EP4219184A1 - Procédé de fabrication d'une feuille multicouche et feuille multicouche ainsi qu'élément de sécurité et document de sécurité - Google Patents

Procédé de fabrication d'une feuille multicouche et feuille multicouche ainsi qu'élément de sécurité et document de sécurité Download PDF

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Publication number
EP4219184A1
EP4219184A1 EP23168899.5A EP23168899A EP4219184A1 EP 4219184 A1 EP4219184 A1 EP 4219184A1 EP 23168899 A EP23168899 A EP 23168899A EP 4219184 A1 EP4219184 A1 EP 4219184A1
Authority
EP
European Patent Office
Prior art keywords
layer
ink
print
replication
multilayer film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP23168899.5A
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German (de)
English (en)
Inventor
Haymo Katschorek
Michael CZICHOS
Klaus PFORTE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Leonhard Kurz Stiftung and Co KG
Original Assignee
Leonhard Kurz Stiftung and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Leonhard Kurz Stiftung and Co KG filed Critical Leonhard Kurz Stiftung and Co KG
Publication of EP4219184A1 publication Critical patent/EP4219184A1/fr
Pending legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B42D25/425—Marking by deformation, e.g. embossing
    • 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
    • B42D25/40—Manufacture
    • B42D25/45—Associating two or more layers
    • B42D25/465—Associating two or more layers using chemicals or adhesives
    • B42D25/47—Associating two or more layers using chemicals or adhesives using adhesives

Definitions

  • the invention relates to a method for producing a multilayer film and a multilayer film. Furthermore, the subject matter of the invention is a security element and a security document, in particular a banknote, security document, identification document, visa document, passport or credit card, with a multilayer film.
  • the individualization of multilayer films in particular with regard to their visual appearance, is generally known.
  • Multilayer film blanks are provided for this purpose. Individualization then takes place in a step that takes place after the production of the multi-layer films. It is therefore in particular a subsequent individualization.
  • the individualizing features are applied at least to an outside of the multilayer films. In particular, the individualization takes place shortly after the application of the multilayer films to a substrate.
  • the disadvantage here is that the individualization features are located on the surface of the multi-layer films, so that they can be easily damaged, either intentionally or unintentionally.
  • the multi-layer body is made particularly counterfeit-proof in that a metal layer is applied in an early production step and is then removed again in certain areas. On the so structured metal layer can then Individualization features are applied, which are then located in the edge region of the multi-layer body and are therefore not optimally protected against manipulation or counterfeiting.
  • WO 2016/092040 A1 a multi-layer body and a method for its production are also described.
  • a visually appealing decorative layer is applied to a reflective layer, which can be partially transparent and partially opaque.
  • Individualized information can be introduced into the multi-layer body through this decorative layer, but this information is located in the edge area and can therefore be manipulated relatively easily.
  • WO 2011/006634 A2 also shows a method for producing a multi-layer body.
  • a multi-layer body is described which has a print which has interference pigments. These pigments are processed or modified in several process steps.
  • the object is achieved by a method for producing a multilayer film according to claim 1.
  • An individualized print is preferably provided.
  • the object is further achieved by a multilayer film according to claim 17.
  • a security element and a security document in particular a bank note, security document, vignette, ticket, seal, identification document, visa document, passport or credit card, with a multilayer film according to the invention are advantageous.
  • the multilayer film is thus used in a wide range of applications.
  • the method or the multilayer film is outstandingly suitable for producing a security element or a security document.
  • the multilayer film can be part of a security document, such as a bank note, an identity document or the like.
  • the pressure is not limited to any specific location within the multilayer film.
  • This arbitrary positioning of the ink or the print within the multi-layer film allows an interaction, in particular an optical interaction of the at least one print with the other layers of the multi-layer body and/or with other optical features or optical elements of the multi-layer film, in particular with optically variable elements , to be reached.
  • color overlays and/or also color interactions can be brought about or effected.
  • desired predetermined breaking points in the multi-layer body and/or locally modified diffractive structures can be realized by the pressure.
  • the print is isolated from the environment. This offers the advantage that the pressure against mechanical influences, such as against mechanical Abrasion on the surface, which can be caused deliberately as well as being protected through simple use. Furthermore, the manipulation of the print is also made more difficult, since manipulation can only take place in connection with the damage to the other layers of the multilayer film.
  • an ink is to be understood in particular as a printing ink, a varnish, an adhesive and/or an ink.
  • the ink is preferably a liquid or paste which can be printed in particular using printing methods, for example inkjet printing, gravure printing, flexographic printing, screen printing. After application, the ink can be dried and/or cured thermally, oxidatively and/or by means of radiation, in particular by means of electromagnetic radiation.
  • an ink can also be understood to mean a dry, liquid or pasty toner material which can be printed by means of xerographic printing processes.
  • Ink can also be understood to mean a dry material, in particular in the form of a transfer layer of a transfer film, for example a thermal transfer film, which can be printed in particular by means of transfer methods, for example in a thermal transfer printer.
  • the ink according to the invention is not limited to any special configuration.
  • the ink can be transparent, translucent, opaque, invisible, colored and/or colorless.
  • the printing is also basically not limited to any specific design.
  • the print can be transparent, translucent, opaque, invisible, colored and/or colorless.
  • transparent is understood to mean in particular a region with a transmissivity in the wavelength range of the light visible to the human observer of more than 50%, preferably more than 70%, particularly preferably more than 80%.
  • opaque is understood in particular to mean a region with a transmissivity in the wavelength range of light visible to the human observer of less than 40%, preferably less than 30%, particularly preferably less than 20%.
  • the print has a luminance L* of 0 to 50, preferably of 0 to 30, in the CIELAB color space.
  • the luminance L* of the layer used is determined in particular by means of the CIE-LAB Datacolor SF 600 measuring system, which is based on a spectrophotometer.
  • the value L* stands for the light/dark axis
  • the value a* for the red/green axis
  • the value b* for the Yellow/Blue Axis The L*a*b* color space is thus described as a three-dimensional coordinate system, with the L* axis describing the brightness and having a value between 0 and 100.
  • the brightness L* is preferably measured under the following conditions: measurement geometry: diffuse / 8° according to DIN 5033 and ISO 2496 Diameter measurement opening: 9mm spectral range: 360 nm to 700 nm according to DIN 6174 standard illuminant: D65
  • invisible is understood in particular to mean something that is imperceptible to the human eye.
  • Colored inks are preferably provided. In this way, color effects and/or additional color effects in the case of films that are already colored can be introduced into the multilayer film.
  • the ink can also be designed in such a way that the ink or the print provided by means of the ink essentially absorbs incident radiation and/or light absorbed.
  • the ink or the print formed from it preferably has a dark appearance.
  • the ink is preferably essentially black and/or dark-colored and/or opaque.
  • inks with metal pigments or metallic-appearing pigments such as mica, which are preferably embedded in a binder are also conceivable, with these pigments preferably reflecting incident radiation to a greater extent and thus contrasting with their surroundings.
  • luminescent inks both transparent and colored luminescent ink, fluorescent inks, both transparent and colored fluorescent ink, phosphorescent including chemiluminescent inks, both transparent and colored phosphorescent inks, and / or liquid-crystalline inks, in particular with dichroic Color effects and/or laser-sensitive inks and/or inks with taggants, whereby the addition of additional machine readability can be achieved.
  • Both light-curing, in particular UV-curing inks, and solvent and/or aqueous inks can be used.
  • the thickness of the applied or printed ink layer is preferably between 0.1 ⁇ m and 30 ⁇ m, in particular between 0.5 ⁇ m and 15 ⁇ m, particularly preferably between 0.5 ⁇ m and 15 ⁇ m and advantageously between 1 ⁇ m and 8 ⁇ m. If solvent and/or aqueous inks are used, the layer thickness is preferably about 0.5 ⁇ m. If UV-curing inks are used, then the layer thickness is approximately between 1 ⁇ m and 30 ⁇ m, preferably between 1 ⁇ m and 15 ⁇ m, particularly preferably between 1 ⁇ m and 8 ⁇ m.
  • the print is preferably formed by applying a single ink.
  • a multilayer film is thus obtained which has a print which is formed by only a single ink.
  • the print in a subsequent step the print is still processed, in particular irradiated, at least in certain areas. This changes the visual appearance of the print in these areas. It is thus possible to obtain a print which—although it only consists of a single ink—comprises at least two areas that differ in terms of their visual appearance. Thus, the print can preferably have at least one visible and at least one invisible area.
  • the print can also be formed by applying a plurality of inks, in particular inks that are designed differently from one another.
  • the multiple inks differ from one another in particular in their visual appearance and/or their composition.
  • the inks can differ from each other in their color, for example. However, it is also conceivable that at least one of the inks used is transparent and/or invisible and at least one other ink used is opaque and/or visible.
  • the inks can preferably be printed next to each other, on top of each other or even overlapping.
  • the print in an optionally subsequent step, if a corresponding ink is used, it is possible for the print to be processed and/or irradiated at least in regions, in particular in that region where the transparent ink is located.
  • the transparent or invisible ink can become visible and can preferably supplement a partial motif or the like caused by the visible or opaque ink, as a result of which an overall motif is created in particular.
  • inks are applied to provide the at least one print, then the inks next to one another, in particular directly next to one another, or at least overlapping in certain areas.
  • the inks can also be printed on top of each other.
  • the multiple inks can be applied at the same time as well as overlapping in time or one after the other.
  • the job is preferably carried out one after the other.
  • one color is printed per head.
  • the Hewlett-Packard Indigo process for example, the final transfer of all inks takes place at the same time, since the print image is first printed on a transfer blanket or is made up of individual, single-color inks there and only then from this transfer blanket to the target substrate is transferred.
  • the ink can be applied inline, i.e. as an integrated step within the production of the film. An interim rolling up and/or storage of the film preferably does not take place here. In principle, however, the ink can also be applied offline and/or at any time. The film may have been rolled up and/or stored here in the meantime.
  • the ink is preferably applied to the layer in regions, in particular as part of a motif or as a motif.
  • a motif can be, for example, a graphically designed outline, a figurative representation, an image, a visually recognizable design element, a symbol, a logo, a portrait, a pattern, an alphanumeric character, a coding, a code pattern, a cryptographic pattern, text, color scheme and the like.
  • the motif can also be individualized.
  • individualized is to be understood in particular as meaning that the print comprises information which is individually unique to each individual print, such as unique serial numbers.
  • the print includes information that is personalized and unique for the respective single print, such as a clear date of birth, a clear tax identification number, passport number, personal identification number or the like.
  • the print comprises information which is identical for a group of prints but is unique for each group of prints, for example a batch number. If print is mentioned below, this can mean an individualized print or a non-individualized print.
  • the ink it is also possible for the ink to be applied to a layer over the entire surface. If the ink is applied over the entire surface of the layer, then it is advantageous if the optical appearance of the ink or the print is changed at least in regions in a later step.
  • At least one of the following layers can be provided to produce the multilayer films: at least one carrier layer, at least one release layer, at least one protective layer, in particular a protective lacquer layer, at least one replication layer, at least one reflective layer, in particular a metallization or a metal layer or an HRI layer , and/or at least one layer of adhesive and/or at least one primer.
  • a multilayer film is thus obtained with at least one carrier layer, at least one release layer, at least one protective layer, at least one replication layer, at least one reflection layer, in particular at least one metallization of at least one metal layer and/or at least one HRI layer and/or at least one adhesive layer and/or or a primer.
  • one of the following further layers is provided: at least one release layer, at least one protective layer, in particular one Protective lacquer layer, at least one replication layer, at least one reflection layer, in particular a metallization or a metal layer or an HRI layer, and/or at least one adhesive layer and/or at least one primer.
  • additional layers may be required, such as filter layers or spacer layers.
  • the carrier layer consists in particular of a self-supporting material and/or of the class of plastics.
  • the carrier layer is preferably made from PET, from a polyolefin, in particular from OPP, BOPP, MOPP, PP and/or PE, from PMMA, from PEN, from PA, from ABS and/or a composite material of these plastics. It is also possible that the carrier layer is already pre-coated by the manufacturer and the multi-layer film is built up on this pre-coated material. It is also possible for the carrier layer to be a biodegradable and/or compostable carrier layer. EVOH is preferably used here.
  • the layer thickness of the carrier layer is advantageously between 4 ⁇ m and 500 ⁇ m, in particular between 4.7 ⁇ m and 250 ⁇ m.
  • the multi-layer film can be designed as a laminating film that has a carrier layer and a multi-layer wear layer, for example a multi-layer decorative layer, and a particularly heat-activatable adhesive layer, with the carrier layer and wear layer being arranged together in the form of an embossed layer on the substrate.
  • a carrier layer and a multi-layer wear layer for example a multi-layer decorative layer, and a particularly heat-activatable adhesive layer, with the carrier layer and wear layer being arranged together in the form of an embossed layer on the substrate.
  • the multilayer film is designed as a transfer film.
  • a transfer film comprises in particular a transfer layer, which is preferably formed from a plurality of layers, in particular comprising at least one adhesive layer, a reflection layer, a replication layer and/or a protective layer, and a carrier layer, the transfer layer being separated from the carrier layer is removable.
  • a detachment layer can be arranged between the transfer layer and the carrier layer.
  • the release layer ensures, in particular, that the layers of the multilayer film can be separated from the carrier layer in a non-destructive manner as transfer layers.
  • the release layer is preferably formed from waxes, polyethylene (PE), polypropylene (PP), cellulose derivatives and/or poly(organo)siloxanes.
  • Aforesaid waxes can be natural waxes, synthetic waxes or combinations thereof.
  • the aforementioned waxes are, for example, carnauba waxes.
  • the aforementioned cellulose derivatives are, for example, cellulose acetate (CA), cellulose nitrate (CN), cellulose acetate butyrate (CAB) or mixtures thereof.
  • the aforementioned poly(organo)siloxanes are, for example, silicone binders, polysiloxane binders or mixtures thereof.
  • the detachment layer preferably has a layer thickness between 1 nm and 500 nm, in particular a layer thickness between 5 nm and 250 nm, particularly preferably between 10 nm and 250 nm.
  • the connection between the carrier layer and subsequent layers or wear layer(s) is generally retained during application.
  • laminating films are generally not provided with a release layer or, for example, in laminating films for security applications, this is implemented in such a way that the carrier layer can preferably only separate from the wear layers after application.
  • the release layer can be produced using known printing methods. In particular, gravure printing, flexographic printing, screen printing, inkjet printing or by means of a slot nozzle is suitable. However, the release layer can also be formed by vapor deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD) and/or sputtering.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the protective layer is preferably a layer made of PMMA, PVC, melamine and/or acrylates.
  • the protective lacquer can also consist of a radiation-curing dual cure lacquer.
  • this Dual Cure paint can be thermally pre-crosslinked during and/or after application in liquid form.
  • the dual-cure coating is preferably post-crosslinked by free radicals, in particular using high-energy radiation, preferably UV radiation.
  • Dual cure coatings of this type can consist of various polymers or oligomers that have unsaturated acrylate or methacrylate groups. These functional groups can be crosslinked with one another free-radically, in particular in the second step.
  • these polymers or oligomers also have at least two or more alcohol groups.
  • These alcohol groups can be crosslinked with multifunctional isocyanates or melamine-formaldehyde resins.
  • Various UV raw materials such as epoxy acrylates, polyether acrylates, polyester acrylates and, in particular, acrylate acrylates are preferably suitable as unsaturated oligomers or polymers.
  • HDI high-ethylene diisocyanate
  • IPDI isophorone diisocyanate
  • the melamine crosslinkers can be fully etherified versions, can be imino types, or can be benzoguanamine types.
  • the protective layer preferably has a layer thickness of between 50 nm and 30 ⁇ m, preferably between 1 ⁇ m and 3 ⁇ m.
  • the protective layer can be produced using gravure printing, flexographic printing, screen printing, inkjet printing, using a slot nozzle and/or using vapor deposition, in particular using physical vapor deposition (PVD), chemical vapor deposition (CVD) and/or sputtering. The vaporization takes place in particular with thinner protective layers below 1 ⁇ m.
  • the replication layer preferably has replication structures at least in regions on one of its upper sides.
  • the replication layer is preferred molded diffractive and/or refractive micro- and/or macrostructures.
  • the replication layer is preferably formed from acrylate, cellulose, PMMA and/or crosslinked isocyanates and preferably has thermoplastic properties.
  • a surface structure is formed in replication layers, preferably by means of heat and pressure through the action of an embossing tool.
  • the replication layer is formed by a UV-crosslinkable lacquer and for the surface structure to be molded into the replication layer by means of UV replication.
  • the surface structure is shaped by the action of an embossing tool in the not yet fully cured replication layer and the replication layer is cured immediately during or after the molding by irradiation with UV light. Additional irradiation with UV light can be carried out before and/or during the impression.
  • the replication layer can be produced by means of the known printing processes.
  • gravure printing, flexographic printing, screen printing or inkjet printing is suitable.
  • production using a slot die is also possible.
  • the surface structure or replication structure formed in the replication layer is preferably a diffractive surface structure, for example a hologram, Kinegram® or some other diffraction-active grating structure.
  • a diffractive surface structure typically have a spacing of the structural elements in the range from 0.1 ⁇ m to 10 ⁇ m, preferably in the range from 0.5 ⁇ m to 4 ⁇ m.
  • the surface structure it is also possible for the surface structure to be a zero-order diffraction structure.
  • this diffractive structure has a period in at least one direction less than the wavelength of visible light, between half the wavelength of visible light and the wavelength of visible light, or less than half the wavelength of visible light. It is also possible that the surface structure is a blazed lattice acts.
  • This is particularly preferably an achromatic blazed grating.
  • Gratings of this type preferably have a period of between 1 ⁇ m and 100 ⁇ m, more preferably between 2 ⁇ m and 10 ⁇ m, in at least one direction.
  • the blaze grating it is also possible for the blaze grating to be a chromatic blaze grating.
  • the surface structure is a linear or crossed sinusoidal diffraction grating, a linear or crossed single-stage or multi-stage rectangular grating.
  • the period of these gratings is preferably in the range from 0.1 ⁇ m to 10 ⁇ m, preferably in the range from 0.5 ⁇ m to 4 ⁇ m.
  • the surface structure is an asymmetrical relief structure, for example an asymmetrical sawtooth structure.
  • the period of these gratings is preferably in the range from 0.1 ⁇ m to 10 ⁇ m, preferably in the range from 0.5 ⁇ m to 4 ⁇ m.
  • the surface structure is a light-diffracting and/or light-refracting and/or light-focusing micro- or nanostructure, a binary or continuous Fresnel lens, a binary or continuous Fresnel free-form surface; a diffractive or refractive macrostructure, in particular a lens structure or microprismatic structure, a mirror surface or matte structure, in particular anisotropic or isotropic matte structure, or a combination structure of several of the aforementioned surface structures.
  • the structure depth of the aforementioned surface structures or replication structures is preferably in the range between 10 nm and 10 ⁇ m, more preferably between 100 nm and 2 ⁇ m.
  • the replication layer preferably has a layer thickness of between 200 nm and 5 ⁇ m. If the replication layer has a diffractive surface structure, then the layer thickness is preferably between 0.3 ⁇ m and 6 ⁇ m. If the replication layer has coarser structures, in particular with a larger period and/or greater depth, for example a so-called “surface relief”, then the layer thickness is preferably about 1 ⁇ m to 10 ⁇ m. Does the Replication layer has a lens-shaped surface structure, then the layer thickness is preferably between 1.5 microns and 10 microns.
  • the replication or structuring of a surface of the replication layer can take place in different ways.
  • thermal replication takes place, in particular under the action of heat and/or pressure.
  • a print may already have been applied to the replication layer at this point.
  • the print or the ink was essentially applied to a smooth surface of the replication layer.
  • UV replication takes place. If the print is made with a UV-curable ink, the UV print can advantageously be protected with the UV-curable replication varnish. In particular, there are reactive groups on the surface of the UV-curable ink, which “crosslink” to the UV-curable replication varnish.
  • the through-curing of the UV-curable ink can also be improved by pouring over and/or encapsulating with the UV-curable replication varnish, because crosslinking, in particular of thin UV-curable layers, can prevent disruptive inhibition effects, for example from atmospheric oxygen.
  • crosslinking in particular of thin UV-curable layers, can prevent disruptive inhibition effects, for example from atmospheric oxygen.
  • this can be particularly advantageous for UV-curable inks applied thinner than approx. 1.5 ⁇ m, since with decreasing layer thickness of the UV-curable ink, inhibition effects have a greater effect or can even prevent surface and layer crosslinking to such an extent that the print or the ink can remain sticky and e.g. a printed multi-layer film cannot be wound up as a roll.
  • the UV drying process used in UV replication also represents an additional and effective post-curing for the UV print due to the minimization of the inhibition.
  • the UV UV replication curing system can also be used without the need for an additional UV curing system for curing the print itself.
  • UV inks can be applied much thinner than would be possible without costly measures due to curing.
  • the "curing" of the UV-curing ink or the UV-curing print on the surrounding matrix of the UV replication varnish results in the print being inextricably linked to the polymer environment on the material side.
  • the print then advantageously no longer represents a discrete layer on its own. This makes manipulation even more difficult.
  • the UV-curable ink experiences the possibility of post-crosslinking as a result of the UV curing of the UV-curing replication varnish, which can lead to higher resistances of the UV-curing ink.
  • UV replication on a print, particularly regardless of the material composition of the print, is that mechanical and/or thermal loads on the print, in particular from contact pressures or, above all, from temperatures, such as occur during thermal replication, are significantly reduced become.
  • the structure-accepting replication layer is applied in particular in liquid form. Printing can have been carried out before the liquid replication layer is applied or can already be present on the previously applied layer of the multi-layer body to which the liquid replication lacquer is then applied.
  • the ink or the print can also be applied only after the structuring and possibly after the replication layer has been cured.
  • the print When the print is provided before the replication, the print is basically located spatially in front of the layer with the replication structure, viewed from the carrier side. In the case of a print after replication, the print is basically located spatially behind the layer with a replication structure, viewed from the carrier side. Both arrangements allow different optical effects. For example, a diffractive structure can be superimposed on the print when viewed from the carrier side in the case of a print after the structure-imparting replication step. This is not possible when viewed from the carrier side if the printing is already carried out before the structuring replication step.
  • the multilayer film is viewed both from the backing layer side and from the side facing away from the backing side, in particular in a window or a transparent substrate area, allows the targeted positioning of the print or prints in front of or viewed from the backing layer side behind a replication layer different visual effects on the viewing side.
  • the positions of the replicated structures relative to the print can in particular also be executed in register with one another.
  • the reflection layer can be opaque, semi-transparent or transparent, with the transparency being able to depend in particular on the viewing angle.
  • the reflective layer can be applied both over the entire surface and in certain areas.
  • the reflection layer is preferably designed in the form of a pattern, in particular for the formation of motifs.
  • the reflection layer can represent a pattern and/or a motif, which in particular can also be arranged in register with the print and/or with the structures of the replication layer.
  • the reflection layer is preferably a metal layer or a metallization.
  • the metal layer or metallization is preferably made of aluminum, chromium, gold, copper, tin, silver or an alloy of such metals.
  • the metal layer or the metallization is preferably produced by means of vapor deposition, in particular by means of vacuum vapor deposition.
  • the vapour-deposited metal layer or metallization can take place over the entire surface and optionally be retained over the entire surface, or it can be structured using known demetallization processes such as etching, lift-off or photolithography and are therefore only partially present.
  • the layer thickness is in particular between 10 nm and 500 nm.
  • the metal layer or the metallization can also consist of a printed layer, in particular a printed layer of metal pigments in a binder. These printed metal pigments can be applied over the entire surface or partially and/or have different colorings in different surface areas.
  • the layer thickness is in particular between 1 ⁇ m and 3 ⁇ m.
  • the reflective layer from a paint with electrically conductive, metallic pigments, in particular to print and/or cast on.
  • the reflection layer is formed by a transparent reflection layer, for example a thin or finely structured metallic layer or an HRI or LRI layer (high refraction index - HRI, low refraction index - LRI).
  • a dielectric reflection layer consists, for example, of a vapor-deposited layer of a metal oxide, metal sulfide, titanium oxide, etc.
  • the layer thickness of such a layer is preferably 10 nm to 500 nm.
  • a first reflection layer in a semi-transparent design as an optical filter layer.
  • a dielectric reflection layer consists, for example, of a vapor-deposited layer of thin metal (Al, Cr) or a thinly applied metal oxide, metal sulfide, silicon oxide, etc.
  • the subsequent dielectric spacer layer required for the thin-film effect can be coated analogously to the replication layer, with the layer thickness preferably being between 0.1 ⁇ m and 1.0 ⁇ m and/or the composition corresponding in particular to the replication layer.
  • the spacer layer can also serve directly as a replication layer.
  • the spacer layer can also be vapour-deposited as a ceramic spacer layer.
  • metal or semi-metal oxides such as SiO 2 , TiO 2 Na3AlF6 or MgF 2 are then vapour-deposited using one of the methods also mentioned for the reflection layer.
  • the layer thicknesses here are in particular between 20 nm and 500 nm.
  • This optical filter layer can also be applied before the replication layer.
  • the replication layer then serves in particular as a dielectric spacer layer, with the layer thickness range preferably being between 0.1 ⁇ m and 1.0 ⁇ m.
  • an opaque or semi-transparent reflection layer is then vapor-deposited, in particular as described above.
  • the adhesive layer or the primer is preferably made of PMMA, PVC, acrylates, polyamide, polyvinyl acetates, hydrocarbon resins, polyesters, polyurethanes, chlorinated polyolefins, polypropylenes, epoxy resins and/or polyurethane polyols, in particular in combination with deactivated isocyanates.
  • the adhesive layer or the primer can also contain fillers such as SiO 2 and/or TiO 2 .
  • the layer thickness of the adhesive layer or the primer is preferably between 0.5 ⁇ m and 20 ⁇ m, particularly preferably between 1.5 ⁇ m and 5 ⁇ m.
  • the layer of adhesive or the primer can be produced by means of gravure printing, flexographic printing, screen printing, inkjet printing and/or by means of a slot nozzle.
  • the ink can be applied at least in regions to each layer of the multilayer film, in particular to the carrier layer, the release layer, the replication layer, the protective layer, the reflection layer and/or the adhesive layer and/or the primer.
  • the ink or the print is used in particular as a marking and/or as a register mark and/or for coloring. If the ink exhibits poor adhesion to the adjacent layers, particularly after curing and/or after drying, the ink or the print provided with it can serve in particular as a predetermined breaking point within the multilayer film and/or cause partial release effects.
  • the layer to which the ink is applied is preferably modified beforehand, if necessary, in such a way that sufficient adhesion or non-adhesion of the ink to this layer can be ensured.
  • This can be done, for example, by using appropriate surface additives in the paint formulation or appropriate design of the layer can be ensured, for example with crosslinkable UV-active groups on the surface. This is particularly advantageous when using a UV-curable ink.
  • the ink is applied to a number of layers of the multi-layer film.
  • the inks applied to the layers can be both identical and different.
  • the ink is applied in register with one another.
  • the printing is provided on multiple layers.
  • the prints can be arranged in register with one another. If prints are provided on several layers of the multilayer film, the individual prints can be designed differently from one another. This is to be understood in particular to the effect that the prints differ from one another in terms of their visual appearance.
  • the prints can, for example, be formed by different inks and/or be formed as different motifs.
  • the prints can be offset from one another or arranged in an overlapping manner. However, the prints can also be arranged next to one another when the multilayer film is viewed from above.
  • the prints are advantageously arranged or formed on the layers in such a way that when the multilayer film is viewed from above, at least some of the prints or parts of some of the prints form an overall motif.
  • One or more of these prints can be individualized or non-individualized. For example, one or more non-individualized prints can complement one or more individualized prints to form an overall motif. This can be understood to mean that one print depicts a human head, for example, and another print depicts a human body. If you look at the multi-layer film from above, the head and the body come together to form a human being.
  • Register or register or register accuracy or register accuracy is to be understood as meaning a positional accuracy of two or more elements and/or layers relative to one another.
  • the register accuracy should move within a specified tolerance and be as low as possible.
  • the register accuracy of several elements and/or layers to one another is an important feature in order to increase process reliability.
  • the positionally accurate positioning can take place in particular by means of sensory, preferably optically detectable fiducial marks or register marks. These registration marks or register marks can either represent special separate elements or areas or layers or themselves be part of the elements or areas or layers to be positioned.
  • the ink is preferably applied to a carrier layer at least in regions.
  • a multilayer film is thus obtained in which at least one print is arranged at least in regions on the carrier layer.
  • the ink applied to the carrier layer is preferably applied so thickly that the ink or the print has tactile and/or tactile properties.
  • the layer thickness range is in particular between 5 ⁇ m and 30 ⁇ m.
  • a haptic surface can be created in particular, which can also be individualized.
  • the ink printed on or the print provided has in particular a surface structure.
  • the ink is applied or the print is provided in such a way that it imparts a certain structure or structuring to a layer that may be applied subsequently, in particular a protective layer.
  • the ink can also be applied to the carrier layer in such a way that after the multilayer film has been applied to a substrate and the carrier layer has subsequently been peeled off, the ink or the print remains at least partially, preferably completely, on the carrier layer.
  • the carrier layer e.g. B.
  • the ink or the print remains at least partially, preferably completely, on the carrier layer.
  • This can be done, for example, by means of serial numbers, batch numbers or control numbers, which are designed as numbers and/or encrypted codes, for example as barcodes.
  • the ink is preferably applied at least in regions to a release layer.
  • a multilayer film is thus obtained in which at least one print is arranged at least in regions on the release layer.
  • the ink is applied to a protective layer at least in some areas.
  • the ink is preferably applied in regions to a protective layer formed over the entire area.
  • a multilayer film is thus obtained in which at least one print is arranged at least in regions on the protective layer.
  • at least one print is arranged below the protective layer in the viewing direction and is therefore protected by the protective layer.
  • the ink can be applied at least in regions to a reflection layer, in particular to a metal layer and/or metallization and/or HRI layer.
  • a multilayer film is thus obtained in which at least one print is arranged at least in regions on the reflection layer.
  • the ink or the print can be used in particular as an etching resist for demetallization. If the ink contains alkali, for example, direct etching can also be caused by the application. If the ink or the print thus provided is in the form of an etching resist, then demetallization can take place in a subsequent step. The metal layer is preferably removed in those areas which are not covered by the print. Is the pressure individualized, an individualized demetallization can also be generated.
  • the ink is preferably applied at least in regions to an adhesive layer and/or to a primer.
  • a multi-layer film is thus obtained in which at least one print is arranged at least in regions on the adhesive layer and/or on the primer.
  • the ink is preferably designed here in such a way that the ink or the print itself can serve as a partial adhesive layer.
  • a desired area can be designed in color by means of printing, for example.
  • individualized information can be incorporated into the adhesive layer, for example.
  • the ink it is also possible for the ink to be applied at least partially to the adhesive layer for passivation, in particular for partial passivation of the adhesive layer.
  • the multilayer film is then only transferred to a substrate in the areas of the adhesive layer that are not printed with ink. In particular, an individualized bond is thus obtained.
  • there is no need for special molds for personalized hot stamping but this is achieved via inkjet printing that passivates the non-embossing areas.
  • the ink is applied at least in regions to a replication layer.
  • a multilayer film is thus obtained in which at least one print is arranged at least in regions on the replication layer.
  • the ink can be applied to a replication layer that has not yet been replicated.
  • the replication layer or the replication varnish has in particular still smooth surfaces.
  • the replication then takes place in particular after the print has been made available. Structures can then be introduced into the print and/or into the replication layer as a result of the replication.
  • non-individualized information in the replication layer can be combined with an individualized print.
  • a replication in the print can represent an additional protective measure against counterfeiting, because the print is thus even more integrated into the overall system of the multi-layer film.
  • the ink is applied to a substantially smooth surface of the replication layer, with the surface then preferably being replicated at least in regions at a later point in time.
  • the ink is applied to a replication layer that has already been replicated, ie also to a replication layer that is already provided with a surface structure, a replication structure.
  • the ink is preferably applied at least in regions to the structured surface or to the replication structure.
  • non-individualized information in the replication layer can be combined with an individualized print.
  • the application is preferably carried out in the register with the replication structure.
  • at least partial areas of the structures, in particular the diffractive structures can be filled up and in particular optically extinguished as a result.
  • the ink has a refractive index that is similar to the replication layer, in particular with a refractive index with a difference of less than 0.2.
  • the ink is applied with a layer thickness that is greater than the depth of the structures.
  • the ink can also be applied in such a way that the ink only partially fills the replication structures, in particular diffractive structures on the surface of the replication layer. Partial filling of the structures occurs in particular when the ink layer thickness ultimately applied is less than the depth of the replication structures. Under certain conditions, the ink can also fill in the structures without optically erasing them. This is particularly the case when the ink has reflective or high-refractive index properties and differs in its complex refractive index by more than 0.2 from the complex refractive index of the replication layer.
  • An example of reflective inks are inks with metal effect pigments or metal flakes.
  • Inks based on liquid crystals are an example of inks with a high refractive index.
  • macroscopic structures i.e. in particular structures in a replication layer that are no longer diffractive, are also suitable for partial filling.
  • An ink is preferably applied to the replication layer with a layer thickness that is greater than the depth of the structures to be introduced into the replication layer.
  • the layer thickness of the applied ink is essentially twice as thick as the layer thickness of the structures to be introduced into the replication layer.
  • a layer thickness of the ink that is at least twice as great as the depth of the structures to be introduced into the replication layer is particularly advantageous if a replication is carried out only after the ink has been applied. This prevents the introduced structures from completely penetrating the applied ink during replication.
  • the ink is preferably printed with a layer thickness smaller than the depth of the structures to be introduced into the replication layer.
  • the ink can be penetrated through the entire layer of the print with the introduced structures during replication, whereby the print has a high-resolution fine structuring that is also visible from the carrier side due to the continuous structures that exceeds the print resolution of inkjet printers and thus represents another security feature.
  • At least one ink is applied to a replication layer that has not yet been replicated and at least one ink to a replicated replication layer. At least one print is provided on a replication layer that has not yet been replicated and at least one print on a replication layer that has already been replicated. Both the same and different inks can be used here. For example, one ink can provide a background color for the other ink, in particular in a different color.
  • the replication layer is replicated together with the print applied to it.
  • the print and the replication layer are each given a replication structure, at least in regions.
  • the replication structure in the print is then optically visible in applications in a transparent area or in a window of a substrate or a document when viewed from the back and represents a further security feature of the different thickness contrasts represent a visually recognizable security feature, which initially seems hidden to the viewer and only becomes visible when viewed in transmitted light, in particular similar to a watermark.
  • the replication preferably takes place in the register for printing.
  • the ink prefferably to be applied in such a way that, during a subsequent replication, the replication structure introduced is pressed into the print, but not into the area of the replication layer covered by the print.
  • the print preferably has a thickness that is greater than the depth of the replication structure introduced into the print.
  • the print has a layer thickness of between 0.5 ⁇ m and 10 ⁇ m.
  • the replication structure is introduced in such a way that a region of the replication layer which is arranged adjacent to the print when the multilayer film is viewed from above is not replicated, in particular is not replicated by the elevation of the print.
  • This area is hereinafter referred to as the courtyard.
  • the court prefers not to come into contact with a replication tool.
  • the halo directly adjoins the print in particular.
  • the area of the replication layer that is not replicated depends on the thickness of the ink application.
  • the halo essentially has a width of between 1 ⁇ m and 100 ⁇ m.
  • the pressure is preferably pressed into the replication layer.
  • the replication layer is generally easier to deform than the ink print. This applies in particular to highly pigmented inks and crosslinked UV inks. This is essentially to be understood to mean that in particular those areas of the replication layer on which the print is arranged or is located lose layer thickness.
  • the thickness of the replication layer in the area of the print preferably decreases uniformly or uniformly over the entire area. In the areas of the replication layer which are arranged adjacent to the print when the multilayer film is viewed from above, i.e. adjoin the print, the layer thickness of the replication layer decreases, particularly during replication, the less, the further one moves away from the print.
  • the print is compressed and/or deformed during replication. This makes it possible, in particular, for the print and the replication layer to be replicated together at least in regions.
  • an adhesion promoter layer is applied to a layer of the multilayer film and/or below and/or on the ink or on the print, at least in some areas.
  • the adhesion promoter layer is preferably only applied in those areas to which the ink will later also be applied.
  • the adhesion promoter layer ensures, in particular, that there is good adhesion between the layers connected to it, so that delamination can be largely prevented.
  • the adhesion promoter layer prevents an undesired predetermined breaking point from forming when the print has hardened.
  • adhesion promoter layers are PVC, mixtures of thermally and UV-curing acrylates, adhesion promoter layers with adhesion-improving surface additives, such as functional acrylates, hydroxy-functional copolymers, block copolymers (suppliers e.g. BYK, TEGO), plasma and/or corona treatments and/or or even contamination by metal vapor deposition is conceivable.
  • the adhesion promoter layer can preferably be produced by means of gravure printing, flexographic printing, inkjet printing, screen printing, slot nozzles and/or spray painting.
  • the adhesion promoter layer preferably has a layer thickness of between 0.1 ⁇ m and 1.5 ⁇ m. If the adhesion promoter layer is produced by vapor deposition, the layer thickness is preferably between 1 nm and 50 nm.
  • an adhesion promoter layer can often be dispensed with.
  • replication of the replication layer together with the print results in improved adhesion of the print to the replication layer.
  • the joint replication also causes a roughening of the surface of the print, which means that subsequent layers also adhere well to the print.
  • a non-stick layer can preferably be applied at least in regions to a layer of the multilayer film and/or to the ink or to the print.
  • the non-stick layer is preferably formed from silicone acrylates, fluorinated polymers and/or waxes.
  • the ink is applied to a layer of the multilayer film, in particular to the carrier layer, the release layer, the replication layer, the reflection layer, the adhesive layer and/or the protective layer, with the interposition of at least one adhesion promoter layer and/or anti-adhesion layer.
  • an ink is preferably provided which comprises laser-sensitive pigments.
  • the pigments can be, for example, ammonium octamolybdate (AOM).
  • AOM ammonium octamolybdate
  • the laser-sensitive pigments offer the advantage that this enables individualization of the multilayer film and/or the print, in particular further, after the printing.
  • the ink containing the laser-sensitive pigments can be transparent or translucent or also colored, at least in certain areas.
  • the optical appearance of the pigments in particular changes.
  • the pigments experience a color change or blackening.
  • modified micas are strongly heated by laser irradiation and burn the surrounding polymers to soot. This can also lead to blackening.
  • the ink or the print is advantageously irradiated at least in regions by means of a radiation source, in particular by means of a laser. This changes the visual appearance of the print.
  • a radiation source in particular by means of a laser.
  • an ink or a print comprising laser-sensitive pigments and/or organic dyes is irradiated with a radiation source.
  • the irradiation in particular the irradiation by means of a laser beam, can result in a color change and/or a blackening and/or a fading of at least parts of the print.
  • the irradiation can also make previously invisible and/or transparent parts or areas of the print preferably partially or completely visible. Partial as well as complete black coloring of at least parts of the print, which can be either invisible or colored before the irradiation, is possible. Colored or visible areas of the print can also fade and, in particular, lead to visible differences in contrast, in particular when, instead of color pigments, less light-resistant organic dyes at least partially form the color of the print.
  • the irradiation can thus in particular achieve a further or supplementary individualization of the print or a personalization of the print or the multilayer film.
  • the supplementary individualization can take place both during production of the multilayer film and after production of the film, in particular after application of the film to a substrate, in particular to a security document.
  • the print is irradiated several times, which creates in particular a first additional individualization or personalization and at least one further additional individualization or personalization becomes.
  • the irradiations preferably take place at different points of the print. However, it is also possible for the irradiations or the irradiation regions to overlap.
  • the multiple irradiations can all take place during the manufacture of the multilayer film or also partly during manufacture and partly after manufacture, in particular after the multilayer film has been applied to a substrate, or else all after manufacture. It is advantageous if the first supplementary individualization takes place during the production of the multilayer film and at least one further individualization takes place after the production of the film, in particular after the film has been applied to a substrate.
  • the further or supplementary individualization is produced.
  • One possibility is, for example, the application of an invisible ink.
  • the ink can be applied either over the entire surface or in certain areas, in particular as a motif.
  • the ink is then irradiated in some areas or completely. As a result, either only areas of the ink or the entire area printed with ink are made visible. It is advantageous if only areas of the applied ink are irradiated.
  • the marking or partial marking can be an ink or an area of a print within the meaning of the invention.
  • the visible marking or partial marking can be a code, a decoration, a decorative design and/or a motif which can be arranged on any of the layers of the multilayer film.
  • the coding, the decorative design and/or the motif can be used in a way that is not specifically specified and manner have been created or manufactured.
  • the at least one ink is now preferably irradiated in such a way that the irradiated area of the at least one ink forms an overall marking with the visible marking or partial marking.
  • the visible marking or partial marking represents part of a code, part of a shape, in particular a geometric shape or a motif, and that the shape or motif is completed by the irradiated ink by irradiating at least regions of the at least one ink becomes.
  • the ink is also possible to apply the ink as a visible and/or colored area and/or structure and/or motif and then to blacken it by irradiating areas or completely with a laser.
  • a print is preferably provided which is in the form of wash varnish.
  • Lift-off methods are known from the prior art. They are used in particular for the production of metallic microstructures.
  • a wash lacquer is applied in the form of a desired design and then overlaid or covered with at least one further layer, in particular a metallization or another lacquer.
  • the wash lacquer can then be removed again together with parts of the further layer or the further layers by means of a solvent treatment, so that the further layer or the further layers only remain where no wash lacquer was previously applied.
  • an ink in particular that has polyvinylpyrrolidone and/or methylcellulose.
  • the resolution of the ink is essentially in the range of the DPI resolution of the inkjet (see table below). Due to some swelling of the pressure in the solvent treatment, a accompanied by an increase in area. The dot gain should not be more than about 10% in order not to significantly impair the resolution of the print.
  • Water, ethanol and/or isopropanol can be used as solvents.
  • a metal layer and/or a metallization is preferably applied over the entire surface.
  • the wash lacquer is then removed again together with parts of the metal layer and/or the metallization, in particular by means of a solvent treatment, so that the metal layer and/or the metallization only remains where no ink has previously been applied or pressure provided.
  • a layer with interference pigments and/or at least one volume hologram can be applied at least in regions.
  • at least one light-absorbing, preferably opaque, particularly preferably black print is preferably provided at least in regions.
  • Interference pigments are well known and have an optically variable color change effect with a changing viewing and/or illumination angle.
  • the pigments are often transparent or translucent and, as a result, are difficult or impossible to see on light backgrounds, and the color change effect is then correspondingly weak.
  • Volume holograms are generally known and have an optically variable effect with a changing viewing and/or illumination angle. Volume holograms are often transparent or translucent and, as a result, are difficult or impossible to see on light backgrounds, and the optically variable effect is then correspondingly weak.
  • the light-absorbing or opaque print ensures in particular that the interference pigments and/or the volume holograms in the area of the print come into their own or become more visible.
  • the print is preferably essentially black.
  • the layer with interference pigments is preferably applied over the entire surface or in the form of a patch, in the form of strips or as a large-area overlay film.
  • Volume holograms are preferably applied in the form of patches or strips or in the form of a large-area overlay film. It is advantageous that here the print, in particular the light-absorbing and/or opaque and/or black print, is only formed partially or in certain areas. This creates the optical impression that the interference pigments and/or the volume hologram are only applied locally, namely in the area that is backed by the print, because the optical effects are particularly effective in the area that is backed by the print come.
  • the print is designed as a code, in particular as a QR code or as a micro QR code or as a barcode or as a data matrix code.
  • the QR codes or the micro QR codes are preferably composed of a large number of code elements.
  • the micro QR codes can, for example, consist of 11x11, 13x13, 15x15 or 17x17 code elements.
  • the QR codes can, for example, consist of 22x22 or 32x32 code elements.
  • the individual code elements are made up of a number of drops of ink.
  • at least 2, preferably 4, ink drops are printed in order to provide a code element in one direction, particularly viewed in the X-direction.
  • 2x2, preferably 4x4 ink drops are printed or required for a code element. The more ink drops the better and the cleaner the edges of the code element and thus the code will come out.
  • the QR codes or the micro QR codes can each have a size of approximately 5 ⁇ 5 mm, preferably 3 ⁇ 3 mm.
  • the information relating to the pressure is preferably stored in a database and the pressure is applied in particular on the basis of the stored information.
  • An ink jet print head with a resolution of 300 to 1200 application nozzles per inch (npi, nozzles per inch) is preferably used to apply the ink in digital printing. This enables a high-resolution application of the ink, so that even fine motif structures can be printed with sharp edges.
  • the resolution of the print head corresponds to the achieved resolution of the drops of adhesive on the layer in dpi (dots per inch).
  • an inkjet print head with a nozzle diameter of 15 ⁇ m to 25 ⁇ m with a tolerance of no more than ⁇ 5 ⁇ m and/or a nozzle spacing of 30 ⁇ m to 150 ⁇ m, in particular or a nozzle spacing of 30 ⁇ m, is used to apply the ink up to 80 ⁇ m, with a tolerance of not more than ⁇ 5 ⁇ m.
  • the small distance between the nozzles - in particular transversely to the printing direction - ensures that the transferred ink is sufficiently close together on the layer or, if necessary, also overlaps, so that good adhesion is achieved over the entire printed area.
  • the ink has a basis weight of 0.5 g/m 2 to 30 g/m 2 and/or a layer thickness of 0.2 ⁇ m to 30 ⁇ m, preferably 0.5 ⁇ m to 15 ⁇ m is applied to the at least one partial area.
  • the application quantity or layer thickness of the ink can be varied depending on the layer used, in particular its absorbency, in order to further optimize the application result.
  • drops of adhesive are provided with a frequency of 6 kHz to 110 kHz by the ink jet print head.
  • conveying speeds of the film to be printed 10 m/min. up to 30 m/min. the desired resolution of 360 dpi to 1200 dpi can be achieved in the conveying direction.
  • Ink droplets with a volume of 2 pl to 50 pl are preferably provided by the ink jet print head with a tolerance of no more than ⁇ 6%. With the described application resolutions and application speeds, the necessary amount of ink is evenly applied to the layer.
  • ink droplets are provided by the ink jet print head at a flight speed of 5 m/s to 10 m/s with a tolerance of no more than ⁇ 15%. This minimizes the deflection of the ink droplets, in particular due to drafts, during the transfer from the print head to the layer, so that the ink droplets land on the layer in the desired, defined arrangement.
  • the ink is applied to the layer at an application temperature of 30° C. to 45° C., preferably 40° C. to 45° C., and/or a viscosity of 7 mPas to 30 mPas, preferably 5 mPas to 20 mPas is applied.
  • the Temperature control of the print head ensures that the ink has the desired viscosity.
  • the pixel size and pixel shape of the ink applied to the layer depend on the viscosity, with the specified values ensuring optimal printability of the ink.
  • the print head can be temperature-controlled, in particular heatable and/or coolable.
  • the distance between the ink jet print head and the layer does not exceed 1 mm when applying the ink. This also reduces the influence of drafts on the ink.
  • a relative speed between the ink jet print head and the layer when applying the ink is preferably 10 m/min to 100 m/min, in particular approximately 10 m/min to 75 m/min.
  • the desired resolution of the ink printed on the layer is achieved at these speeds, in particular in combination with the parameters specified above.
  • composition of a UV-curable ink in black color is given below (percentages mean percentage by volume): 2-phenoxyethyl acrylate 10% to 60%, preferably 25% to 50%; 4-(1-Oxo-2-propenyl)-morpholine 5% to 40%, preferably 10% to 25%; Exo-1,7,7-trimethylbicyclo[2.2.1]hept-2-yl acrylate 10% to 40%, preferably 20% to 25%; 2,4,6-trimethylbenzoyldiphenylphosphine oxide 5% to 35%, preferably 10% to 25%; dipropylene glycol diacrylate 1% to 20%, preferably 3% to 10%; urethane acrylate oligomer 1% to 20%, preferably 1% to 10%; carbon black pigment 0.01% to 10%, preferably 2.5 to 5.0%.
  • composition of a thermal-drying cyan ink is given below (percentages mean percent by volume): 2-pyrrolidone 5% to 15%, preferably 7% to 10%; 1,5-pentanediol 6% to 10%, preferably 8% to 9%; 2-pyrrolidone 5% to 15%, preferably 7% to 10%; 2-ethyl-2-hydroxymethyl-1,3-propanediol 5% to 15%, preferably 7% to 10%; Dye (for cyan e.g. DB 199) 5% to 10%, preferably 7% to 10%; Water 30% to 80%, preferably 60%-70%.
  • composition of a thermally drying pigmented ink is given below (percentages mean volume percent): N-methyl-N-oleyl taurate 0.5% to 2%, preferably 1% to 1.5%; diethylene glycol 5% to 10%, preferably 7% to 8%; glycerin 10% to 15%, preferably 11% to 13%; pigment 1% to 5%, preferably 2% to 3% Water 20% to 80%, preferably 60% to 75%.
  • Such formulations provide in particular the desired properties, in particular rapid curing and/or drying and a viscosity which enables good printability with stable and sharp application at the same time.
  • a light-curing, in particular UV-curing, ink is preferably printed on.
  • light is understood not only to mean the part of the electromagnetic radiation that is visible to the human eye, but also in particular the areas adjacent to the visible light, in particular the infrared and/or ultraviolet radiation. Essentially, the physical definition of light applies, namely that light covers the entire electromagnetic spectrum.
  • the ink can be partially cured or precured and/or cured by radiation, preferably by UV radiation, in particular by UV LED radiation.
  • UV radiation preferably by UV radiation, in particular by UV LED radiation.
  • Such inks are referred to below as UV inks.
  • the ink is used with a density of 1 g/ml to 1.5 g/ml, preferably 1.0 g/ml to 1.1 g/ml.
  • the UV inks are pre-hardened.
  • the ink is preferably pre-hardened 0.02 s to 0.025 s after the ink has been applied.
  • the ink is fixed on the layer very quickly after printing by hardening, so that the ink droplets are largely prevented from running or spreading the high print resolution is retained as well as possible.
  • UV pre-curing is not necessary due to the properties of the layer. This is not necessary if the applied ink droplets do not run or spread on the layer even without pre-curing.
  • the UV ink is pre-cured with UV light, of which at least 90% of the energy is emitted in the wavelength range between 380 nm and 420 nm. At these wavelengths, the free-radical curing is reliably initiated, particularly in the case of the UV ink formulations described above.
  • the UV ink is pre-cured with a gross irradiance of 2 W/cm 2 to 5 W/cm 2 and/or a net irradiance of 0.7 W/cm 2 to 2 W/cm 2 and/or an energy input in the ink of 8 mJ/cm 2 to 112 mJ/cm 2 takes place.
  • This ensures in particular that the ink undergoes the desired increase in viscosity, so that when the UV ink is applied to the layer, running or spreading of the UV ink is largely minimized in the time until it has passed through the UV curing station for complete curing.
  • the precuring of the UV ink is preferably carried out with an exposure time of 0.02 s to 0.056 s. With the mentioned transport speeds of the layer and the specified irradiation intensities, the necessary input of energy for the precuring is thus ensured.
  • the viscosity of the UV ink increases to 50 mPas to 200 mPas during pre-curing. Such an increase in viscosity guarantees that the UV ink does not spread or run on the layer and that the digital print can be transferred to the layer with essentially the resolution achieved when printing the UV ink.
  • the curing, in particular the complete curing, of the ink takes place in particular 0.2 s to 1.7 s after application to the layer.
  • Curing preferably takes place in a UV curing station, which is usually arranged downstream for reasons of space.
  • the UV ink is cured with UV light, of which at least 90% of the energy is emitted in the wavelength range between 380 nm and 420 nm. At these wavelengths, the free-radical curing is reliably initiated, particularly in the case of the UV ink formulations described above.
  • the UV ink is cured with a gross irradiance of 12 W/cm 2 to 20 W/cm 2 and/or a net irradiance of 4.8 W/cm 2 to 8 W/cm 2 and/or an energy input into the adhesive of 200 mJ/cm 2 to 900 mJ/cm 2 , preferably 200 mJ/cm 2 to 400 mJ/cm 2 .
  • the ink is reliably hardened, so that after the hardening step the digital print is no longer sticky and the printed layer or foil can basically be wound up.
  • UV ink is cured with an exposure time of 0.04 s to 0.112 s. With the specified gross radiation levels and the usual transport speeds, the necessary net energy input for curing the UV ink is thus ensured.
  • inks which dry and/or are dried by themselves after application or after printing.
  • Inks with solvents and/or water are particularly suitable for this.
  • Thermally drying inks are preferably used. Parts of the solvent and/or the water can already evaporate during the flight phase of the ink drops. At least another part can then be evaporated with the aid of tools.
  • IR radiation infrared
  • the use of convection dryers is also conceivable.
  • the duration of the drying is preferably between 1 s and 60 s and/or the temperature is between 40°C and 120°C.
  • the print is arranged on a replication layer.
  • the print is advantageously replicated at least in certain areas. This means that the print has a replication structure at least in certain areas. It is advantageous if the replication structure is arranged in register for printing.
  • the tolerance of replication to printing is within +/-1.0 mm, preferably within +/-0.7 mm, particularly preferably less than +/-0.4 mm.
  • this area has no replication structure.
  • the surface of the area is preferably smooth. In particular, this area ensures a contrast-enhancing effect in relation to the print.
  • the width of this area without structure transfer depends in particular on the type of replication tool, in particular whether it is rigid or flexible, the application thickness of the print and/or the layout of the print, i.e. for example the distance between the printed areas of the print.
  • the halo essentially has a width of between 1 ⁇ m and 100 ⁇ m.
  • the elevation of the print can prevent complete contact of the structuring layer with the entire surface of the replication layer.
  • the ink applied or the print preferably fills the replication structures, in particular diffractive structures of the replication layer, only partially. However, it is also possible that in the areas where the ink or the print occurs, they completely fill the replication structures. Furthermore, it is also conceivable that the ink or the print follow the topography of the replication structures.
  • the multilayer film can have an adhesion promoter layer at least in regions, with the adhesion promoter layer preferably only in those regions is applied where the print is placed.
  • the print is preferably directly adjacent to the adhesion promoter layer.
  • the multi-layer film can have a non-stick layer at least in regions.
  • the non-stick layer is preferably arranged on the print.
  • the ink or the print preferably comprises laser-sensitive pigments.
  • the print is formed from a single ink and has at least a first area and a second area, with the areas differing from one another in terms of their visual appearance.
  • One area can be transparent or invisible and the other area can be opaque and/or colored. It is also conceivable that one of the areas has a black coloration.
  • the print has visible and invisible areas. It is advantageous if this is a print with laser-sensitive pigments.
  • the multilayer film can have a layer with interference pigments and/or at least one volume hologram at least in regions, preferably over the entire surface.
  • the print is preferably light-absorbing, in particular opaque, particularly preferably black.
  • the interference pigments or the volume hologram come into their own as a result of the pressure and are therefore clearly visible to the viewer.
  • viewing and/or illumination angle-dependent color impressions can also be produced only in individual surface areas of the interference pigments and/or volume holograms.
  • the print is preferably only arranged in regions on the volume hologram and/or on the layer containing interference pigments. This creates the impression that the volume hologram and/or the interference pigments are only applied in certain areas.
  • the layer comprising interference pigments is formed over the entire area or the volume hologram is formed as a patch or strip or as a large-area overlay film.
  • the print does not necessarily have to be arranged directly adjacent to the layer containing interference pigments or on the volume hologram. It is entirely possible for additional layers to be arranged between the print and the layer containing interference pigments and/or the volume hologram.
  • the print is advantageously designed as a code, in particular as a QR code or as a micro QR code or as a barcode or as a data matrix code.
  • prints are applied to a plurality of layers of the multilayer film.
  • the prints applied to the respective layers can preferably differ from one another.
  • the prints are arranged in register with one another and/or overlapping and/or next to one another.
  • figure 1 shows a schematic representation of possible arrangements of at least one print 100 in a multilayer film 10.
  • the ink can in principle be applied at least in regions to each layer of the multilayer film 10 so that the print 100 can in principle be provided or arranged on each layer of the multilayer film 10 .
  • the print 100 is arranged on the carrier layer 12, the release layer 14, the replication layer 18, the protective layer 16, the reflective layer 20 and/or the adhesive layer 22.
  • the print 100 can be an individualized print or a non-individualized print.
  • the layer to which the ink is applied is preferably modified beforehand, if necessary, in such a way that sufficient adhesion or non-adhesion of the ink or the print 100 to this layer can be ensured. This can be ensured, for example, by using appropriate surface additives in the paint formulation or by designing the layer appropriately, for example with crosslinkable UV-active groups on the surface.
  • the ink is applied to a number of layers of the multi-layer film.
  • the inks applied to the layers can be both identical and different.
  • the ink is applied in register with one another.
  • a multi-layer film 10 is obtained, in which at least one first print 100 is formed on several layers.
  • the prints 100 can be arranged in register with one another.
  • the individual prints 100 can be configured differently from one another. This is to be understood in particular to the effect that the prints 100 differ from one another in terms of their visual appearance.
  • the prints 100 can, for example, be formed by different inks and/or be formed as different motifs.
  • the prints 100 can be offset from one another in a top view of the multilayer film 10 or can also be arranged in an overlapping manner. However, the prints 100 can also be arranged next to one another when the multilayer film 10 is viewed from above.
  • the prints 100 are advantageously arranged or formed on the layers in such a way that when the multilayer film is viewed from above, at least some of the prints 100 or parts of some of the prints 100 together form an overall motif.
  • the ink is preferably applied to a carrier layer 12 at least in regions.
  • a multilayer film 10 is thus obtained, in which at least one print 100 is arranged at least in regions on the carrier layer 12 .
  • the ink applied to the carrier layer 12 is preferably applied in such a way that the ink or the print 100 has tactile and/or tactile properties. In this way, in particular, an individualized haptic surface can be created if the print 100 is individualized.
  • the printed ink or the print 100 provided has, in particular, a surface structure.
  • the ink is applied or the print is provided in such a way that it imparts a certain structure or structuring to a layer that may be applied subsequently, in particular a protective layer 16 .
  • the ink can also be applied to the carrier layer 12 in such a way that after the multilayer film 10 has been applied to a substrate and the carrier layer 12 has been subsequently peeled off, the ink or the print 100 remains at least partially, preferably completely, on the carrier layer 12. In this way, for example, by reading out the print 100 remaining on the carrier layer 12, e.g. B. be subsequently documented, which parts of the multilayer film 10 have actually been applied.
  • the carrier layer 12 consists in particular of a self-supporting material and/or of the class of plastics.
  • the carrier layer 12 is preferably made from PET, from polyolefin, in particular from OPP, BOPP, MOPP, PP and/or PE, from PMMA, from PEN, from PA, from ABS and/or a composite material of these plastics. It is also possible that the carrier layer 12 is already pre-coated by the manufacturer and the multi-layer film 10 is built up on this pre-coated material. It is also possible for the carrier layer 12 to be a biodegradable and/or compostable carrier layer 12 . EVOH is preferably used here.
  • the layer thickness of the carrier layer 12 is advantageously between 4 ⁇ m and 500 ⁇ m, in particular between 4.7 ⁇ m and 250 ⁇ m.
  • the multi-layer film 10 can be designed as a laminating film, which has a carrier layer 12 and a multi-layer wear layer, for example a has a multi-layer decorative layer, and in particular a heat-activatable adhesive layer, the carrier layer 12 and the wear layer being arranged together in the form of an embossed layer on the substrate.
  • the multilayer film 10 is designed as a transfer film.
  • a transfer film comprises in particular a transfer layer, which is preferably formed from a plurality of layers, in particular at least one adhesive layer 22, a reflection layer 20, a replication layer 18 and/or a protective layer 16, and a carrier layer 12, the transfer layer being detachable from the carrier layer 12 .
  • a detachment layer 14 can be arranged between the transfer layer and the carrier layer 12 .
  • the ink is preferably applied to a detachment layer 14 at least in regions.
  • a multilayer film 10 is thus obtained in which at least one print is arranged at least in regions on the release layer 14 .
  • the detachment layer can be present both partially 14 ′ and over the entire surface 14 .
  • the detachment layer 14 ensures, in particular, that the layers of the multilayer film 10 can be separated from the carrier layer 12 in a non-destructive manner.
  • the detachment layer 14 is preferably formed from waxes, polyethylene (PE), polypropylene (PP), cellulose derivatives and/or poly(organo)siloxanes.
  • Aforesaid waxes can be natural waxes, synthetic waxes or combinations thereof.
  • the aforementioned waxes are, for example, carnauba waxes.
  • the aforementioned cellulose derivatives are, for example, cellulose acetate (CA), cellulose nitrate (CN), cellulose acetate butyrate (CAB) or mixtures thereof.
  • the aforementioned poly(organo)siloxanes are, for example, silicone binders, polysiloxane binders or mixtures thereof.
  • the detachment layer 14 preferably has a layer thickness between 1 nm and 500 nm, in particular a layer thickness between 5 nm and 250 nm, particularly preferably between 10 nm and 250 nm.
  • the release layer 14 can be produced using known printing processes. In particular, gravure printing, flexographic printing, screen printing, inkjet printing or by means of a slot nozzle is suitable. However, the release layer 14 can also be formed by vapor deposition, physical vapor deposition (PVD), chemical vapor deposition (CVD) and/or sputtering.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the ink is applied to a protective layer 16 at least in some areas.
  • the ink is preferably applied in regions to a protective layer 16 formed over the entire area.
  • a multilayer film 10 is thus obtained, in which a print 100 is arranged at least in regions on the protective layer 16 .
  • the print 100 is arranged below the protective layer 16 in the viewing direction and is therefore also protected by the protective layer 16 .
  • the protective layer 16 is preferably a layer made of PMMA, PVC, melamine and/or acrylates.
  • the protective lacquer can also consist of a radiation-curing dual cure lacquer.
  • this Dual Cure paint can be thermally pre-crosslinked during and/or after application in liquid form.
  • the dual-cure coating is preferably post-crosslinked by free radicals, in particular using high-energy radiation, preferably UV radiation.
  • Dual cure coatings of this type can consist of various polymers or oligomers that have unsaturated acrylate or methacrylate groups. These functional groups can be crosslinked with one another free-radically, in particular in the second step.
  • these polymers or oligomers also have at least two or more alcohol groups.
  • These alcohol groups can be crosslinked with multifunctional isocyanates or melamine-formaldehyde resins.
  • the melamine crosslinkers can be fully etherified versions, can be imino types, or can be benzoguanamine types.
  • the protective layer 16 preferably has a layer thickness of between 50 nm and 30 ⁇ m, preferably 1 ⁇ m to 5 ⁇ m.
  • the protective layer 16 can be produced using gravure printing, flexographic printing, screen printing, inkjet printing or using a slot nozzle and/or using vapor deposition, in particular using physical vapor deposition (PVD), chemical vapor deposition (CVD) and/or sputtering.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the ink is also possible for the ink to be applied at least in regions to a reflection layer 20, in particular to a metal layer and/or metallization and/or HRI layer.
  • a multilayer film 10 is thus obtained, in which at least one print 100 is arranged at least in regions on the reflection layer 20 .
  • the ink or the print 100 can serve in particular as an etching resist for demetallization. If the ink or the print 100 thus provided is in the form of an etching resist, then a demetallization can take place in a subsequent step. The metal layer is preferably removed in those areas that are not covered by the print 100 . If the ink contains alkali, for example, direct etching can also be caused by the application. If the print 100 is individualized, an individualized demetallization can also be produced with it.
  • the reflection layer 20 can be applied both over the entire surface and in certain areas.
  • the reflection layer 20 is preferably designed in the form of a pattern, in particular for the formation of motifs.
  • the reflective layer 20 can represent a pattern and/or a motif which, in particular, is also Register to the print 100 can be arranged on other layers of the multilayer film 10 and/or to the structures of the replication layer 18.
  • the reflection layer 20 is preferably a metal layer or a metallization.
  • the metal layer or metallization is preferably made of aluminum, chromium, gold, copper, tin, silver or an alloy of such metals.
  • the metal layer or the metallization is preferably produced by means of vapor deposition, in particular by means of vacuum vapor deposition.
  • the vapour-deposited metal layer or metallization can take place over the entire surface and optionally be retained over the entire surface, or it can be structured using known demetallization processes such as etching, lift-off or photolithography and are therefore only partially present.
  • the layer thickness is in particular between 10 nm and 500 nm.
  • the metal layer or the metallization can also consist of a printed layer, in particular a printed layer of metal pigments in a binder. These printed metal pigments can be applied over the entire surface or partially and/or have different colorings in different surface areas.
  • the layer thickness is in particular between 1 ⁇ m and 3 ⁇ m.
  • reflection layer 20 from a paint with electrically conductive, metallic pigments, in particular to print and/or cast on.
  • the reflection layer 20 is formed by a transparent reflection layer 20, for example a thin or finely structured metallic layer or an HRI or LRI layer (high refraction index - HRI, low refraction index - LRI).
  • a dielectric reflection layer 20 consists, for example, of a vapor-deposited layer a metal oxide, metal sulfide, titanium oxide, etc.
  • the layer thickness of such a layer is preferably 10 nm to 500 nm.
  • the ink is preferably applied at least in regions to an adhesive layer 22 and/or to a primer.
  • a multi-layer film 10 is thus obtained, in which at least one print 100 is arranged at least in regions on the adhesive layer 22 and/or on the primer.
  • the adhesive layer 22, 22' can be applied both partially and over the entire surface. In principle, the adhesive layer can also be a partial adhesive layer 22'. It is also conceivable that the adhesive layer is a full-surface adhesive layer 22 .
  • the ink is preferably designed in such a way that the ink or the print 100 itself can serve as a partial adhesive layer 22'. An individualized bond is thus obtained in particular if the print 100 is individualized. However, it is also possible for the ink to be applied at least partially to the adhesive layer 22 for passivation, in particular for partial passivation of the adhesive layer 22 . In the case of later application or hot stamping, the multilayer film is then only transferred to a substrate in the areas of the adhesive layer 22 that are not printed with ink.
  • the adhesive layer 22, 22' or the primer is preferably made of PMMA, PVC, acrylates, polyamides, polyvinyl acetates, hydrocarbon resins, polyesters, polyurethanes, chlorinated polyolefins, polypropylene, epoxy resins and/or polyurethane polyols, in particular in combination with deactivated isocyanates.
  • the adhesive layer 22 or the primer can also contain fillers such as SiO 2 and/or TiO 2 .
  • the layer thickness of the adhesive layer 22, 22' or the primer is preferably between 0.5 ⁇ m and 20 ⁇ m, particularly preferably between 1.5 ⁇ m and 5 ⁇ m.
  • the adhesive layer or the primer can be applied using gravure printing, Flexographic printing, screen printing, inkjet printing and/or produced by means of a slot nozzle.
  • the ink is advantageously applied to a replication layer or a replication lacquer 18, 24 at least in regions.
  • a multilayer film 10 is obtained in which at least one print 100 is arranged at least in regions on the replication layer 18, 24.
  • the ink can be applied to a replication layer 24 that has not yet been replicated.
  • the replication layer or the replication lacquer 24 still has, in particular, smooth surfaces.
  • the replication then takes place in particular after the print 100 has been provided. Structures 28 can then be introduced into the print 100 and/or into the replication layer 24 as a result of the replication.
  • non-individualized information in the replication layer 18 can be combined with an individualized print 100.
  • a replication in the print 100 can represent an additional protective measure against counterfeiting because the print 100 is integrated even more into the overall system of the multilayer film 10 as a result.
  • the ink is advantageously applied to a substantially smooth surface of the replication layer 18 or the replication lacquer 24, with the surface then preferably being replicated at least in regions at a later point in time.
  • the ink is applied to a replication layer 18 that has already been replicated, ie also to a replication layer 18 that is already provided with a surface structure, a replication structure 28 .
  • the ink is preferably applied to the structured surface or to the replication structure 28 at least in certain areas.
  • the ink is applied to a replication layer 18 that has already been replicated or if a print 100 is provided on a replication layer 18 that has already been replicated, at least partial areas of the structures 28, in particular the diffractive structures, can then be erased as a result if the ink has a refractive index similar to the replication layer 18, in particular with a refractive index with a difference of less than 0.2. This occurs in particular when the ink is applied with a layer thickness that is greater than the depth of the structures. However, it is also possible for the ink to be applied in a smaller layer thickness in such a way that the ink or the print 100 follows the topology of the structures and thus in particular becomes part of the diffraction. This is particularly conceivable if a solvent ink is used.
  • the ink can also be applied in such a way that the ink or the print 100 only partially fills the replication structures 28, in particular diffractive structures on the surface of the replication layer 18. Only partial filling of the structures occurs in particular when the ink layer thickness ultimately applied is less than the depth of the replication structures 28. Under certain conditions, the ink can also fill the structures without optical erasure occurring. This is the case in particular when the ink has reflective or high-refractive index properties and differs in its complex refractive index in particular by more than 0.2 from the complex refractive index of the replication layer 18 .
  • An example of reflective inks are inks with metal effect pigments or metal flakes.
  • Inks based on liquid crystals are an example of inks with a high refractive index.
  • An ink is preferably applied to the replication layer 18, 24 with a layer thickness that is greater than the depth of the structures to be introduced into the replication layer 18, 24.
  • the layer thickness of the applied ink is essentially twice as thick as the layer thickness of the structures to be introduced into the replication layer 18, 24.
  • a layer thickness of the ink that is at least twice as great as the depth of the structures to be introduced into the replication layer is advantageous if replication is only carried out after the ink has been applied. This will prevent at the Replication the introduced structures completely penetrate the applied ink.
  • the ink is preferably printed with a layer thickness smaller than the depth of the structures to be introduced into the replication layer 18 .
  • the ink can be penetrated through the entire layer of print 100 with the structures introduced, with which print 100 can have high-resolution fine structuring that is also visible from carrier layer 12 through the continuous structures, which exceeds the print resolution of inkjet printers and thus another security feature.
  • the replication layer 18 preferably has replication structures 28 at least in regions on one of its upper sides. Microstructures and/or macrostructures with a diffractive and/or refractive effect are preferably molded into the replication layer 18 .
  • the replication layer 18, 24 is preferably formed from acrylate, cellulose, PMMA and/or crosslinked isocyanates.
  • the replication layer 18, 24 can also consist of a thermoplastic lacquer.
  • a surface structure 28 is molded into the paint, preferably by means of heat and pressure through the action of an embossing tool.
  • the replication layer 18, 24 it is also possible for the replication layer 18, 24 to be formed by a UV-crosslinkable lacquer and for the surface structure to be molded into the replication layer 24 by means of UV replication. In this case, the surface structure is shaped by the action of an embossing tool on the unhardened replication layer 24 and the replication layer 18 is hardened immediately during or after the shaping by irradiation with UV light.
  • the replication layer 18, 24 can be produced by means of the known printing processes.
  • gravure printing, flexographic printing, screen printing or inkjet printing is suitable.
  • production using a slot die is also possible.
  • the surface structure or replication structure 28 formed in the replication layer 18 is preferably a diffractive surface structure, for example a hologram, Kinegram® or some other diffraction-active grating structure.
  • a diffractive surface structure typically have a spacing of the structural elements in the range from 0.1 ⁇ m to 10 ⁇ m, preferably in the range from 0.5 ⁇ m to 4 ⁇ m.
  • the surface structure it is also possible for the surface structure to be a zero-order diffraction structure.
  • this diffractive structure has a period in at least one direction less than the wavelength of visible light, between half the wavelength of visible light and the wavelength of visible light, or less than half the wavelength of visible light. It is also possible that the surface structure is a blazed lattice.
  • This is particularly preferably an achromatic blazed grating.
  • Gratings of this type preferably have a period of between 1 ⁇ m and 100 ⁇ m, more preferably between 2 ⁇ m and 10 ⁇ m, in at least one direction.
  • the blaze grating it is also possible for the blaze grating to be a chromatic blaze grating.
  • the surface structure is a linear or crossed sinusoidal diffraction grating, a linear or crossed single-stage or multi-stage rectangular grating.
  • the period of these gratings is preferably in the range from 0.1 ⁇ m to 10 ⁇ m, preferably in the range from 0.5 ⁇ m to 4 ⁇ m.
  • the surface structure is an asymmetrical relief structure, for example an asymmetrical sawtooth structure.
  • the period of these gratings is preferably in the range from 0.1 ⁇ m to 10 ⁇ m, preferably in the range from 0.5 ⁇ m to 4 ⁇ m.
  • the surface structure is a light-diffracting and/or light-refracting and/or light-focusing micro- or nanostructure, a binary or continuous Fresnel lens, a binary or continuous Fresnel free-form surface; a diffractive or refractive macrostructure, in particular a lens structure or microprismatic structure, a mirror surface or matte structure, in particular anisotropic or isotropic matte structure, or a combination structure of several of the aforementioned surface structures.
  • the structure depth of the aforementioned surface structures or replication structures 28 is preferably in the range between 10 nm and 10 ⁇ m, more preferably between 100 nm and 2 ⁇ m.
  • the replication layer 18, 24 preferably has a layer thickness of between 200 nm and 5 ⁇ m. If the replication layer has a diffractive surface structure, then the layer thickness is preferably between 0.3 ⁇ m and 6 ⁇ m. If the replication layer has coarser structures, in particular with a larger period and/or greater depth, for example a so-called “surface relief”, then the layer thickness is preferably about 1 ⁇ m to 10 ⁇ m. If the replication layer has a lenticular surface structure, the layer thickness is preferably between 1.5 ⁇ m and 10 ⁇ m.
  • the replication or structuring of a surface of the replication layer can take place in different ways.
  • thermal replication takes place, in particular under the action of heat and/or pressure.
  • a print 100 may already have been applied to the replication layer 24 at this point in time. In this case, the print 100 or the ink was essentially applied to a smooth surface of the replication layer.
  • UV replication takes place.
  • the print 100 is formed with a UV-curable ink
  • the UV print can advantageously be protected with the UV-curable replication varnish 24 .
  • the crosslinking and thus also the resistance of particularly thin prints with UV-curing inks can be improved in particular because the encapsulation in the UV replication varnish during UV curing minimizes the inhibiting effects that are then particularly effective in the case of thin UV-curing layers.
  • the encapsulation described also allows a realize lower layer thickness of the print formed with the UV-curing ink.
  • the reflection layer can be opaque, semi-transparent or transparent, with the transparency being able to depend in particular on the viewing angle.
  • the multilayer film 100 has an adhesion promoter layer at least in regions, which can in principle be arranged on each layer of the multilayer film 10 and/or below and/or on the print 100.
  • the adhesion promoter layer is preferably only applied in those areas to which the ink will later also be applied.
  • the adhesion promoter layer ensures, in particular, that there is good adhesion between the layers connected to it. As a result, delamination can be largely prevented. In particular, the adhesion promoter layer prevents an undesired predetermined breaking point from forming when the print 100 has hardened.
  • PVC polyvinyl styrene
  • adhesion-promoting layers with adhesion-improving surface additives such as functional acrylates, hydroxy-functional copolymers, block copolymers (suppliers such as BYK, TEGO), plasma and/or corona treatments and/or or even contamination by metal vapor deposition is conceivable.
  • the adhesion promoter layer can preferably be produced by means of gravure printing, screen printing, slot nozzle, flexographic printing, inkjet printing and/or spray painting.
  • the adhesion promoter layer preferably has a layer thickness of between 0.1 ⁇ m and 1.5 ⁇ m. If the adhesion promoter layer is produced by vapor deposition, the layer thickness is preferably between 1 nm and 50 nm.
  • the multilayer film 10 can have a non-stick layer.
  • the non-stick layer can be arranged on each layer of the multilayer film 10 and/or on the print 100 .
  • the non-stick layer is preferably formed from silicone acrylates, fluorinated polymers and/or waxes.
  • the ink is applied to a layer of the multilayer film 10, in particular to the carrier layer 12, the release layer 14, the replication layer 18, the reflection layer 20, the adhesive layer 22 and/or the protective layer, with the interposition of at least one adhesion promoter layer and/or anti-adhesion layer 16, is applied.
  • the multilayer film 10 can have a layer with interference pigments and/or at least one volume hologram, at least in regions.
  • at least one light-absorbing, preferably an opaque, particularly preferably a black print 100 is preferably arranged in the multilayer film 10 at least in regions.
  • the layer with interference pigments and/or the volume hologram can also be applied over the entire surface or in the form of a patch, in the form of strips or as a large-area overlay film, in which case the print 100, in particular the light-absorbing and/or opaque and/or black print, is only partially or regionally formed .
  • Interference pigments are well known and have an optically variable color change effect with a changing viewing and/or illumination angle.
  • the pigments are often transparent or translucent and, as a result, are difficult or impossible to see on light backgrounds, and the color change is then correspondingly weak.
  • Volume holograms are generally known and have an optically variable effect with a changing viewing and/or illumination angle. Volume holograms are often transparent or translucent and, as a result, are difficult or impossible to see on light backgrounds, and the optically variable effect is then correspondingly weak.
  • the light-absorbing or opaque print 100 ensures in particular that the interference pigments and/or the volume hologram come into their own or become visible better.
  • the print 100 is preferably essentially black.
  • figure 2 shows a schematic sequence of the application of a print 100 to a replication layer 18 or to a replication varnish 24 with subsequent replication.
  • a first step A an ink is applied to a replication lacquer 24 at least in certain areas. At least one pressure 100 is thereby provided.
  • the ink according to the invention is not limited to any special configuration.
  • the ink can be transparent, translucent, opaque, invisible, colored and/or colorless.
  • the print 100 is also fundamentally limited to a specific configuration.
  • the print 100 can be transparent, translucent, opaque, invisible, colored and/or colorless.
  • the ink can be a fluorescent ink, both a transparent and a colored fluorescent ink and/or a luminescent ink, both transparent and colored luminescent ink and/or phosphorescent, including chemiluminescent, inks, both transparent and colored phosphorescent ink and/or liquid-crystalline ink, in particular with dichroic color effects and/or inks with taggants and/or with laser-sensitive pigments.
  • Both light-curing, in particular UV-curing inks, and solvent and/or aqueous inks can be used.
  • the thickness of the applied or printed ink layer is preferably between 0.1 ⁇ m and 30 ⁇ m, in particular between 0.5 ⁇ m and 15 ⁇ m, particularly preferably between 0.5 ⁇ m and 15 ⁇ m and advantageously between 1 ⁇ m and 3 ⁇ m. If solvent and/or aqueous inks are used, the layer thickness is preferably about 0.5 ⁇ m. If UV-curing inks are used, then the layer thickness is approximately between 1 ⁇ m and 30 ⁇ m, preferably between 1 ⁇ m and 15 ⁇ m, particularly preferably between 1 ⁇ m and 8 ⁇ m.
  • the print 100 is preferably formed by applying a single ink.
  • the print 100 is at least partially processed, in particular irradiated.
  • the visual appearance of the print 100 preferably changes in these areas. It is thus possible to obtain a print 100 which—although it only consists of a single ink—comprises at least two areas that differ in terms of their visual appearance.
  • the print 100 can preferably have at least one visible and at least one invisible area.
  • the print 100 can also be formed by applying a plurality of inks, in particular inks that are designed differently from one another.
  • the several inks differ from each other in particular in their visual appearance and/or their composition.
  • the inks can differ from each other in their color, for example.
  • at least one of the inks used is transparent and/or invisible and at least one other ink used is opaque and/or visible.
  • the inks can be printed next to each other, on top of each other or overlapping.
  • the print 100 to be processed and/or irradiated at least in regions, in particular in that region where the transparent ink is located.
  • the transparent or invisible ink can become visible and can preferably supplement a partial motif or the like caused by the visible or opaque ink, as a result of which an overall motif is created in particular.
  • the inks can be arranged next to one another, in particular directly next to one another, or at least overlapping in some areas.
  • the inks can also be printed on top of each other.
  • the multiple inks can be applied at the same time as well as overlapping in time or one after the other. In the case of inkjet printers, for example, the order will be placed one after the other. In particular, one color is printed per head. In particular, it is not possible for several heads to be in the same place at the same time.
  • the final transfer of all inks preferably takes place at the same time, since the print image is first printed on a transfer blanket or is built up there from individual, single-color inks and only then from this transfer blanket to the target substrate is transferred.
  • Steps B to D essentially represent the replication.
  • both at least regions of the replication layer 18 and the pressure 100 applied thereto are replicated.
  • a replication that is in the register for printing 100 is thus obtained.
  • the ink is applied in such a way that, during a replication in the area a covered by the print 100, the replication structure 28 introduced is only pressed into the print 100 and not into the replication layer 24.
  • the print 100 Prior to replication, the print 100 preferably has a thickness that is greater than the depth of the replication structure introduced into the print 100 .
  • the print has a layer thickness of between 0.5 ⁇ m and 6 ⁇ m.
  • the layer thickness of the pressure 100 applied before the replication is preferably about twice as thick as the depth of the structure introduced into the replication layer 24 .
  • the print 100 is preferably pressed into the replication layer 24 (step B). This is essentially to be understood to mean that in particular those regions a of the replication layer 24 on which the print 100 is arranged lose layer thickness.
  • the thickness of the replication layer 24 in area a of the print 100 preferably decreases uniformly or uniformly over this area.
  • the layer thickness of the replication layer 24 decreases, especially during replication, the less, the further one moves from the Pressure 100 removed. There is essentially a linear increase in the layer thicknesses.
  • the print 100 is preferably compressed (step C) during the replication. This makes it possible, in particular, for the print 100 and the replication layer 18 to be replicated together at least in regions.
  • a method step D the print 100 is replicated together with the replication varnish 24 .
  • a replication structure 28 is introduced at least in regions.
  • the replication structure 28 is advantageously introduced in such a way that a region b of the replication layer, which is arranged adjacent to the print 100 when the multilayer film 10 is viewed from above, is not replicated.
  • This area is referred to as court 26 in the present case.
  • the area b, the courtyard 26, preferably does not come into contact with a replication tool.
  • the area is directly adjacent to the print 100 in a plan view of the multilayer film 10 .
  • the size of the area of the replication layer that is not replicated depends in particular on the application thickness of the ink and/or the strength of the pressing into the replication layer 18 .
  • the halo 26 essentially has a width of between 1 ⁇ m and 100 ⁇ m.
  • an adhesion promoter layer can often be dispensed with.
  • co-replication of the replication layer 24 with the print 100 results in improved adhesion of the print 100 to the replication layer 18.
  • the joint replication also causes a surface roughening of the print 100, as a result of which subsequent layers also adhere well to the print 100.
  • FIG 3 shows a schematic sequence of the production of a multilayer film 10 in one embodiment.
  • a carrier layer 12 is provided.
  • a detachment layer 14 can be applied to the carrier layer 12 at least in regions.
  • the presence of a detachment layer is advantageous if the multilayer film 10 is designed as a transfer film and the carrier layer 12 is to be removed after the multilayer film 10 has been applied to a substrate.
  • the presence of a release layer 14 is not necessary.
  • a release layer should be dispensed with.
  • a protective layer 16 is also provided.
  • a replication layer or a replication lacquer 24 is then advantageously applied to the protective layer 16 .
  • the replication layer or the replication lacquer 24 is preferably a layer which has not yet been replicated, ie does not yet have any replication structures 28 and/or in particular which still has essentially smooth surfaces.
  • At least one ink is preferably applied to the replication layer or to the replication lacquer 24 by means of inkjet printing. A pressure 100 is thereby provided. It is pointed out that the layer thickness ratios do not necessarily correspond to the real layer thickness ratios.
  • a replication structure 28 is therefore preferably shaped or introduced into the print 100 and/or the replication layer or the replication lacquer 26 . Even if the replication structure 28 extends over the entire surface in step B, this is not absolutely necessary in the present case.
  • the replication structure 28 or replication structures can also be introduced into the print 100 or into the replication layer 18 only in certain areas.
  • a reflection layer 20 is applied to the print 100 and/or to the replication layer 18 or the replication lacquer 24 .
  • the reflection layer 20 is preferably a metal layer or metallization.
  • the reflection layer 20 can be applied both in areas and over the entire surface.
  • the reflection layer 20 is first applied essentially over the entire surface and then partially removed again.
  • the lift-off method is suitable for this. This is particularly advantageous when a print 100 is provided which is in the form of wash varnish.
  • the print 100 is preferably applied in the form of a desired design and then coated or covered with the metallization and/or at least one further lacquer.
  • the print 100 can then be treated with a solvent together with parts of the further layer or the further Layers are removed again, so that the further layer or the further layers, in particular the metallization or the reflection layer 20 only remain where no pressure 100 was previously applied.
  • an ink is provided in particular, which has polyvinylpyrrolidone and/or methylcellulose.
  • an adhesive layer 22 is then applied.
  • the adhesive layer 22 can be applied both over the entire surface and also partially.
  • the Figures 4 to 6 each show a schematic representation of a multilayer film 10 in an embodiment before and after laser irradiation L.
  • an ink is preferably provided that includes laser-sensitive pigments.
  • the pigments can be, for example, ammonium octamolybdate (AOM).
  • AOM ammonium octamolybdate
  • the laser-sensitive pigments offer the advantage that this allows individualization or personalization of the multilayer film 10 and/or the print 100, 102, in particular further, after the printing.
  • the ink containing the laser-sensitive pigments can be transparent or translucent or also colored, at least in certain areas. If the laser-sensitive pigments or the ink or the print 100 comprising the laser-sensitive pigments are exposed to laser radiation L, for example, then the optical appearance of the pigments in particular changes. In particular, the pigments experience a color change or blackening.
  • the additional individualization or personalization can take place both during the production of the multilayer film 10 and after the production of the film 10, in particular after the application of the film 10 to a substrate, in particular to a security document.
  • the print 100, 102 it is also conceivable for the print 100, 102 to be irradiated several times, as a result of which in particular a first supplementary individualization or personalization and at least one further supplementary individualization or personalization is created.
  • the irradiations preferably take place at different points of the print 100, 102.
  • the multiple irradiations can all take place during the manufacture of the multilayer film 10 or also partly during manufacture and partly after manufacture, in particular after application of the multilayer film 10 to a substrate, or also all after manufacture. It is advantageous if the first supplementary individualization takes place during the production of the multilayer film 10 and at least one further individualization takes place after the production of the film 10, in particular after the film has been applied to a substrate.
  • the inside figure 4 Print 102 shown is designed as a square area.
  • a transparent or invisible ink was applied to one layer for this purpose.
  • the print 102 is therefore invisible before the laser irradiation and is therefore basically not visible to the human observer.
  • At least part of the print 102 is irradiated with a laser L, whereby this part 104 is made visible; blackening can occur, for example.
  • the other parts 106 of the print remain invisible.
  • the print 102 was already visible or colored before the laser treatment L and its optical appearance changes as a result of the laser treatment L, as a result of which the irradiated area 106 differs from the remaining area 106 of the print.
  • the pressure 102 shown is cloud-shaped. Before laser irradiation L, the print 102 can be made invisible.
  • the print 102 is preferably completely irradiated with a laser, whereby the print 104 becomes visible, in particular turns black.
  • the print 102 is visible, in particular colored, and changes its optical appearance as a result of the laser irradiation L, in particular a color change and/or fading and/or blackening occurs.
  • the further or supplementary individualization is produced.
  • One possibility is, for example, the application of an invisible ink.
  • the ink can be applied either over the entire surface or in certain areas, in particular as a motif.
  • the ink is then irradiated in some areas or completely. As a result, either only areas of the ink or the entire area printed with ink are made visible. It is advantageous if only areas of the applied ink are irradiated.
  • figure 6 10 shows a print 102 placed adjacent to a motif 108.
  • the print 102 is preferably provided by applying a transparent and/or invisible ink. the inside figure 6
  • the print 102 shown is therefore transparent and/or invisible. In principle, however, the print 102 can also be colored and/or opaque.
  • the motif 108 can be an ink or a print within the meaning of the invention. However, it is also possible for the motif 108 to be any coding, any decoration, a decorative design and/or a motif which is/are arranged on any layer of the multi-layer film. The motif does not have to have been created or produced in any particular way.
  • the print 102 is preferably irradiated in such a way that the irradiated area 104 of the print forms an overall motif with the visible motif 108 .
  • FIG 7 shows a schematic plan view of a multilayer film 10 with a print 100 in one embodiment.
  • the print 100 is in the form of a code, in particular a data matrix code, a QR code and/or a micro QR code.
  • the QR code and the micro QR code are composed of a large number of code elements 108 . It is advantageous if the individual code elements 108 are in turn composed of a plurality of ink drops.
  • to provide a code element 108 in one direction viewed in particular in the X direction, at least 2, preferably 4, ink drops are printed.
  • ink drops are printed or required for a code element. The more ink drops the better and the cleaner the edges of the code element 108 and thus also the code come out.
  • the inside figure 7 Print 100 shown is surrounded by a halo 26 .
  • the halo 26 is in particular an area in the replication layer or the replication lacquer 24 which is not provided with a replication structure.
  • the halo 26 can promote visibility or recognition of the print 100 .
  • the halo 26 serves in particular as a contrast-enhancing means.
  • the width of the halo 26 is in particular between 1 ⁇ m and 100 ⁇ m.
  • the Figures 8a to 8d show schematic plan views of a print 100 in further configurations.
  • the in the Figures 8a to 8d The prints 100 shown are in the form of micro QR codes.
  • the inside Figure 8a Micro QR code shown has 11x11 code elements 108 that are in Figure 8b
  • Micro QR code shown has 13x13 code elements 108, which in Figure 8c
  • the micro QR code shown has 15x15 code elements 108 and the in Figure 8d
  • the micro QR code shown has 17 ⁇ 17 code elements 108 .
  • the micro QR codes can have a size of 3 mm or 5 mm. If a micro QR code has an overall size of 3 mm and comprises 11 ⁇ 11 code elements 108, then each code element 108 has a size of 272.7 ⁇ m. A Micro QR code has an overall size of 3mm and is 13x13 Code elements 108, each code element 108 has a size of 230.8 ⁇ m. If a micro QR code has an overall size of 3 mm and comprises 15 ⁇ 15 code elements 108, then each code element 108 has a size of 200 ⁇ m. If a micro QR code has an overall size of 3 mm and comprises 17 ⁇ 17 code elements 108, then each code element 108 has a size of 176.5 ⁇ m.
  • each code element 108 has a size of 454.5 ⁇ m. If a micro QR code has an overall size of 5 mm and comprises 13 ⁇ 13 code elements 108, then each code element 108 has a size of 384.6 ⁇ m. If a micro QR code has an overall size of 5 mm and includes 15 ⁇ 15 code elements 108, then each code element 108 has a size of 333.3 ⁇ m. If a micro QR code has an overall size of 5 mm and comprises 17 ⁇ 17 code elements 108, then each code element 108 has a size of 294.1 ⁇ m.
  • Micro QR code 3mm micro QR code 5mm micro QR code Number of code elements Size code element in X direction ( ⁇ m) Size code element in X-direction ( ⁇ m) 11x11 272.7 454.5 13x13 230.8 384.6 15x15 200.0 333.3 17x17 176.5 294.1
  • the individual code elements 108 are then composed of several ink drops. Examples of this are given in the following table: Micro QR code 3mm Number of drops of ink that make up a code element size one 11x11 code 13x13 code 15x15 code 17x17 code Ink drop ( ⁇ m) elements elements elements elements elements 84.7 3.22 2.73 2.36 2.08 70.6 3.87 3.27 2.83 2.50 42.3 6.44 5.45 4.72 4:17 28.2 9.66 8:18 7.09 6.25 21.2 12.88 10.90 9.45 8.34 Micro QR code 5mm Number of drops of ink that make up a code element Size of an ink drop ( ⁇ m) 11x11 code elements 13x13 code elements 15x15 code elements 17x17 code elements 84.7 5.37 4.54 3.94 3.47 70.6 6.44 5.45 4.72 4:17 42.3 10.74 9.09 7.87 6.95 28.2 16:11 13.63 11.81 10:42 21.2 21:47 18:17 15.75 13.90
  • the Figures 9a and 9b show schematic plan views of a print 100 in further configurations.
  • the in the Figures 9a and 9b Prints 100 shown are in the form of QR codes.
  • the inside Figure 9a QR code shown has 22x22 code elements 108 and the in Figure 9b
  • the QR code shown has 32x32 code elements 108 .
  • the QR codes can have a size of 3 mm or 5 mm. If a QR code has an overall size of 3 mm and comprises 22 ⁇ 22 code elements 108, then each code element 108 has a size of 136.4 ⁇ m. If a QR code has an overall size of 3 mm and comprises 32 ⁇ 32 code elements 108, then each code element 108 has a size of 93.8 ⁇ m.
  • each code element 108 has a size of 227.3 ⁇ m. If a QR code has an overall size of 5 mm and includes 32 ⁇ 32 code elements 108, then each code element 108 has a size of 156.3 ⁇ m.
  • the individual code elements 108 are then composed of several ink drops. Examples of this are given in the following table: QR code 3mm Number of ink drops that make up a code element Size of an ink drop ( ⁇ m) 22x22 code elements 32x32 code elements 84.7 1.61 1:11 70.6 1.93 1.33 42.3 3.22 2:21 28.2 4.83 3.32 21.2 6.44 4.43 QR code 5mm Number of ink drops that make up a code element Size of an ink drop ( ⁇ m) 22x22 code elements 32x32 code elements 84.7 2.68 1.85 70.6 3.22 2:21 42.3 5.37 3.69 28.2 8.05 5.54 21.2 10.74 7.38
  • the Figure 10a shows a microscope image (x100) of a 3 mm QR code with 32x32 code elements, where the QR code was printed at 600 dpi.
  • the Figure 10b shows a microscope image (x100) of a 5 mm QR code with 32x32 code elements, where the QR code was printed at 600 dpi. Values or dimensions of individual code elements are shown in the figures.

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EP23168899.5A 2017-03-29 2018-03-26 Procédé de fabrication d'une feuille multicouche et feuille multicouche ainsi qu'élément de sécurité et document de sécurité Pending EP4219184A1 (fr)

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DE102017106721.3A DE102017106721A1 (de) 2017-03-29 2017-03-29 Verfahren zum Herstellen einer Mehrschichtfolie und eine Mehrschichtfolie sowie ein Sicherheitselement und ein Sicherheitsdokument
EP18713893.8A EP3600907B1 (fr) 2017-03-29 2018-03-26 Procédé de fabrication d'une feuille multicouche et feuille multicouche ainsi qu'élément de sécurité et document de sécurité
PCT/EP2018/057619 WO2018178000A1 (fr) 2017-03-29 2018-03-26 Procédé de fabrication d'une feuille multicouche et feuille multicouche ainsi qu'élément de sécurité et document de sécurité

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EP3600907A1 (fr) 2020-02-05
TW201841781A (zh) 2018-12-01
DE102017106721A1 (de) 2018-10-04
JP7264823B2 (ja) 2023-04-25
EP3600907B1 (fr) 2023-06-14
CA3059176A1 (fr) 2018-10-04
FI3600907T3 (fi) 2023-08-09
CN110678337B (zh) 2022-03-18
AR111148A1 (es) 2019-06-05
WO2018178000A1 (fr) 2018-10-04
US10960704B2 (en) 2021-03-30
TWI757464B (zh) 2022-03-11
US20200070566A1 (en) 2020-03-05

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Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR