EP2578414A1 - Security element with colour-switching effect, use of same and method for producing same - Google Patents
Security element with colour-switching effect, use of same and method for producing same Download PDFInfo
- Publication number
- EP2578414A1 EP2578414A1 EP11007998.5A EP11007998A EP2578414A1 EP 2578414 A1 EP2578414 A1 EP 2578414A1 EP 11007998 A EP11007998 A EP 11007998A EP 2578414 A1 EP2578414 A1 EP 2578414A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- security element
- layer
- optically variable
- carrier substrate
- applying
- 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.)
- Granted
Links
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- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- DCSIADKYJYMWMM-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene;1,1,2,2-tetrafluoroethene Chemical compound FC(F)=C(F)F.FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F DCSIADKYJYMWMM-UHFFFAOYSA-N 0.000 description 1
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- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- MURCDOXDAHPNRQ-ZJKZPDEISA-N L-685,458 Chemical compound C([C@@H]([C@H](O)C[C@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC=1C=CC=CC=1)C(N)=O)CC=1C=CC=CC=1)NC(=O)OC(C)(C)C)C1=CC=CC=C1 MURCDOXDAHPNRQ-ZJKZPDEISA-N 0.000 description 1
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- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
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- QHSJIZLJUFMIFP-UHFFFAOYSA-N ethene;1,1,2,2-tetrafluoroethene Chemical group C=C.FC(F)=C(F)F QHSJIZLJUFMIFP-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
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- B42D25/405—Marking
- B42D25/43—Marking by removal of material
- B42D25/445—Marking by removal of material using chemical means, e.g. etching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/45—Associating two or more layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/40—Manufacture
- B42D25/45—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, a Farbkipp bin exhibiting, security element, which additionally recognizable in transmitted light has recesses, a method for its preparation, and its use.
- Color-shift effects can be achieved by various means, such as thin-layer interference, such as structures having an electromagnetic wave reflecting layer, a spacer layer, and a metallic cluster layer.
- Such security elements are, for example, in US 2005/042449 A or in EP 1 558 449 A described.
- Another way to provide a security element that has a color shift effect is to use a coating of liquid crystals, either in the form of a pigmented layer or a polymerized film.
- EP 0 435 129 A For example, a data carrier with a liquid crystal security element is known, wherein the material is a liquid crystal polymer which is in an oriented form and solid at room temperature.
- a security element comprising an optically variable material, which may be, for example, a liquid crystalline material, and at least one additional machine-readable feature substance in the same layer.
- a light-absorbing, preferably black, background In order to optimally recognize the color shift effect, it is necessary to provide a light-absorbing, preferably black, background.
- background light is clearly visible as a dark area on the back of a security element, such as a thread or strip at least partially embedded in a value document, such as a banknote or the like.
- This light-absorbing background must therefore be covered so as not to discern the security element from the outset. This cover can be done for example by a metallic layer.
- a method for producing a substrate comprising the steps of applying a resist to at least a portion of a metal layer on a first side of a transparent polymer film, removing metal from the areas not covered by the cap layer to form metal-free portions, and depositing another A layer for covering the resist and the metal-free portions, wherein the further layer is a layer of liquid crystal polymer material, and the resist is dark colored and the underlying metal areas masked and in the areas covered by the liquid crystal polymer material when viewed in reflection from the first side to a Color change effect leads and wherein the contrast between the metallized and the metal-free areas can be clearly distinguished.
- Out EP 1 580 297 A is a film material, in particular for security elements, known having a full-surface or partial opaque coating, wherein the opaque coating is made of a single material component by means of a PVD or CVD method and has different color impressions from different sides.
- the object of the invention was to provide a security element comprising a material having an optically variable effect, preferably a color shift effect, and recesses recognizable in transmitted light, wherein the security element is designed such that it provides both optimum recognition of the optically variable effect allowed, as viewed in reflection in a value document in at least partially embedded state, from the back through the paper surface is not recognizable.
- the invention therefore provides a security element which has a coating of a material which has an optically variable effect, in particular a color shift effect and recognizable recesses in the transmitted light, wherein the security element comprises a carrier substrate and a partial layer with recesses, characterized in that the Partial layer is formed of an opaque coating on the, the coating of the material having an optically variable effect, side facing light-absorbing properties and on the, the coating of the material having an optically variable effect, side facing away has a metallic coloring, wherein the partial opaque coating consists of a light-absorbing metallic layer and a reflective metallic layer.
- the recesses When viewed in transmitted light, the recesses can be seen as a clear contrast to the areas which have a light-absorbing and a reflective metallic layer.
- the security element if it is embedded in a document of value, is not or barely recognizable even in incident light from the back through the paper surface. From the back, however, the recesses are clearly visible in transmitted light. From the front of the oprisch variable effect and the recesses in reflected light are clearly visible.
- carrier films preferably transparent flexible plastic films, for example from PI, PP, MOPP, PE, PPS, PEEK, PEK, PEI, PSU, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC, PTFE, ETFE (ethylene tetrafluoroethylene), PFA (tetrafluoroethylene-perfluoropropyl vinyl ether fluorocopolymer), MFA (tetrafluoromethylene-perfluoropropyl vinyl ether fluorocopolymer), PTFE (polytetrafluoroethylene), PVF (polyvinyl fluoride), PVDF (polyvinylidene fluoride), and EFEP (ethylene-tetrafluoroethylene-hexafluoropropylene Fluoropolymer).
- the carrier films preferably have a thickness of 5 to 700 .mu.m, preferably 5 to 200 .mu.m, particularly
- the material having an optically variable effect may be an ink containing pigments of liquid crystal material.
- the pigments consist of cholesteric or a mixture of nematic and cholesteric liquid crystals.
- OMI pigments optically variable interference pigments
- Such pigments are for example in US 2003/0207113 described.
- iridescent pigments for example, Iriodine ® pigments can be used. Iriodine ® is based on naturally occurring mineral mica flakes encased in semi-transparent metal oxides.
- the material having an optically variable effect may consist of a liquid crystal polymer which is applied as a solution of the cholesteric monomers or the mixture of cholesteric and nematic monomers and then crosslinked.
- the crosslinking can be effected thermally or by treatment with UV radiation or electron radiation.
- a light-absorbing metallic layer are preferably non-stoichiometric alumina and stoichiometric or unstoichiometric copper oxide in question.
- the light absorbing metallic Layer has a preferably dark to black color. The stronger the absorption of the background in the visible spectral range (350 - 800 nm), the stronger the visible optically variable effect.
- metals such as Al, Sn, Cu, Zn, Pt, Au, Ag, Cr, Ti, Mo, Fe, Pd, Ni, Co or their alloys, for example Cu / Al in question.
- the light-absorbing metallic layer may consist of unstoichiometric alumina, preferably having an oxygen content of about 19-58 at%, and the reflective metallic layer of aluminum.
- the recesses in the light absorbing metallic layer and the reflective metallic layer are perfectly congruent and may be in the form of characters, letters, numbers, images, symbols, lines, guilloches, and the like. Also combinations of these forms are possible.
- the recesses may also be in negative form, that is, for example, the area around a character, a letter and the like forms the recess.
- the security element according to the invention can also have further security features which can be present in further layers.
- These security features for example, can have certain chemical, physical and also optical or optical active properties.
- paramagnetic, diamagnetic and also ferromagnetic substances such as iron, nickel and cobalt or their compounds or salts (for example oxides or sulfides) can be used.
- magnétique pigment inks with pigments based on Fe oxides, iron, nickel cobalt and their alloys, barium or cobalt ferrites, hard and soft magnetic iron and steel grades in aqueous or solvent-containing dispersions.
- suitable solvents are i-propanol, ethyl acetate, methyl ethyl ketone, methoxypropanol and mixtures thereof.
- the pigments are preferably incorporated in acrylate polymer dispersions having a molecular weight of from 150,000 to 300,000, in nitrocellulose, acrylate-urethane dispersions, acrylate-styrene or PVC-containing dispersions or in solvent-containing dispersions of this type.
- the magnetic layer may also have a coding. Both magnetic materials of the same coercivity and / or remanence as well as different coercivity and / or remanence can be used to form the coding.
- the reflective metallic layer may itself have magnetic properties. This is achieved, for example, by the use of a magnetic material such as Fe, Ni, Co.
- the optical properties of the layer can be influenced by visible dyes or pigments, luminescent dyes or pigments which fluoresce or phosphoresce in the visible, in the UV region or in the IR region, heat-sensitive inks or pigments. These can be used individually or in all possible combinations.
- optically active characteristics are here diffraction structures, diffraction gratings, kinegrams, holograms, DID understood ® (0th order in conjunction with thin films microstructures). These optically active features can be obtained, for example, by known UV embossing methods, as used, for example, in US Pat EP 1 310 381 A are described or produced by hot stamping
- this adhesive coating can be carried out either in the form of a heat-seal, cold-seal or self-adhesive coating.
- the adhesive may also be pigmented, using as pigments all known pigments or dyes, for example TiO 2 , ZnS, kaolin, ATO, FTO, aluminum, chromium and silicon oxides or, for example, organic pigments such as pthalocyanine blue, i-indolid yellow, dioxazine violet and the like can.
- thermosensitive dyes or pigments to luminescent dyes or pigments which fluoresce or phosphoresce in the visible, in the UV region or in the IR region.
- luminescent pigments can also be used alone or in combination with other dyes and / or pigments.
- the security element can also be protected by one or more protective lacquer layer (s), which may be pigmented or unpigmented, or further refined, for example, by laminating or the like.
- protective lacquer layer may be pigmented or unpigmented, or further refined, for example, by laminating or the like.
- the recesses are achieved in the light-absorbing and the reflective metallic layer.
- the recesses can be seen as a clear contrast to the areas which have a light-absorbing and a reflective metallic layer.
- the security element if it is embedded in a value document, is not or hardly recognizable even in incident light when viewed from the side of the reflective metallic layer by the covering paper layer.
- a paint application soluble in a solvent in the form of the later recesses is applied to the carrier substrate, in a second step this layer is optionally treated by means of an in-line plasma, corona or flame process and in a third step, the reflective and then the light-absorbing metallic coating is applied by means of a PVD or CVD process, whereupon in a fourth step the paint application with the overlying layers is removed by means of a solvent, optionally combined with a mechanical action.
- the application of paint takes place either in the form of characters, letters, numbers, images, symbols, lines, guilloches or a dot or line grid or a halftone screen and the like, or such that the application of color the outlines of the characters, letters, numbers, images, symbols , Lines, guilloches, a dot or line raster or halftone raster, and the like.
- the recesses in the finished structure in transmitted light
- the characters, letters, numbers, images, symbols, lines, guilloches, and the like are dark in transmitted light, the areas around these characters, letters , Numerals, images, symbols, lines, guilloches and the like form the recesses recognizable by transmitted light.
- the application of the paint can be done by any method, for example by gravure printing, flexographic printing, screen printing, digital printing and the like.
- the color or lacquer used is soluble in a solvent, preferably water, but it is also possible to use a dye soluble in any solvent, for example in alcohol, esters and the like.
- the color or the colored lacquer can be customary compositions based on natural or artificial macromolecules.
- the soluble color may be pigmented or unpigmented.
- pigments all known pigments can be used. Particularly suitable are TiO 2 , ZnS, kaolin and the like.
- a pretreatment of the carrier substrate provided with the inking takes place prior to the application of the metallic layers by means of an inline plasma, (low pressure or atmospheric plasma), corona or flame process.
- This pretreatment improves the adhesion of the metallic layer.
- the surface is activated. In this case, terminal polar groups are generated on the surface.
- a thin metal or metal oxide layer can be applied as adhesion promoter, for example by sputtering or vapor deposition.
- Particularly suitable are Cr, Ti, TiO 2 , Si oxides or chromium oxides.
- This adhesive layer generally has a thickness of 0.1 nm - 5 nm, preferably 0.2 nm - 2 nm, particularly preferably 0.2 to 1 nm.
- the application of the reflective metallic layer by PVD or CVD method such as by thermal evaporation, by sputtering or Elektronenstrahlbedampfung.
- the coating is applied under vacuum (to 10 -12 mbar, preferably 10 -2 to 10 -6 mbar) at a temperature dependent on the vapor pressure and the thickness of the applied coating on the carrier substrate, for example by thermal evaporation, arc or Electron beam evaporation deposited.
- Another possibility is the application of the coating by AC or DC sputtering, wherein the appropriate method is selected depending on the thickness of the layer to be applied and the material used.
- gaseous precursor compounds eg organometallic precursor compounds
- precursors gaseous precursor compounds
- an inert carrier gas eg N 2 , argon
- gaseous precursors can be, for example, CO, CO 2 , oxygen, silanes, methane, ammonia, ferrocene, trimethylaluminum, or the like.
- the introduction of energy can be done for example by means of an ion or electron beam, a plasma or at elevated temperature.
- a light-absorbing metallic layer is deposited analogously by PVD or CVD methods, for example by thermal evaporation, by sputtering or electron beam vapor deposition.
- the coating is oxidized by appropriately metered oxygen supply to unstoichiometric oxides, whereby the appearance is changed.
- unstoichiometric alumina or stoichiometric or unstoichiometric copper oxide appears black to form a light-absorbing metallic layer.
- the color layer is removed by a suitable solvent, which is adapted to the composition of the color layer.
- a suitable solvent which is adapted to the composition of the color layer.
- the application of paint is preferably water-soluble.
- the separation can be supported by mechanical action.
- the recesses may also be made by a known etching process.
- the reflective and the light-absorbing metallic layer are applied to the carrier substrate, and then an etching resist is applied, which leaves open the later recesses.
- the areas of the two layers not covered by the etch resist are removed by etching. Possibly. the etch resist can then be removed.
- a full-surface or partial layer of an optically variable effect material is applied.
- Application may be by any method, such as gravure, flexo, screen, digital, roll or reverse, curtain coating, spin coating, and the like.
- the structure of the layers having recognizable recesses in the transmitted light is applied to a second carrier substrate, while the layer of an optically variable effect material is applied to the first carrier substrate.
- this embodiment is preferred.
- the molecular chains can thereby orient themselves on the carrier substrate.
- the layers applied to the second carrier substrate are laminated against the layers present on the first carrier substrate, optionally the first carrier substrate can be removed depending on the use of the security element.
- security features having optically, optically active, electrically conductive or magnetic properties can be applied to the first and / or the second carrier substrate or to the layers present thereon, or already applied thereto.
- the security element produced in this way can then be provided on one or both sides with one or more protective lacquer layer (s) and / or an adhesive coating.
- a release layer may be applied to the carrier substrate before the application of the layer of a material having an optically variable effect, whose adhesion to the carrier substrate is lower than to the layers applied thereon.
- a release layer may be applied to the carrier substrate before the application of the layer of a material having an optically variable effect, whose adhesion to the carrier substrate is lower than to the layers applied thereon.
- other known poorly adhering coating compositions for example methacrylate-based or oil-based, polyamide, polyethylene or fluoropolymer wax layers.
- the application of a release layer is not necessary if the layer of a material which has an optically variable effect is releasable.
- the security element produced in this way can be applied to a substrate with the adhesive coating, wherein the first carrier substrate is removed, if necessary, after the application.
- a security element suitable for at least partial embedding and application is shown.
- the structure of the layers is carried out on a carrier substrate 8.
- a carrier substrate 8 In this case, first the partial reflective metallic layer 5 and the partial light-absorbing metallic layer 4 with the recesses 10 and then a full-surface layer 2 of a material having an optically variable effect applied.
- Fig. 1a shows that in FIG. 1 illustrated security element when viewed in incident light from the side of the layer 2, which has an optically variable effect.
- the optically variable effect may be, for example, a color shift effect.
- a strong color is recognizable. If one tilts the security element, so that the viewing angle changes, a color change is visible especially in the areas in which the layers 2, 4 and 5 are superimposed.
- the areas in which the layer 2 comes to rest over the recesses 10, show no or only slightly recognizable color impression in reflected light.
- the area in which the layers 2, 4 and 5 lie one above the other appears opaque.
- the recesses 10 are visible in transmitted light as a bright area with a strong contrast to the surrounding dark areas
- Fig. 2 an inventive security element is shown, in which the layer structure on two carrier substrates (8, 9) takes place.
- the material 2 having an optically variable effect is applied to the first carrier substrate 9, and the structure of the reflective metallic layer 5 and the light-absorbing metallic layer 4 with the recesses 10 takes place on the second carrier substrate 8.
- the two carrier substrates with the layers applied thereto are formed by means of a laminating adhesive layer 3 so interconnected that the optically variable effect layer having on the side of the light-absorbing metal layer comes to rest. If the security element is now viewed through the carrier substrate 10a, it is shown in a similar manner as in FIG Fig. 1 described, a viewing angle-dependent color impression.
- the security element according to the invention is shown as a transfer element.
- a transfer element is preferably used when the security element is not embedded in a value document but is applied to the surface of a value document.
- the Construction ( Fig. 3 ) is carried out on a carrier substrate 8, wherein as the first layer, the layer of a material 2 having an optically variable effect, and then the light-absorbing metallic layer 4 and the reflective metallic layer 5 with the recesses 10 are applied.
- the security element is provided with a protective lacquer layer 6 and an adhesive coating 1, preferably a heat seal adhesive coating.
- the adhesion of the layers 2 to layer 8 is less than the adhesion of the layers 2, 4, 5, 6, 1 and 8 with each other.
- Fig. 4 For example, the transfer element applied to a substrate of a value document, such as banknote paper, is shown.
- the transfer element is applied by means of the heat seal adhesive coating 1 on the substrate of the document of value 12, the carrier substrate 8 is then removed.
- the structure remaining on the document of value is then only a few ⁇ m thick and does not lead to a significant thickening of the document of value at this point in order to avoid thickness-related problems during stacking.
- a security element according to the invention is shown, the structure of which essentially corresponds to that in the Fig. 1 corresponds structure shown, but additionally has a partial magnetic layer 7. Further, an additional partial reflective metallic layer 11 is provided to cover the dark magnetic regions 7.
- the security element is usually still provided on both sides with an adhesive coating, which ensures a secure anchoring of the thread in the document of value.
- the security elements according to the invention are optionally after appropriate assembly as security features in data carriers, in particular value documents such as identity cards, cards, banknotes or Labels, seals and the like suitable, but also suitable as packaging material, for example in the pharmaceutical, electronics and / or food industry, for example in the form of blister films, cartons, covers, film packaging and the like.
- the substrates or film materials are preferably cut into strips, threads or patches, wherein the width of the strips or threads may preferably be 0.5-20 mm and the patches preferably have average widths or lengths of 0.3. 20 mm.
- the film material is preferably cut into strips, tapes, threads or patches, the width of which of the threads, strips or tapes being preferably 0.5-50 mm and the patches preferably being average widths and lengths of 2 - 30 mm.
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Abstract
Description
Die Erfindung betrifft ein, einen Farbkippeffekt aufweisendes, Sicherheitselement, des zusätzlich im Durchlicht erkennbare Aussparungen aufweist, ein Verfahren zu dessen Herstellung, sowie dessen Verwendung.The invention relates to a, a Farbkippeffekt exhibiting, security element, which additionally recognizable in transmitted light has recesses, a method for its preparation, and its use.
Sicherheitselemente, die einen Farbkippeffekt aufweisen sind bekannt. Farbkippeffekte können durch unterschiedliche Maßnahmen erzielt werden, beispielsweise durch Dunnschichtinterferenz, wie durch Aufbauten, die eine elektromagnetische Wellen reflektierende Schicht, eine Abstandsschicht und eine Schicht gebildet aus metallischen Cluster aufweisen. Derartige Sicherheitselemente sind beispielsweise in
Eine weitere Möglichkeit ein Sicherheitselement bereitzustellen, das einen Farbkippeffekt aufweist, ist die Verwendung einer Beschichtung aus Flüssigkristallen, entweder in Form einer pigmentierten Schicht oder eines polymerisierten Films.Another way to provide a security element that has a color shift effect is to use a coating of liquid crystals, either in the form of a pigmented layer or a polymerized film.
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Um den Farbkippeffekt optimal zu erkennen, ist es erforderlich einen lichtabsorbierenden, vorzugsweise schwarzen, Hintergrund bereitzustellen. Der lichtabsorbierende, vorzugsweise schwarze, Hintergrund ist jedoch auf der Rückseite eines Sicherheitselements, wie beispielsweise eines Fadens oder Streifens, das zumindest teilweise in ein Wertdokument, wie eine Banknote oder dergleichen eingebettet ist, deutlich als dunkler Bereich sichtbar. Dieser lichtabsorbierende Hintergrund muss also, um das Sicherheitselement nicht von vornherein erkennbar zu machen, abgedeckt werden. Diese Abdeckung kann beispielsweise durch eine metallische Schicht erfolgen.In order to optimally recognize the color shift effect, it is necessary to provide a light-absorbing, preferably black, background. The However, background light is clearly visible as a dark area on the back of a security element, such as a thread or strip at least partially embedded in a value document, such as a banknote or the like. This light-absorbing background must therefore be covered so as not to discern the security element from the outset. This cover can be done for example by a metallic layer.
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Gegenstand der Erfindung ist daher ein Sicherheitselement, das eine Beschichtung aus einem Material aufweist, das einen optisch variablen Effekt, insbesondere einen Farbkippeffekt und im Durchlicht erkennbare Aussparungen aufweist, wobei das Sicherheitselement ein Trägersubstrat und eine partielle Schicht mit Aussparungen umfasst, dadurch gekennzeichnet, dass die partielle Schicht gebildet ist aus einer opaken Beschichtung, die auf der, der Beschichtung aus dem Material, das einen optisch variablen Effekt aufweist, zugewandten, Seite lichtabsorbierende Eigenschaften aufweist und auf der, der Beschichtung aus dem Material das einen optisch variablen Effekt aufweist, abgewandten Seite eine metallische Färbung aufweist, wobei die partielle opake Beschichtung aus einer lichtabsorbierenden metallischen Schicht und einer reflektierenden metallischen Schicht besteht.The invention therefore provides a security element which has a coating of a material which has an optically variable effect, in particular a color shift effect and recognizable recesses in the transmitted light, wherein the security element comprises a carrier substrate and a partial layer with recesses, characterized in that the Partial layer is formed of an opaque coating on the, the coating of the material having an optically variable effect, side facing light-absorbing properties and on the, the coating of the material having an optically variable effect, side facing away has a metallic coloring, wherein the partial opaque coating consists of a light-absorbing metallic layer and a reflective metallic layer.
Bei der Betrachtung im Durchlicht sind die Aussparungen als deutlicher Kontrast gegenüber den Bereichen, die eine lichtabsorbierende und eine reflektierende metallische Schicht aufweisen, erkennbar. Durch die reflektierende metallische Schicht ist das Sicherheitselement, wenn es in ein Wertdokument eingebettet ist, auch im Auflicht von der Rückseite durch die Papieroberfläche nicht bzw. kaum erkennbar. Von der Rückseite sind im Durchlicht die Aussparungen aber deutlich erkennbar. Von der Vorderseite sind der oprisch variable Effekt und die Aussparungen im Auflicht deutlich erkennbar.When viewed in transmitted light, the recesses can be seen as a clear contrast to the areas which have a light-absorbing and a reflective metallic layer. As a result of the reflective metallic layer, the security element, if it is embedded in a document of value, is not or barely recognizable even in incident light from the back through the paper surface. From the back, however, the recesses are clearly visible in transmitted light. From the front of the oprisch variable effect and the recesses in reflected light are clearly visible.
Als Trägersubstrate kommen beispielsweise Trägerfolien vorzugsweise transparente flexible Kunststofffolien, beispielsweise aus PI, PP, MOPP, PE, PPS, PEEK, PEK, PEI, PSU, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC, PTFE, ETFE (Ethylentetrafluorethylen), PFA (Tetrafluorethylen-Perfluorpropylvinylether-Fluorcopolymer), MFA (Tetrafluormethylen-Perfluorpropylvinylether-Fluorcopolymer), PTFE (Polytetrafluorethylen), PVF (Polyvinylfluorid), PVDF (Polyvinylidenfluorid), und EFEP (Ethylen-Tetrafluorethylen-Hexafluorpropylen-Fluorterpolymer) in Frage. Die Trägerfolien weisen vorzugsweise eine Dicke von 5 - 700 µm, bevorzugt 5 - 200 µm, besonders bevorzugt 5 - 50 µm auf.As carrier substrates, for example carrier films preferably transparent flexible plastic films, for example from PI, PP, MOPP, PE, PPS, PEEK, PEK, PEI, PSU, PAEK, LCP, PEN, PBT, PET, PA, PC, COC, POM, ABS, PVC, PTFE, ETFE (ethylene tetrafluoroethylene), PFA (tetrafluoroethylene-perfluoropropyl vinyl ether fluorocopolymer), MFA (tetrafluoromethylene-perfluoropropyl vinyl ether fluorocopolymer), PTFE (polytetrafluoroethylene), PVF (polyvinyl fluoride), PVDF (polyvinylidene fluoride), and EFEP (ethylene-tetrafluoroethylene-hexafluoropropylene Fluoropolymer). The carrier films preferably have a thickness of 5 to 700 .mu.m, preferably 5 to 200 .mu.m, particularly preferably 5 to 50 .mu.m.
Das Material, das einen optisch variablen Effekt aufweist, kann eine Druckfarbe sein, die Pigmente aus flüssigkristallinem Material enthält. Insbesondere bestehen die Pigmente aus cholesterischen oder einer Mischung aus nematischen und cholesterischen Flüssigkristallen.
Ferner können optisch variable Interferenzpigmente (OVI-Pigmente) verwendet werden. Derartige Pigmente sind beispielsweise in
In einer weiteren Ausführungsform können irisierende Pigmente, beispielsweise Iriodine® Pigmente verwendet werden. Iriodine® basieren auf natürlich vorkommenden mineralischen Glimmerplättchen, die mit halbtransparenten Metalloxiden ummantelt sind.
Weiters kann das Material, das einen optisch variablen Effekt aufweist, aus einem Flüssigkristallpolymer bestehen, das als Lösung der cholesterischen Monomere oder der Mischung aus cholesterischen und nematischen Monomeren aufgetragen und anschließend vernetzt wird. Die Vernetzung kann thermisch oder durch Behandlung mit UV- Strahlung oder Elektronenstrahlung erfolgen.The material having an optically variable effect may be an ink containing pigments of liquid crystal material. In particular, the pigments consist of cholesteric or a mixture of nematic and cholesteric liquid crystals.
Furthermore, optically variable interference pigments (OVI pigments) can be used. Such pigments are for example in
In another embodiment, iridescent pigments, for example, Iriodine ® pigments can be used. Iriodine ® is based on naturally occurring mineral mica flakes encased in semi-transparent metal oxides.
Furthermore, the material having an optically variable effect may consist of a liquid crystal polymer which is applied as a solution of the cholesteric monomers or the mixture of cholesteric and nematic monomers and then crosslinked. The crosslinking can be effected thermally or by treatment with UV radiation or electron radiation.
Als lichtabsorbierende metallische Schicht kommen vorzugsweise unstöchiometrisches Aluminiumoxid und stöchiometrisches oder unstöchiometrisches Kupferoxid in Frage. Die lichtabsorbierende metallische Schicht weist eine vorzugsweise dunkle bis schwarze Färbung auf. Je stärker die Absorption des Hintergrundsim sichtbaren Spektralbereich (350 - 800 nm), desto stärker der sichtbare optisch variable Effekt.As a light-absorbing metallic layer are preferably non-stoichiometric alumina and stoichiometric or unstoichiometric copper oxide in question. The light absorbing metallic Layer has a preferably dark to black color. The stronger the absorption of the background in the visible spectral range (350 - 800 nm), the stronger the visible optically variable effect.
Als reflektierende metallische Schicht kommen Metalle, wie Al, Sn, Cu, Zn, Pt, Au, Ag, Cr, Ti, Mo, Fe, Pd, Ni, Co oder deren Legierungen, beispielsweise Cu/Al in Frage.As a reflective metallic layer, metals such as Al, Sn, Cu, Zn, Pt, Au, Ag, Cr, Ti, Mo, Fe, Pd, Ni, Co or their alloys, for example Cu / Al in question.
In einer besonderen Ausführungsform kann die lichtabsorbierende metallische Schicht aus unstöchiometrischem Aluminiumoxid, vorzugsweise mit einem Sauerstoffgehalt von etwa 19 - 58 at%, und die reflektierende metallische Schicht aus Aluminium bestehen.In a particular embodiment, the light-absorbing metallic layer may consist of unstoichiometric alumina, preferably having an oxygen content of about 19-58 at%, and the reflective metallic layer of aluminum.
Die Aussparungen in der lichtabsorbierenden metallischen Schicht und der reflektierenden metallischen Schicht sind vollkommen deckungsgleich und können in Form von Zeichen, Buchstaben, Ziffern, Bildern, Symbolen, Linien, Guillochen und dergleichen vorliegen. Auch Kombinationen dieser Formen sind möglich.
Die Aussparungen können auch in negativer Form vorliegen, das heißt, dass beispielsweise der Bereich um ein Zeichen, einen Buchstaben und dergleichen die Aussparung bildet.The recesses in the light absorbing metallic layer and the reflective metallic layer are perfectly congruent and may be in the form of characters, letters, numbers, images, symbols, lines, guilloches, and the like. Also combinations of these forms are possible.
The recesses may also be in negative form, that is, for example, the area around a character, a letter and the like forms the recess.
Das erfindungsgemäße Sicherheitselement kann auch weitere Sicherheitsmerkmale aufweisen, die in weiteren Schichten vorliegen können. Diese Sicherheitsmerkmale beispielsweise können bestimmte chemische, physikalische und auch optische oder optische aktive Eigenschaften aufweisen.The security element according to the invention can also have further security features which can be present in further layers. These security features, for example, can have certain chemical, physical and also optical or optical active properties.
Zur Einstellung der magnetischen Eigenschaften einer Schicht können paramagnetische, diamagnetische und auch ferromagnetische Stoffe, wie Eisen, Nickel und Cobalt oder deren Verbindungen oder Salze (beispielsweise Oxide oder Sulfide) verwendet werden.To adjust the magnetic properties of a layer, paramagnetic, diamagnetic and also ferromagnetic substances such as iron, nickel and cobalt or their compounds or salts (for example oxides or sulfides) can be used.
Besonders geeignet sind Magnetpigmentfarben mit Pigmenten auf Basis von Fe-oxiden, Eisen, Nickel Cobalt und deren Legierungen, Barium oder Cobaltferrite, hart- und weich magnetische Eisen- und Stahlsorten in wässrigen bzw. lösungsmittelhaltigen Dispersionen. Als Lösungsmittel kommen beispielsweise i-Propanol, Ethylacetat, Methylethylketon, Methoxypropanol und deren Mischungen in Frage.
Vorzugsweise sind die Pigmente in Acrylat- Polymerdispersionen mit einem Molekulargewicht von 150.000 bis 300.000, in Nitrocellulose, Acrylat-Urethan-Dispersionen, Acrylat- Styrol oder PVC-haltigen Dispersionen oder in lösemittelhaltige derartige Dispersionen eingebracht.Particularly suitable are magnetic pigment inks with pigments based on Fe oxides, iron, nickel cobalt and their alloys, barium or cobalt ferrites, hard and soft magnetic iron and steel grades in aqueous or solvent-containing dispersions. Examples of suitable solvents are i-propanol, ethyl acetate, methyl ethyl ketone, methoxypropanol and mixtures thereof.
The pigments are preferably incorporated in acrylate polymer dispersions having a molecular weight of from 150,000 to 300,000, in nitrocellulose, acrylate-urethane dispersions, acrylate-styrene or PVC-containing dispersions or in solvent-containing dispersions of this type.
Die magnetische Schicht kann auch eine Codierung aufweisen. Dabei können sowohl magnetische Materialien gleicher Koerzitivtät und/oder Remanenz, als auch unterschiedlicher Koerzitivität und/oder Remanenz zur Bildung der Codierung verwendet werden.
In einer weiteren Ausführungsform kann die reflektierende metallische Schciht selbst magnetische Eigenschaften aufweisen. Die wird beispielsweise durch die Verwendung eines magnetischen Materials, wie Fe, Ni, Co, erreicht.The magnetic layer may also have a coding. Both magnetic materials of the same coercivity and / or remanence as well as different coercivity and / or remanence can be used to form the coding.
In a further embodiment, the reflective metallic layer may itself have magnetic properties. This is achieved, for example, by the use of a magnetic material such as Fe, Ni, Co.
Die optischen Eigenschaften der Schicht lassen sich durch sichtbare Farbstoffe bzw. Pigmente, lumineszierende Farbstoffe bzw. Pigmente, die im sichtbaren, im UV-Bereich oder im IR-Bereich fluoreszieren bzw. phosphoreszieren, wärmeempfindliche Farben bzw. Pigmente beeinflussen. Diese sind einzeln bzw. in allen möglichen Kombinationen einsetzbar.The optical properties of the layer can be influenced by visible dyes or pigments, luminescent dyes or pigments which fluoresce or phosphoresce in the visible, in the UV region or in the IR region, heat-sensitive inks or pigments. These can be used individually or in all possible combinations.
Unter optisch aktiven Merkmalen, werden hier Beugungsstrukturen, Beugungsgitter, Kinegramme, Hologramme, DID® (Mikrostrukturen 0. Ordnung in Verbindung mit Dünnschichten) verstanden.
Diese optisch aktiven Merkmale können beispielsweise durch bekannte UV-Prägeverfahren, wie sie beispielsweise in
These optically active features can be obtained, for example, by known UV embossing methods, as used, for example, in US Pat
Um das Sicherheitselement im oder am Wertdokument zu verankern, wird dieses üblicherweise ein- oder beidseitig mit einer Klebebeschichtung versehen. Diese Klebebeschichtung kann entweder in Form einer Heißsiegel-, Kaltsiegel- oder Selbstklebebeschichtung ausgeführt sein. Der Kleber kann auch pigmentiert sein, wobei als Pigmente alle bekannte Pigmente oder Farbstoffe, beispielsweise TiO2, ZnS, Kaolin, ATO, FTO, Aluminium, Chrom-und Siliziumoxide oder beispielsweise organische Pigmente wie Pthalocyaninblau, i-Indolidgelb, Dioxazinviolett und dergleichen verwendet werden können. Ferner können lumineszierende Farbstoffe bzw. Pigmente, die im sichtbaren, im UV-Bereich oder im IR-Bereich fluoreszieren bzw. phosphoreszieren, wärmeempfindliche Farben bzw. Pigmente zugegeben werden. Diese sind in allen möglichen Kombinationen einsetzbar. Zusätzlich können auch lumineszierende Pigmente allein oder in Kombination mit anderen Farbstoffen und/oder Pigmenten eingesetzt werden.To anchor the security element in or on the document of value, this is usually provided on one or both sides with an adhesive coating. This adhesive coating can be carried out either in the form of a heat-seal, cold-seal or self-adhesive coating. The adhesive may also be pigmented, using as pigments all known pigments or dyes, for example TiO 2 , ZnS, kaolin, ATO, FTO, aluminum, chromium and silicon oxides or, for example, organic pigments such as pthalocyanine blue, i-indolid yellow, dioxazine violet and the like can. Furthermore, it is possible to add heat-sensitive dyes or pigments to luminescent dyes or pigments which fluoresce or phosphoresce in the visible, in the UV region or in the IR region. These can be used in all possible combinations. In addition, luminescent pigments can also be used alone or in combination with other dyes and / or pigments.
Gegebenenfalls kann das Sicherheitselement auch noch durch eine oder mehrere Schutzlackschicht(en) geschützt werden, die pigmentiert oder unpigmentiert sein kann, oder beispielsweise durch Kaschieren oder dergleichen weiterveredelt werden.Optionally, the security element can also be protected by one or more protective lacquer layer (s), which may be pigmented or unpigmented, or further refined, for example, by laminating or the like.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines Sicherheitselements, das ein Material aufweist, das einen optisch variablen Effekt, insbesondere einen Farbkippeffekt hervorruft und im Durchlicht erkennbare Aussparungen aufweist, umfassend folgende Verfahrensschritte:
- o Bereitstellen eines Trägersubstrats,
- o Aufbringen eines in einem Lösungsmittel löslichen Farbauftrags in Form der Aussparungen auf das Trägersubstrat,
- o Aufbringen einer vollflächigen reflektierenden metallischen Schicht,
- o Aufbringen einer vollflächigen lichtabsorbierenden metallischen Schicht,
- o Entfernen des Farbauftrags gemeinsam mit den darüber liegenden Schichten mittels eines Lösungsmittels, gegebenenfalls kombiniert mit einer mechanischen Einwirkung,
- o Aufbringen einer vollflächigen oder partiellen Schicht aus einem einen optisch variablen Effekt aufweisenden Material.
- o providing a carrier substrate,
- applying a solvent-soluble paint in the form of the recesses onto the carrier substrate,
- o application of a full-surface reflective metallic layer,
- o applying a full-surface light-absorbing metallic layer,
- removing the paint application together with the overlying layers by means of a solvent, optionally combined with a mechanical action,
- Applying a full-surface or partial layer of a material having an optically variable effect.
Dadurch werden absolut deckungsgleiche Aussparungen in der lichtabsorbierenden und der reflektierenden metallischen Schicht erreicht. Bei der Betrachtung im Durchlicht sind die Aussparungen als deutlicher Kontrast gegenüber den Bereichen, die eine lichtabsorbierende und eine reflektierende metallische Schicht aufweisen, erkennbar. Durch die reflektierende metallische Schicht ist das Sicherheitselement, wenn es in ein Wertdokument eingebettet ist, auch im Auflicht bei bei Betrachtung von der Seite der reflektierenden metallischen Schicht durch die bedeckende Papierlage nicht bzw. kaum erkennbar.As a result, absolutely congruent recesses are achieved in the light-absorbing and the reflective metallic layer. When viewed in transmitted light, the recesses can be seen as a clear contrast to the areas which have a light-absorbing and a reflective metallic layer. As a result of the reflective metallic layer, the security element, if it is embedded in a value document, is not or hardly recognizable even in incident light when viewed from the side of the reflective metallic layer by the covering paper layer.
Auf das Trägersubstrat wird in einem ersten Schritt ein in einem Lösungsmittel löslicher Farbauftrag in Form der späteren Aussparungen aufgebracht, in einem zweiten Schritt diese Schicht gegebenenfalls mittels eines Inline-Plasma-, Corona- oder Flammprozesses behandelt und
in einem dritten Schritt die reflektierende und anschließend die lichtabsorbierende metallische Beschichtung mittels eines PVD- oder CVD-Verfahrens aufgebracht, worauf in einem vierten Schritt der Farbauftrag mit den darüberliegenden Schichten mittels eines Lösungsmittels, gegebenenfalls kombiniert mit einer mechanischen Einwirkung entfernt wird.In a first step, a paint application soluble in a solvent in the form of the later recesses is applied to the carrier substrate, in a second step this layer is optionally treated by means of an in-line plasma, corona or flame process and
in a third step, the reflective and then the light-absorbing metallic coating is applied by means of a PVD or CVD process, whereupon in a fourth step the paint application with the overlying layers is removed by means of a solvent, optionally combined with a mechanical action.
Der Farbauftrag erfolgt entweder in Form von Zeichen, Buchstaben, Ziffern, Bildern, Symbolen, Linien, Guillochen oder eines Punkt- oder Linienrasters oder eines Halbtonrasters und dergleichen, oder derart, dass der Farbauftrag die Umrisse der Zeichen, Buchstaben, Ziffern, Bilder, Symbole, Linien, Guillochen, eines Punkt- oder Linienrasters oder eines Halbtonrasters und dergleichen bildet. Im ersten Fall sind die Aussparungen im fertigen Aufbau im Durchlicht in Form von Zeichen, Buchstaben, Ziffern, Bildern, Symbolen, Linien, Guillochen und dergleichen erkennbar, im zweiten Fall sind die Zeichen, Buchstaben, Ziffern, Bildern, Symbolen, Linien, Guillochen und dergleichen im Durchlicht dunkel, die Bereiche um diese Zeichen, Buchstaben, Ziffern, Bildern, Symbolen, Linien, Guillochen und dergleichen bilden die im Durchlicht erkennbaren Aussparungen.The application of paint takes place either in the form of characters, letters, numbers, images, symbols, lines, guilloches or a dot or line grid or a halftone screen and the like, or such that the application of color the outlines of the characters, letters, numbers, images, symbols , Lines, guilloches, a dot or line raster or halftone raster, and the like. In the first case, the recesses in the finished structure in transmitted light in In the second case, the characters, letters, numbers, images, symbols, lines, guilloches, and the like are dark in transmitted light, the areas around these characters, letters , Numerals, images, symbols, lines, guilloches and the like form the recesses recognizable by transmitted light.
Die Aufbringung des Farbauftrags kann durch ein beliebiges Verfahren, beispielsweise durch Tiefdruck, Flexodruck, Siebdruck, Digitaldruck und dergleichen erfolgen. Die verwendete Farbe bzw. der verwendete Farblack ist in einem Lösungsmittel, vorzugsweise in Wasser löslich, es kann jedoch auch eine in jedem beliebigen Lösungsmittel, beispielsweise in Alkohol, Estern und dergleichen lösliche Farbe verwendet werden. Die Farbe bzw. der Farblack können übliche Zusammensetzungen auf Basis von natürlichen oder künstlichen Makromolekülen sein. Die lösliche Farbe kann pigmentiert oder nicht pigmentiert sein. Als Pigmente können alle bekannten Pigmente verwendet werden. Besonders geeignet sind TiO2, ZnS, Kaolin und dergleichen.The application of the paint can be done by any method, for example by gravure printing, flexographic printing, screen printing, digital printing and the like. The color or lacquer used is soluble in a solvent, preferably water, but it is also possible to use a dye soluble in any solvent, for example in alcohol, esters and the like. The color or the colored lacquer can be customary compositions based on natural or artificial macromolecules. The soluble color may be pigmented or unpigmented. As pigments, all known pigments can be used. Particularly suitable are TiO 2 , ZnS, kaolin and the like.
Anschließend erfolgt gegebenenfalls eine Vorbehandlung des mit dem Farbauftrag versehenen Trägersubstrats vor der Aufbringung der metallischen Schichten mittels eines Inline-Plasma-, (Niederdruck- oder Atmosphärenplasma-), Corona- oder Flammprozesses. Diese Vorbehandlung verbessert die Haftung der metallischen Schicht. Gleichzeitig wird die Oberfläche aktiviert. Dabei werden endständige polare Gruppen an der Oberfläche erzeugt.Subsequently, if appropriate, a pretreatment of the carrier substrate provided with the inking takes place prior to the application of the metallic layers by means of an inline plasma, (low pressure or atmospheric plasma), corona or flame process. This pretreatment improves the adhesion of the metallic layer. At the same time, the surface is activated. In this case, terminal polar groups are generated on the surface.
Gegebenenfalls kann gleichzeitig mit der Anwendung der Plasma- bzw. Corona- oder Flammbehandlung eine dünne Metall- oder Metalloxidschicht als Haftvermittler, beispielsweise durch Sputtern oder Aufdampfen aufgebracht werden. Besonders geeignet sind dabei Cr, Ti, TiO2, Si-Oxide oder Chromoxide. Diese Haftvermittlerschicht weist im allgemeinen eine Dicke von 0,1 nm - 5 nm, vorzugsweise 0,2 nm - 2 nm, besonders bevorzugt 0,2 bis 1 nm auf.Optionally, simultaneously with the application of the plasma or corona or flame treatment, a thin metal or metal oxide layer can be applied as adhesion promoter, for example by sputtering or vapor deposition. Particularly suitable are Cr, Ti, TiO 2 , Si oxides or chromium oxides. This adhesive layer generally has a thickness of 0.1 nm - 5 nm, preferably 0.2 nm - 2 nm, particularly preferably 0.2 to 1 nm.
Anschließend erfolgt die Aufbringung der reflektierenden metallischen Schicht durch PVD- oder CVD-Verfahren, etwa durch thermisches Verdampfen, durch Sputtern oder Elektronenstrahlbedampfung.Subsequently, the application of the reflective metallic layer by PVD or CVD method, such as by thermal evaporation, by sputtering or Elektronenstrahlbedampfung.
In einem PVD- Verfahren wird die Beschichtung unter Vakuum (bis 10-12 mbar, vorzugsweise 10-2 bis 10-6 mbar) bei einer vom Dampfdruck und der Dicke der aufzubringenden Beschichtung abhängigen Temperatur auf dem Trägersubstrat beispielsweise durch thermisches Verdampfen, Lichtbogen- oder Elektronenstrahlverdampfen abgeschieden.In a PVD process, the coating is applied under vacuum (to 10 -12 mbar, preferably 10 -2 to 10 -6 mbar) at a temperature dependent on the vapor pressure and the thickness of the applied coating on the carrier substrate, for example by thermal evaporation, arc or Electron beam evaporation deposited.
Eine weitere Möglichkeit ist das Aufbringen der Beschichtung durch AC- oder DC-Sputtern, wobei je nach Dicke der aufzubringenden Schicht und eingesetztem Material das entsprechende Verfahren gewählt wird.Another possibility is the application of the coating by AC or DC sputtering, wherein the appropriate method is selected depending on the thickness of the layer to be applied and the material used.
In einem CVD-Verfahren werden die aufzubringenden Stoffe in Form von gasförmigen (z.B. organometallischen) Vorläuferverbindungen (sogenannten Precursoren) mittels eines inerten Trägergases (z.B. N2, Argon) in ein Vakuumbeschichtungssystem eingebracht, durch Eintrag von Energie aufgebrochen und zur Reaktion gebracht. Ein Teil der Reaktionsprodukte kondensiert auf dem Substrat und bildet dort die gewünschte Schicht, die übrigen Reaktionsprodukte werden über ein Vakuumsystem entfernt. Gasförmige Precursoren können z.B. CO, CO2, Sauerstoff, Silane, Methan, Ammoniak, Ferrocen, Trimethylaluminium, oder dergleichen sein.
Die Einbringung der Energie kann z.B. mittels eines lonen- oder Elektronenstrahls, eines Plasmas oder über erhöhte Temperatur erfolgen.In a CVD process, the substances to be applied in the form of gaseous (eg organometallic) precursor compounds (so-called precursors) by means of an inert carrier gas (eg N 2 , argon) introduced into a vacuum coating system, broken up by the entry of energy and reacted. Part of the reaction products condenses on the substrate where it forms the desired layer, the remaining reaction products are removed via a vacuum system. Gaseous precursors can be, for example, CO, CO 2 , oxygen, silanes, methane, ammonia, ferrocene, trimethylaluminum, or the like.
The introduction of energy can be done for example by means of an ion or electron beam, a plasma or at elevated temperature.
In folgenden Schritt wird analog eine lichtabsorbierende metallische Schicht durch PVD- oder CVD-Verfahren, etwa durch thermisches Verdampfen, durch Sputtern oder Elektronenstrahlbedampfung abgeschieden.In the following step, a light-absorbing metallic layer is deposited analogously by PVD or CVD methods, for example by thermal evaporation, by sputtering or electron beam vapor deposition.
Für die Aufbringung der lichtabsorbierenden metallischen Schicht wird die Beschichtung durch entsprechend dosierte Sauerstoffzufuhr zu unstöchiometrischen Oxiden oxidiert, wodurch auch das Erscheinungsbild verändert wird. So erscheint unstöchiometrisches Aluminiumoxid oder stöchiometrisches oder unstöchiometrisches Kupferoxid schwarz und bildet so eine lichtabsorbierende metallische Schicht.For the application of the light-absorbing metallic layer, the coating is oxidized by appropriately metered oxygen supply to unstoichiometric oxides, whereby the appearance is changed. Thus, unstoichiometric alumina or stoichiometric or unstoichiometric copper oxide appears black to form a light-absorbing metallic layer.
Anschließend wird die Farbschicht durch ein geeignetes Lösungsmittel, das auf die Zusammensetzung der Farbschicht abgestimmt ist, entfernt. Bevorzugt ist der Farbauftrag wasserlöslich. Gegebenenfalls kann die Ablösung durch mechanische Einwirkung unterstützt werden.Subsequently, the color layer is removed by a suitable solvent, which is adapted to the composition of the color layer. The application of paint is preferably water-soluble. Optionally, the separation can be supported by mechanical action.
Alternativ können die Aussparungen auch durch ein bekanntes Ätzverfahren hergestellt werden. Dabei werden zuerst die reflektierende und die lichtabsorbierende metallische Schicht auf das Trägersubstrat aufgebracht, und anschließend ein Ätzresist aufgetragen, der die späteren Aussparungen freilässt. In einem weiteren Schritt werden die nicht mit dem Ätzresist bedeckten Bereiche der beiden Schichten durch Ätzen entfernt. Ggf. kann der Ätzresist anschließend entfernt werden.Alternatively, the recesses may also be made by a known etching process. In this case, first the reflective and the light-absorbing metallic layer are applied to the carrier substrate, and then an etching resist is applied, which leaves open the later recesses. In a further step, the areas of the two layers not covered by the etch resist are removed by etching. Possibly. the etch resist can then be removed.
In einem weiteren Schritt wird eine vollflächige oder partielle Schicht eines einen optisch variablen Effekt aufweisenden Materials aufgebracht. Die Aufbringung kann durch ein beliebiges Verfahren, beispielsweise durch Tiefdruck, Flexodruck, Siebdruck, Digitaldruck, Walzenauftragsverfahren mit Mit- oder Gegenlauf, Curtain Coating, Spin-Coating und dergleichen erfolgen.In a further step, a full-surface or partial layer of an optically variable effect material is applied. Application may be by any method, such as gravure, flexo, screen, digital, roll or reverse, curtain coating, spin coating, and the like.
In einer weiteren Ausführungsform kann das Verfahren zur Herstellung des Sicherheitselements wie folgt durchgeführt werden:
- o Bereitstellen eines ersten Trägersubstrats,
- o Aufbringen einer vollflächigen oder partiellen Schicht aus einem einen optisch variablen Effekt aufweisenden Material,
- o Bereitstellen eines zweiten Trägersubstrats,
- o Aufbringen eines in einem Lösungsmittel löslichen Farbauftrags in Form der Aussparungen auf das zweite Trägersubstrat,
- o Aufbringen einer vollflächigen reflektierenden metallischen Schicht
- o Aufbringen einer vollflächigen lichtabsorbierenden metallischen Schicht,
- o Entfernen des Farbauftrags gemeinsam mit den darüber liegenden Schichten mittels eines Lösungsmittels, gegebenenfalls kombiniert mit einer mechanischen Einwirkung,
- o Kaschieren der Schichten auf dem zweiten Trägersubstrat gegen die Schichten auf dem ersten Trägersubstrat,
- o gegebenenfalls Entfernen des ersten Trägersubstrats.
- o providing a first carrier substrate,
- applying a full-surface or partial layer of a material having an optically variable effect,
- o providing a second carrier substrate,
- o application of a solvent-soluble paint in the form of the recesses on the second carrier substrate,
- Applying a full-surface reflective metallic layer
- o applying a full-surface light-absorbing metallic layer,
- removing the paint application together with the overlying layers by means of a solvent, optionally combined with a mechanical action,
- laminating the layers on the second carrier substrate against the layers on the first carrier substrate,
- Optionally, removing the first carrier substrate.
Dabei erfolgt auf einem zweiten Trägersubstrat der Aufbau der, die im Durchlicht erkennbaren Aussparungen aufweisenden, Schichten, während auf dem ersten Trägersubstrat die Schicht aus einem einen optisch variablen Effekt aufweisenden Material aufgebracht ist.
Insbesondere bei Verwendung von Flüssigkristallpolymeren, die in Form ihrer Monomere in einer Lösung aufgebracht und anschließend vernetzt werden, als Schicht mit einem optisch variablen Effekt, ist diese Ausführungsform bevorzugt. Die Molekülketten können sich dabei auf dem Trägersubstrat orientieren.
Anschließend werden die auf dem zweiten Trägersubstrat aufgebrachten Schichten, gegen die auf dem ersten Trägersubstrat vorhandenen Schichten kaschiert, gegebenenfalls kann je nach Verwendung des Sicherheitselements das erste Trägersubstrat entfernt werden.In this case, the structure of the layers having recognizable recesses in the transmitted light is applied to a second carrier substrate, while the layer of an optically variable effect material is applied to the first carrier substrate.
In particular, when using liquid crystal polymers, which are applied in the form of their monomers in a solution and then crosslinked, as a layer having an optically variable effect, this embodiment is preferred. The molecular chains can thereby orient themselves on the carrier substrate.
Subsequently, the layers applied to the second carrier substrate are laminated against the layers present on the first carrier substrate, optionally the first carrier substrate can be removed depending on the use of the security element.
Gegebenenfalls können auf das erste und/oder auf das zweite Trägersubstrat bzw. auf die auf diesen vorhandenen Schichten weitere Sicherheitsmerkmale mit optischen, optisch aktiven, elektrisch leitfähigen oder magnetischen Eigenschaften aufgebracht werden oder bereits auf diesen aufgebracht sein. Das so hergestellte Sicherheitselement kann anschließend ein- oder beidseitig mit einer oder mehreren Schutzlackschicht(en) und/oder einer Klebebeschichtung versehen werden.Optionally, further security features having optically, optically active, electrically conductive or magnetic properties can be applied to the first and / or the second carrier substrate or to the layers present thereon, or already applied thereto. The security element produced in this way can then be provided on one or both sides with one or more protective lacquer layer (s) and / or an adhesive coating.
Ein weiterer Gegenstand der Erfindung ist ein Verfahren zur Herstellung eines transferierbaren Sicherheitselements, das ein Material aufweist, das einen optisch variablen Effekt, insbesondere einen Farbkippeffekt hervorruft und im Durchlicht erkennbare Aussparungen aufweist, umfassend folgende Verfahrensschritte:
- o Bereitstellen eines ersten Trägersubstrats,
- o Aufbringen einer vollflächigen oder partiellen Schicht aus einem einen optisch variablen Effekt aufweisenden Material,
- o Aufbringen eines in einem Lösungsmittel löslichen Farbauftrags in Form der Aussparungen
- o Aufbringen einer vollflächigen lichtabsorbierenden metallischen Schicht,
- o Aufbringen einer vollflächigen reflektierenden metallischen Schicht,
- o Entfernen des Farbauftrags gemeinsam mit den darüber liegenden Schichten mittels eines Lösungsmittels, gegebenenfalls kombiniert mit einer mechanischen Einwirkung,
- o Aufbringen einer Heißsiegel-, Kaltsiegel- oder Selbstklebebeschichtung.
- o providing a first carrier substrate,
- applying a full-surface or partial layer of a material having an optically variable effect,
- Applying a soluble in a solvent paint in the form of recesses
- o applying a full-surface light-absorbing metallic layer,
- o application of a full-surface reflective metallic layer,
- removing the paint application together with the overlying layers by means of a solvent, optionally combined with a mechanical action,
- o Apply a heat-seal, cold-seal or self-adhesive coating.
Dabei erfolgt der komplette Schichtaufbau auf dem ersten Trägersubstrat, wobei alle angeführten Verfahrensschritte analog zu dem oben beschriebenen Verfahren erfolgen.
Gegebenenfalls kann dabei vor der Aufbringung der Schicht aus einem einen optisch variablen Effekt aufweisenden Material eine Releaseschicht auf das Trägersubstrat aufgebracht werden, deren Haftung zum Trägersubstrat geringer ist als zu den darauf aufgebrachten Schichten. Als Releaseschichten kommen vorteilhafterweise UV-Lackschichten in Frage, es ist aber auch möglich andere bekannte schlecht haftende Lackzusammensetzungen, beispielsweise auf Methacrylatbasis oder Ölschichten, Polyamid-, Polyethylen-oder Fluorpolymerwachsschichten zu verwenden. Das Aufbringen einer Releaseschicht ist nicht erforderlich, falls die Schicht aus einem Material, das einen optisch variablen Effekt aufweist, releasefähig ist.
Das so hergestellte Sicherheitselement kann mit der Klebebeschichtung auf ein Substrat appliziert werden, wobei das erste Trägersubstrat ggf. nach der Applikation entfernt wird.In this case, the complete layer structure takes place on the first carrier substrate, with all the method steps mentioned being carried out analogously to the method described above.
Optionally, a release layer may be applied to the carrier substrate before the application of the layer of a material having an optically variable effect, whose adhesion to the carrier substrate is lower than to the layers applied thereon. As release stories For example, it is also possible to use other known poorly adhering coating compositions, for example methacrylate-based or oil-based, polyamide, polyethylene or fluoropolymer wax layers. The application of a release layer is not necessary if the layer of a material which has an optically variable effect is releasable.
The security element produced in this way can be applied to a substrate with the adhesive coating, wherein the first carrier substrate is removed, if necessary, after the application.
In den
- 1 eine Klebebeschichtung ( beispielsweise eine Heißsiegellackschicht)
- 2 die Schicht aus einem einen optisch variablen Effekt hervorrufenden Material
- 3 eine Kaschierklebeschicht
- 4 eine lichtabsorbierende metallische Schicht
- 5 eine reflektierende metallische Schicht
- 6 eine Schutzlackschicht
- 7 eine partielle Schicht mit magnetischen Eigenschaften
- 8 ein Trägersubstrat
- 9 ein weiteres Trägersubstrat
- 10 die Aussparungen in der lichtabsorbierenden und der reflektierenden metallischen Schicht
- 11 eine weitere reflektierende metallische Schicht
- 12 das Substrat eines Wertdokuments, beispielweise Papier.
- 1 an adhesive coating (for example a heat sealing lacquer layer)
- FIG. 2 shows the layer of a material causing an optically variable effect. FIG
- 3 a laminating adhesive layer
- 4 a light absorbing metallic layer
- 5 a reflective metallic layer
- 6 a protective lacquer layer
- 7 a partial layer with magnetic properties
- 8 a carrier substrate
- 9, a further carrier substrate
- 10 the recesses in the light-absorbing and the reflective metallic layer
- 11 another reflective metallic layer
- 12 the substrate of a document of value, for example paper.
In
In
In den
Die Haftung der Schichten 2 zu Schicht 8 ist geringer als die Haftung der Schichten 2, 4, 5, 6, 1 und 8 untereinander.In the
The adhesion of the
In
In
Die erfindungsgemäßen Sicherheitselemente sind gegebenenfalls nach entsprechender Konfektionierung als Sicherheitsmerkmale in Datenträgern, insbesondere Wertdokumenten wie Ausweisen, Karten, Banknoten oder Etiketten, Siegeln und dergleichen geeignet, aber auch als Verpackungsmaterial beispielsweise in der pharmazeutischen, der Elektronik-und/oder Lebensmittelindustrie, beispielsweise in Form von Blisterfolien, Faltschachteln, Abdeckungen, Folienverpackungen und dergleichen geeignet.The security elements according to the invention are optionally after appropriate assembly as security features in data carriers, in particular value documents such as identity cards, cards, banknotes or Labels, seals and the like suitable, but also suitable as packaging material, for example in the pharmaceutical, electronics and / or food industry, for example in the form of blister films, cartons, covers, film packaging and the like.
Für die Anwendung als Sicherheitsmerkmale werden die Substrate bzw. Folienmaterialien bevorzugt in Streifen, Fäden oder Patches geschnitten, wobei die Breite der Streifen oder Fäden vorzugsweise 0,5 - 20 mm betragen kann und die Patches vorzugsweise mittlere Breiten bzw. Längen von 0,3 - 20 mm aufweisen.For use as security features, the substrates or film materials are preferably cut into strips, threads or patches, wherein the width of the strips or threads may preferably be 0.5-20 mm and the patches preferably have average widths or lengths of 0.3. 20 mm.
Für die Anwendung in oder auf Verpackungen wird das Folienmaterial bevorzugt in Streifen, Bänder, Fäden oder Patches geschnitten, wobei die Breite der der Fäden, Streifen bzw. Bänder vorzugsweise 0,5 - 50 mm beträgt und die Patches vorzugsweise mittlere Breiten und Längen von 2 - 30 mm aufweisen.For use in or on packaging, the film material is preferably cut into strips, tapes, threads or patches, the width of which of the threads, strips or tapes being preferably 0.5-50 mm and the patches preferably being average widths and lengths of 2 - 30 mm.
Claims (16)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL11007998T PL2578414T3 (en) | 2011-10-04 | 2011-10-04 | Security element with colour-switching effect, use of same and method for producing same |
| SI201130128T SI2578414T1 (en) | 2011-10-04 | 2011-10-04 | Security element with colour-switching effect, use of same and method for producing same |
| ES11007998.5T ES2441352T3 (en) | 2011-10-04 | 2011-10-04 | Security element with color change effect, method for its manufacture and use |
| EP11007998.5A EP2578414B1 (en) | 2011-10-04 | 2011-10-04 | Security element with colour-switching effect, use of same and method for producing same |
| US14/344,076 US9387718B2 (en) | 2011-10-04 | 2012-10-03 | Security element with color-switching effect, use of same and method for producing same |
| CA2847297A CA2847297A1 (en) | 2011-10-04 | 2012-10-03 | Security element with colour-switching effect, use of same and method for producing same |
| KR1020147011808A KR102014562B1 (en) | 2011-10-04 | 2012-10-03 | A security element with a color shift effect, and methods for the production and use thereof |
| RU2014117705/12A RU2600088C2 (en) | 2011-10-04 | 2012-10-03 | Protective element with effect of color change and method of its production and use |
| PCT/EP2012/004141 WO2013050140A1 (en) | 2011-10-04 | 2012-10-03 | A security element with a color shift effect, and methods for the production and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP11007998.5A EP2578414B1 (en) | 2011-10-04 | 2011-10-04 | Security element with colour-switching effect, use of same and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP2578414A1 true EP2578414A1 (en) | 2013-04-10 |
| EP2578414B1 EP2578414B1 (en) | 2013-12-11 |
Family
ID=46982520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP11007998.5A Revoked EP2578414B1 (en) | 2011-10-04 | 2011-10-04 | Security element with colour-switching effect, use of same and method for producing same |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US9387718B2 (en) |
| EP (1) | EP2578414B1 (en) |
| KR (1) | KR102014562B1 (en) |
| CA (1) | CA2847297A1 (en) |
| ES (1) | ES2441352T3 (en) |
| PL (1) | PL2578414T3 (en) |
| RU (1) | RU2600088C2 (en) |
| SI (1) | SI2578414T1 (en) |
| WO (1) | WO2013050140A1 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102016000592A1 (en) * | 2015-12-30 | 2017-07-06 | Giesecke & Devrient Gmbh | Plastic film molding, manufacturing process and blister |
| EP3290225A1 (en) * | 2016-09-01 | 2018-03-07 | Giesecke+Devrient Currency Technology GmbH | Security element with a plurality of security features |
| DE102018004054A1 (en) * | 2018-05-18 | 2019-11-21 | Giesecke+Devrient Currency Technology Gmbh | Manufacturing method for a security element |
| EP3738785A1 (en) * | 2019-05-14 | 2020-11-18 | Hueck Folien Gesellschaft m.b.H. | Security element with machine readable features |
| EP3939802A1 (en) * | 2020-09-29 | 2022-01-19 | Hueck Folien Gesellschaft m.b.H. | Substrate for producing security papers or security papers |
| WO2022033653A1 (en) * | 2020-08-14 | 2022-02-17 | Giesecke+Devrient Currency Technology Gmbh | Elongate security element and method for producing an elongate security element |
| EP4000942A1 (en) * | 2020-11-16 | 2022-05-25 | Hueck Folien Gesellschaft m.b.H. | Security element having machine readable security features |
| RU2814380C1 (en) * | 2020-09-29 | 2024-02-28 | Хуек Фолиен Гезелльшафт М.Б.Х. | Substrate for obtaining security papers or counterfeit-proof documents |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT516128B1 (en) * | 2014-07-17 | 2018-05-15 | Hueck Folien Gmbh | Security element with color shift effect and tamper evidence |
| FR3026988B1 (en) | 2014-10-13 | 2021-07-02 | Arjowiggins Security | SECURITY ELEMENT FOR SECURE DOCUMENT |
| DE102015003665A1 (en) * | 2015-03-20 | 2016-09-22 | Giesecke & Devrient Gmbh | security element |
| EP3178660B2 (en) | 2015-12-07 | 2022-12-28 | Hueck Folien Ges.m.b.H | Personalisable security element |
| EP3576956A1 (en) * | 2017-02-02 | 2019-12-11 | Fedrigoni S.p.A. | Double metal security element having transparent pattern |
| RU2660408C1 (en) * | 2017-08-11 | 2018-07-06 | Российская Федерация, от имени которой выступает Государственная корпорация по атомной энергии "Росатом" (Госкорпорация "Росатом") | Method of manufacturing light-absorbing elements of optical systems on titanium substrates |
| DE102018007096A1 (en) * | 2018-09-07 | 2020-03-12 | Giesecke+Devrient Currency Technology Gmbh | Security element |
| KR102432996B1 (en) * | 2020-05-13 | 2022-08-17 | 엔비에스티(주) | Means Preventing Forgery and Falsification Comprising Cholesteric Liquid Crystal Layer |
| DE102021003199A1 (en) * | 2021-06-22 | 2022-12-22 | Giesecke+Devrient Currency Technology Gmbh | Security element with a marking layer with a plurality of gaps and method for producing a security element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102016000592A1 (en) * | 2015-12-30 | 2017-07-06 | Giesecke & Devrient Gmbh | Plastic film molding, manufacturing process and blister |
| US11059643B2 (en) | 2015-12-30 | 2021-07-13 | Giesecke+Devrient Currency Technology Gmbh | Molded plastic film article, manufacturing method, and blister |
| EP3290225A1 (en) * | 2016-09-01 | 2018-03-07 | Giesecke+Devrient Currency Technology GmbH | Security element with a plurality of security features |
| DE102018004054A1 (en) * | 2018-05-18 | 2019-11-21 | Giesecke+Devrient Currency Technology Gmbh | Manufacturing method for a security element |
| EP3738785A1 (en) * | 2019-05-14 | 2020-11-18 | Hueck Folien Gesellschaft m.b.H. | Security element with machine readable features |
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| RU2814380C1 (en) * | 2020-09-29 | 2024-02-28 | Хуек Фолиен Гезелльшафт М.Б.Х. | Substrate for obtaining security papers or counterfeit-proof documents |
| EP4000942A1 (en) * | 2020-11-16 | 2022-05-25 | Hueck Folien Gesellschaft m.b.H. | Security element having machine readable security features |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2441352T3 (en) | 2014-02-04 |
| KR20140085481A (en) | 2014-07-07 |
| WO2013050140A1 (en) | 2013-04-11 |
| US9387718B2 (en) | 2016-07-12 |
| US20140342105A1 (en) | 2014-11-20 |
| RU2600088C2 (en) | 2016-10-20 |
| KR102014562B1 (en) | 2019-08-26 |
| SI2578414T1 (en) | 2014-08-29 |
| CA2847297A1 (en) | 2013-04-11 |
| RU2014117705A (en) | 2015-11-10 |
| EP2578414B1 (en) | 2013-12-11 |
| PL2578414T3 (en) | 2014-05-30 |
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