switchable layer (O) are preferably positioned in the window so that they are located at the same location in the document and largely overlap in the viewing direction of a viewer, so show a combined optical function.
• the transparent optically switchable layer (O) is preferably a layer comprising at least one photochromic and / or thermochromic material, the same being composed of photochromic and / or thermochromic material.
• thermochromic materials change their light absorption properties with exposure to UV or visible light. With the change of the light absorption properties in the irradiation by infrared light (heat radiation) one speaks i.d.R. of thermochromic substances. However, thermochromic substances additionally include the systems which also change the color by heating / cooling.
• thermochromic inorganic substances are: 3d transition metal complexes, especially those based on cobalt, copper.
• II Dichlorobisethanol cobalt
• M N, N-diethylethylenediamino 3d transition metal complexes
• Silver disulfide mixed samarium lanthanum sulfides Sm (1-x) Ln (x) S, vanadium dioxide, divanadium trioxide. Furthermore, europium, terbium. Gadolinium and neodymium complexes of trifluoroaceteonates, betadic tonates and benzoylacetonates.
• thermochromic and partly also photochromic organic substances may be mentioned, which are mentioned in K. Nassau "The Physics and Chemistry of Color", John Wiley & Sons Inc., New York 1983, pp 77 et seq ..
• Examples being spiropyranes, spirooxazines, which can be switched between a colorless spiral crude cyclic form and a colored merocyanine form, for example spiro [indoline naphtopyran], spiro [indoline-napthooxazine], spiro [indolino-quinoxazine], spiro [indoline-benzopyran], spiropyrane of 2-oxaindane , of azaindanone with chromenes, of 5 ', 7' -dimethoxybenzooxazine; spiropyrane of dithiolane, perimidine-spirocyclohexadienone.
• Schiff bases of salicylaldehydes and aromatic amines, aminopyridines, aryl and alkylthienylamines can be used.
• bianthrones, bianthrylenes, and other sterically hindered ethenes e.g.
• thermochromic compositions based on pH indicators, which respond to a thermally induced pl [change, reversibly thermochromic leuco dyes in which a melting at a temperature capsule forms the color and solidifies when cooled again in such a capsule can.
• Possible leuco dyes are e.g. Spirolactones, fluorans (such as eosin), spiropyrans and fulgides.
• Weak acids include phenols (bisphenol A), parabens, 1,2,3-triazoie and 4-hydroxycoumarins. It is also possible to provide gel-like systems with pH indicators that change color when the temperature changes.
• Polyvinyl alcohol / borax / surfactant or polyalkoxide / lithium chloride / (water) systems are suitable.
• Thermochromic layer structures based on liquid crystal compositions can be applied by using pure liquid crystals, liquid crystal slurries or microencapsulated liquid crystals.
• optically switchable layer (O) contains organic thermochromic substances, compositions containing liquid crystal compositions and pH indicator compositions.
• Suitable photochromic dyes are certain spiro compounds, such as spiro [indoline-napthooxazine], such as, for example, 1,3,3-trimethylsprio [indoline-2,3- [3H] naphth [2, 1b] [1,4] oxazine (NISO), spiro [indolino-quinoxazine], spiro [indoline-naphthopyrane], spiro [indoline-benzopyran], especially 2-substituted adamantylpyrano-spiro compounds, spiro [l, 8a] dihydroindolizines (DHIs), 6-nitro- , 3 "3 " -trimethylspiro [2H-1-benzopyran-2,2 " indoline] (6-nitro-BIPS), furthermore fulgides (Aberchrome 540, Aberchrome 670, Aberchrome 850) and fulg
• the transparent optically switchable layer (O) is a layer of at least one transparent thermoplastic material containing at least one photochromic pigment or at least one photochromic dye, most preferably a photochromic pigment.
• Thermoplastic plastics selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds are suitable as transparent thermoplastics for the layer (O).
• Particularly suitable transparent thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or co-polyethacrylates such as, by way of example and preferably, polymethyl methacrylate, poly- or copolymers with styrene such as, for example, and preferably transparent polystyrene or polystyrene-acrylonitrile (SAN), transparent thermoplastic polyurethanes, and polyolefins, such as for example and preferably transparent polypropylene types, or polyolefins on the basis of cyclic olefins (for example, TOPAS ®, Hoechst), poly- or copolycondensates of terephthalic acid or Naphthalmdicarbonkla such as for example and preferably poly- or copolyethylene terephthalate (PET or CoPET) glycol-modified PET (PETG) or poly- or C-polybutylene terephthalate (PBT or
• thermoplastic polyurethanes are thermoplastic polyurethanes.
• thermoplastic polyurethanes are for example composed of linear polyols (macrodiols), such as polyester, polyether or polycarbonate diols, organic diisocyanates and optionally short-chain, usually difunctional alcohols (chain extenders). They can be produced continuously or discontinuously.
• linear polyols such as polyester, polyether or polycarbonate diols, organic diisocyanates and optionally short-chain, usually difunctional alcohols (chain extenders).
• chain extenders optionally short-chain, usually difunctional alcohols (chain extenders).
• the best known production methods are the belt process (GB-A 1 057 018) and the extruder process (DE-A 19 64 834).
• the transparent optically switchable layer (O) is particularly preferably a layer of at least one transparent thermoplastic material comprising at least one photochromic or thermochromic material or composition, very particularly preferably at least one transparent thermoplastic polyurethane containing at least one photochromic or thermochromic one Material or composition.
• thermoplastic polyurethanes for the layer K in the security and / or value document according to the invention are reaction products of a) organic diisocyanates b) polyester and / or polyether diols, preferably polyether diols and c) optionally chain extenders.
• diisocyanates a) it is possible to use aromatic, aliphatic, araliphatic, heterocyclic and cycloaliphatic diisocyanates or mixtures of these diisocyanates (compare HOUBEN-WEYL "Methods of Organic Chemistry", Volume E20 "Macromolecular Materials", Georg Thieme Verlag, Stuttgart, New York 1987, pp. 1587-1593 or Justus Liebigs Annalen der Chemie, 562, pages 75 to
• aliphatic diisocyanates such as hexamethylene diisocyanate
• cycloaliphatic diisocyanates such as isophorone diisocyanate, 1, 4-cyclohexane diisocyanate, 1-methyl 1-2,4-cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixtures
• 4,4'-dicyclohexylmethane diisocyanate 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures
• aromatic diisocyanates such as 2,4-tolylene diisocyanate, mixtures of 2, 4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-
• diisocyanates mentioned can be used individually or in the form of mixtures with one another. They may also be used together with up to 15% by weight (calculated on the total amount of diisocyanate) of a polyisocyanate, for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl-polymethylene-polyisocyanates.
• a polyisocyanate for example triphenylmethane-4,4 ', 4 "-triisocyanate or polyphenyl-polymethylene-polyisocyanates.
• thermoplastic polyurethanes are distinguished by high lightfastness. Therefore, the use of aliphatic or cycloaliphatic diisocyanates and aliphatic polydiols, more preferably polyether diols is preferred.
• Preferred organic diisocyanates a) are aliphatic or cycloaliphatic diisocyanates such as hexamethylene diisocyanate, 2,2,5-trimethylene-hexamethylene diisocyanate (TMDI) and its isomers, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate and 1-methyl-2,6-cyclohexane diisocyanate and the corresponding isomer mixtures, 4,4'-dicyclohexylmethane diisocyanate, 2,4'-dicyclohexylmethane diisocyanate and 2,2'-dicyclohexylmethane diisocyanate and the corresponding isomer mixtures.
• TMDI 2,2,5-trimethylene-hexamethylene diisocyanate
• isophorone diisocyanate 1,4-cyclohexane diisocyan
• Preferred polyether diols b) preferably have number-average molecular weights M 1 of from 500 to 10,000 g / l, more preferably from 500 to 6,000 g / mol. They can be used both individually and in the form of mixtures with one another. Number average molecular weights can be determined by Ol I number determination according to ASTM D 4274.
• Suitable polyether diols can be prepared by reacting one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical with a starter molecule which contains two active hydrogen atoms bonded.
• alkylene oxides e.g. called: ethylene oxide, 1, 2-propylene oxide, epichlorohydrin, 1, 2-butylene oxide and 2,3-butylene oxide.
• the alkylene oxides can be used individually, alternately in succession or as mixtures.
• Suitable starter molecules are, for example: water, amino alcohols, such as N-alkyl-diethanolamine, for example - methyl-diethanolamine and diols, such as ethylene glycol, diethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol and 1, 6-hexanediol.
• Suitable polyether diols are also the hydroxyl-containing polymerization of tetrahydrofuran and / or 1, 3-propylene glycol. It is also possible to use trifunctional polyethers in proportions of from 0 to 30% by weight, based on the bifunctional polyethers, but at most in such an amount that a still thermoplastically processable product is formed.
• Preferred polyether diols are Zerewitinoff-active polyether diols having on average at least 1, 8 to at most 3.0, preferably 1, 8 to 2.2, Zerewitinoff-active hydrogen atoms.
• Zerewitinoff-active hydrogen atoms are all hydrogen atoms bonded to N, O or S which, according to a process discovered by Zerewitinoff, provide methane by reaction with methyl metha h a 1 og en i d. The determination is carried out according to the Zerewitinoff reaction, wherein methylmagnesium iodide is reacted with the compound to be investigated and reacted with acidic hydrogen to form a magnesium salt and the corresponding hydrocarbon. The resulting methane is determined gas volumetric.
• Preferred chain extenders c) are Zerewitinoff-active chain extenders which have on average from 1.8 to 3.0 Zerewitinoff-active hydrogen atoms.
• amino groups “amino groups”, “thiol groups” or “carboxyl groups” is meant those having two to three, preferably two, hydroxyl groups.
• Hxdroxyl-16en having two to three, preferably two hydroxyl groups are particularly preferred as chain extenders.
• chain extenders for example, and preferably diols or diamines having a molecular weight of 60 to 500 g / mol, preferably aliphatic diols having 2 to 14 carbon atoms are used, such as 1, 2-ethanediol (ethylene glycol), 1, 2-propanediol, 1, 3rd Propanediol, 1, 4-butanediol, 2,3-butanediol, 1, 5-pentanediol, 1,6-hexanediol, diethylene glycol and dipropylene glycol.
• 1, 2-ethanediol ethylene glycol
• 1, 2-propanediol 1, 2-propanediol
• 1, 3rd Propanediol 1, 4-butanediol, 2,3-butanediol, 1, 5-pentanediol, 1,6-hexanediol
• diethylene glycol and dipropylene glycol
• terephthalic acid with diols having 2 to 4 carbon atoms for example terephthalic acid bis-ethylene glycol or terephthalic acid bis- 1, 4-butanediol, hydroxyalkylene ethers of Hydroquinone, for example, 1, 4 -Di (ß -hy dr oxy ethyl) -hy dro quinone, ethoxylated bisphenols, for example, 1,4-di (ß-hydroxyethyl) bisphenol A, (cyclo) aliphatic diamines, such as isophoronediamine, ethylenediamine , 1, 2-propylenediamine, 1, 3-propylenediamine, N-methyl-propylene-1,3-diamine, N, N'-dimethylethylenediamine and aromatic diamines, such as 2,4-toluenediamine, 2,6-toluenediamine, 3, 5-diethyl-2,4-
• Particularly preferred chain extenders are ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6,1-hexanediol. 1,4-di ( ⁇ -hydroxyethyl) hydroquinone or 1,4-di ( ⁇ -hydroxyethyl) bisphenol A. It is also possible to use mixtures of the abovementioned chain extenders. In addition, smaller amounts of triols can be added.
• Particularly preferred chain extenders c) are, for example, diols, such as ethylene glycol, 1, 4-butanediol, 1, 6-1-hexanediol or mixtures thereof.
• the relative amounts of the compounds b) and c) are preferably chosen such that the ratio of the sum of the isocyanate groups in a) to the sum of the Zerewitinoff-active hydrogen atoms in b) and c) is 0.85: 1 to 1.2: 1 is more preferably 0.9: 1 to 1.1: 1.
• the thermoplastic polyurethanes may optionally contain catalysts d).
• Suitable catalysts are the tertiary amines known and customary in the art, e.g. Triethylamine, dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo [2,2,2] octane and the like, and in particular organic metal compounds such as titanic acid esters, iron compounds or tin compounds such as tin diacetate, Tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids such as di-butyltin diacetate or dibutyltin dilaurate or the like.
• Preferred catalysts are organic metal compounds, in particular titanic acid esters, iron and tin compounds.
• the total amount of catalysts in the thermoplastic polyurethanes is generally about 0 to 5 wt .-%, preferably 0 to 2 wt .-%, based on the total weight of the TPU.
• the thermoplastic polyurethanes may optionally contain as auxiliaries and additives e) 0 up to a maximum of 20% by weight, preferably 0 to 10% by weight, based on the total weight of the TPU, of customary auxiliaries and additives.
• auxiliaries and additives are pigments, dyes, flame retardants, stabilizers against aging and weathering, plasticizers, lubricants and mold release agents, chain terminators, fungistatic and baktostatic substances and fillers and mixtures thereof.
• Suitable are, for example, monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine or cyclohexylamine, monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, the various amyl alcohols, cyclohexanol and ethylene glycol monomethyl ether.
• monoamines such as butyl and dibutylamine, octylamine, stearylamine, N-methylstearylamine, pyrrolidine, piperidine or cyclohexylamine
• monoalcohols such as butanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, the various amyl alcohols, cyclohexanol and ethylene glycol mono
• lubricants such as fatty acid esters, their metal soaps, fatty acid amides.
• Fatty acid ester amides and silicone compounds antiblocking agents, inhibitors, stabilizers against hydrolysis, light, heat and discoloration, flame retardants, dyes, pigments, inorganic and / or organic fillers, for example polycarbonates, and plasticizers and reinforcing agents.
• Reinforcing agents are in particular fibrous reinforcing materials such as e.g. inorganic fibers which are produced according to the state of the art and can also be beaten with a sizing agent. Further details of the abovementioned auxiliaries and additives can be found in the specialist literature, for example the monograph by J.H.
• TPU transparent th plastic in the layer (O)
• TPU hot melt adhesive TPU and thus both sufficient adhesion to the layer (P) and to any other outer layers can be generated in the window or in the security and / or value document according to the invention, which among other things, due to the integrated photo or thermochromic materials in this layer can not be solved without destruction again.
• Transparency in the context of this invention means a transmission for light of the wavelength of 380 nm to 800 nm of more than 70%, preferably of more than 80%, particularly preferably of more than 85%.
• the transmission can be measured with a BYK Haze-gard plus from BYK Additives & Instruments according to ASTM D 1003.
• the photopolymer in the layer (P) is preferably one prepared from a photopolymer formulation comprising an isocyanate-reactive component A), a polyisocyanate component B), a writing monomer C) and a photoinitiator D).
• the polyisocyanate component A) comprises at least one organic compound having at least two NCO groups (polyisocyanate).
• polyisocyanate it is possible to use all compounds which are well known to the person skilled in the art or mixtures thereof. These compounds may be aromatic, araliphatic, aliphatic or cycloaliphatic. In minor amounts, the polyisocyanate Component A) also monoisocyanates, ie organic compounds having an NCO group, and / or unsaturated group-containing polyisocyanates include ..
• polyisocyanates examples include butylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate and its isomers (TM DI), isophorone diisocyanate (IPDI), 1, 8-diisocyanato-4- (isocyanatomethyl) octane, the isomeric bis- (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof of any isomer content, isocyanatomethyl-l, 8-octane diisocyanate, 1,4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1, 4-phenylene diisocyanate, 2,4- and / or 2,6- Toluylene diisocyanate, 1, 5-naphthylene diisocyanate, 2,4'- and / or 4.4 " -Diphen
• Monomeric di- or triisocyanates with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione and / or iminooxadiazinedione structures can also be used.
• the polyisocyanates are particularly preferably di- or oligomerized aliphatic and / or cycloaliphatic di- or triisocyanates.
• Very particularly preferred polyisocyanates are isocyanurates, uretdiones and / or iminooxadiazinediones based on 1-IDI. TM DI. l, 8-diisocyanato-4- (isocyanatomethyl) octane or mixtures thereof.
• the polyisocyanate component A) may also comprise or consist of NCO-functional prepolymers.
• the prepolymers may comprise urethane, allophanate, biuret and / or amide groups. Such prepolymers are obtainable, for example, by reacting polyisocyanates AI) with isocyanate-reactive compounds A2).
• Suitable polyisocyanates AI are all known aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanate.
• the known higher molecular weight derivatives of monomeric di- and / or triisocyanates with urethane, urea, carbodiimide, Acylhamstoff-, isocyanurate, allophanate, biuret, Oxadiazintrion-, uretdione, Iminooxadiazindion MAY each individually or in any mixtures with each other be used.
• Suitable monomeric di- or triisocyanates which can be used as polyisocyanate al) are butylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, trimethyl hexamethylene diisocyanate (TMDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, isocyanatomethyl-1,8-octane diisocyanate (TIN), 2,4- and / or 2,6-toluene diisocyanate
• isocyanate-reactive compounds A2 it is possible with preference to use OH-functional compounds. These may in particular be polyols. With very particular preference as isocyanate-reactive compound A2), the polyols of component B) described below can be used.
• amines as isocyanate-reactive compounds A2).
• suitable amines are ethylenediamine, diethylenetriamine, triethylenetetramine, propylenediamine.
• the isocyanate-reactive compounds A2) have a number average molecular weight of
• the prepolymers of polyisocyanate component A) may in particular have a residual content of free monomeric isocyanate ⁇ 1% by weight, more preferably ⁇ 0.5% by weight and most preferably ⁇ 0.2% by weight.
• the polyisocyanate component A) may also comprise mixtures of the aforementioned polyisocyanates and prepolymers.
• the polyisocyanate component A) contains proportionally polyisocyanates which are partially reacted with isocyanate-reactive, ethylenically unsaturated compounds.
• isocyanate-reactive, ethylenically unsaturated compounds ⁇ ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleinates, fumarates, maleimides, arylamides, and vinyl ethers, propenyl ethers.
• Particularly preferred are acrylates and methacrylates having at least one isocyanate-reactive group.
• the proportion of polyisocyanates in the polyisocyanate component A), which is partially reacted with isocyanate-reactive, ethylenically unsaturated compounds, can be 0 to 99% by weight, preferably 0 to 50% by weight, particularly preferably 0 to 25% by weight. and most preferably 0 to 15 wt .-% amount.
• the polyisocyanate component A) contains polyisocyanates which are wholly or partly known from coating technology.
• blocking agents are implemented. Examples of blocking agents are alcohols, lactams, oximes, malonic esters, alkylacetoacetates, triazoles, phenols, imidazoles, pyrazoles and amines, such as butanone oxime, diisopropylamine, 1, 2,4-triazole, dimethyl-1, 2,4-triazole, imidazole, Malonic acid diethyl ester, acetoacetic ester, acetone oxime, 3,5-dimethylpyrazole, ⁇ -caprolactam, N-tert-butylbenzylamine, cyclopentanonecarboxyethylester or mixtures thereof.
• the polyisocyanate component A) comprises or consists of an aliphatic polyisocyanate or an aliphatic prepolymer and preferably an aliphatic polyisocyanate or aliphatic prepolymer with primary N ( " (-) sipping.
• the isocyanate-reactive component B) comprises at least one organic compound which has at least two isocyanate-reactive groups (isocyanate-reactive compound), in the context of the present invention hydroxy, amino or thio groups are considered as isocyanate-reactive groups. Hydroxy and amino groups are preferred as isocyanate-reactive groups, and hydroxyl groups are particularly preferably used as isocyanate-reactive groups.
• isocyanate-reactive component it is possible to use all systems which have on average at least 1.5 and preferably from 2 to 3 isocyanate-reactive groups.
• Suitable isocyanate-reactive compounds are, for example, polyester, polyether, polycarbonate, poly (meth) acrylate and / or polyurethane polyols.
• polyester polyols are, for example, linear or branched polyester polyols obtainable from aliphatic, cycloaliphatic or aromatic di- or polycarboxylic acids or their anhydrides by reaction with polyhydric alcohols having an OH functionality> 2.
• the polyester polyols can also be based on natural raw materials such as castor oil. It is also possible that the polyester polyols are based on homopolymers or copolymers of lactones. These may preferably be obtained by addition of lactones or lactone mixtures such as butyrolactone, c-caprolactone and / or methyl-e-caprolactone to hydroxy-functional compounds such as polyhydric alcohols having an OH functionality> 2, for example of the abovementioned type.
• the polyester polyols preferably have number-average molar masses of> 400 and ⁇ 4000 g / 'mol, more preferably of> 500 and ⁇ 2000 g / mol.
• the OH functionality of the polyester polyols is preferably 1.5 to 3.5, more preferably 1.8 to 3.0.
• polyesters of particularly suitable di- or polycarboxylic acids or anhydrides are succinic, glutaric, adipic, pimelic, cork, azelaic, sebacic, nonandicarboxylic, decandibric carbon, terephthalic, isophthalic, o-phthalic, tetrahydrophthalic, hexahydr ophthalic or trimellitic acid and acid anhydrides such as o-phthalic, trimellitic or succinic anhydride or mixtures thereof.
• Alcohols which are particularly suitable for the preparation of the polyesters are, for example, ethanediol, di-, tri-, tetraethylene glycol, 1,2-propanediol, di-, tri-, tetrapropylene glycol, 1,3-propanediol, butanediol-1,4-butanediol-1, 3, butanediol-2,3, pentanediol-1, 5, hexanediol-1, 6, 2,2-dimethyl-1,3-propanediol, 1, 4-dihydroxycyclohexane, 1, 4-dimethylolcyclohexane, octanediol-1, 8, decanediol-1, 10, dodecanediol-1, 12, trimethylolpropane, glycerol or mixtures thereof.
• Suitable polycarbonate polyols are obtainable in a manner known per se by reacting organic carbonates or phosgene with dioxides or diol mixtures.
• Suitable organic carbonates for this purpose are, for example, dimethyl, diethyl and diphenyl carbonate.
• Suitable polyhydric alcohols include the above-mentioned in the discussion of polyester polyols polyhydric alcohols having an OH functionality> 2.
• 1,4-butanediol, 1, 6-hexanediol and / or 3-methylpentanediol can be used.
• Polyester polyols can also be converted to polycarbonate polyols. Particular preference is given to using dimethyl carbonate or diethyl carbonate in the reaction of the stated alcohols to form polycarbonate polyols.
• the polycarbonate polyols preferably have number-average molar masses of> 400 and ⁇ 4000 g / mol, more preferably of> 500 and ⁇ 2000 g / mol.
• the OH functionality of the polycarbonate polyols is preferably 1.8 to 3.2, more preferably 1.9 to 3.0.
• Suitable polyether polyols are optionally block-formed polyaddition of cyclic ether of Ol 1- or NH-functional starter molecules.
• Suitable cyclic ethers are, for example, styrene oxides, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and any desired mixtures thereof.
• starter molecules the above-mentioned in the discussion of polyester polyols polyhydric alcohols having an OH functionality> 2 and primary or secondary amines and amino alcohols can be used.
• Preferred polyether polyols are those of the aforementioned type which are based exclusively on propylene oxide. Also preferred are polyether polyols of the abovementioned type which are random copolymers or block copolymers based on propylene oxide with further 1-alkylene oxides, where
• Alykenoxidanteil in particular not higher than 80 wt .-% is.
• Very particular preference is given to propylene lenoxid homopolymers and random copolymers or block copolymers having oxyethylene, oxypropylene and / or oxybutylene, wherein the proportion of oxypropylene units based on the total amount of all oxyethylene, oxypropylene and oxybutylene units in particular> 20 wt .-%, preferably> 45% by weight.
• Oxypropylene and oxybutylene here include all linear and branched C3 and C4 isomers.
• the polyether polyols preferably have number-average molar masses of> 250 and ⁇ 10000 g / mol, particularly preferably of> 500 and ⁇ 8500 g / mol and very particularly preferably of> 600 and ⁇ 4500 g / mol.
• Their OH functionality is preferably 1.5 to 4.0 and more preferably 1.8 to 3.1.
• R is an alkyl or an aryl radical which may also be substituted or interrupted by heteroatoms (such as ether oxygens) or is hydrogen and Y is the parent initiator ,
• the radical R may preferably be a hydrogen, methyl, butyl, hexyl, octyl or an ether group-containing alkyl radical.
• Preferred ether group-containing alkyl radicals are based on oxyalkylene units.
• N is preferably an integer from 2 to 6, more preferably 2 or 3 and most preferably equal to 2.
• i is an integer from 1 to 6, more preferably from 1 to 3, and most preferably equal to 1.
• the proportion of the segments Xi, based on the total amount of the segments Xi and Y is> 50% by weight and preferably> 66% by weight.
• the proportion of the segments Y., relative to the total amount of the segments X, and Y is ⁇ 50% by weight and preferably ⁇ 34% by weight.
• the multiblock copolymers Y (Xi-H) "preferably have number-average molecular weights of> 1200 g / mol, more preferably> 1950 g / mol, but preferably ⁇ 12000 g / mol, particularly preferably ⁇ 8000 g / mol.
• the blocks X. may be 1 lomopoly mers, which consist solely of the same oxyalkylene repeating units. They can also be constructed statistically from different oxyalkylene units or in turn block by block from different oxyalkylene units.
• the segments X. are based exclusively on propylene oxide or random or blockwise mixtures of propylene oxide with further 1-alkylene oxides, wherein the proportion of further I-alkylene oxides is preferably not> 80% by weight.
• Particularly preferred segments X. are propylene oxide homopolymers as well as random copolymers or block copolymers having oxyethylene and / or oxypropylene units.
• the proportion of oxypropylene units, based on the total amount of all oxyethylene and oxypropylene units, is very particularly preferably> 20% by weight and even more preferably> 40% by weight.
• the blocks X a can be added by ring-opening polymerization of the above-described alkylene oxides onto an n-fold hydroxy- or amino-functional starter Y (H) ".
• the starter Y (H) n may consist of di- and / or higher hydroxy-functional polymer structures based on cyclic ethers or of di- and / or higher hydroxy-functional polycarbonate, polyester, poly (meth) acrylate, epoxy resin and / or Polyurethan Designeinh eiten or corresponding I lybriden exist.
• Suitable starters Y (H) n are the abovementioned polyester, polycarbonate and polyether polyols.
• the polyester polyols preferably have number-average molar masses of from 200 to 2000 g / 'mol, more preferably from 400 to 1400 g / mol.
• the polycarbonate polyols preferably have number average molecular weights of from 400 to 2000 g / mol, particularly preferably from 500 to 1400 g / mol and very particularly preferably from 650 to 1000 g / mol.
• the polyether polyols preferably have number-average molar masses of from 200 to 2000 g / 'mol, particularly preferably from 400 to 1400 g / mol and very particularly preferably from 650 to 1000 g / mol.
• starters Y (H) are, in particular, difunctional polymers of tetrahydrofuran, in particular difunctional aliphatic polycarbonate polyols and polyester polyols, and also polymers of ⁇ -caprolactone, in particular having number-average molar masses ⁇ 3100 g / mol, preferably> 500 g / mol and ⁇ 2100 g / mol ,
• the writing monomer C) comprises at least one mono- and / or one multi-functional writing monomer, which may in particular be mono- and multi-functional acrylate writing monomer. More preferably, the writing monomer may comprise at least one monofunctional and one multi-functional urethane (meth) acrylate.
• the acrylate writing monomers may in particular be compounds of the general formula (II)
• R independently of one another are hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radicals.
• R 2 is particularly preferably hydrogen or methyl and / or R 1 is a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radical.
• unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleinates, fumarates, maleimides, acrylamides, further vinyl ether, propenyl ether, allyl ether and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such.
• Styrene, ⁇ -methylstyrene, vinyltoluene, olefins, e.g. I - octene and / or I-decene, vinyl esters, (meth) acrylonitrile, (meth) acrylamide, methacrylic acid, acrylic acid may be added.
• Acrylates or methacrylates are generally esters of acrylic acid or methacrylic acid.
• suitable acrylates and methacrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert. Butyl acrylate, tert.
• Tribromophenyl methacrylate pentachloromethyl acrylate, pentachloromethyl methacrylate, pentabromo- nylacrylate, Pentabromphenylmethacrylat, Pentabrombenzyla rylat.
• Urethane acrylates are understood as meaning compounds having at least one acrylic acid ester group which additionally have at least one urethane bond. It is known that such compounds can be obtained by reacting a hydroxy-functional acrylic ester with an isocyanate-functional compound.
• Suitable isocyanate-functional compounds are aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates. Examples of suitable di-.
• Tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDi), 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof any isomer content, isocyanatomethyl-l, 8-octane diisocyanate, 1, 4-cyclohexylene diisocyanate, the isomeric cyclohexanedimethylene diisocyanates, 1, 4-phenylene diisocyanate, 2,4- and / or 2, 6-tolylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'- or 4,4'-diphenylmethane diisocyanate
• Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates are, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly (e-caprolactone ) mono (meth) acrylates, such as Tone ® Ml 00 (Dow, Schwalbach, Germany), 2-hydroxy propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyi- ( meth) acrylate, hydroxypropyl (meth) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl ester), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols, such as trimethylolpropane, glycerol, penta- erythritol, dipent
• isocyanate-reactive oligomeric or polymeric unsaturated acrylate and / or methacrylate groups containing compounds alone or in combination with the aforementioned monomeric compounds are suitable.
• hydroxyl-containing epoxy (meth) acrylates known per se with Ol [contents of 20 to 300 mg KOI I g or hydroxyl-containing polyurethane (meth) acrylates having Ol 1 contents of 20 to 300 mg KOl I g or acrylated polyacrylates with Ol [contents of 20 to 300 mg KOI I g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyester with polyester (meth ) acrylates.
• urethane anacrylates obtainable from the reaction of tris (p-isocyanatophenyl) thiophosphate and m-methylthiophenyl isocyanate with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
• the photopolymer formulation additionally contains urethanes as additives, it being possible for the urethanes in particular to be substituted by at least one fluorine atom.
• the urethanes may preferably have the general formula (III)
• (III) have in which m> 1 and m ⁇ 8 and RR 4 , R 5 are independently hydrogen, linear, branched, cyclic or heterocyclic unsubstituted or optionally substituted with hetero atoms organic radicals, wherein preferably at least one of the radicals RR 4 , R 5 is substituted with at least one fluorine atom and more preferably R 'is an organic radical having at least one fluorine atom.
• R 4 is particularly preferably a linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by heteroatoms such as fluorine organic radical.
• the photoinitiators D) used are usually activatable by actinic radiation compounds which can initiate a polymerization of the corresponding groups.
• photoinitiators In the photoinitiators, a distinction can be made between unimolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, they are distinguished in photoinitiators for radical, anionic, cationic or mixed type of polymerization.
• Type I photoinitiators for radical photopolymerization form free radicals upon irradiation by unimolecular bond cleavage.
• type I photoinitiators are triazines. such as Tris (trichloromethyl) triazine, oximes, benzoin ethers, benzil ketals, alpha-alpha-dialkoxyacetophenone, phenylglyoxylic acid esters, bis-imidazoles, aroylphosphine oxides, e.g. 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide, sulfonium and iodonium salts.
• Tris (trichloromethyl) triazine such as Tris (trichloromethyl) triazine, oximes, benzoin ethers, benzil ketals, alpha-alpha-dialkoxyacetophenone, phenylglyoxylic acid esters, bis-imidazoles, aroylphosphine oxides, e.g. 2,4,6-trimethyl-benzoyl-diphenylphosphine oxide,
• Radical polymerization type II photoinitiators undergo a bimolecular reaction upon irradiation, the excited state photoinitiator reacting with a second molecule, the coinitiator, and the polymerization initiating radicals by electron or proton transfer or direct hydrogen abstraction forms.
• type-ii photoinitiators are quinones, such as. As camphor quinone, aromatic K et o compounds such. Benzophenones in combination with tertiary amines, alkylbenzophenones, halogenated benzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone,, methyl p- (di-1-yl-1-amino) -benzene at. Thioxanthone, ketocoumarin. alpha-aminoalkylphenol, alpha-hydroxyalkylphenone and cationic dyes, such as. As methylene blue, in combination with tertiary amines.
• photoinitiator systems described in EP 0 223 587 A consisting of a mixture of an ammonium alkylaryl borate and one or more dyes, can also be used as photoinitiator of the type II for free-radical polymerization.
• Ammoniumalkylarylborat suitable For example, tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetraethylammonium trinaphthylhexylborate, tetrabutylammonium tris (4-tert-butyl) phenylbutylborate, tetrabutylammonium tris (3-fluorophenyl) hexylborate, tetraethylammonium triphenylbenzylborate, tetra (n-hexyl ) ammonium (sec-butyl) triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate and tetrabutylammonium tris (3-chloro-4-metbylphenyl) -hexylborate (Cunningham
• the photoinitiators used for anionic polymerization are typically type I systems and are derived from transition metal complexes of the first series.
• chromium salts such as trans-Cr (NH 3) 2 (CS) 4 " (Kutal et al, Macromolecules 1991, 24, 6872) or ferrocenyl compounds (Yamaguchi et al., Macromolecules 2000, 33, 1 152) to call.
• anionic polymerization is the use of dyes, such as crystal violet leuconitrile or malachite green leuconitrile, which can polymerize cyanoacrylates by photolytic decomposition (Neckers et al., Macromolecules 2000, 33, 7761). The chromophore is incorporated into the polymers, so that the resulting polymers are colored through.
• dyes such as crystal violet leuconitrile or malachite green leuconitrile
• the photoinitiators which can be used for the cationic polymerization essentially consist of three classes: aryldiazonium salts, onium salts (in particular: iodonium, sulfonium and selenonium salts) and organometallic compounds.
• Phenyldiazonium salts upon irradiation in both the presence and absence of a hydrogen donor, can produce a cation that initiates polymerization.
• the efficiency of the overall system is determined by the nature of the counterion used for the diazonium compound.
• onium salts especially sulfonium and iodonium salts.
• the photochemistry of these compounds has been extensively studied. Initially, the iodonium salts decompose homolytically after excitation and thus generate a radical and a radical cation, which initially undergoes I [-raction into a cation which finally releases a proton and thereby initiates cationic polymerization (Dektar et al., J. Org Chem., 1990, 55, 639; J. Org. Chem., 1991, 56, 1838). This mechanism also allows the use of iodonium salts for radical photopolymerization. Here, the election of the counter-ion is again of great importance.
• iodonium and sulfonium salts are ⁇ 300 nm, these compounds should be appropriately sensitized for photopolymerization with near UV or short wavelength visible light. This is achieved by the use of longer-wavelength absorbing aromatics such. Anthracene and derivatives (Gu et al., Am. Chem. Soc., Polymer Preprints, 2000, 41 (2), 1266) or phenothiazine or its derivatives (Hua et al, Macromolecules 2001, 34, 2488-2494).
• Preferred photoinitiators are mixtures of tetrabutylammonium T etrahexylborat, tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium tris (3-fluorophenyl) hexylborate ([191726-69-9], CGI 7460, product of BASF SE, Basel, Switzerland) and tetrabutylammonium Tris (3-chloro-4-methylphenyl) hexyl borate ([1 147315-1 1-4], CGI 909, product of BASF SE, Basel, Switzerland) with cationic dyes, as used, for example, in IT. Berneth in Ullmann's Encyclopedia of Industrial Chemistry, Cationic Dyes, Wiley-VCH Verlag, 2008.
• cationic dyes are Astrazon Orange G, Basic Blue 3, Basic Orange 22, Basic Red 13, Basic Violet 7, Methylene Blue, New Methylene Blue, Azure A, Pyrillium I, Safranine O, Cyanine, Gallocyanine, Brilliant Green. Crystal violet, ethyl violet and thionin.
• the photopolymer formulation according to the invention contains a cationic dye of the formula F ' An.
• Cationic dyes of the formula F are preferably understood to mean those of the following classes: acridine dyes, xanthene dyes, thioxanthene dyes, phenazine dyes, phenoxazine dyes, phenothiazine dyes, tri (het) arylmethane dyes - in particular diamino- and triamino (het) arylmethane dyes, mono-, di- and trimethycyanine dyes, hemicyanine dyes, externally cationic merocyanine dyes, externally cationic neutrocyanine dyes, zero methine dyes - in particular naphtholactam dyes, Streptocyanine Dyes Such dyestuffs are described, for example, in 1 1.
• C 1 to C 25 alkanesulfonate preferably C 1 to C 6 alkanesulfonate, C 3 to C 6 perfluoroalkanesulfonate, C 4 to C 6 perfluoroalkanesulfonate which carries at least 3 hydrogen atoms in the alkyl chain
• C 9 to C 25 alkanoates C9 to C25 alkenoate, C5 to C25 alkyl sulphate, preferably C5 to C25 alkyl sulphate, C5 to C25 alkenyl sulphate, preferably C13 to C25 alkenyl sulphate, C3 to C18 perfluoroalkyl sulphate, C4 bis C 18-p erfluoroalkyl sulfate bearing at least 3 hydrogen atoms in the alkyl chain, polyether sulfates based on at least 4 equivalents of ethylene oxide and / or equivalents 4 propylene oxide, bis (C
• Particularly preferred anions are sec-Cn to Cis alkanesulfonate, C 13 to C 25 alkyl sulfate, branched Cs to C 25 Aikylsulfat, optionally branched bis-Ce to C25 alkyl sulfosuccinate, sec- or tert-C4 to C25 Alkylbenzenesulfonate, sulfonated or sulfated, optionally at least monounsaturated Cs to C25-fatty acid esters of aliphatic Ci- to Cs-alcohols or glycerol, bis (sulfo-C2- to Ce- alkyl) -C.3- to C12-alkanedicarboxylic acid esters, (sulfo-C2- to C6-alkyl) -C6 to C 1 g-alkanecarboxylic acid ester, triscatechol phosphate substituted by up to 12 halo radicals, cyanotripheny
• the anion An of the dye has an AClogP in the range from 1 to 30, particularly preferably in the range from 1 to 12 and particularly preferably in the range from 1 to 6.5.
• Dyes F ' An with a water absorption ⁇ 5% by weight are particularly preferred.
• the water absorption results from the formula (Fl)
• W (mi / m t -i) * 100% (Fl), where mf is the mass of the dye after water saturation and m t is the mass of the dried dye. m. is determined by drying a certain amount of dye to constant mass, for example at elevated temperature in vacuo, mf is determined by standing a certain amount of dye in the air at a defined humidity to constant weight.
• the photoinitiator comprises a combination of dyes whose absorption spectra at least partially cover the spectral range of 400 to 800 11m with at least one co-initiator adapted to the dyes.
• the layer (P) may preferably have a layer thickness of 5 ⁇ to 100 ⁇ , more preferably from 5 ⁇ to 30 ⁇ , most preferably from 10 ⁇ to 25 ⁇ .
• the window preferably contains at least one further transparent layer containing at least one thermoplastic which is located on the side of the layer (P) facing away from the layer (O).
• this layer can improve the adhesion between the layer (P) and optionally present outer cover layers and prevent separation of the security and / or value document according to the invention without destruction of the transparent window.
• the layer (P) can be applied in preferred embodiments of the invention to a substrate layer (S), which is incorporated as a just such additional transparent layer in the window of the security and / or value document according to the invention.
• the substrate layer (S) is preferably one containing at least one transparent thermoplastic, more preferably at least one transparent polycarbonate or copolycarbonate.
• the layer (P) is located between the layer (O) and a substrate layer (S), wherein the substrate layer (S) preferably contains a similar or the same thermoplastic as the transparent cover layer, which is applied to the substrate layer (S). borders.
• a similar plastic is to be understood as one which, when laminated, forms an inseparable, preferably monolithic layer composite with the other plastic.
• At least the transparent cover layer adjoining the substrate layer (S) contains, most preferably both transparent cover layers and the substrate layer
• (S) at least one poly- or co-polycarbonate.
• the window may also include further transparent layers of at least one thermoplastic.
• the window contains at least two further transparent layers comprising at least one thermoplastic material, one of which is on the side of the layer P facing away from the layer 0 and preferably a TPU film (K) and the other one is located on the side facing away from the layer P side of the layer O and also a TPU film (K).
• the function of the TPU films is to increase the adhesion between the outer layers D and the layer P or the O layer.
• the cover layers containing at least one thermoplastic material and in the other transparent layers containing at least one thermoplastic material in the multi-layer composite of the window to those containing at least one poly- or Copoiycarbonat.
• the security and / or value document according to the invention is preferably an identification document, preferably an identification card (ID card), such as e.g. an identity card, passport, driving license, bank card, credit card, insurance card, other identity card etc ..
• ID card an identification card
• an identity card e.g. an identity card, passport, driving license, bank card, credit card, insurance card, other identity card etc .
• the security and / or value document according to the invention may preferably have a total thickness of 150 ⁇ to 1500 ⁇ , more preferably from 500 ⁇ to 1000 ⁇ .
• the security and / or value document according to the invention may have, in addition to the layers mentioned above, further thermoplastic polymer layers, preferably layers containing at least one polycarbonate or copoiycarbonate.
• the security and / or value documents according to the invention can be produced in a simple manner by forming the multilayer composite by means of lamination of a corresponding layer stack.
• the present invention therefore further provides a method for producing a security and / or value document according to the invention, characterized in that a) a recess is made in a single-layer or multilayer base body for a security and / or value document the cutout has a multi-layer composite cut to correspond with the cutout, containing at least one layer (P) containing at least one photopolymer into which at least one hologram (H) has been introduced, and o at least one transparent optically switchable layer (O) which does not heat or irradiate c) the arrangement obtained according to b) is laid between at least two transparent foils containing at least one thermoplastic material which are at least the same size as the arrangement obtained according to b), d) the arrangement obtained according to c) is laminated.
• P a layer
• O transparent optically switchable layer
• the multi-layer composite introduced into the recess in b) additionally contains at least one further transparent layer (S) containing at least one thermoplastic and is produced by
• the layer (S) On a substrate film, which forms the layer (S), from a photopolymer formulation, the layer (P) is applied, preferably, the layer (S) consists of polycarbonate or the same material as the carcass body.
• Figure 1 is a schematic representation of a film coating system for producing a photopolymer film
• Figure 2 is a schematic representation of an apparatus for forming a hologram in a photopolymer film for exposure wavelengths of 633 nm (red);
• FIG. 3 shows the elliptical shape of a hologram written with the apparatus of FIG. 2;
• Figure 4 is a schematic representation of a first security document according to the invention.
• Figure 5 is a schematic representation of a second security document according to the invention.
• Figure 6 is a schematic representation of a third security document according to the invention.
• Figure 7 is a schematic representation of a fourth security document according to the invention.
• FIG. 1 shows a schematic representation of a film bonder for the production of
• Figure 2 shows an apparatus for producing a hologram in a photopolymer film for a scanning wavelength of 633 nm (red) "Preparation of reflection holograms in photopolymer" described.
• FIG. 3 shows by way of example a hologram produced with the apparatus of FIG.
• FIG. 4 schematically shows a first security document according to the invention.
• This comprises two cover layers (D), a white core layer (W), a photopolymer layer (P) and a transparent optically switchable layer (O).
• the two outer layers (D) are transparent.
• a hologram is imprinted in the photopolymer layer (P).
• the white core layer (K) is arranged, which has an oval recess.
• the photopolymer layer (P) and the optically switchable layer (O) are arranged.
• the layers are laminated together.
• FIG. 5 shows a further security document according to the invention. Deviating from the exemplary embodiment of FIG. 4, this additionally deviates from another transparent layer (K). which is arranged in the drawing below the photomolecular polymer (P) in the recess of the white core layer (K). The layer (K) effects better adhesion between the photopolymer layer (P) and the lower cover layer (D).
• K transparent layer
• FIG. 6 once again shows an embodiment of a security document according to the invention, in which a substrate layer (S) is additionally present. This is in the drawing below the Photop olymers layer (P) in the recess of the white core layer (K) arranged.
• FIG. 7 shows yet another embodiment of a security document according to the invention.
• this also comprises a further transparent layer (K), which in the drawing above the transparent optically switchable layer (O) in the recess of the white core layer is arranged.
• K transparent layer
• O transparent optically switchable layer
• Texin DP7-3007 ® is a commercial product of Bayer Material Science LLC, Deerlield. USA (transparent TPU film, 100 ⁇ thickness, containing UV photochromic pigment).
• Photopolymer layer containing a volume reflection hologram It is a transparent polycarbonate carrier film coated with a photopolymer layer prepared as described below, Gests cht chi chtdi cke of 143 ⁇ (Bayer MaterialScience AG). A volume reflection hologram is imprinted into the photopolymer layer as described below.
• the film thickness of 4 should correspond approximately to the total thickness of film 2 and 3, because from 2 and 3 pieces of film are punched, which are placed in the recess of 4.
• Makrofol ® ID 6-2 transparent polycarbonate film, one side - matt (6), one side finely matt (2 side); 300 ⁇ m thickness (Bayer MaterialScience AG).
• Photopolymer film prepared as described below to produce holographic media on a film coater.
• Feedstock for the holocaust media
• Component D Fascat 4102 0.07%, urethanization catalyst, butyltin tris (2-ethylhexanoate), product of Arkema GmbH, Dusseldorf, Germany.
• Component E CI Basic Blue 3 (resalted as bis (2-ethylhexyl) sulfosuccinate) 0.26%, safranine O (resalted as bis (2-ethylhexyl) sulfosuccinate) 0.13%, and Astrazon Orange G (resalted as Bis - (2-ethylhexyl) sulfosuccinate) 0, 13% with CGI 909 (test product of the Fa.BASF SE, Basel, Switzerland) 1, 5%, dissolved as a solution in 5.8% ethyl acetate. Percentages refer to the overall formulation of the medium.
• Component F ethyl acetate (CAS No. 141 -78-6).
• Component G Desmodur ® N 3900, a product of Bayer MaterialScience AG, Leverkusen, Germany, hexane diisocyanate-based polyisocyanate, proportion of iminooxadiazinedione at least 30%, NCO content: 23.5%.
• Carrier substrate Macro fol ® DE 1-1 CC 125 ⁇ (Bayer MaterialScience AG, Leverkusen, Germany).
• 304,3g component were B (polyol) in a stirred tank for the preparation of the photopolymer formulation with a gradually Schreibmonomermischung from 138g 138g Cl and C2, with 191g additive, 0.60 g of component D, 2,55g BYK ® offset 310 and 101g component F and mixed. Then, 66.5 g of Component E was added to the mixture in the dark and mixed to give a clear solution. If necessary, the formulation was heated at 60 ° C for a short time in order to dissolve the feeds more quickly. This mixture was introduced into one of the two reservoirs 1 of the coating system. In the second reservoir 1, the component ⁇ (polyisocyanate) was filled.
• Both components were then each conveyed through the metering devices 2 in the ratio of 942.2 to 57.8 to the vacuum degassing device 3 and degassed. From here they were then each passed through the filter 4 in the static mixer 5, in which the mixing of the components was carried out for photopolymer formulation. The resulting liquid mass was then fed to the coater 6 in the dark.
• the coating device 6 in the present case was a slot nozzle known to the person skilled in the art. Alternatively, however, a doctor blade system (Doctor Blade). be used. With the aid of the coating device 6, the photopolymer formulation was used in a processing Application temperature of 20 ° C on a carrier substrate (macro fol 1 - 1 DE 125 ⁇ ) applied and dried for 5.8 minutes at a crosslinking temperature of 80 ° C in a convection dryer 7. In this case, a medium in the form of a film was obtained, which was then provided with a 40 ⁇ m thick polyethylene foil as cover layer 9 and wound up.
• a doctor blade system doctor Blade
• the achieved layer thickness of the film was 18 ⁇ .
• a hologram was imprinted into the holgraphic medium according to II. These were monochromatic holograms with 633 nm laser wavelength. For this purpose, pieces of the film were cut off in the dark, the laminating film was removed and the photopolymer films were laminated bubble-free down to a glass of size 50 ⁇ 75 mm and thickness 1 mm. As glasses Coming glasses of the company Schott AG, Mainz, Germany were used.
• the beam of a laser (emission wavelength 633 nm) is widened to a diameter of -3 cm -3 with the aid of an optional widening lens (AF) and the collimation lens (CL) placed after the shutter S.
• the diameter of the expanded laser beam is determined by the aperture of the opened shutter. It is consciously paid attention to an inhomogeneous intensity distribution of the expanded laser beam.
• the edge intensity PR ⁇ is only half the intensity Pz in the center of the expanded laser beam. P is to be understood here as performance / area.
• the expanded laser beam first passes through an obliquely inclined glass plate, which serves as a sheathing plate (SP).
• the single mode can be achieved by adjusting the pumping current.
• the expanded beam passes through the approximately 15 ° inclined holographic medium (P), this part forms the reference beam, and then from the parallel to P object (O) to be reflected back into P. This part then forms the signal beam of the Denisyuk arrangement.
• the interference of signal and reference beam in P generates the hologram in the holographic medium.
• 0 is made of a metal plate covered with white paper, with the paper side P facing. On the paper is a square grid created by black lines. The edge length of a square is 0.5 cm.
• This raster is imaged by the holographic exposure of P in the hologram.
• the average exposure dose E ave is set by the opening time t of S. At fixed laser power, t therefore represents the quantity proportional to E ave . Since the expanded laser beam has an inhomogeneous (bell-shaped) intensity distribution, the local dose E varies to produce the hologram in P. This, together with the skew of P and O to the optical axis that the written hologram has elliptical shape, as shown in Fig. 5.
• 0 is a diffuse reflector
• the hologram is easily reconstructed by illumination with a point light source (eg flashlight or LED light).
• a point light source eg flashlight or LED light
• the hologram When viewing the finished laminate, a transparent window was visible in the area of the film piece from b), which was seamlessly connected to the rest of the laminate. Looking at the Window under normal room light, the hologram was very faintly visible. When lighting the window with a UV flashlight WF 501 B Ultrafrre the window darkens and the visibility of the hologram has been significantly improved. In the optically switched, darkened state, the hologram was seen only from the side from which it was directly facing the viewer, so when viewed through the film 1. From the other side with a direct view of the film 3, the hologram was not visible, noticeable. A few minutes after the UV irradiation, the photochromic effect lost its effect and the window was again transparent.

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